Laminated curable resin structures, dry films, cured materials, and electronic components

Abstract

A laminated curable resin structure is provided that can obtain a cured product with high resolution, crack resistance, and excellent adhesion to metal plating. The laminated curable resin structure comprises a two-layer resin layer in which an X layer containing an alkali-soluble resin composition X and a Y layer containing an alkali-soluble resin composition Y are laminated, wherein the X layer is laminated to the Y layer and the X layer is 5% or more and 30% or less of the total thickness of the two-layer resin layer combined with the Y layer, and a cured product with a thickness of 20 to 30 μm obtained by light irradiation of 1000 mJ / cm2 and heat treatment at 160°C for 1 hour, wherein the coefficient of thermal expansion at 200 to 250°C as determined by thermomechanical analysis is 110 ppm / °C or less.

Description

Technology Field

[0001] The present invention relates to a laminated curable resin structure, a dry film, a cured product, and an electronic component. Background Technology

[0002] In recent years, due to the rapid advancement of semiconductor components, electronic devices have tended to become smaller, lighter, higher in performance, and more multifunctional. Following this trend, high-density mounted semiconductor packages have been proposed that are miniaturized, multi-pinned, and even incorporate chips of different performance capabilities into a single package.

[0003] Specifically, as high-density IC packages, FC-CSP (Flip-Chip Chip Scale Package), FC-BGA (Flip-Chip Ball Grid Array), and FO-WLP (Fan-Out Wafer Level Package) for applications such as smartphone APs (Application Processors) have been commercialized. In organic interposers used in these high-density IC packages, and in some cases, glass or silicon interposers, the diameter of the conductive vias formed in the insulating layer containing a curable resin has been reduced. In addition, circuit wiring has also become finer and denser. Therefore, high insulation reliability and patternability (resolution) are required for the insulating materials applied to these interposers.

[0004] In addition, when forming high-density wiring by the semi-additive method, excellent adhesion between the curable resin and the plated metal, specifically copper, is required. This is because when copper for conductivity is filled by electroless copper plating by the semi-additive method into vias formed in an insulating layer containing the curable resin after curing, the adhesion between the curable resin and the copper affects the reliability of the wiring.

[0005] Regarding a high-resolution photosensitive resin composition, in order to suppress warping caused by the difference in thermal expansion coefficients between the semiconductor chip and the substrate accompanying the thinning of the package substrate, the photosensitive resin composition for a permanent mask resist may be highly filled with inorganic fillers, and the highly filled inorganic fillers may include two types with different average particle sizes and may also contain organic fillers (Patent Document 1). Prior art literature

[0006] Japanese Patent No. 6210060 The problem to be solved

[0007] However, in the technology described in Patent Document 1, the adhesion to the metal plating was not necessarily sufficient.

[0008] In order to improve adhesion to metal plating, methods are being considered to achieve an anchoring effect by surface roughening through dry plasma treatment or wet desmear treatment as a pretreatment method for curable resins after curing. However, if dry plasma treatment is performed for a long time on a curable resin containing a filler as described in Patent Document 1, the filler contained in the resin is prone to being exposed to the surface. Since the filler does not have good adhesion to metal plating, it was difficult to obtain sufficient adhesion strength if a large amount was exposed to the surface. If the filler is surface-treated, adhesion to organic materials can be expected even if the filler is exposed to the surface by plasma, as the surface is modified; however, regarding adhesion to metal plating, it was also difficult to obtain sufficient adhesion if the filler was coordinated to the surface.

[0009] In addition, as another pretreatment method to improve adhesion, a method of surface roughening using a desmearing solution is being considered. When using a desmearing solution, it is expected that high adhesive strength will be obtained because, compared to plasma treatment, it is difficult to maintain the state in which fillers in the curable resin coordinate to the surface, and the contact interface with the metal plating is mainly the resin. However, if the surface of the curable resin composition is immersed in the desmearing solution for a long time to create a sufficient anchor shape, adhesion is not obtained because the cured material is damaged by the desmearing solution and its strength decreases. In particular, when the curable resin is an alkali-soluble resin, it is difficult to form an ideal rough surface because it has low resistance to the high pH of the desmearing solution.

[0010] In this regard, while conventional alkali-soluble resins have improved alkali resistance, they suffer from poor developability during patterning, low productivity, and difficulty in achieving high resolution.

[0011] Therefore, the object of the present invention is to provide a laminated curable resin structure capable of obtaining a cured product having high resolution, crack resistance, and excellent adhesion to metal plating, a dry film having a resin layer obtained from said laminated curable resin structure, a cured product of the resin layer of said laminated curable resin structure or said dry film, and an electronic component having said cured product. means of solving the problem

[0012] The inventors have repeatedly conducted research to develop an alkali-soluble resin composition having high resolution, crack resistance, and high adhesion to metal plating. As a result, they have discovered that by forming the alkali-soluble resin composition into a two-layer laminated curable resin structure in which a layer with increased adhesion to metal plating and a layer with increased physical properties regarding reliability are laminated in the thickness direction, the alkali-soluble resin composition can maintain high resolution while possessing insulation reliability including high crack resistance and high adhesion to metal plating, thereby arriving at the present invention.

[0013] That is, the laminated curable resin structure of the first embodiment of the present invention is,

[0014] It is composed of two layers of resin, wherein a layer X containing an alkali-soluble resin composition X and a layer Y containing an alkali-soluble resin composition Y are laminated, and the thickness of the two layers of resin combined with the layer Y is 5% or more and 30% or less.

[0015] 1000 mJ / cm² 2 A cured product with a thickness of 20 to 30 μm, produced by light irradiation and heat treatment at 160°C for 1 hour, is characterized by having a coefficient of thermal expansion (CTE) of 200 to 250°C as determined by Thermal Mechanical Analysis (TMA) of 110 ppm / °C or less.

[0016] In the first embodiment of the present invention, the laminated curable resin structure preferably comprises alkali-soluble resin compositions X and Y of the X layer and the Y layer, additionally comprising at least one selected from radical polymerizable compounds and epoxy resins.

[0017] In addition, the alkali-soluble resin compositions X and Y of the X layer and the Y layer comprise at least one selected from rubber particles and elastomers having an average particle size of 100 nm or more to 1 μm or less, and it is preferable that the total amount of the rubber particles and elastomers in the X layer is greater than the total amount of the rubber particles and elastomers in the Y layer, and furthermore, the alkali-soluble resin compositions X and Y of the X layer and the Y layer comprise inorganic particles, and said inorganic particles comprise silica.

[0018] The silica in the X layer has an average particle size of 50 nm or less and is less than 25 mass% of the alkali-soluble resin composition X of the X layer, and

[0019] Preferably, the silica in the Y layer has an average particle size of 200 nm or more and constitutes 25 mass% or more and less than 50 mass% of the alkali-soluble resin composition Y of the Y layer.

[0020] In addition, it is preferable that the inorganic particles in the alkali-soluble resin composition Y of the above Y layer include inorganic particles comprising metal elements having O, S, or N in their coordination electrons, in an amount of less than 20% of the corresponding alkali-soluble resin composition Y of the Y layer.

[0021] The alkali-soluble resin composition X of the X layer of the laminated curable resin structure of the first embodiment of the present invention comprises inorganic particles, wherein the inorganic particles comprise silica, and wherein the silica has an average particle size of 50 nm or less and is less than 25 mass% of the resin composition.

[0022] In addition, the alkali-soluble resin composition Y of the Y layer of the laminated curable resin structure of the first embodiment of the present invention comprises inorganic particles, wherein the inorganic particles comprise silica, and wherein the silica has an average particle size of 200 nm or less and is characterized in that it is 25 mass% or more and less than 50 mass% of the alkali-soluble resin composition Y.

[0023] The dry film of the present invention is characterized by having a resin layer obtained by applying and drying a laminated curable resin structure of the first embodiment of the present invention onto a film.

[0024] The cured product of the present invention is characterized by being obtained by curing the resin layer of the laminated curable resin structure of the first embodiment of the present invention or the dry film.

[0025] The electronic component of the present invention is characterized by having the above-mentioned hardened material.

[0026] That is, the laminated curable resin structure of the second embodiment of the present invention is,

[0027] It is composed of a two-layer resin layer in which an X layer containing an alkali-soluble resin composition X and a Y layer containing an alkali-soluble resin composition Y are laminated, wherein the X layer is 5% or more and 30% or less of the total thickness of the two-layer resin layer combined with the Y layer.

[0028] The alkali-soluble resin compositions X and Y of the X layer and the Y layer are characterized in that they comprise inorganic particles, wherein the inorganic particles of the X layer comprise inorganic particles comprising metal elements having O, S, or N in their coordination electrons, and the inorganic particles of the Y layer comprise silica.

[0029] In the second embodiment of the present invention, the laminated curable resin structure preferably comprises alkali-soluble resin compositions X and Y of the X layer and the Y layer, additionally comprising at least one selected from radical polymerizable compounds and epoxy resins.

[0030] In addition, it is preferable that the alkali-soluble resin compositions X and Y of the X layer and the Y layer comprise at least one selected from rubber particles and elastomers having an average particle size of 100 nm or more to 1 μm or less.

[0031] In addition, it is preferable that the alkali-soluble resin compositions X and Y of the X layer and the Y layer include a curing accelerator.

[0032] The dry film of the present invention is characterized by having a resin layer obtained by applying and drying a laminated curable resin structure of the second embodiment of the present invention onto a film.

[0033] The cured product of the present invention is characterized by being obtained by curing the resin layer of the laminated curable resin structure of the second embodiment of the present invention or the dry film.

[0034] The electronic component of the present invention is characterized by having the above-mentioned hardened material. Effects of the invention

[0035] According to the laminated curable resin structure of the first embodiment and the laminated curable resin structure of the second embodiment of the present invention, a laminated curable structure having high resolution (shape sharpness), crack resistance (cold and heat resistance) and high adhesion to metal plating, a dry film having a resin layer obtained from said laminated curable structure, a cured product of the resin layer of said laminated curable structure or said dry film, and an electronic component having said cured product can be provided. Brief explanation of the drawing

[0036] FIG. 1 is a schematic cross-sectional view of an example of a dry film of the present invention. Figure 2 is a sketch of an SEM image showing the resolution (shape sharpness) evaluation performed on Example 1-1. Figure 3 is a sketch of an SEM image showing the resolution (shape sharpness) evaluation for Comparative Examples 1-2. Figure 4 is a sketch of an SEM image showing the resolution (shape sharpness) evaluation for Example 2-1. Figure 5 is a sketch of an SEM image showing the resolution (shape sharpness) evaluation for Comparative Example 2-2. Specific details for implementing the invention

[0037] The laminated curable resin structure, dry film, cured product, and electronic component of the first embodiment of the present invention will be described in more detail.

[0038] A laminated curable resin structure of the first embodiment of the present invention comprises two resin layers, wherein an X layer comprising an alkali-soluble resin composition X and a Y layer comprising an alkali-soluble resin composition Y are laminated. As a two-layer structure laminated in the thickness direction of the resin, it is formed on a substrate such as a printed circuit board or a flexible printed circuit board in which a circuit is pre-formed using copper, etc., and the bottom side of a via formed in this structure becomes the Y layer, and the top side of the via becomes the X layer. For such a two-layer laminated curable resin structure of the first embodiment of the present invention, as a combination of X layer and Y layer having different characteristics, the ratio of the X layer is less than or equal to a specific ratio relative to the sum of the X layer and Y layer in terms of layer thickness, and the coefficient of thermal expansion in a specific test is small when the entire two resin layers are cured. Specifically, the X layer is 5% or more and 30% or less of the total thickness of the two resin layers combined with the Y layer, and the coefficient of thermal expansion is 1000 mJ / cm². 2In a cured product with a thickness of 20 to 30 μm obtained by light irradiation and heat treatment at 160°C for 1 hour, the coefficient of thermal expansion at 200 to 250°C as determined by thermomechanical analysis is 110 ppm / °C or less, thereby enabling the simultaneous achievement of resolution (shape sharpness), crack resistance, and high adhesion to metal plating. Furthermore, the laminated curable resin structure of the first embodiment of the present invention may be a structure having another layer located outside the X layer or outside the Y layer of the laminate of the X layer and the Y layer.

[0039] The thickness of the X layer is 30% or less of the total thickness of the two resin layers combined with the Y layer. By being 30% or less, sufficient adhesion to the metal plating by the X layer can be secured, while the physical properties of the Y layer, specifically crack resistance, can be secured. Although the lower limit of the thickness of the X layer is not particularly limited, it is preferable that it be 5% or more of the total thickness of the two resin layers combined with the Y layer.

[0040] In addition, having a coefficient of thermal expansion within the above range allows for a high crosslinking density of the resin and can improve resistance to alkaline solutions, such as electroless copper plating solutions. The coefficient of thermal expansion (CTE) in the laminated curable resin structure of the first embodiment of the present invention is 1000 mJ / cm² 2 This is the coefficient of linear expansion at 200 to 250°C by thermomechanical analysis of a cured product with a thickness of 20 to 30 μm obtained by light irradiation and heat treatment at 160°C for 1 hour.

[0041] In order to make the coefficient of thermal expansion (CTE) of the present invention 110 ppm / ℃ or less, more preferably 100 ppm / ℃ or less, it is preferable to adjust the composition of at least one of the following: the laminated curable resin structure comprising at least one selected from radical polymerizable compounds and epoxy resins, comprising inorganic particles of a specific particle size, and comprising rubber particles of a specific particle size.

[0042] For example, in order to adjust the coefficient of thermal expansion (CTE) of the present invention, a radical polymerizable compound such as maleimide or a radical novolak-based epoxy acrylate resin is used as an alkali-soluble resin, and an inorganic filler that has undergone surface treatment to form a strong bond with the epoxy resin is used, and by adjusting each of these components within the range of the amounts of each component described below, the coefficient of thermal expansion (CTE) of the present invention can be made 110 ppm / ℃ or less.

[0043] As for the inorganic filler described above, spherical silica is preferred, and as for the surface treatment, using a methacrylate-based silane coupling agent is optimal for making the coefficient of thermal expansion (CTE) of the present invention 110 ppm / ℃ or less because it produces the greatest toughness.

[0044] In addition, as the epoxy resin described above, a phenol novolak type epoxy resin and / or an epoxy resin having three or more functional groups and an epoxy equivalent of 250 g / eq or less is preferred. The phenol novolak type epoxy resin has good heat resistance as it has a rigid backbone, and the epoxy resin having three or more functional groups and an epoxy equivalent of 250 g / eq or less is effective in making the coefficient of thermal expansion (CTE) of the present invention 110 ppm / ℃ or less because the crosslinking is dense due to the relatively small epoxy equivalent of 250 g / eq or less.

[0045] In addition, adhesion to metal plating can be achieved by using different resin compositions in the X layer and the Y layer.

[0046] The X layer of the laminated curable resin structure of the first embodiment of the present invention can be a layer that improves the adhesion to metal plating when either plasma pretreatment or desmear pretreatment is performed, by including silica with a small particle size as an inorganic particle with respect to adhesion to metal plating, and by having a smaller amount of silica than the Y layer to reduce exposure of inorganic particles and make the surface almost entirely resin, and by including rubber particles or elastomer and having a larger amount of rubber particles or elastomer than the Y layer, making it easier to form anchors. In addition, since there are fewer inorganic particles and it is almost entirely a resin layer, light scattering is reduced, and the sharpness at the top of the via can be improved.

[0047] The Y layer of the stackable resin structure of the first embodiment of the present invention may be a layer that prioritizes physical properties to ensure insulation reliability through high crack resistance of the entire stackable resin structure, and includes silica particles with a particle size of submicron as inorganic particles, thereby providing a good tapered shape to the bottom of the via. In addition, to improve the plating adhesion to the wall surface of the via, the Y layer may include inorganic particles containing a metal element having O, S, or N in its coordination electrons, thereby improving the adhesion of the metal plating and providing excellent adhesion to the substrate.

[0048] A laminated curable resin structure, a dry film, a cured product, and an electronic component of a second embodiment of the present invention will be described in more detail.

[0049] A laminated curable resin structure of the second embodiment of the present invention comprises two layers of resin, wherein an X layer comprising an alkali-soluble resin composition X and a Y layer comprising an alkali-soluble resin composition Y are laminated. As a structure of a two-layer structure laminated in the thickness direction of the resin, it is formed on a substrate such as a printed circuit board or a flexible printed circuit board in which a circuit is formed in advance by copper, and the bottom side of the via formed in this structure becomes the Y layer, and the top side of the via becomes the X layer. For such a two-layer laminated curable resin structure, as a combination of X layer and Y layer with different characteristics, the ratio of the X layer is less than or equal to a specific ratio relative to the sum of the X layer and Y layer in terms of layer thickness, and the alkali-soluble resin compositions X and Y of the X layer and Y layer contain inorganic particles, wherein the inorganic particles of the X layer are inorganic particles containing metal elements having O, S, and N in their coordination electrons, and the inorganic particles of the Y layer are composed of silica, thereby enabling the combination of resolving power, crack resistance, and high adhesion to metal plating. In addition, the laminated curable resin structure of the second embodiment of the present invention may be a structure having another layer located outside the X layer or outside the Y layer of the laminate of the X layer and the Y layer.

[0050] The thickness of the X layer of the laminated curable resin structure of the second embodiment of the present invention is 30% or less of the total thickness of the two resin layers combined with the Y layer. By being 30% or less, sufficient adhesion to the metal plating by the X layer can be secured, while the physical properties of the Y layer, specifically crack resistance, can be secured. The lower limit of the thickness of the X layer is not particularly limited, but it is preferable that it be 5% or more of the total thickness of the two resin layers combined with the Y layer.

[0051] In addition, adhesion to metal plating can be achieved by using different resin compositions for the X layer and the Y layer of the laminated curable resin structure of the second embodiment of the present invention.

[0052] The X layer of the laminated curable resin structure of the second embodiment of the present invention can be a layer that improves the adhesion of metal plating by including inorganic particles containing metal elements having O, S, and N in coordination electrons as inorganic particles, and preferably by including rubber particles or elastomers to facilitate the formation of anchors, thereby improving the adhesion of metal plating when either plasma pretreatment or desmear pretreatment is performed. In addition, since there are few inorganic particles and it is almost entirely a resin layer, light scattering is minimal, and the sharpness of the via's top can be improved.

[0053] The Y layer of the laminated curable resin structure of the second embodiment of the present invention may be a layer that prioritizes physical properties to ensure insulation reliability through high crack resistance of the entire laminated curable resin structure, and includes silica particles as inorganic particles, thereby imparting a good tapered shape to the bottom of the via.

[0054] Hereinafter, each component of the laminated curable resin structure of the first and second embodiments of the present invention will be described. Furthermore, in this specification, the term (meth)acrylate is a collective term for acrylates, methacrylates, and mixtures thereof, and the same applies to other similar expressions.

[0055] [(A) Alkali-soluble resin]

[0056] The alkali-soluble resin compositions X and Y of the X and Y layers of the laminated curable resin structure of the first and second embodiments of the present invention both comprise an alkali-soluble resin. The alkali-soluble resin is, for example, a resin containing one or more alkali-soluble groups among phenolic hydroxyl groups, thiol groups, and carboxyl groups, and preferably, examples include a compound having two or more phenolic hydroxyl groups, a carboxyl group-containing resin, a compound having phenolic hydroxyl groups and carboxyl groups, and a compound having two or more thiol groups. (A) As the alkali-soluble resin, a carboxyl group-containing resin or a phenolic hydroxyl group-containing resin may be used, but (B) a carboxyl group-containing resin is preferred from the perspective of reactivity with the epoxy resin.

[0057] In addition, (A) alkali-soluble resin is preferably of lower weight average molecular weight, as this increases the proportion of alkali-soluble groups in the alkali-soluble resin and increases the crosslinking density of the cured product. (A) The weight average molecular weight of the alkali-soluble resin is preferably 20,000 or less when measured by weight average molecular weight (Mw) in terms of polystyrene equivalent by gel permeation chromatography (GPC).

[0058] (A) In terms of developability, photocurability, and development resistance, it is preferable for the alkali-soluble resin to have an ethylenically unsaturated group in addition to the carboxyl group. In addition, only a carboxyl group-containing resin that does not have an ethylenically unsaturated group may be used. As for the ethylenically unsaturated group, it is preferable that it be derived from acrylic acid, methacrylic acid, or derivatives thereof.

[0059] Specific examples of carboxyl group-containing resins include the compounds listed below (which may be either oligomers or polymers).

[0060] (1) A photosensitive resin containing carboxyl groups, wherein (meth)acrylic acid is reacted with a difunctional or polyfunctional epoxy resin to add a dibasic acid anhydride, such as phthalic anhydride, tetrahydrophthalic anhydride, or hexahydrophthalic anhydride, to the hydroxyl groups present in the side chains. Here, the difunctional or polyfunctional epoxy resin is preferably in solid form.

[0061] (2) A photosensitive resin containing a carboxyl group, wherein a dibasic acid anhydride is added to a polyfunctional epoxy resin in which the hydroxyl group of a difunctional epoxy resin is epoxidized with epichlorohydrin, and (meth)acrylic acid is reacted to generate the hydroxyl group. Here, the difunctional epoxy resin is preferably solid.

[0062] (3) A carboxyl group-containing photosensitive resin obtained by reacting a compound having at least one alcoholic hydroxyl group and one phenolic hydroxyl group in one molecule with an epoxy resin having two or more epoxy groups in one molecule and a monocarboxylic acid containing an unsaturated group such as (meth)acrylic acid, and then reacting the alcoholic hydroxyl group of the reaction product with a polybasic acid anhydride such as maleic anhydride, tetrahydrophthalic anhydride, trimellitic anhydride, pyrromellitic anhydride, or adipic anhydride.

[0063] (4) A carboxyl group-containing photosensitive resin obtained by reacting a reaction product obtained by reacting a compound having two or more phenolic hydroxyl groups in one molecule, such as bisphenol A, bisphenol F, bisphenol S, novolak-type phenol resin, poly-p-hydroxystyrene, a condensate of naphthol and aldehydes, a condensate of dihydroxynaphthalene and aldehydes, with an alkylene oxide such as ethylene oxide or propylene oxide, and then reacting the reaction product obtained by reacting a monocarboxylic acid containing an unsaturated group, such as (meth)acrylic acid, with a polybasic acid anhydride.

[0064] (5) A carboxyl group-containing photosensitive resin obtained by reacting a reaction product obtained by reacting a compound having two or more phenolic hydroxyl groups in one molecule with a cyclic carbonate compound such as ethylene carbonate or propylene carbonate with a monocarboxylic acid containing an unsaturated group, and then reacting the reaction product obtained with a polybasic acid anhydride.

[0065] (6) A carboxyl group-containing photosensitive 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, and isobutylene.

[0066] (7) A carboxyl group-containing polyester resin in which a dicarboxylic acid such as adipic acid, phthalic acid, or hexahydrophthalic acid is added to the primary hydroxyl group generated by reacting a polyfunctional oxetane resin with a dicarboxylic acid.

[0067] (8) A carboxyl group-containing photosensitive resin to which a compound having a cyclic ether group and a (meth)acryloyl group in one molecule is added to the carboxyl group-containing resins of (1) to (7) described above.

[0068] (9) A carboxyl group-containing photosensitive resin having a copolymer structure formed by adding a compound having one epoxy group and one or more (meth)acryloyl groups in a molecule such as glycidyl (meth)acrylate, α-methylglycidyl (meth)acrylate, epoxycyclohexylmethyl (meth)acrylate to a carboxyl group-containing copolymer resin having a monomer of a maleimide or maleimide derivative such as N-phenylmaleimide, N-benzylmaleimide, (meth)acrylate, an unsaturated group-containing compound having a hydroxyl group such as (meth)acrylate, and an unsaturated group-containing compound having an aromatic ring such as styrene, α-methylstyrene, α-chlorostyrene, vinyltoluene.

[0069] As for a carboxyl group-containing resin having an ethylenically unsaturated group (also called a carboxyl group-containing photosensitive resin), it is preferable to have a structure in which the ethylenically unsaturated group of the main chain and the ethylenically unsaturated group of the side chain are spaced apart, such as in phenolic resin or epoxy resin. In other words, when introducing an ethylenically unsaturated group into the side chain, it is preferable to introduce a chain extension structure such that a certain distance is created between the main chain and the ethylenically unsaturated group. Such a structure is desirable because it improves the reactivity between the ethylenically unsaturated groups of the side chain. As for a carboxyl group-containing resin having a chain extension structure and an ethylenically unsaturated group, for example, the carboxyl group-containing resins described in (3), (4), (5), and (8) above are preferred.

[0070] (A) The double bond equivalent of the alkali-soluble resin and the double bond equivalent of the compound having an ethylenically unsaturated group described below is 1000 g / eq or less. By being 1000 g / eq or less, along with the epoxy equivalent of the (B) epoxy resin described below being 1000 g / eq or less, the reactivity of the double bond equivalent of the double bond equivalent is improved, stable resistance to electroless copper plating solution is obtained, and furthermore, an ideal rough surface can be formed.

[0071] It is preferable that the acid value of the alkali-soluble resin be 40 to 150 mgKOH / g. By making the acid value of the carboxyl group-containing resin 40 mgKOH / g or higher, the alkali phenomenon is improved. In addition, by making the acid value 150 mgKOH / g or lower, it is easy to draw a normal cured product pattern. More preferably, it is 50 to 130 mgKOH / g.

[0072] The amount of (A) alkali-soluble resin in each alkali-soluble resin composition X and Y of the X layer and Y layer of the laminated curable resin structure of the first and second embodiments of the present invention is, for example, 10 to 70 mass% and preferably 20 to 60 mass% based on the total amount of solids of each alkali-soluble resin composition X and Y of the X layer and Y layer excluding solvent. By making it 10 mass% or more, preferably 20 mass% or more, the film strength can be improved. In addition, by making it 70 mass% or less, processability is improved. More preferably, it is 30 to 50 mass%.

[0073] [(B) Epoxy Resin]

[0074] The alkali-soluble resin compositions X and Y of the X and Y layers of the laminated curable resin structure of the first and second embodiments of the present invention may both include epoxy resins, which are thermosetting resins. By including epoxy resins, the crosslinking density can be improved, thereby further enhancing resistance to alkaline solutions such as electroless plating solutions.

[0075] As epoxy resins, bisphenol A type epoxy resin; hydroquinone type epoxy resin; bisphenol type epoxy resin; thioether type epoxy resin; brominated epoxy resin; novolak type epoxy resin; biphenol novolak type epoxy resin; bisphenol F type epoxy resin; hydrogenated bisphenol A type epoxy resin; glycidylamine type epoxy resin; hydantoin type epoxy resin; alicyclic epoxy resin; trihydroxyphenylmethane type epoxy resin; alkylphenol type epoxy resin (e.g., bixylenol type epoxy resin); biphenol type epoxy resin; bisphenol S type epoxy resin; bisphenol A novolak type epoxy resin; tetraphenylolethane type epoxy resin; heterocyclic epoxy resin; diglycidyl phthalate resin; tetraglycidylxylenoylene resin; naphthalene group-containing epoxy resin; epoxy resin having a dicyclopentadiene backbone; triphenylmethane type epoxy resin; epoxy resin having a silsesquioxane backbone; Examples include glycidyl methacrylate copolymer epoxy resin; copolymer epoxy resin of cyclohexyl maleimide and glycidyl methacrylate; epoxy-modified polybutadiene rubber derivative; CTBN-modified epoxy resin, etc. Epoxy resins may be used individually or in combination of two or more types. Among these, at least one of novolak-type epoxy resin, bisphenol-type epoxy resin, bixylenol-type epoxy resin, biphenol-type epoxy resin, biphenol-novolak-type epoxy resin, naphthalene-type epoxy resin, epoxy resin having a silsesquioxane backbone, and triphenylmethane-type epoxy resin is particularly preferred.

[0076] In addition, an epoxy resin having the structure of the following formula (I) containing trisphenolmethane and bisphenol A in the backbone may also be used.

[0077]

[0078] The epoxy resin having the structure of formula (I) above has excellent toughness and heat resistance as it is an aromatic polyfunctional epoxy with a high softening point. For example, it can be obtained as Tecmore (registered trademark) VG3101L manufactured by Mitsui Kagaku Co., Ltd. or NC-6300H manufactured by Nippon Kagaku Co., Ltd. Tecmore VG3101L has a softening point of 60°C, a pale yellow solid with a Gardner color number of 3 or less, an epoxy equivalent weight of 210 g / eq., and a total chlorine content of 1000 ppm or less, and possesses characteristics such as high heat resistance, low water absorption, and low curing shrinkage.

[0079] It is preferable that the epoxy resin comprises two or more types of polyfunctional epoxy resins from the perspective of lowering CTE by increasing the crosslinking density. In this specification, "polyfunctional" means two or more functionalities.

[0080] As an epoxy resin used in the alkali-soluble resin composition Y of the Y layer, among the epoxy resins, it is particularly preferable to include a trifunctional or higher epoxy resin to improve adhesion to the substrate. The structure of the trifunctional or higher epoxy resin is not particularly limited and can be any epoxy resin having three or more epoxy groups.

[0081] Specific examples of commercially available epoxy resins having three or more functional epoxy groups include: the trifunctional aminophenol-type epoxy resin with the trade name "jER-630" (manufactured by Mitsubishi Chemical); the trifunctional triazine backbone-containing epoxy resins with trade names "TEPIC-S," "TEPIC-HP," and "TEPIC-VL" (manufactured by Nissan Chemical); the trifunctional aromatic epoxy resin with the trade name "Tecmore VG3101" (manufactured by Printec); the tetrafunctional aromatic epoxy resin with the trade name "GTR-1800" (manufactured by Nippon Chemical); the modified novolak-type epoxy resin with the trade name "EPICLON-N740" (manufactured by DIC); the dicyclopentadiene-type epoxy resin with the trade name "EPICLON-HP7200H-75M" (manufactured by DIC); and the cresol novolak-type epoxy resin with the trade name Examples include “EPICLON-N660” (manufactured by DIC), the trade name of the phenol novolak type epoxy resin “jER-152” (manufactured by Mitsubishi Chemical), and the trade name of the naphthalene type epoxy resin “ESN-175S” (manufactured by Nittetsu Chemical & Material).

[0082] The amount of (B) epoxy resin in each alkali-soluble resin composition X and Y of the X and Y layers is, for example, 1 to 100 parts by mass with respect to 100 parts by mass of (A) alkali-soluble resin in each alkali-soluble resin composition X and Y of the X and Y layers, preferably 10 to 80 parts by mass, and more preferably 20 to 60 parts by mass. If the amount of (B) thermosetting component is 1 part by mass or more, adhesion and mechanical properties are improved, and if it is 100 parts by mass or less, storage stability is improved. In addition, as in the examples described below, when rubber particles are dispersed in the epoxy resin, the amount of the epoxy resin in which the rubber particles are dispersed is also included in the amount of the epoxy resin.

[0083] The laminated curable resin structure comprising the (B) epoxy resin described above has an epoxy equivalent of 1000 g / eq or less. By having an epoxy equivalent of 1000 g / eq or less, stable resistance to metal plating treatment solution is obtained in addition to the double bond equivalent of the (A) alkali-soluble resin described above having 1000 g / eq or less. Additionally, an ideal rough surface can be formed.

[0084] [Radical polymerizable compounds]

[0085] The alkali-soluble resin compositions X and Y of the X and Y layers of the laminated curable resin structure of the first and second embodiments of the present invention may both contain a radical polymerizable compound instead of, or together with, the epoxy resin of the present invention. The radical polymerizable compound, like the epoxy resin described above, can improve crosslinking density and further enhance resistance to alkaline solutions, such as electroless plating solutions. Such radical polymerizable compounds include radical polymerizable resins and radical polymerizable monomers.

[0086] As radical polymerizable resins, unsaturated polyester, epoxy acrylate, urethane acrylate, polyester acrylate, polyether (meth)acrylate, polybutadiene modified (meth)acrylate, etc. may be used. When using these radical polymerizable resins, it is preferable to use 80 parts by weight or less of the radical polymerizable resin with respect to 100 parts by weight of the (A) carboxyl group-containing photosensitive resin in each of the alkali-soluble resin compositions X and Y of the X layer and Y layer. A more preferable upper limit is 70 parts by weight, and an even more preferable upper limit is 60 parts by weight.

[0087] As radical polymerizable monomers, both monofunctional monomers (having one radical polymerizable double bond) and polyfunctional monomers (having two or more radical polymerizable double bonds) can be used. Since radical polymerizable monomers are involved in polymerization, the viscosity of the resin composition may be adjusted to improve the properties of the resulting cured product. When using radical polymerizable monomers, the preferred amount is 300 parts by weight or less, more preferably 100 parts by weight or less, per 100 parts by weight of (A) carboxyl group-containing photosensitive resin in each of the X layer and Y layer alkali-soluble resin compositions X and Y. The preferred lower limit is 1 part by weight, more preferably 5 parts by weight, per 100 parts by weight of (A) carboxyl group-containing photosensitive resin. In addition, when (A) a carboxyl group-containing photosensitive resin and (A) a carboxyl group-containing resin other than (A) are used together, the amount of radical polymerizable monomer used is within the above range with respect to 100 parts by mass of the total amount of (A) a carboxyl group-containing photosensitive resin and (A) a carboxyl group-containing resin other than (A).

[0088] Specific examples of radical polymerizable monomers include N-phenylmaleimide, N-(2-methylphenyl)maleimide, N-(4-methylphenyl)maleimide, N-(2,6-diethylphenyl)maleimide, N-(2-chlorophenyl)maleimide, N-methylmaleimide, N-ethylmaleimide, N-isopropylmaleimide, N-laurylmaleimide, N-cyclohexylmaleimide, N-phenylmethylmaleimide, N-(2,4,6-tribromophenyl)maleimide, N-[3-(triethoxysilyl)propyl]maleimide, N-octadecenylmaleimide, N-dodecenylmaleimide, N-(2-methoxyphenyl)maleimide, N-(2,4,6-trichlorophenyl)maleimide, N-(4-hydroxyphenyl)maleimide, N-substituted maleimide group-containing monomers such as N-(1-hydroxyphenyl)maleimide; styrene derivatives such as styrene, α-methylstyrene, α-chlorostyrene; aromatic vinyl monomers such as vinyltoluene, p-hydroxystyrene, divinylbenzene, diallylphthalate, diallylbenzenephosphonate; allyl compounds such as trialylisocyanurate, diallyl isophthalate; vinyl ester monomers such as vinyl acetate, vinyl adipoyl adipose, vinyl butyrate, or vinyl benzoate;(Meth)acrylic acid, methyl(meth)acrylate, ethyl(meth)acrylate, butyl(meth)acrylate, methoxyethyl(meth)acrylate, ethoxyethyl(meth)acrylate, 2-hydroxyethyl(meth)acrylate, 3-hydroxypropyl(meth)acrylate, 2-hydroxypropyl(meth)acrylate, 4-hydroxybutyl(meth)acrylate, 4-hydroxymethyl(meth)acrylamide, pentaerythritol mono(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol mono(meth)acrylate, trimethylolpropane mono(meth)acrylate, butanediol di(meth)acrylate, 1,6-Hexanediol mono(meth)acrylate, glycerol mono(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, (di)ethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, trimethylolpropane di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, ethoxylated trimethylolpropane triacrylate, propoxylated trimethylolpropane tri(meth)acrylate, tris[2-(meth)acryloyloxyethyl]triazine, dendritic acrylate, (Meta)acrylic monomers such as hydroxypivalsan neopentyl glycol ester di(meth)acrylate; esters of (meth)acrylic acid such as 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, isoboronyl (meth)acrylate, phenyl (meth)acrylate, phenoxyethyl (meth)acrylate; isocyanurate-type poly(meth)acrylates such as tris[(meth)acryloxyethyl]isocyanurate; (meth)acrylates such as acrylamide, methacrylamide, N-hydroxymethylacrylamide, N-hydroxymethylmethacrylamide, N-methoxymethylacrylamide, N-ethoxymethylacrylamide, N-butoxymethylacrylamide;(hydroxy)alkyl vinyl(thio)ethers such as n-propyl vinyl ether, isopropyl vinyl ether, vinyl-n-butyl ether, vinyl-t-butyl ether, vinyl-n-amyl ether, vinyl isoamyl ether, vinyl-n-octadecyl ether, isobutyl vinyl ether, n-hexyl vinyl ether, cyclohexyl vinyl ether, 2-ethylhexyl vinyl ether, 4-hydroxybutyl vinyl ether, ethylene glycol monobutyl vinyl ether, triethylene glycol monomethyl vinyl ether, etc.; Examples include vinyl(thio)ethers having radical polymerizable double bonds such as (meth)acrylic acid 2-(vinyloxyethoxy)ethyl, (meth)acrylic acid 2-(isopropenoxyethoxyethoxy)ethyl, (meth)acrylic acid 2-(isopropenoxyethoxyethoxyethoxy)ethyl, and (meth)acrylic acid 2-(isopropenoxyethoxyethoxyethoxy)ethyl; monomers containing acid anhydrides such as maleic anhydride, or monomers obtained by ring-opening the acid anhydride group therefrom using alcohols, amines, water, etc.; N-vinyl monomers such as N-vinylpyrrolidone and N-vinyloxazolidone; and compounds having one or more radical polymerizable double bonds such as allyl alcohol and trialyl cyanurate.

[0089] These are appropriately selected according to the intended use or required characteristics, and one or more types can be used in combination.

[0090] [(C-1) Inorganic Particles]

[0091] The alkali-soluble resin compositions X and Y of the X and Y layers of the laminated curable resin structure of the first embodiment of the present invention may both include inorganic particles, among others, silica, as inorganic fillers. By including inorganic particles, the coefficient of thermal expansion can be lowered and the alkali resistance of the cured product can be improved. It is preferable that the silica be slurried, and after slurrying, it is preferable that the average particle size of the X layer be 50 nm or less, and the average particle size of the Y layer be 200 nm or more. Since the silica of the X layer has an average particle size of 50 nm or less, the exposure of silica to the surface of the X layer is suppressed, and by making the surface almost resinous, adhesion to the metal plating can be improved. In addition, since the silica of the X layer has an average particle size of 50 nm or less, light scattering is reduced, and sharpness of the via top can be achieved. Since the silica of the Y layer has an average particle size of 200 nm or more, adhesion to the metal plating can be secured while imparting a tapered shape to the via bottom. It is more preferable that the silica in the Y layer has an average particle size of 700 nm or less. Furthermore, in this specification, the average particle size of the inorganic particles is the 50% cumulative particle diameter (D50 volume%) that includes not only the particle size of the primary particles but also the particle size of the secondary particles (aggregates). The average particle size can be obtained by a laser diffraction particle diameter distribution measuring device and a measuring device based on dynamic light scattering. Examples of measuring devices based on laser diffraction include the Microtrac MT3300EXII manufactured by Microtrac Bell, and examples of measuring devices based on dynamic light scattering include the Nanotrac Wave II UT151 manufactured by Microtrac Bell. Among silicas, spherical silica is a preferred inorganic particle because, compared to other silicas, it has a relatively small surface area, stress is distributed throughout so it is unlikely to become a crack initiation point, and it also has excellent packing properties.

[0092] It is preferable that silica be included in an amount of less than 25 mass% relative to the total solid content of the alkali-soluble resin composition X of the X layer in the X layer of the laminated curable resin structure of the first embodiment of the present invention. By keeping the silica content at less than 25 mass%, the exposure of silica to the surface of the X layer is suppressed, and the surface is made almost entirely resinous, thereby improving adhesion to the metal plating. In addition, since the silica in the X layer has an average particle size of 50 nm or less, light scattering is reduced, and sharpness of the via top can be achieved. The lower limit of the silica content in the X layer is not particularly limited, but is more preferably 5 to 20 mass%.

[0093] It is preferable that silica be included in an amount of 25 mass% or more and less than 50 mass% with respect to the total solid content of the alkali-soluble resin composition Y of the Y layer in the Y layer of the laminated curable resin structure of the first embodiment of the present invention. By having silica in an amount of 25 mass% or more and less than 50 mass%, the CTE can be lowered while imparting a tapered shape to the via bottom, thereby improving plating adhesion and crack resistance to the cured product.

[0094] The alkali-soluble resin composition Y of the Y layer of the laminated curable resin structure of the first embodiment of the present invention may include, as inorganic particles, particles of an inorganic component comprising a metal element having O, S, or N in a coordination electron. By including an inorganic component comprising a metal element having O, S, or N in a coordination electron together with the silica, the adhesion of the metal plating can be improved, thereby providing excellent adhesion to the substrate. Specifically, the inorganic component comprising a metal element having O, S, or N in a coordination electron is Al2O3, AlN, BaSO4, BaCO3, CaCO3, Ca(OH)2, MgO, Mg(OH)2, Mg3Si4O 10Examples include (OH)2, hydrotalcite, and hydrotalcite-type compounds. The average particle size of the inorganic component particles containing these specific metal elements is not particularly limited, but a range of 1 nm to 2 µm is preferred from the perspective of appropriately mixing with spherical silica in the curable resin.

[0095] The above hydrotalcite and hydrotalcite-type compounds are a type of naturally occurring clay mineral, for example, a positively charged base layer [Mg 1-X Al X (OH)2] X+ and negatively charged intermediate layer [(CO3) X / 2 ·mH2O] X- It is a layered inorganic compound containing [it]. Many divalent and trivalent metals have a layered structure similar to this, and their general structural formulas are represented by the following formula (II).

[0096]

[0097] During the meal, M 2+ Silver Mg 2+ , Fe 2+ , Zn 2+ , Ca 2+ , Li 2+ , Ni 2+ , Co 2+ , Cu 2+ Divalent metal cations such as M 3+ Al 3+ , Fe 3+ , Mn 3+ trivalent metal cations such as A n- CO3 2- It represents, and the subscripts attached below each element and atomic group indicate the ratio of each element and atomic group, and X is 0 <X≤0.33, m은 m≥0이다. m은 m≥0이지만, 탈수에 의해 크게 변한다.

[0098] Specific examples of the above layered multiple oxides (A) include indigirite Mg2Al2[(CO3)4(OH)2]·15H2O, Fe 2+4Al2[(OH) 12 [CO3]·3H2O, Quintinite Mg4Al2(OH) 12 CO3·H2O, Manasseite Mg6Al2[(OH) 16 [CO3]·4H2O, SjOegrenite Mg6Fe 3+ 2[(OH) 16 [CO3]·4H2O, Zaccagnaite Zn4Al2(CO3)(OH) 12 ·3H2O, Desautelsite Mg6Mn 3+ 2[(OH) 16 [CO3]·4H2O, Hydrotalcite Mg6Al2[(OH) 16 [CO3]·4H2O, Pyroaurite Mg6Fe 3+ 2[(OH) 16 [CO3]·4H2O, Reevesite Ni6Fe 3+ 2[(OH) 16 [CO3]·4H2O, Stichtite Mg6Cr2[(OH) 16 [CO3]·4H2O, Takovite Ni6Al2[(OH) 16 Examples include CO3]·4H2O, and can be used alone or in combination of two or more types.

[0099] In addition, commercially available synthetic hydrotalcites include Kyowa Chemical Co., Ltd.’s Alkamizer, DHT-4A, Kyowad 500, Kyowad 1000, and Sakai Chemical Co., Ltd.’s STABIACE series HT-1, HT-7, HT-P, etc.

[0100] It is particularly desirable to use synthetic hydrotalcites, with an average particle size of 2 μm or less, and more preferably 1 μm or less. In addition, these hydrotalcites can be used in their hydrated state or in an anhydrous state after calcination.

[0101] It is preferable that particles of an inorganic component containing a metal element having O, S, or N in its coordination electrons be included in the Y layer in an amount of less than 20 mass% relative to the total solid content of the alkali-soluble resin composition Y of the Y layer. By including less than 20 mass%, the adhesion of the metal plating to the via diameter wall surface can be improved. The lower limit of the content is not particularly limited, but is more preferably 3 to 15 mass%.

[0102] It is preferable that the spherical silica of the inorganic particles and the inorganic component containing the specific metal component are both surface-treated. Surface treatment using a coupling agent is preferred. As coupling agents, silane coupling agents, titanium coupling agents, zirconium coupling agents, aluminum coupling agents, etc., may be used. Among these, silane coupling agents are preferred. For the inorganic particles containing the specific metal element, a surface treatment of the inorganic particles that can be expected to improve compatibility with the organic component may be used.

[0103] For silane coupling, a silane coupling agent capable of introducing a reactive group into an inorganic particle is preferred. Examples of silane coupling agents capable of introducing a reactive group into an inorganic particle include a silane coupling agent having a vinyl group, a silane coupling agent having a methacrylic group, a silane coupling agent having an acrylic group, a silane coupling agent having an epoxy group, a silane coupling agent having a carboxyl group, and the like; among these, a silane coupling agent having at least one of a (meth)acrylic group and a vinyl group is preferred.

[0104] Surface-treated inorganic particles may be incorporated into a laminated curable resin structure in a surface-treated state. Although surface-untreated inorganic particles and a surface treatment agent may be mixed separately to surface-treat the inorganic particles within the composition, it is preferable to incorporate pre-surface-treated inorganic particles. By incorporating pre-surface-treated inorganic particles, it is possible to prevent a decrease in crack resistance, etc., caused by unconsumed surface treatment agents that may remain when mixed separately. When pre-surface treating, it is preferable to incorporate a pre-dispersion solution in which the inorganic particles are pre-dispersed in a solvent or resin component. It is even more preferable to pre-disperse the surface-treated inorganic particles in a solvent and then incorporate the said pre-dispersion solution into the composition, or to sufficiently surface-treat the surface-untreated inorganic particles when pre-dispersing them in a solvent and then incorporate the said pre-dispersion solution into the composition.

[0105] [(C-2) Inorganic Particles]

[0106] The alkali-soluble resin compositions X and Y of the X and Y layers of the laminated curable resin structure of the second embodiment of the present invention both include inorganic particles as inorganic fillers. By including inorganic particles, the coefficient of thermal expansion can be lowered and the alkali resistance of the cured product can be improved.

[0107] The X layer of the second aspect of the present invention comprises inorganic particles as inorganic particles, wherein the inorganic particles comprise metal elements having O, S, or N in their coordination electrons. By including an inorganic component comprising metal elements having O, S, or N in their coordination electrons, the adhesion of the metal plating can be improved, thereby providing excellent adhesion to the via diameter wall. Specifically, the inorganic component comprising metal elements having O, S, or N in their coordination electrons is Al2O3, AlN, BaSO4, BaCO3, CaCO3, Ca(OH)2, MgO, Mg(OH)2, Mg3Si4O 10Examples include (OH)2, hydrotalcite, and hydrotalcite-type compounds. The average particle size of the inorganic component particles containing these specific metal elements is not particularly limited, but a range of 1 nm to 2 µm is preferred from the perspective of appropriately mixing with spherical silica in the curable resin.

[0108] The above hydrotalcite and hydrotalcite-type compounds are as described in the above (C-1) inorganic particles.

[0109] In the X layer of the second embodiment of the present invention, it is preferable to include particles of an inorganic component containing a metal element having O, S, or N in its coordination electrons in an amount of less than 20 mass% relative to the total solid content of the alkali-soluble resin composition X of the X layer. By including less than 20 mass%, the adhesion of the metal plating to the via diameter wall surface can be improved. The lower limit of the content is not particularly limited, but is more preferably 3 to 15 mass%.

[0110] The Y layer of the second embodiment of the present invention comprises silica as an inorganic particle. It is preferable that the silica be slurried, and it is preferable that the average particle size after slurrying be 1 to 900 nm. It is more preferable that the silica of the Y layer of the second embodiment of the present invention have an average particle size of 700 nm or less. Furthermore, this average particle size is as described in the (C-1) inorganic particle above. In addition, among silicas, spherical silica is a preferred inorganic particle because, compared to other silicas, it has a relatively small surface area, stress is distributed throughout so it is unlikely to become a crack initiation point, and it also has excellent packing properties.

[0111] It is preferable that silica be included in an amount of 25 mass% or more and less than 50 mass% with respect to the total solid content of the alkali-soluble resin composition Y of the Y layer in the second embodiment of the present invention. By having silica in an amount of 25 mass% or more and less than 50 mass%, a tapered shape can be imparted to the via bottom while lowering the CTE, thereby improving plating adhesion and crack resistance to the cured product.

[0112] (C-2) It is preferable that the spherical silica of the inorganic particles and the inorganic component including the specific metal component are all surface-treated. This surface treatment is as described in the (C-1) inorganic particles above.

[0113] [(D) At least one selected from rubber particles and thermoplastic elastomers]

[0114] The alkali-soluble resin compositions X and Y of the X and Y layers of the laminated curable resin structure of the first and second embodiments of the present invention both include at least one type selected from rubber particles and thermoplastic elastomers, which includes a flexible polymer and serves as a stress reliever for impact resistance, etc., as an organic filler.

[0115] (rubber particles)

[0116] Specifically, regarding the crack resistance, adhesion, and electrical insulation properties of the cured film, examples of rubber particles include silicone rubber particles, acrylic rubber particles, cross-linked acrylonitrile butadiene, cross-linked styrene-butadiene rubber particles, and core-shell type rubber particles, but core-shell type rubber particles are particularly preferred. Core-shell rubber particles refer to a rubber material with a multilayer structure consisting of a core layer of different compositions and one or more shell layers covering it. As for the core-shell rubber particles, as described below, by composing the core layer with a material having excellent flexibility and the shell layer with a material having excellent affinity for other components, good dispersibility is achieved while achieving a low elastic modulus through the formulation of rubber components.

[0117] As the constituent material of the core layer, a material with excellent flexibility is used. Examples include silicone-based elastomers, butadiene-based elastomers, styrene-based elastomers, acrylic-based elastomers, polyolefin-based elastomers, silicone / acrylic composite elastomers, etc., but it is preferable to include a (meth)acrylate-based polymer.

[0118] As for the (meth)acrylate-based polymer constituting the core layer, specifically,

[0119] · Polymer of ethyl acrylate and methyl methacrylate,

[0120] · Methyl acrylate and methyl methacrylate polymer,

[0121] ·2-ethylhexyl acrylate and methyl methacrylate polymer,

[0122] · Polymer of butyl acrylate, butyl methacrylate, and methyl methacrylate,

[0123] ·2-ethylhexyl acrylate, methyl acrylate, and methyl methacrylate polymer,

[0124] · Butyl methacrylate, methyl acrylate, and methyl methacrylate polymer,

[0125] · Polymer of butyl acrylate, ethyl acrylate, and methyl methacrylate,

[0126] · Polymer of butyl acrylate and methyl methacrylate,

[0127] · Polymer of butyl methacrylate and 2-ethylhexyl acrylate,

[0128] · Polymer of isobutyl acrylate and methyl methacrylate,

[0129] · Polymer of ethyl acrylate, methyl acrylate, and methyl methacrylate,

[0130] · Polymer of butyl acrylate, 2-ethylhexyl acrylate, and methyl methacrylate,

[0131] · Polymer of butyl methacrylate, ethyl acrylate, and methyl methacrylate,

[0132] · Polymer of butyl acrylate and isobutyl methacrylate,

[0133] · Polymer of butyl acrylate, ethyl methacrylate, and methyl acrylate,

[0134] · Polymer of butyl acrylate, methyl acrylate, and methyl methacrylate,

[0135] · Polymer of ethyl acrylate and ethyl methacrylate,

[0136] · Polymer of isobutyl acrylate and octadecyl methacrylate,

[0137] · Polymer of butyl acrylate, isobutyl methacrylate, and methyl methacrylate,

[0138] · Polymer of butyl acrylate, methyl acrylate, and octadecyl methacrylate,

[0139] · Polymers of ethyl acrylate, ethyl methacrylate, and methyl acrylate,

[0140] · Polymer of butyl acrylate, butyl methacrylate, 2-ethylhexyl acrylate, and methyl methacrylate,

[0141] · Polymer of ethyl acrylate, isooctyl acrylate, and methyl methacrylate,

[0142] · Polymer of butyl acrylate and dodecyl methacrylate,

[0143] · Polymer of butyl acrylate, butyl methacrylate, and 2-ethylhexyl acrylate,

[0144] ·2-ethylhexyl acrylate, methyl methacrylate, and octadecyl methacrylate polymer,

[0145] · Polymer of butyl acrylate, methyl methacrylate, and octadecyl methacrylate,

[0146] · Polymer of dodecyl methacrylate, 2-ethylhexyl acrylate, and tridecyl methacrylate,

[0147] ·2-ethylhexyl acrylate, methyl methacrylate, pentadecyl methacrylate, and tetradecyl methacrylate polymer,

[0148] · Polymer of butyl acrylate, butyl methacrylate, tert-butyl methacrylate, and methyl methacrylate,

[0149] Examples include polymers of dodecyl methacrylate, ethyl acrylate, methyl methacrylate, and tridecyl methacrylate.

[0150] It is preferable that the constituent material of the core layer includes at least one of the above (meth)acrylate-based polymers.

[0151] Meanwhile, as the constituent material of the shell layer, a material having excellent affinity for other components is used. For example, when an alkali-soluble resin composition contains epoxy resin, it is preferable to use core-shell rubber particles having a shell layer composed of a material having excellent affinity for epoxy resin.

[0152] The material constituting the core layer is preferably a rubbery polymer with a glass transition temperature of -30°C or lower, while the material constituting the shell layer is preferably a glassy polymer with a glass transition temperature of 70°C or higher. Such core-shell rubber particles can be manufactured by a multi-stage seed emulsion polymerization method in which at least two stages are consecutive. Additionally, it is possible to form a shell by partially aggregating the seed latex prepared in the first stage by solvent coagulation or the like, and then further graft polymerizing it.

[0153] In the first polymerization step, a (meth)acrylate-based monomer having 2 to 8 carbon atoms of an alkyl group is polymerized, preferably with a crosslinkable monomer, to prepare a rubbery seed polymer having a glass transition temperature of -30°C or lower.

[0154] As crosslinkable monomers, those having two or more double bonds of substantially equivalent reactivity may be used, for example, ethylene glycol diacrylate, ethylene glycol dimethacrylate, butylene glycol diacrylate, butylene glycol dimethacrylate, trimethylolpropane diacrylate, trimethylolpropane dimethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, hexanediol diacrylate, hexanediol methacrylate, oligoethylene diacrylate, oligoethylene dimethacrylate, further aromatic divinyl monomers such as divinylbenzene, trialyl trimellitate, trialyl isocyanurate, etc. These crosslinkable monomers may each be used individually or in combination of two or more types, and the amount used is typically selected in the range of 0.01 to 5 weight%, preferably 0.1 to 2 weight%, based on the total weight of the monomers.

[0155] In addition, other copolymerizable monomers may be used in conjunction with the above (meth)acrylate-based monomers and crosslinkable monomers if desired. Examples of other copolymerizable monomers used for this purpose include aromatic vinyl compounds such as styrene, vinyltoluene, and α-methylstyrene; vinyl cyanide compounds such as acrylonitrile and methacrylonitrile; furthermore, vinylidene cyanide, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 3-hydroxybutyl acrylate, 2-hydroxyethyl fumarate, hydroxybutyl vinyl ether, monobutyl maleate, glycidyl methacrylate, butoxyethyl methacrylate, etc. These may be used individually or in combination of two or more types, and the amount used is typically selected within a range of 50% by weight or less based on the total weight of the monomers.

[0156] Next, the (meth)acrylate-based polymer particles obtained in this manner are referred to as the core, and a second emulsion polymerization is performed to form a shell by graft copolymerizing the (meth)acrylate-based monomer having 1 to 4 carbon atoms in the alkyl group and a crosslinkable monomer. Examples of (meth)acrylate-based monomers having 1 to 4 carbon atoms in the alkyl group used at this time include ethyl acrylate, n-butyl acrylate, methyl methacrylate, butyl methacrylate, etc., and these may be used individually or in combination of two or more types, but among these, methyl methacrylate is particularly suitable.

[0157] In addition, as the crosslinkable monomer, one or more of those exemplified in the description of the (meth)acrylate-based polymer forming the core may be selected and used. The amount of this crosslinkable monomer used is typically selected in the range of 0.01 to 10 weight%, preferably 0.1 to 5 weight%, based on the total weight of the monomer.

[0158] In addition, other copolymerizable monomers may be used together with the above (meth)acrylate-based monomer and crosslinkable monomer if desired. As for the other copolymerizable monomers used for this purpose, one or more of those exemplified in the description of the (meth)acrylate-based polymer forming the core may be selected and used. The amount used is typically selected in the range of 50% by weight or less based on the total weight of the monomer.

[0159] The core-shell rubber particles obtained by such multi-stage emulsion polymerization are typically spray-dried directly to obtain core-shell type rubber particles with excellent dispersibility in resin components such as epoxy resin. These core-shell rubber particles can be obtained by at least two stages of multi-stage seed emulsion polymerization as described above, but in some cases, they may be produced by partially agglomerating the seed latex produced in the first stage and then graft polymerizing on it, or furthermore, after emulsion polymerization, the latex particles may be coagulated and separated by a salting-out method or a freezing method, and the prepared wet cake may be dried in a fluidized bed or the like to obtain them as aggregated particles.

[0160] In the core-shell type rubber particles obtained in this way, it is preferable that the content of the constituent material of the core layer is 20 to 80 weight%, and the content of the constituent material of the shell layer is in the range of 80 to 20 weight%.

[0161] In addition, the core weight-average particle diameter of the core-shell type powder polymer is preferably in the range of 0.1 to 2.0 μm. The core particles may be polymerized by polymerizing the shell component following the polymerization of the core component, or the core particles may be aggregated by solvent coagulation or salting-out coagulation, and then polymerized for coating the shell component. Regarding the secondary aggregation method, there are many known methods, and all of them can be used. If the particle diameter of the core particles is less than 0.1 μm, the surface area increases for the same weight, resulting in reduced dispersibility, and the mechanical strength and storage stability of the composition incorporating the core-shell type powder polymer are significantly reduced. Furthermore, if the particle diameter of the core particles exceeds 2.0 μm, the shear strength and peel strength tend to decrease. Additionally, the shell average thickness of the core-shell type powder polymer is preferably 50 Å or more; if it is less than 50 Å, the coating of the shell component is insufficient, which causes a decrease in storage stability. The content of these core-shell type rubber particles is preferably 10 to 100 parts by weight, and more preferably 10 to 50 parts by weight, with respect to 100 parts by weight of alkali-soluble resin for each of the X layer and the Y layer.

[0162] The core-shell rubber particles may have curable reactive groups on their surface, and may also have thermosetting reactive groups or photocurable reactive groups. In addition, the core-shell rubber particles may have two or more types of curable reactive groups.

[0163] Examples of thermosetting reaction groups include hydroxyl groups, carboxyl groups, isocyanate groups, imino groups, epoxy groups, oxetanyl groups, mercapto groups, methoxymethyl groups, methoxyethyl groups, ethoxymethyl groups, ethoxyethyl groups, oxazoline groups, etc. More preferably, it is an epoxy group. Examples of photocuring reaction groups include ethylenically unsaturated groups such as vinyl groups, styryl groups, methacrylic groups, and acrylic groups.

[0164] The method of introducing curable reactive groups on the surface of rubber particles is not particularly limited and can be introduced using known and conventional methods. For example, when forming a shell layer around a core layer, a material having a curable reactive group different from the functional group for polymerization reaction with the core layer can be introduced as a constituent material of the shell layer by polymerizing it into the core layer.

[0165] It is preferable that the average particle size of the rubber particles be 1 nm or more and 2 μm or less in both the X layer and the Y layer, as this does not interfere with crosslinking. More preferably, it is 0.05 to 1 μm.

[0166] In the X and Y layers of the laminated curable resin structure of the first and second embodiments of the present invention, it is preferable that the content of rubber particles be 0.01 to 20 mass% with respect to the total solid content of each layer of the alkali-soluble resin compositions X and Y. If the content is 0.01 mass% or more, it is preferable because the roughening effect by pretreatment before plating is excellent, and it forms a dense irregularity different from inorganic fillers to form a desirable anchor shape and excellent adhesion of metal plating. On the other hand, if the content is 20 mass% or less, it is preferable because it does not hinder the crosslinking density of the resin. More preferably, it is 0.01 to 15 mass%. In addition, the alkali-soluble resin compositions X and Y may contain rubber particles that do not have curable reactive groups, within a range that does not impair the effects of the invention.

[0167] The total amount of rubber particles and elastomer in the alkali-soluble resin composition X of the X layer is greater than the total amount of rubber particles and elastomer in the alkali-soluble resin composition Y of the Y layer. By having a larger amount of rubber particles and elastomer in the X layer than in the Y layer, it is easier to form anchors on the surface of the X layer, thereby improving the adhesion of the metal plating when either plasma pretreatment or desmear pretreatment is performed.

[0168] (Thermoplastic elastomer)

[0169] The alkali-soluble resin compositions X and Y of the X and Y layers of the laminated curable resin structure of the first and second embodiments of the present invention may both include a thermoplastic elastomer as an organic filler, either in place of the rubber particles or in combination with the rubber particles.

[0170] As thermoplastic elastomers, known elastomers may be used. As thermoplastic elastomers, polyester-based elastomers, polyurethane-based elastomers, polyester-urethane-based elastomers, polyamide-based elastomers, polyesteramide-based elastomers, acrylic-based elastomers, olefin-based elastomers, etc., may be used. In addition, resins in which some or all of the epoxy groups of an epoxy resin having various frameworks are modified into butadiene-acrylonitrile rubber modified with carboxylic acids at both ends may also be used. Furthermore, epoxy-containing polybutadiene-based elastomers, acrylic-containing polybutadiene-based elastomers, hydroxyl-containing polybutadiene-based elastomers, hydroxyl-containing isoprene-based elastomers, block copolymers, etc., may also be used.

[0171] For example, as product names, R-45HT, Poly bd HTP-9 (both manufactured by Idemitsu Kosan Co., Ltd.), Epolyd PB3600 (manufactured by Daicel Co., Ltd.), Denarex R-45EPT (manufactured by Nagase Chemtex Co., Ltd.), Tafselen (manufactured by Sumitomo Chemical Co., Ltd.), 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 130MA13, Ricon 130MA20, Ricon 131MA5, Ricon 131MA10, Ricon 131MA17, Ricon 131MA20, Ricon Examples include 184MA6, Ricon 156MA17 (both manufactured by Cray Valley), etc. These elastomers can be used alone or in combination of two or more types.

[0172] (Polyester polyol)

[0173] As a polyester-based elastomer according to the present invention, for example, a polyester polyol obtained by the polycondensation of a polycarboxylic acid and a polyhydric alcohol may be used. In addition, the polyester polyol included in the X layer and Y layer of the present invention may be one type or multiple types.

[0174] (polycarboxylic acid)

[0175] Examples of polyvalent carboxylic acids include malonic acid, succinic acid, succinic anhydride, glutaric acid, adipic acid, azelaic acid, sebacic acid, phthalic acid, phthalic anhydride, hexahydrophthalic anhydride, tetrahydrophthalic anhydride, isophthalic acid, terephthalic acid, anhydride, maleic acid, maleic anhydride, fumaric acid, itaconic acid, citraconic acid, trimellitic acid, trimellitic anhydride, pyromellitic acid, and pyromellitic anhydride, and among these, aliphatic polyvalent carboxylic acids such as succinic acid, adipic acid, and sebacic acid are preferably used.

[0176] (Daga alcohol)

[0177] Examples of polyhydric alcohols include ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,3-butylene glycol, 1,4-butylene glycol, 1,2-butylene glycol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, diethylene glycol, dipropylene glycol, 2,2,4-trimethyl-1,3-pentanediol, cyclohexanediol, bisphenol A ethylene oxide adduct, bisphenol A propylene oxide adduct, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, glycerin, trimethylolpropane, trimethylolethane, and pentaerythritol, among others, 1,2-propylene glycol, 1,4-butylene glycol, and 1,6-hexanediol are preferably used.

[0178] In particular, as a polyester polyol used as a modifier according to the present invention, an aliphatic polyester polyol that is a polycondensate of an aliphatic polycarboxylic acid and an aliphatic polyalcohol is preferred in that a fiber-reinforced composite material with high mechanical properties is obtained, and an aliphatic polyester polyol that uses succinic acid, adipic acid, or sebacic acid, etc. as the aliphatic polycarboxylic acid and 1,2-propylene glycol, 1,4-butylene glycol, or 1,6-hexanediol, etc. as the aliphatic polyalcohol is more preferred in that a fiber-reinforced composite material with high 90° bending strength is obtained.

[0179] The weight average molecular weight of the polyester polyol is preferably 40,000 or less from the perspective of developmentability, more preferably 20,000 or less, and even more preferably 10,000 or less.

[0180] For example, product names include Polylite OD-X-2068 and OD-X-3100 (both polyester polyols manufactured by DIC).

[0181] One type of elastomer may be used alone, or two or more types may be used in combination. The amount of elastomer blended is preferably 0.01 to 20 mass% based on the total amount of solids of each alkali-soluble resin composition X and Y of the X layer and Y layer.

[0182] [(E) Photopolymerization Initiator]

[0183] The alkali-soluble resin compositions X and Y of the X and Y layers of the laminated curable resin structure of the first and second embodiments of the present invention may both include a photopolymerization initiator. By including a photopolymerization initiator, radical polymerization by light becomes possible. In particular, it may be a negative-type curable resin composition. As the photopolymerization initiator, any photopolymerization initiator known as a photopolymerization initiator or a photoradical generator may be used.

[0184] As a photopolymerization initiator, bis-acylphosphine oxides such as bis-(2,6-dichlorobenzoyl)phenylphosphine oxide, bis-(2,6-dichlorobenzoyl)-2,5-dimethylphenylphosphine oxide, bis-(2,6-dichlorobenzoyl)-4-propylphenylphosphine oxide, bis-(2,6-dichlorobenzoyl)-1-naphthylphosphine oxide, bis-(2,6-dimethoxybenzoyl)phenylphosphine oxide, bis-(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide, bis-(2,6-dimethoxybenzoyl)-2,5-dimethylphenylphosphine oxide, and bis-(2,4,6-trimethylbenzoyl)-phenylphosphine oxide (Omnirad 819 manufactured by IGM Resins); Monoacylphosphine oxides such as 2,6-dimethoxybenzoyldiphenylphosphine oxide, 2,6-dichlorobenzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoylphenylphosphine methyl ester, 2-methylbenzoyldiphenylphosphine oxide, pivaloylphenylphosphine isopropyl ester, and 2,4,6-trimethylbenzoyldiphenylphosphine oxide; Hydroxyacetophenones such as 1-hydroxy-cyclohexylphenylketone, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propionyl)-benzyl]phenyl}-2-methyl-propan-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one; benzoins such as benzoin, benzyl, benzoin methyl ether, benzoin ethyl ether, benzoin n-propyl ether, benzoin isopropyl ether, benzoin n-butyl ether, etc.; benzoin alkyl ethers; Benzophenones such as benzophenone, p-methylbenzophenone, mihler ketone, methylbenzophenone, 4,4'-dichlorobenzophenone, 4,4'-bisdiethylaminobenzophenone;Acetophenones such as acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 1-hydroxycyclohexylphenyl ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-1-propanone, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1,2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone, N,N-dimethylaminoacetophenone; Thioxantones such as thioxantone, 2-ethylthioxantone, 2-isopropylthioxantone, 2,4-dimethylthioxantone, 2,4-diethylthioxantone, 2-chlorothioxantone, 2,4-diisopropylthioxantone; anthraquinones such as anthraquinone, chloroanthraquinone, 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 1-chloroanthraquinone, 2-amylanthraquinone, 2-aminoanthraquinone; ketal compounds such as acetophenone dimethyl ketal and benzyl dimethyl ketal; benzoic acid esters such as ethyl-4-dimethylaminobenzoate, 2-(dimethylamino)ethyl benzoate, and p-dimethylbenzoate ethyl ester; Oxime esters such as 1,2-octanedione, 1-[4-(phenylthio)-, 2-(O-benzoyloxime)], ethannon, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-, 1-(O-acetyloxime); titanocenes such as bis(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-phil-1-yl)ethyl)phenyl]titanium;Examples include phenyldisulfide 2-nitrofluorene, butyloin, anisophosphorus ethyl ether, azobisisobutyronitrile, tetramethylthiuram disulfide, etc. A photopolymerization initiator may be used alone or in combination of two or more types. Among these, monoacylphosphine oxides and oxime esters are preferred, and high-sensitivity oxime esters are most preferred. As for oxime esters, it is preferable to have one or more oxime ester groups, and examples such as ethanol, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-, and 1-(O-acetyloxime) are more preferred.

[0185] (E) The amount of photopolymerization initiator is preferably 0.5 to 30 parts by weight per 100 parts by weight of (A) alkali-soluble resin in each of the X layer and Y layer of the laminated curable resin structure of the first and second embodiments of the present invention. When the amount is 0.5 parts by weight or more, the surface curability is improved, and when the amount is 30 parts by weight or less, it is difficult for halation to occur and good resolution is obtained.

[0186] (Curing accelerator)

[0187] Preferably, each alkali-soluble resin composition X and Y of the X layer and Y layer of the laminated curable resin structure of the first and second embodiments of the present invention contains a curing accelerator. Such curing accelerators include, for example, imidazole derivatives such as imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-(2-cyanoethyl)-2-ethyl-4-methylimidazole; amine compounds such as dicyandiamide, benzyldimethylamine, 4-(dimethylamino)-N,N-dimethylbenzylamine, 4-methoxy-N,N-dimethylbenzylamine, 4-methyl-N,N-dimethylbenzylamine; and hydrazine compounds such as adipic acid dihydrazide, sebacic acid dihydrazide. Examples include phosphorus compounds such as triphenylphosphine. In addition, S-triazine derivatives such as guanamine, acetoguanamin, benzoguanamine, melamine, 2,4-diamino-6-methacryloyloxyethyl-S-triazine, 2-vinyl-2,4-diamino-S-triazine, 2-vinyl-4,6-diamino-S-triazine·isocyanuric acid adduct, and 2,4-diamino-6-methacryloyloxyethyl-S-triazine·isocyanuric acid adduct may be used, and preferably, compounds that also function as adhesion promoters are used in combination with a curing accelerator.

[0188] The amount of curing accelerator is preferably 0.05 to 20 parts by mass, more preferably 0.1 to 15 parts by mass, with respect to 100 parts by mass of the (B) epoxy resin of X and Y in each alkali-soluble resin composition of the X layer and Y layer of the laminated curable resin structure of the first and second embodiments of the present invention.

[0189] (Hardening agent)

[0190] Each of the alkali-soluble resin compositions X and Y of the X layer and Y layer of the laminated curable resin structure of the first and second embodiments of the present invention may contain a curing agent. Examples of curing agents include phenolic resin, polycarboxylic acid and its acid anhydride, cyanate ester resin, active ester resin, maleimide compound, alicyclic olefin polymer, etc. One type of curing agent may be used alone or in combination of two or more types.

[0191] (coloring agent)

[0192] Each of the alkali-soluble resin compositions X and Y of the X and Y layers of the laminated curable resin structure of the first and second embodiments of the present invention may contain a coloring agent. As the coloring agent, known coloring agents such as red, blue, green, yellow, black, and white may be used, and any of pigments, dyes, or colorants may be used. However, it is preferable that it does not contain halogens from the perspective of reducing environmental burden and impact on the human body.

[0193] There is no particular limitation on the amount of coloring agent added, but it is sufficient to have a ratio of preferably 10 parts by weight or less, particularly preferably 0.1 to 10 parts by weight, with respect to 100 parts by weight of alkali-soluble resin (A) in each of the X layer and Y layer of the laminated curable resin structure of the first and second embodiments of the present invention.

[0194] (Organic solvent)

[0195] In each of the alkali-soluble resin compositions X and Y of the X layer and Y layer of the laminated curable resin structure of the first and second embodiments of the present invention, an organic solvent may be included for purposes such as preparing the composition or adjusting the viscosity when applied to a substrate or a first film. As organic solvents, ketones such as methyl ethyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene; glycol ethers such as cellosolve, methyl cellosolve, butyl cellosolve, carbitol, methyl carbitol, butyl carbitol, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol diethyl ether, diethylene glycol monomethyl ether acetate, and tripropylene glycol monomethyl ether; Known and commonly used organic solvents may be used, such as esters including ethyl acetate, butyl acetate, butyl lactate, cellosolve acetate, butyl cellosolve acetate, carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether acetate, and propylene carbonate; aliphatic hydrocarbons including octane and decane; and petroleum-based solvents including petroleum ether, petroleum naphtha, and solvent naphtha. These organic solvents may be used alone or in combination of two or more types.

[0196] (Other optional components)

[0197] In addition, other additives known and commonly used in the field of electronic materials may be incorporated into each of the alkali-soluble resin compositions X and Y of the X layer and Y layer of the laminated curable resin structure of the first and second embodiments of the present invention. Examples of other additives include thermal polymerization inhibitors, ultraviolet absorbers, silane coupling agents, plasticizers, flame retardants, antistatic agents, antioxidants, antibacterial and antifungal agents, defoaming agents, leveling agents, thickeners, adhesion promoters, thixotropic promoters, photoinitiators, sensitizers, thermoplastic resins, core organic fillers, release agents, surface treatment agents, dispersants, dispersion promoters, surface modifiers, stabilizers, phosphors, AB-type or ABA-type block copolymers, etc.

[0198] [Dry Film]

[0199] The laminated curable resin structure of the first and second embodiments of the present invention may be used as a dry film or as a liquid. When used as a liquid, it may be one-component or two-component or more-component.

[0200] Next, the dry film of the laminated curable resin structure of the first embodiment of the present invention has a resin layer obtained by applying and drying the laminated curable resin structure of the first embodiment of the present invention or the alkali-soluble resin composition X, Y of the laminated curable resin structure of the first embodiment of the present invention onto the first film.

[0201] In addition, the dry film of the laminated curable resin structure of the second embodiment of the present invention has a resin layer obtained by applying and drying the laminated curable resin structure of the second embodiment of the present invention or the alkali-soluble resin composition X, Y of the laminated curable resin structure of the second embodiment of the present invention on the first film.

[0202] FIG. 1 illustrates a schematic cross-sectional view of an example of a dry film (1) of a laminated curable resin structure according to the first and second embodiments of the present invention. The dry film (1) of FIG. 1 has a laminated curable resin structure (11) in which an X layer (11X) and a Y layer (11Y) are laminated, a first film (12) is provided to cover the surface of the X layer (11X) of the laminated curable resin structure (11), and a second film (13) is provided to cover the surface of the Y layer (11Y) of the laminated curable resin structure (11).

[0203] When forming a dry film, first, the alkali-soluble resin composition X of the X layer of the laminated curable resin structure of the first embodiment of the present invention is diluted with the organic solvent to adjust the viscosity to an appropriate level, and then applied to the first film with a uniform thickness using a comma coater, blade coater, lip coater, rod coater, squeeze coater, reverse coater, transfer roll coater, gravure coater, spray coater, etc. After that, the applied composition can be dried at a temperature of typically 40 to 130°C for 1 to 30 minutes to form a resin layer of the X layer. Subsequently, the alkali-soluble resin composition Y of the Y layer is applied to the X layer with a uniform thickness in the same manner as the X layer, and by drying, a resin layer of the Y layer is formed over the X layer, thereby obtaining the laminated curable resin structure of the present invention. Although there are no particular limitations on the total thickness of the coating film, the film thickness after drying is generally appropriately selected in the range of 3 to 150 μm, preferably 5 to 60 μm.

[0204] When forming a dry film with the laminated curable resin structure of the second embodiment of the present invention, it can be formed in the same manner as the laminated curable resin structure of the first embodiment of the present invention described above.

[0205] As the first 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, etc., may be used. There are no particular limitations on the thickness of the first film, but generally, it is appropriately selected in the range of 10 to 150 μm. More preferably, it is in the range of 15 to 130 μm.

[0206] After forming a resin layer containing the laminated curable resin structure of the present invention on a first film, it is preferable to laminate a peelable second film on the surface of the resin layer for purposes such as preventing dust from adhering to the surface of the resin layer. As the peelable second film, for example, a polyethylene film, a polytetrafluoroethylene film, a polypropylene film, or surface-treated paper may be used. As for the second film, it is sufficient that the adhesion force between the resin layer and the first film is smaller than the adhesion force between the second film when the second film is peeled.

[0207] In addition, in the present invention, a resin layer may be formed by applying and drying the laminated curable resin structure of the present invention onto the second film, and the first film may be laminated on the surface thereof. That is, when manufacturing a dry film in the present invention, either the first film or the second film may be used as the film on which the laminated curable resin structure of the present invention is applied.

[0208] [Electronic Components]

[0209] The electronic component of the present invention, for example, a printed circuit board, has a cured product obtained from the resin layer of the laminated curable resin structure or dry film of the present invention. As a method for manufacturing the printed circuit board of the present invention, for example, an alkali-soluble resin composition Y of the Y layer of the laminated curable resin structure of the present invention is adjusted to a viscosity suitable for a coating method using the organic solvent, and then applied onto a substrate by a method such as a dip coating method, a flow coating method, a roll coating method, a bar coater method, a screen printing method, or a curtain coating method, and then the organic solvent contained in the composition is evaporated and dried (pre-dried) at a temperature of 60 to 100°C for 1 to 30 minutes to form a tack-free resin layer of the Y layer. Subsequently, an alkali-soluble resin composition X of the X layer is applied to the Y layer in the same manner as the Y layer to form a resin layer of the X layer overlaid on the Y layer, and dried to form the laminated curable resin structure of the present invention. In addition, in the case of a dry film, a resin layer is bonded onto a substrate so that it comes into contact with the substrate using a laminator or the like, and then the first film is peeled off to form a resin layer on the substrate.

[0210] In addition to printed circuit boards or flexible printed circuit boards with circuits formed in advance using copper, etc., the above description may use materials such as paper phenol, paper epoxy, glass cloth epoxy, glass polyimide, glass cloth / non-woven epoxy, glass cloth / paper epoxy, synthetic fiber epoxy, copper-clad laminates for high-frequency circuits using fluoropolymer, polyethylene, polyphenylene ether, polyphenylene oxide, cyanate, etc., copper-clad laminates of all grades (FR-4, etc.), and other materials such as metal substrates, polyimide films, PET films, polyethylene naphthalate (PEN) films, glass substrates, ceramic substrates, wafer boards, etc.

[0211] Volatile drying performed after applying alkali-soluble resin compositions X and Y can be carried out using a hot air circulation type dryer, an IR oven, a hot plate, a convection oven, etc. (a method of making counter-flow contact of hot air inside the dryer using a heat source equipped with a steam-based air heating method, and a method of spraying onto a support from a nozzle).

[0212] After forming a resin layer on a printed circuit board, the material is selectively exposed to an active energy beam through a photomask that has a predetermined pattern formed thereon, and the unexposed portion is developed with a dilute alkaline aqueous solution (e.g., an aqueous solution of sodium carbonate at a mass of 0.3 to 3 mass%) to form a pattern of the cured material. In addition, the cured material is irradiated with an active energy beam and then heat-cured (e.g., 100 to 220°C, 20 to 120 minutes), or heat-cured and then irradiated with an active energy beam, or heat-cured alone and then heat-cured to perform final finishing curing (main curing), thereby forming a cured film with excellent various properties such as adhesion and hardness.

[0213] As the exposure device used for the above active energy irradiation, it is sufficient to be a device equipped with a high-pressure mercury lamp, ultra-high-pressure mercury lamp, metal halide lamp, mercury short arc lamp, etc., that irradiates ultraviolet rays in the range of 350 to 450 nm; additionally, a direct imaging device (for example, a laser direct imaging device that draws an image directly with a laser based on CAD data from a computer) may also be used. As for the lamp light source or laser light source of the direct imaging device, it is sufficient to have a maximum wavelength in the range of 350 to 450 nm. The exposure amount for image formation varies depending on the film thickness, etc., but is generally 10 to 1000 mJ / cm² 2 , preferably 20 to 800 mJ / cm² 2 It can be done within the range of.

[0214] The above development method may be by dipping, showering, spraying, brushing, etc., and as the developer, an alkaline aqueous solution such as potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, ammonia, or amines may be used.

[0215] The stackable curable resin structure of the present invention is suitably used to form a cured film on a printed circuit board, more suitably to form a permanent film, and even more suitably to form a solder resist, an interlayer insulating layer, or a cover layer. In addition, it is suitable for forming a permanent film (especially a solder resist) for high-density wiring applications, such as package substrates, for printed circuit boards having fine-pitch wiring patterns requiring high reliability, particularly for FC-CSP, FC-BGA, and FO-WLP applications. In particular, the stackable curable resin structure of the present invention is suitable for applications exposed to high temperatures, such as vehicle mounting applications, in that a cured product with excellent crack resistance under high-temperature loads can be obtained.

[0216] Examples

[0217] 《Example of a laminated curable resin structure of the first aspect of the present invention》

[0218] Hereinafter, a laminated curable resin structure of the first embodiment of the present invention will be described in more detail using examples, but the present invention is not limited to the following examples. Furthermore, in the following, "parts" and "%" are all based on mass unless otherwise specified.

[0219] [Synthesis of Alkali-Soluble Resin A-1-1]

[0220] 1070g of orthocresol novolak type epoxy resin (DIC EPICLON N-695, softening point 95°C, epoxy equivalent 214, average number of functional groups 7.6) (number of glycidyl groups (total number of aromatic rings): 5.0 mol), 360g of acrylic acid (5.0 mol), and 1.5g of hydroquinone were added to 600g of ethylene glycol monoethyl ether acetate and heated and stirred at 100°C to homogeneously dissolve the mixture. Subsequently, 4.3g of triphenylphosphine was added and heated at 110°C for 2 hours, after which the temperature was raised to 120°C and the reaction was carried out for another 12 hours. 415 g of aromatic hydrocarbon (sorbetso 150) and 456.0 g (3.0 mol) of tetrahydrophthalic anhydride were added to the obtained reaction solution, and the reaction was carried out at 110°C for 4 hours and cooled to obtain an alkali-soluble resin of A-1-1.

[0221] [Synthesis of Alkali-Soluble Resin A-1-2]

[0222] 450 parts of bisphenol A, 200 parts of water, and 650 parts of 37% formalin were added to a flask equipped with a cooling tube and a stirrer, and 230 parts of a 25% aqueous sodium hydroxide solution were added. After the reaction was completed, the mixture was cooled to 40°C and neutralized with a 37% aqueous phosphoric acid solution. After separating the aqueous layer, 300 parts of methyl isobutyl ketone were added and uniformly dissolved, after which water, solvent, etc., were removed. The obtained polymethylol compound was dissolved in 550 parts of methanol to obtain 1,000 parts of a methanol solution of the polymethylol compound.

[0223] 500 parts of the methanol solution of the obtained polymethylol compound and 440 parts of 2,6-xylenol were added to a flask equipped with a condenser and a stirrer, and uniformly dissolved. Subsequently, 8 parts of oxalic acid were added, and the reaction was carried out at 100°C. After the reaction was completed, the effluent was removed at 180°C under reduced pressure of 50 mmHg to obtain 550 parts of novolak resin A. 130 parts of novolak resin A, 3 parts of a 50% aqueous sodium hydroxide solution, and 100 parts of toluene / methylisobutyl ketone (mass ratio = 2 / 1) were added to an autoclave equipped with a thermometer, a nitrogen introduction device and an alkylene oxide introduction device, and a stirring device. The system was nitrogen-purged while stirring, and then heated to 150°C at 8 kg / cm². 260 parts of propylene oxide were slowly introduced and the reaction was carried out. After continuing the reaction for about 4 hours, it was cooled to room temperature. 3 parts of a 36% hydrochloric acid solution were added and mixed to this reaction solution, and sodium hydroxide was neutralized. The neutralization reaction product was diluted with toluene, washed with water three times, and desolvated using an evaporator to obtain a propylene oxide adduct of novolak resin A with a hydroxyl value of 189 g / eq. This had an average of 1 mole of propylene oxide added per 1 equivalent of phenolic hydroxyl group. 189 parts of propylene oxide adduct of obtained novolak resin A, 36 parts of acrylic acid, 3 parts of p-toluenesulfonic acid, 0.1 parts of hydroquinone monomethyl ether, and 140 parts of toluene were introduced into a reactor equipped with a stirrer, a thermometer, and an air blower, stirred while blowing air, and heated to 115°C. The water produced by the reaction was removed by distillation as an azeotropic mixture with toluene, and the reaction was carried out for 4 hours, after which it was cooled to room temperature. The obtained reaction solution was washed with a 5% NaCl aqueous solution and toluene was removed by vacuum distillation to obtain a 7% acrylate resin solution. Next, 320 parts of the obtained acrylate resin solution, 0.1 parts of hydroquinone monomethyl ether, and 0.3 parts of triphenylphosphine were added to a 4-neck flask equipped with a stirrer and a reflux condenser, the mixture was heated at 110°C, 60 parts of tetrahydrophthalic anhydride were added and reacted for 4 hours, and after cooling, the mixture was removed to obtain the alkali-soluble resin of A-1-2.

[0224] [Synthesis of Alkali-Soluble Resin A-1-3]

[0225] 80 parts of carbitol acetate were added to a separable flask equipped with a cooling tube serving as a reaction vessel, and after purging with nitrogen, the temperature was raised to 80°C. Meanwhile, a mixture of 30 parts of N-phenylmaleimide and 120 parts of carbitol acetate was added to dropper 1; a mixture of 30 parts of styrene and 20 parts of 2-hydroxyethyl methacrylate was added to dropper 2; a mixture of 20 parts of acrylic acid and 10 parts of carbitol acetate was added to dropper 2; and a mixture of 10 parts of Luperox 11 (manufactured by Arkma Yoshitomi Co., Ltd., a hydrocarbon solution containing 70% t-butylperoxypivalate) and 20 parts of carbitol acetate was added to dropper 2 as a polymerization initiator. Dropping was performed from the dropper while maintaining the reaction temperature at 80°C. After the dropping was finished, the reaction was continued at 80°C for 30 minutes. Subsequently, the reaction temperature was raised to 95°C and the reaction was continued for 1.5 hours to obtain a polymer solution prior to the radical polymerization double bond introduction reaction. Next, 10 parts of glycidyl methacrylate, 7 parts of carbitol acetate, 0.7 parts of triphenylphosphine as a reaction catalyst, and 0.2 parts of Anteji W-400 (manufactured by Kawaguchi Kagaku Kogyo Co., Ltd.) as a polymerization inhibitor were added to this polymer solution, and the reaction was carried out at 115°C while bubbling a mixed gas of nitrogen and oxygen (oxygen concentration 7%) to obtain an alkali-soluble resin of A-1-3.

[0226] [Synthesis of Alkali-Soluble Resin A-1-4]

[0227] 120 parts of novolak-type cresol resin (Aika Kogyo "Shonol CRG-951", OH equivalent: 120), 1 part of potassium hydroxide, and 120 parts of toluene were introduced into an autoclave equipped with a thermometer, a nitrogen introduction device and an alkylene oxide introduction device, and a stirring device. The system was heated and raised while stirring and nitrogen was introduced. Subsequently, 64 parts of propylene oxide were slowly added dropwise and reacted at 130°C. Afterward, the solution was cooled to room temperature, and 2 parts of 89% phosphoric acid were added and mixed to the reaction solution to neutralize the potassium hydroxide, thereby obtaining a reaction solution of novolak-type cresol resin with propylene oxide having a non-volatile content of 60% and a hydroxyl value of 180 mgKOH / g.

[0228] 300 parts of the propylene oxide reaction solution of the obtained novolak-type cresol resin, 40 parts of acrylic acid, 10 parts of methanesulfonic acid, 0.2 parts of methylhydroquinone, and 250 parts of toluene were introduced into a reactor equipped with a stirrer, a thermometer, and an air blower, and the reaction was carried out at 110°C while stirring and blowing air at a rate of 10 ml / min. Afterward, the mixture was cooled to room temperature, the resulting reaction solution was neutralized with a 15% aqueous sodium hydroxide solution, and then washed with water. Subsequently, the toluene was removed by distillation using an evaporator while replacing it with 120 parts of diethylene glycol monoethyl ether acetate to obtain a novolak-type acrylate resin solution. Next, 300 parts of the obtained novolak-type acrylate resin solution and 1 part of triphenylphosphine were introduced into a reactor equipped with a stirrer, a thermometer, and an air blower, air was blown in at a rate of 10 ml / min, and 60 parts of tetrahydrophthalic anhydride were slowly added while stirring, reacted at 100°C, and after cooling, removed to obtain the alkali-soluble resin of A-1-4.

[0229] [Adjustment of Inorganic Particle C-1-1]

[0230] 50g of spherical silica (Admanano, manufactured by Admatex, average particle size 50nm) produced by the sol-gel method, 100g of MEK (methyl ethyl ketone), and 20g of an amino-based silane coupling agent (KBE-573, manufactured by Shin-Etsu Chemical Co., Ltd.) were uniformly dispersed to obtain silica solvent dispersion product C-1-1.

[0231] [Adjustment of Weapon Particle C-1-2]

[0232] 100g of spherical silica (MEK-ST-40 manufactured by Nissan Chemical Co., Ltd., average particle size: 12nm), 200g of MEK (methyl ethyl ketone), and 80g of mercapto-based silane coupling agent (KBM-802 manufactured by Shin-Etsu Chemical Co., Ltd.) were uniformly dispersed to obtain silica solvent dispersion product C-1-2.

[0233] [Adjustment of Inorganic Particle C-1-3]

[0234] 60g of spherical silica (SFP-30M, manufactured by Denka Co., Ltd., average particle size: 600nm), 40g of MEK (methyl ethyl ketone) as a solvent, and 1g of methacrylate silane coupling agent (KBM-503, manufactured by Shin-Etsu Chemical Co., Ltd.) were uniformly dispersed to obtain silica solvent dispersion product C-1-3.

[0235] [Adjustment of Inorganic Particle C-1-4]

[0236] 60g of spherical silica (SFP-30M, manufactured by Denka, average particle size: 600nm), 40g of MEK (methyl ethyl ketone) as a solvent, and 1g of isocyanate-based silane coupling agent (KBM-9007, manufactured by Shin-Etsu Chemical Co., Ltd.) were uniformly dispersed to obtain silica solvent dispersion product C-1-4.

[0237] [Adjustment of Inorganic Particle C-1-5]

[0238] 60g of spherical silica (SFP-30M, manufactured by Denka, average particle size: 600nm), 40g of MEK (methyl ethyl ketone) as a solvent, and 1g of vinyl silane coupling agent (KBM-1003, manufactured by Shin-Etsu Chemical Co., Ltd.) were uniformly dispersed to obtain silica solvent dispersion product C-1-5.

[0239] [Adjustment of Inorganic Particle C-1-6]

[0240] 70g of barium sulfate (B-33 manufactured by Sakai Kagaku Kogyo Co., Ltd., average particle size: 300nm) and 40g of MEK (methyl ethyl ketone) as a solvent were uniformly dispersed to obtain barium solvent dispersion product C-1-6.

[0241] [Adjustment of Inorganic Particle C-1-7]

[0242] 70g of a hydrotalcite compound (DHT-4C manufactured by Kyowa Kagaku Kogyo Co., Ltd., average particle diameter 400nm) and 40g of MEK (methyl ethyl ketone) as a solvent were uniformly dispersed to obtain a hydrotalcite compound solvent dispersion product C-1-7.

[0243] [Epoxy resin dispersion of rubber particles D-1-1]

[0244] (Production of core-shell rubber particles having curable reactors on the surface)

[0245] 1300g of rubber latex and 440g of pure water were placed in a 3-liter glass reactor, and the mixture was heated to 70°C while stirring under the introduction of nitrogen. The rubber latex contained 480g of polybutadiene particles with an average particle size of 0.1㎛ and 1.5% by mass of sodium dodecylbenzenesulfonate, with the polybutadiene making up 100% by mass. To this, 1.2g of azoisobutyronitrile was added, followed by the addition of a mixture of 36g of styrene, 48g of methyl methacrylate, 24g of acrylonitrile, and 12g of glycidyl methacrylate over a period of 3 hours. Afterward, the mixture was stirred for another 2 hours to obtain core-shell rubber particles (latex (L)). The solid content of the latex (L) was 32%. In addition, the gel fraction of the core-shell copolymer in the latex (L) was 98%. In addition, the diameter of the rubber particles in the latex (L) was 0.5 μm.

[0246] [Preparation of an alkali-soluble resin composition of a laminated curable resin structure of the first embodiment of the present invention]

[0247] Each alkali-soluble resin obtained by the above synthesis was mixed with each varnish solution (described in Table 1 as solid content) adjusted to a solid content of 60% with propylene glycol methyl ether acetate, a rubber particle dispersion, and inorganic particles together with the various components shown in Table 1 in the ratio (parts by mass) shown in Table 1, pre-mixed with a stirrer, and then kneaded with a three-roll mill to prepare alkali-soluble resin compositions X-1-1 to X-1-9 for the X layer and alkali-soluble resin compositions Y-1-1 to Y-1-8 for the Y layer.

[0248]

[0249] The footnotes in the heading column of Table 1 are as follows.

[0250] *1: Alkali-soluble resin A-1-1 synthesized above

[0251] *2: Alkali-soluble resin A-1-2 synthesized above

[0252] *3: Alkali-soluble resin A-1-3 synthesized above

[0253] *4: Alkali-soluble resin A-1-4 synthesized above

[0254] *5: HF-1M Meiwa Gasei Pharmaceuticals Phenolnovolak Resin Hydroxyl equivalent 106

[0255] *6: YX-4000, manufactured by Mitsubishi Chemical, biphenyl-type epoxy resin, epoxy equivalent 186 g / eq

[0256] *7: NC-3000H manufactured by Nippon Kayaku Co., Ltd., biphenylnovolak type epoxy resin, epoxy equivalent 290g / eq

[0257] *8: Tecmore (registered trademark) VG3101L manufactured by Mitsui & Kagaku Inc., an epoxy resin having the structure of Formula (III) below, epoxy equivalent 210 g / eq

[0258]

[0259] *9: Nissan Kagaku TEPIC-VL, heterocyclic epoxy resin, trifunctional, liquid, epoxy equivalent: 128g / eq

[0260] *10: The inorganic particle C-1-1 adjusted above

[0261] *11: The inorganic particle C-1-2 adjusted above

[0262] *12: Inorganic particle C-1-3 adjusted above

[0263] *13: The inorganic particle C-1-4 adjusted above

[0264] *14: Inorganic particle C-1-5 adjusted above

[0265] *15: The inorganic particle C-1-6 adjusted above

[0266] *16: The inorganic particle C-1-7 adjusted above

[0267] *17: Epoxy resin dispersion of rubber particles prepared above D-1-1

[0268] *18: DIC Polyester Polyol Polylite OD-X-2068

[0269] *19: Photopolymerization initiator E-1: IGM Resins Omnirad 907 (2-methyl-1-(4-methylthiophenyl)-2-morpholinopropane-1-one)

[0270] *20: Photopolymerization initiator E-2: BASF Japan IRGACURE OXE02 (ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-1-(o-acetyloxime)

[0271] *21: Acylphosphine oxide-based photopolymerization initiator E-3, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide

[0272] *22: DPHA (Dipentaerythritol Hexaacrylate) manufactured by Nippon Kayaku Co.

[0273] *23: Shikoku Kasei 2E4MZ-A (2-ethyl-4-methylimidazole)

[0274] (Examples 1-1 to 1-15, Comparative Examples 1-1 to 1-8)

[0275] <Production of a dry film of a laminated curable resin structure of the first embodiment of the present invention>

[0276] 300g of methyl ethyl ketone was added to each alkali-soluble resin composition obtained as described above to dilute it, and the mixture was stirred with a stirrer for 15 minutes to obtain a coating solution. On a polyethylene terephthalate film (hereinafter also referred to as PET film) (first film) with a thickness of 38㎛, the coating solution was first applied such that the X layer and Y layer were applied in the ratio of the thicknesses of the X layer and Y layer in Examples 1-1 to 1-15 and Comparative Examples 1-3, 1-4, 1-7, and 1-8 of Table 2, dried at 80℃ for 5 minutes using a hot air circulating dryer, cooled, then applied the Y layer thereon, and dried at a temperature of 80℃ for 15 minutes to form a laminated resin layer (two-layer resin layer) with a total thickness of 25㎛. In addition, Comparative Examples 1, 2, 5, and 6 were each applied as a single layer with a thickness of 25㎛, and dried at a temperature of 80℃ for 15 minutes.

[0277] Next, a biaxially stretched polypropylene film (second film) was bonded onto the laminated resin layer to produce a dry film.

[0278] The dry films of Examples 1-1 to 1-15 and Comparative Examples 1-1 to 1-8 were subjected to the tests and evaluations described below. The results are shown in Table 2.

[0279] Crack Resistance (Cold & Heat Resistance) Evaluation

[0280] After peeling off the second film from the dry films of each example and comparative example produced in <Production of a Dry Film of a Laminated Curable Resin Structure of the First Embodiment of the Present Invention> above, each dry film was laminated in a first chamber at 80°C using a vacuum laminator (CVP-600: manufactured by Nikko Material Co., Ltd.) under conditions of vacuum pressure 3 hPa and vacuum time 30 seconds, and then pressed under conditions of press pressure 0.5 MPa and press time 30 seconds to obtain an evaluation substrate. Subsequently, after exposure using a DI exposure machine with an exposure amount that obtains 10 steps on a step tablet (41 steps), the PET film was peeled off (Example 150,000: PET film peeled off after heat treatment at 80°C for 45 minutes), and development (1 mass% Na2CO3, 30°C, 0.2 MPa) was performed for 60 seconds to form a pattern of the resin layer. Subsequently, at 1 J / cm² in a UV conveyor furnace equipped with a high-pressure mercury lamp. 2 After irradiating the resin layer with an exposure amount, the resin layer was fully cured by heating at 160°C for 60 minutes to fabricate an evaluation substrate with a square resist pattern of 3 mm on each side formed on a copper line. This substrate was placed in a thermal cycle machine in which a temperature cycle was performed between -50°C and 150°C to perform a Thermal Cycle Test (TCT). Then, cracks were checked after evaluating up to 1000 cycles.

[0281] ◎: No cracks occurred up to 2000 cycles.

[0282] ○: No cracks occurred at 1500 cycles.

[0283] △: Cracks occur up to 1500 cycles.

[0284] ×: Cracks occur up to 1000 cycles.

[0285] <TMA에 의한 CTE(열팽창 계수) 측정>

[0286] The dry films of each example and comparative example prepared in <Preparation of a Dry Film of a Laminated Curable Resin Structure of the First Aspect of the Present Invention> above were heat-laminated using a vacuum laminator after peeling off the second film in the same manner as above. The obtained laminate was exposed to light on its entire surface to peel off the PET film, and then a 1 mass% aqueous Na2CO3 solution at 30°C was sprayed at a pressure of 2 kg / cm² 2 Development was performed for 60 seconds under the specified conditions. After development, an integrated light intensity of 1000 mJ / cm² was applied via a UV conveyor. 2 A resist film was obtained by irradiating with light and heat-curing in a drying oven at 160°C for 60 minutes. The obtained cured film was cut to obtain a measurement size (3 mm × 10 mm) and the CTE was measured using a TMA6100 manufactured by Hitachi Hitech. The measurement conditions were a test load of 5 g, and the sample was heated at a heating rate of 10°C / min in tensile mode, with the temperature raised from room temperature being measured twice. The average linear coefficient of thermal expansion was calculated in the range of 200°C to 250°C during the second measurement.

[0287] ◎: 100 ppm / ℃ or less.

[0288] ○: Greater than 100 ppm / ℃ and less than or equal to 110 ppm / ℃.

[0289] ×: Exceeds 110 ppm / ℃.

[0290] Resolution (Shape Sharpness)

[0291] After peeling off the second film from the dry films of each example and comparative example produced in <Production of a Dry Film of a Laminated Curable Resin Structure of the First Embodiment of the Present Invention> above onto the copper of a copper-clad laminate that has been CZ-treated, the dry films were laminated using a vacuum laminator (CVP-600: manufactured by Nikko Material Co., Ltd.) in a first chamber at 100°C under conditions of vacuum pressure 3 hPa and vacuum time 30 seconds, and then pressed under conditions of press pressure 0.5 MPa and press time 30 seconds to obtain an evaluation substrate. Subsequently, a φ30㎛ SRO pattern was exposed using a projection exposure machine (i-line) with an exposure amount that obtained 10 steps on a step tablet (41 steps), the PET film was peeled off (Example 15: the PET film was peeled off after heat treatment at 80°C for 45 minutes), and a pattern of the resin layer was formed by developing (1 mass% Na2CO3, 30°C, 0.2 MPa) for 60 seconds. Subsequently, a UV conveyor furnace equipped with a high-pressure mercury lamp was heated at 1 J / cm² 2 After irradiating the resin layer with an exposure amount, the resin layer was heated at 160°C for 60 minutes to fully cure it, thereby fabricating an evaluation substrate having a patterned cured film, and the shape of the shoulder of the aperture top was observed at 3000x magnification using SEM.

[0292] ◎: The shoulders of the top have a sharp shape.

[0293] ○: The shoulders of the top are slightly rounded.

[0294] △: The shoulders of the top have become rounded.

[0295] ×: The shoulders of the top are rounded or varied and not sharp.

[0296] <Metal Plating Adhesion Evaluation>

[0297] The dry films of each example and comparative example prepared in the above <Preparation of a Dry Film of a Laminated Curable Resin Structure of the First Aspect of the Present Invention> were laminated onto acid-treated FR-4 after peeling off the second film, using a vacuum laminator (CVP-600: manufactured by Nikko Material Co., Ltd.) in a first chamber at 80°C under conditions of a vacuum pressure of 3 hPa and a vacuum time of 30 seconds, and then pressed under conditions of a press pressure of 0.5 MPa and a press time of 30 seconds to obtain an evaluation substrate. Subsequently, after exposure with a contact exposure machine, the PET film was peeled off (in Example 15, the PET film was peeled off after heat treatment at 80°C for 45 minutes), and development (1 mass% Na2CO3, 30°C, 0.2 MPa) was performed for 60 seconds, followed by a UV conveyor furnace equipped with a high-pressure mercury lamp at 1 J / cm² 2 After irradiating the resin layer with an exposure amount, an evaluation substrate was prepared by heating the resin layer at 160°C for 60 minutes to fully cure the resin layer.

[0298] The commercially available wet permanganate desmear, electroless copper plating, and electrolytic copper plating treatments were performed in that order, and copper plating was carried out on the resin layer under the same conditions to achieve a thickness of 25 μm. Subsequently, an annealing treatment was performed at 190°C for 60 minutes in a hot air circulating drying oven to obtain a test substrate. Using a cutter knife, a grid pattern of 25 squares with a size of 1 mm × 1 mm was created on the copper-plated surface of the test substrate (JIS-K5600-5-61999, adhesion (based on the cross-cut method)). Afterward, a polyester tape (Product No. 9394: adhesion strength 3.3 N / cm, manufactured by 3M) was attached to the surface of the cut cured film, and the end of the tape was immediately grasped and held perpendicular to the surface of the cured film to instantly peel off the tape. The condition of the film after peeling was judged according to the following criteria.

[0299] ◎: Less than 1 peeled section.

[0300] ○: 1 or more peeled sections, but less than 5.

[0301] △: 5 or more peeled sections, but less than 10.

[0302] ×: 10 or more peeled sections.

[0303]

[0304]

[0305] From the results shown in Tables 2 and 3, the cured products of the laminated curable resin structures of Examples 1-1 to 1-15 had a CTE of 110 ppm / °C or lower, and exhibited excellent crack resistance (cold / heat resistance), resolution (shape sharpness), and metal plating adhesion. In contrast, for the cured products of the laminated curable resin structures of each Comparative Example, the CTE was greater than 110 ppm / °C, except for Comparative Examples 1-2 and 1-8, and at least one of crack resistance (cold / heat resistance), resolution (shape sharpness), and metal plating adhesion was poor. Specifically, Comparative Example 1-1 is a single-layer structure consisting only of X-1-1 layers, which is an example of a low CTE and low crack resistance (cold / heat resistance). Comparative Example 1-2 is a single-layer structure consisting only of Y-1-1 layers, which is an example of low resolution (shape sharpness) and low metal plating adhesion. Comparative Example 1-3 is an example where the thickness of the X layer was greater than the thickness of the Y layer, and the CTE was lower, and the crack resistance (cold / heat resistance) was lower. Comparative Example 1-4 is an example where the CTE was lower, and the crack resistance (cold / heat resistance) was lower. Comparative Example 1-5 is an example of a single-layer structure consisting only of X-1-7 layers, and the CTE was lower, and the crack resistance (cold / heat resistance) and resolution (shape sharpness) were lower. Comparative Example 1-6 is an example of a single-layer structure consisting only of Y-1-8 layers, and the CTE was lower, and the crack resistance (cold / heat resistance), resolution (shape sharpness), and metal plating adhesion were lower. Comparative Example 1-7 is an example where the ratio of the thickness of the X layer to the total thickness of the resin composition combined with the Y layer was too large, and the CTE and crack resistance (cold / heat resistance) were lower. Comparative Examples 1-8 were examples where the ratio of the thickness of the X layer to the total thickness of the resin composition combined with the Y layer was too small, and the resolution (shape sharpness) and metal plating adhesion were poor.

[0306] FIG. 2 shows a sketch of an SEM image in which the resolution (shape sharpness) was evaluated for Example 1-1, and FIG. 3 shows a sketch of an SEM image in which the resolution (shape sharpness) was evaluated for Comparative Example 1-2. In Example 1-1, the shoulder of the opening of the X layer (11X) of the laminated curable resin structure was sharp, whereas in Comparative Example 1-2, the shoulder of the opening of the curable resin 111 was rounded. Also, in FIG. 2 and FIG. 3, reference numeral 14 is a copper laminate.

[0307] 《Example of a laminated curable resin structure of the second aspect of the present invention》

[0308] Hereinafter, a laminated curable resin structure of a second aspect of the present invention will be described in more detail using examples, but the present invention is not limited to the following examples. Furthermore, in the following, "parts" and "%" are all based on mass unless otherwise specified.

[0309] [Synthesis of Alkali-Soluble Resin A-2-1]

[0310] To 400 parts of phenol novolak type epoxy resin EPPN-201 (Nippon Kayaku, epoxy equivalent 187), 117 parts of ethylene glycol salicylate, 56 parts of acrylic acid, 67 parts of methacrylic acid, 274 parts of ethyl carbitol acetate, 3 parts of triphenylphosphine, and 0.5 parts of methylhydroquinone were added, and an ethyl carbitol acetate solution was obtained by reacting at 110°C for 12 hours. To 400 parts of this solution, 64 parts of tetrahydrophthalic anhydride were added, and the mixture was reacted at 100°C for 5 hours. An alkali-soluble resin (A-2-1) containing 74% of a carboxyl group-containing curable resin with an acid value of 80 mgKOH / g was obtained.

[0311] [Synthesis of Alkali-Soluble Resin A-2-2]

[0312] 130 parts of biphenyl-type epoxy resin “YX4000” (manufactured by Mitsubishi Chemical), 43.3 parts of bisphenol S, 182.7 parts of propylene glycol monomethyl ether acetate, and 0.4 parts of benzyl triethylammonium chloride as a reaction catalyst were added and reacted at 140°C for 6 hours. After confirming the completion of the reaction between the phenolic hydroxyl group and the epoxy group by quantitative analysis of the epoxy group, 176.3 parts of bisphenol A-type epoxy resin (product name “jER834”; manufactured by Japan Epoxy Resin; epoxy equivalent 255) and 182.7 parts of propylene glycol monomethyl ether acetate were added and dissolved to form a homogeneous solution. Next, 90.2 parts of methacrylic acid, 1.3 parts of triphenylphosphine as an esterification catalyst, and 0.6 parts of methylhydroquinone as a polymerization inhibitor were added, and the mixture was reacted at 120°C for 20 hours, confirming that the acid value of the reaction product was 2.9 mgKOH / g. Subsequently, 131.7 parts of tetrahydrophthalic anhydride were added and the mixture was reacted at 110°C for 5 hours, thereby obtaining an alkali-soluble resin (A-2-2) containing 61% of a mixture of an acid-modified vinyl ester with an acid value of 90 mgKOH / g and a carboxyl group-containing bisphenol A type epoxy acrylate.

[0313] [Synthesis of Alkali-Soluble Resin A-2-3]

[0314] 120 parts of novolak-type cresol resin (Aika Kogyo "Shonol CRG-951", OH equivalent: 120), 1 part of potassium hydroxide, and 120 parts of toluene were introduced, and the system was heated while stirring and nitrogen was substituted. Subsequently, 64 parts of propylene oxide were slowly added dropwise and reacted at 130°C. Afterward, the solution was cooled to room temperature, and 2 parts of 89% phosphoric acid were added and mixed to the reaction solution to neutralize the potassium hydroxide, thereby obtaining a reaction solution of novolak-type cresol resin with propylene oxide having a non-volatile content of 60% and a hydroxyl value of 180 mgKOH / g. 300 parts of the propylene oxide reaction solution of the obtained novolak-type cresol resin, 40 parts of acrylic acid, 10 parts of methanesulfonic acid, 0.2 parts of methylhydroquinone, and 250 parts of toluene were introduced into a reactor equipped with a stirrer, a thermometer, and an air blower, and the reaction was carried out at 110°C while stirring and blowing air at a rate of 10 ml / min. Afterward, the mixture was cooled to room temperature, the resulting reaction solution was neutralized with a 15% aqueous sodium hydroxide solution, and then washed with water. Subsequently, the toluene was removed by distillation using an evaporator while replacing it with 120 parts of diethylene glycol monoethyl ether acetate to obtain a novolak-type acrylate resin solution. Next, 300 parts of the obtained novolak-type acrylate resin solution and 1 part of triphenylphosphine were introduced into a reactor equipped with a stirrer, a thermometer, and an air blower, air was blown in at a rate of 10 ml / min, and 60 parts of tetrahydrophthalic anhydride were slowly added while stirring, and the mixture was reacted at 100°C to obtain an alkali-soluble resin (A-2-3).

[0315] [Synthesis of Alkali-Soluble Resin A-2-4]

[0316] 450 parts of bisphenol A, 200 parts of water, and 650 parts of 37% formalin were added, and 230 parts of a 25% aqueous sodium hydroxide solution were added. After the reaction was complete, the mixture was cooled to 40°C and neutralized with a 37% aqueous phosphoric acid solution. After separating the aqueous layer, 300 parts of methylisobutyl ketone were added and uniformly dissolved, after which water, solvent, etc., were removed. The obtained polymethylol compound was dissolved in 550 parts of methanol to obtain 1,000 parts of a methanol solution of the polymethylol compound. 500 parts of the obtained methanol solution of the polymethylol compound and 440 parts of 2,6-xylenol were added to a flask equipped with a cooling tube and a stirrer and uniformly dissolved. Subsequently, 8 parts of oxalic acid were added, and the reaction was carried out at 100°C. After the reaction was completed, the effluent was removed at 180°C and a reduced pressure of 50 mmHg to obtain 550 parts of Novolak Resin A. 130 parts of Novolak Resin A, 3 parts of a 50% aqueous sodium hydroxide solution, and 100 parts of toluene / methylisobutyl ketone (mass ratio = 2 / 1) were added to an autoclave equipped with a thermometer, a nitrogen introduction device and an alkylene oxide introduction device, and a stirring device; the system was then nitrogen-purged while stirring; subsequently, the temperature was raised to 150°C and 8 kg / cm² 260 parts of propylene oxide were slowly introduced and the reaction was carried out. After continuing the reaction for about 4 hours, it was cooled to room temperature. 3 parts of a 36% hydrochloric acid solution were added and mixed to this reaction solution, and sodium hydroxide was neutralized. The neutralization reaction product was diluted with toluene, washed with water three times, and desolvated using an evaporator to obtain a propylene oxide adduct of novolak resin A with a hydroxyl value of 189 g / eq. This had an average of 1 mole of propylene oxide added per 1 equivalent of phenolic hydroxyl group. 189 parts of propylene oxide adduct of obtained novolak resin A, 36 parts of acrylic acid, 3 parts of p-toluenesulfonic acid, 0.1 parts of hydroquinone monomethyl ether, and 140 parts of toluene were introduced into a reactor equipped with a stirrer, a thermometer, and an air blower, stirred while blowing air, and heated to 115°C. The water produced by the reaction was removed by distillation as an azeotropic mixture with toluene, and the reaction was carried out for 4 hours, after which it was cooled to room temperature. The obtained reaction solution was washed with a 5% NaCl aqueous solution and toluene was removed by vacuum distillation to obtain a 7% acrylate resin solution. Next, 320 parts of the obtained acrylate resin solution, 0.1 parts of hydroquinone monomethyl ether, and 0.3 parts of triphenylphosphine were added to a 4-neck flask equipped with a stirrer and a reflux condenser, the mixture was heated at 110°C, 60 parts of tetrahydrophthalic anhydride were added, and the mixture was reacted for 4 hours to obtain an alkali-soluble resin (A-2-4).

[0317] [Synthesis of Alkali-Soluble Resin A-2-5]

[0318] 80 parts of carbitol acetate were added to a separable flask equipped with a cooling tube serving as a reaction vessel, and after purging with nitrogen, the temperature was raised to 80°C. Meanwhile, a mixture of 30 parts of N-phenylmaleimide and 120 parts of carbitol acetate was added to dropper 1; a mixture of 30 parts of styrene and 20 parts of 2-hydroxyethyl methacrylate was added to dropper 2; a mixture of 20 parts of acrylic acid and 10 parts of carbitol acetate was added to dropper 2; and a mixture of 10 parts of Luperox 11 (manufactured by Arkma Yoshitomi Co., Ltd., a hydrocarbon solution containing 70% t-butylperoxypivalate) and 20 parts of carbitol acetate was added to dropper 2 as a polymerization initiator. Dropping was performed from the dropper while maintaining the reaction temperature at 80°C. After the dropping was finished, the reaction was continued at 80°C for 30 minutes. Subsequently, the reaction temperature was raised to 95°C and the reaction was continued for 1.5 hours to obtain a polymer solution prior to the radical polymerization double bond introduction reaction. Next, 10 parts of glycidyl methacrylate, 7 parts of carbitol acetate, 0.7 parts of triphenylphosphine as a reaction catalyst, and 0.2 parts of Anteji W-400 (manufactured by Kawaguchi Kagaku Kogyo Co., Ltd.) as a polymerization inhibitor were added to this polymer solution, and the reaction was carried out at 115°C while bubbling a mixed gas of nitrogen and oxygen (oxygen concentration 7%) to obtain an alkali-soluble resin of A-2-5.

[0319] [Adjustment of Weapon Particle C-2-1]

[0320] 60g of spherical silica (SFP-30M, manufactured by Denka, average particle size: 600nm), 40g of MEK (methyl ethyl ketone) as a solvent, and 1g of methacrylate silane coupling agent (KBM-503, manufactured by Shin-Etsu Chemical Co., Ltd.) were uniformly dispersed to obtain silica solvent dispersion product C-2-1.

[0321] [Adjustment of Weapon Particle C-2-2]

[0322] 50g of spherical silica (IX-3-NP manufactured by Nippon Shokubai Co., Ltd., average particle size 20nm) produced by the sol-gel method, 100g of MEK (methyl ethyl ketone), and 20g of an amino-based silane coupling agent (KBE-573 manufactured by Shin-Etsu Chemical Co., Ltd.) were uniformly dispersed to obtain silica solvent dispersion product C-2-2.

[0323] [Adjustment of Inorganic Particle C-2-3]

[0324] 70g of a hydrotalcite compound (DHT-4C manufactured by Kyowa Kagaku Kogyo Co., Ltd., average particle diameter 400nm) and 40g of MEK (methyl ethyl ketone) as a solvent were uniformly dispersed to obtain a hydrotalcite compound solvent dispersion product C-2-3.

[0325] [Epoxy resin dispersion of rubber particles D-2-1]

[0326] (Production of core-shell rubber particles having curable reactors on the surface)

[0327] 1300g of rubber latex and 440g of pure water were introduced into a 3-liter glass reactor, and the mixture was heated to 70°C while stirring under nitrogen introduction. The rubber latex contained 480g of polybutadiene particles with an average particle size of 0.1㎛ and 1.5% by mass of sodium dodecylbenzenesulfonate, with the polybutadiene making up 100% by mass. To this, 1.2g of azoisobutyronitrile was added, followed by the addition of a mixture of 36g of styrene, 48g of methyl methacrylate, 24g of acrylonitrile, and 12g of glycidyl methacrylate over a period of 3 hours. Afterward, the mixture was stirred for another 2 hours to obtain core-shell rubber particles (latex (L)). The solid content of the latex (L) was 32%. Additionally, the gel fraction of the core-shell copolymer in the latex (L) was 98%. In addition, the diameter of the rubber particles in the latex (L) was 0.5 μm.

[0328] [Preparation of an alkali-soluble resin composition of a laminated curable resin structure of the second aspect of the present invention]

[0329] Each alkali-soluble resin obtained by the above synthesis was mixed with each varnish solution (described in Table 4 as solid content) adjusted to have a solid content of 60% using propylene glycol methyl ether acetate, and epoxy resin, inorganic particles, and other raw materials in the ratio (parts by mass) shown in Table 4, pre-mixed with a stirrer, and then kneaded with a three-roll mill to prepare alkali-soluble resin compositions X-2-1 to X-2-10 for the X layer and alkali-soluble resin compositions Y-2-1 to Y-2-10 for the Y layer.

[0330]

[0331] The footnotes in the heading column of Table 4 are as follows.

[0332] *1: Alkali-soluble resin A-2-1 synthesized above

[0333] *2: Alkali-soluble resin A-2-2 synthesized above

[0334] *3: Alkali-soluble resin A-2-3 synthesized above

[0335] *4: Alkali-soluble resin A-2-4 synthesized above

[0336] *5: Alkali-soluble resin A-2-5 synthesized above

[0337] *6: Meiwa Gasei Co., Ltd. HF-1M, Phenolnovolak Resin, Hydroxyl Equivalent 106

[0338] *7: Nissan Kagaku TEPIC-VL, heterocyclic epoxy resin, trifunctional, liquid, epoxy equivalent: 128g / eq

[0339] *8: NC-3000H manufactured by Nippon Kayaku Co., Ltd., biphenylnovolak type epoxy resin, epoxy equivalent 290g / eq

[0340] *9: DIC EPICLON HP7200L, dicyclopentadiene-type epoxy resin

[0341] *10: The inorganic particle C-2-1 adjusted above

[0342] *11: The inorganic particle C-2-2 adjusted above

[0343] *12: The inorganic particle C-2-3 adjusted above

[0344] *13: Epoxy resin dispersion of rubber particles prepared above D-2-1

[0345] *14: DIC Polyester Polyol Polylite OD-X-2068

[0346] *15: Mitsubishi Chemical Corporation's Phenoxy Resin YX7200B35

[0347] *16: Acylphosphine oxide-based photopolymerization initiator E-2-1, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide

[0348] *17: Photopolymerization initiator E-2-2: IGM Resins Omnirad 907 (2-methyl-1-(4-methylthiophenyl)-2-morpholinopropane-1-one)

[0349] *18: Shinnakamura Kagaku High School Teacher's Detergent A-DCP (Tricyclodecanedimethanol diacrylate)

[0350] (Examples 2-1 to 2-17, Comparative Examples 2-1 to 2-7)

[0351] <Production of a dry film of a laminated curable resin structure of the second embodiment of the present invention>

[0352] 300g of methyl ethyl ketone was added to each alkali-soluble resin composition obtained as described above to dilute it, and the mixture was stirred with a stirrer for 15 minutes to obtain a coating solution. The coating solution was applied first to a polyethylene terephthalate film (hereinafter also referred to as a PET film) (first film) with a thickness of 38㎛, such that the ratio of the thickness of the X layer to the Y layer in Examples 2-1 to 2-17 and Comparative Examples 2-3, 2-5, and 2-6 of Table 4 was such that the X layer was dried at 80℃ for 5 minutes using a hot air circulating dryer, and after cooling, the Y layer was applied thereon and dried at a temperature of 80℃ for 15 minutes to form a laminated resin layer (two-layer resin layer) with a total thickness of 25㎛. In addition, Comparative Examples 2-1, 2-2, 2-4, and 2-7 were each applied as a single layer with a thickness of 25㎛, and the drying was performed at a temperature of 80℃ for 15 minutes.

[0353] Next, a biaxially stretched polypropylene film (second film) was bonded onto the laminated resin layer to produce a dry film.

[0354] The dry films of Examples 2-1 to 2-17 and Comparative Examples 2-1 to 2-7 were subjected to the tests and evaluations described below. The results are shown in Table 5.

[0355] Crack Resistance (Cold & Heat Resistance) Evaluation

[0356] After peeling off the second film from the dry films of each example and comparative example produced in <Production of a Dry Film of a Laminated Curable Resin Structure of the Second Embodiment of the Present Invention>, each dry film was laminated in a first chamber at 80°C under conditions of vacuum pressure 3 hPa and vacuum time 30 seconds using a vacuum laminator (CVP-600: manufactured by Nikko Material Co., Ltd.) under conditions of vacuum pressure 3 hPa and vacuum time 30 seconds, and then pressed under conditions of press pressure 0.5 MPa and press time 30 seconds to obtain an evaluation substrate. After that, the PET film was peeled off after exposure with a DI exposure machine to obtain an exposure amount that yields 10 steps on a step tablet (41 steps) (only in Example 6, after heat drying at 80°C for 40 minutes), and then developed (1 mass% Na2CO3, 30°C, 0.2 MPa) for 60 seconds to form a pattern of the resin layer. Continuing, 1 J / cm² in a UV conveyor furnace equipped with a high-pressure mercury lamp 2 After irradiating the resin layer with an exposure amount, the resin layer was fully cured by heating at 160°C for 60 minutes to fabricate an evaluation substrate with a square resist pattern of 3 mm on each side formed on a copper line. This substrate was placed in a thermal cycle machine in which a temperature cycle was performed between -50°C and 150°C to perform a Thermal Cycle Test (TCT). Then, cracks were checked after evaluating up to 1000 cycles.

[0357] ◎: No cracks occurred up to 2000 cycles.

[0358] ○: No cracks occurred at 1500 cycles.

[0359] △: Cracks occur up to 1500 cycles.

[0360] ×: Cracks occur up to 1000 cycles.

[0361] Resolution (Shape Sharpness)

[0362] After peeling off the second film from the dry films of each example and comparative example prepared in <Preparation of a Dry Film of a Laminated Curable Resin Structure of the Second Aspect of the Present Invention> above onto the copper of a copper-clad laminate that has been CZ-treated, the dry films were laminated using a vacuum laminator (CVP-600: manufactured by Nikko Material Co., Ltd.) in a first chamber at 100°C under conditions of vacuum pressure 3 hPa and vacuum time 30 seconds, and then pressed under conditions of press pressure 0.5 MPa and press time 30 seconds to obtain an evaluation substrate. Subsequently, a φ30㎛ SRO pattern was exposed using a projection exposure machine (i-line) with an exposure amount that obtained 10 steps on a step tablet (41 steps) (Example 6, after heat drying at 80°C for 40 minutes), the PET film was peeled off, and a pattern of the resin layer was formed by developing (1 mass% Na2CO3, 30°C, 0.2 MPa) for 60 seconds. Subsequently, a UV conveyor furnace equipped with a high-pressure mercury lamp at 1 J / cm² 2 After irradiating the resin layer with an exposure amount, the resin layer was heated at 160°C for 60 minutes to fully cure it, thereby fabricating an evaluation substrate having a patterned cured film, and the shape of the shoulder of the aperture top was observed at 3000x magnification using SEM.

[0363] ◎: The shoulders of the top have a sharp shape.

[0364] ○: The shoulders of the top are slightly rounded.

[0365] △: The shoulders of the top have become rounded.

[0366] ×: The shoulders of the top are rounded or varied and not sharp.

[0367] <Metal Plating Adhesion Evaluation>

[0368] The dry films of each example and comparative example prepared in the above <Preparation of a Dry Film of a Laminated Curable Resin Structure of the Second Aspect of the Present Invention> were laminated onto acid-treated FR-4 after peeling off the second film, using a vacuum laminator (CVP-600: manufactured by Nikko Material Co., Ltd.) in a first chamber at 80°C under conditions of a vacuum pressure of 3 hPa and a vacuum time of 30 seconds, and then pressed under conditions of a press pressure of 0.5 MPa and a press time of 30 seconds to obtain an evaluation substrate. Subsequently, after exposure with a contact exposure machine (only in Example 6, after heat drying at 80°C for 40 minutes), the PET film was peeled off, and development (1 mass% Na2CO3, 30°C, 0.2 MPa) was performed for 60 seconds, followed by a UV conveyor furnace equipped with a high-pressure mercury lamp at 1 J / cm² 2 After irradiating the resin layer with an exposure amount, an evaluation substrate was prepared by heating the resin layer at 160°C for 60 minutes to fully cure the resin layer.

[0369] The commercially available wet permanganate desmear, electroless copper plating, and electrolytic copper plating treatments were performed in that order, and copper plating was carried out on the resin layer under the same conditions to achieve a thickness of 25 μm. Subsequently, an annealing treatment was performed at 190°C for 60 minutes in a hot air circulating drying oven to obtain a test substrate. Using a cutter knife, a grid pattern of 25 squares with a size of 1 mm × 1 mm was created on the copper-plated surface of the test substrate (JIS-K5600-5-61999, adhesion (based on the cross-cut method)). Afterward, a polyester tape (Product No. 9394: adhesion strength 3.3 N / cm, manufactured by 3M) was attached to the surface of the cut cured film, and the end of the tape was immediately grasped and held perpendicular to the surface of the cured film to instantly peel off the tape. The condition of the film after peeling was judged according to the following criteria.

[0370] ◎: Less than 1 peeled section.

[0371] ○: 1 or more peeled sections, but less than 5.

[0372] △: 5 or more peeled sections, but less than 10.

[0373] ×: 10 or more peeled sections.

[0374]

[0375]

[0376] From the results shown in Tables 5 and 6, the cured products of the laminated curable resin structures of Examples 2-1 to 2-17 exhibited excellent crack resistance (cold / heat resistance), resolution (shape sharpness), and metal plating adhesion. In contrast, in the cured products of the laminated curable resin structures of each Comparative Example, at least one of crack resistance (cold / heat resistance), resolution (shape sharpness), and metal plating adhesion was poor. Specifically, Comparative Example 2-1 had a single-layer structure consisting only of X-2-1 layers, and its crack resistance (cold / heat resistance) was poor. Comparative Example 2-2 had a single-layer structure consisting only of Y-2-1 layers, and its shape sharpness and metal plating adhesion were poor. Comparative Example 2-3 had a thickness of the X layer greater than the thickness of the Y layer, and its crack resistance (cold / heat resistance) was poor. Comparative Example 2-4 is a single-layer structure consisting only of X-2-10 layers that do not contain hydrotalcite in the X layer, and has poor crack resistance (cold / heat resistance) and poor metal plating adhesion. Comparative Example 2-5 is an example in which the Y layer does not contain silica, and has poor crack resistance (cold / heat resistance). Comparative Example 2-6 is an example in which the ratio of the thickness of the X layer to the total thickness of the resin composition combined with the X layer and the Y layer was too large, and has poor crack resistance (cold / heat resistance) and shape sharpness. Comparative Example 2-7 is an example in which the Y layer does not contain rubber particles or elastomer, and has a single-layer structure consisting only of Y-2-8 layers, and has poor crack resistance (cold / heat resistance) and metal plating adhesion.

[0377] FIG. 4 shows a sketch of an SEM image in which a resolution evaluation was performed on Example 2-1, and FIG. 5 shows a sketch of an SEM image in which a resolution evaluation was performed on Comparative Example 2-2. In Example 2-1, the shoulder of the opening of the X layer (11X) of the laminated curable resin structure was sharp, whereas in Comparative Example 2, the shoulder of the opening of the curable resin 111 was rounded. Also, in FIG. 4 and FIG. 5, reference numeral 14 is a copper laminate. Explanation of the symbols

[0378] 1: Dry film 11: Laminated curable resin structure 11X: Xth floor 11Y: Y-layer 12: Film 1 13: Second Film 14: Copper laminate 111: Curable resin

Claims

Claim 1 It is composed of a two-layer resin layer formed by laminating an X layer containing an alkali-soluble resin composition X and a Y layer containing an alkali-soluble resin composition Y, wherein the X layer is 5% or more and 30% or less of the total thickness of the two-layer resin layer combined with the Y layer, and the alkali-soluble resin compositions X and Y of the X layer and the Y layer both contain inorganic particles, and furthermore, said inorganic particles contain silica, wherein the silica of the X layer has an average particle size of 50 nm or less and is less than 25 mass% of the alkali-soluble resin composition X of the X layer, and the silica of the Y layer has an average particle size of 200 nm or more and is 25 mass% or more and less than 50 mass% of the alkali-soluble resin composition Y of the Y layer, and 1000 mJ / cm² 2 A laminated curable resin structure characterized by a thickness of 20 to 30 μm, obtained by light irradiation and heat treatment at 160°C for 1 hour, wherein the coefficient of thermal expansion at 200 to 250°C as determined by thermomechanical analysis is 110 ppm / °C or less. Claim 2 A laminated curable resin structure according to claim 1, wherein the alkali-soluble resin compositions X and Y of the X layer and the Y layer each additionally comprise at least one selected from radical polymerizable compounds and epoxy resins. Claim 3 A laminated curable resin structure according to claim 2, wherein the alkali-soluble resin compositions X and Y of the X layer and the Y layer each comprise at least one selected from rubber particles with an average particle size of 100 nm or more to 1 μm or less and thermoplastic elastomers, and the total amount of the rubber particles and thermoplastic elastomers in the X layer is greater than the total amount of the rubber particles and thermoplastic elastomers in the Y layer. Claim 4 A laminated curable resin structure according to claim 1, wherein the inorganic particles of the alkali-soluble resin composition Y of the Y layer comprise inorganic particles having a metal element having O, S, or N in coordination electrons, in an amount of less than 20% of the alkali-soluble resin composition Y. Claim 5 A dry film characterized by having a resin layer obtained by applying and drying a laminated curable resin structure described in any one of claims 1 to 4 onto a film. Claim 6 A cured product characterized by being obtained by curing a resin layer of a dry film having a resin layer obtained by applying and drying the laminated curable resin structure described in any one of claims 1 to 4, or said laminated curable resin structure onto a film. Claim 7 An electronic component characterized by having a hardened material as described in paragraph 6. Claim 8 A laminated curable resin structure comprising two layers of resin, wherein the X layer containing an alkali-soluble resin composition X and the Y layer containing an alkali-soluble resin composition Y are laminated, wherein the X layer is 5% or more and 30% or less of the total thickness of the two layers of resin combined with the Y layer, wherein the alkali-soluble resin compositions X and Y of the X layer and the Y layer both contain inorganic particles, wherein the inorganic particles of the X layer are inorganic particles containing metal elements having O, S, and N in their coordination electrons, and the inorganic particles of the Y layer contain silica, and wherein the inorganic particles containing metal elements having O, S, and N in their coordination electrons of the X layer are contained in an amount of less than 20 mass% with respect to the total solid content of the alkali-soluble resin composition X. Claim 9 A laminated curable resin structure according to claim 8, wherein the alkali-soluble resin compositions X and Y of the X layer and the Y layer each additionally comprise at least one selected from radical polymerizable compounds and epoxy resins. Claim 10 A laminated curable resin structure according to claim 9, wherein the alkali-soluble resin compositions X and Y of the X layer and the Y layer each comprise at least one selected from rubber particles with an average particle size of 100 nm or more to 1 μm or less and thermoplastic elastomers. Claim 11 A laminated curable resin structure according to any one of claims 8 to 10, wherein the alkali-soluble resin compositions X and Y of the X layer and the Y layer both comprise a curing accelerator. Claim 12 A dry film characterized by having a resin layer obtained by applying and drying a laminated curable resin structure described in any one of claims 8 to 10 onto a film. Claim 13 A cured product characterized by being obtained by curing a resin layer of a dry film having a resin layer obtained by applying and drying the laminated curable resin structure described in any one of claims 8 to 10, or said laminated curable resin structure onto a film. Claim 14 An electronic component characterized by having the cured material described in Clause 13. Claim 15 delete Claim 16 delete Claim 17 delete

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