JP2022107466A - Photosensitive resin composition, dry film, cured product and printed wiring board - Google Patents

Abstract

To provide a photosensitive resin composition that contains a carboxyl group-containing resin and gives a cured product, which easily gets a low dielectric loss tangent and keeps flexibility, and is less susceptible to excessive corrosion even when treated with an oxidizing agent.SOLUTION: A photosensitive resin composition contains a carboxyl group-containing resin (A), a photopolymerization initiator (B), a photopolymerizable compound (C), an epoxy compound (D), 50 mass% or more and 300 mass% or less of silica (E) relative to the carboxyl group-containing resin (A), and 21 mass% or more and 100 mass% or less of a blocked isocyanate compound (F) relative to the carboxyl group-containing resin (A).SELECTED DRAWING: Figure 1

Description

The present invention relates to a photosensitive resin composition, a dry film, a cured product, and a printed wiring board. Specifically, a photosensitive resin composition containing a carboxyl group-containing resin, a dry film containing this photosensitive resin composition, and the like. The present invention relates to a cured product of a photosensitive resin composition and a printed wiring board provided with a solder resist layer or an interlayer insulating layer containing the cured product.

Patent Document 1 discloses a curable resin composition in which the cured product has a low dielectric constant and a low dielectric loss tangent. Patent Document 1 states that the curable resin composition contains an alkali-soluble resin, an inorganic filler, a photocurable compound having no hydroxyl group and a carboxyl group, an adhesion imparting agent, and a photopolymerization initiator. It is also disclosed that blocked isocyanate is preferable as the sex-imparting agent, and that the blending amount of the adhesion-imparting agent is 0.01 to 20 parts by mass with respect to 100 parts by mass of the (A) alkali-soluble resin in terms of solid content. Has been done.

JP-A-2017-68242

According to the findings independently obtained by the inventor through research and development, when preparing a solder resist layer, an interlayer insulating layer, etc. from a cured product of a resin composition containing a carboxyl group-containing resin, an inorganic filler is used to reduce dielectric loss tangent. When the above is blended, the cured product tends to become brittle. Further, when the surface of the cured product is treated with an oxidizing agent or the like to adjust the roughness in order to improve the adhesion between the cured product, particularly the interlayer insulating layer and the conductor overlapping the cured product, the inorganic filler is removed from the cured product. It is easy for the cured product to be excessively corroded by the oxidant.

The subject of the present invention is that it contains a carboxyl group-containing resin, it is easy to make the cured product low dielectric normal contact, it is easy to maintain the flexibility of this cured product, and it is difficult for the cured product to be excessively corroded even if it is treated with an oxidizing agent. Provided is a printed wiring board provided with a photosensitive resin composition, a dry film containing the photosensitive resin composition, a cured product of the photosensitive resin composition, and a solder resist layer or an interlayer insulating layer containing the cured product. Is.

The photosensitive resin composition according to one aspect of the present invention includes a carboxyl group-containing resin (A), a photopolymerization initiator (B), a photopolymerizable compound (C), an epoxy compound (D), and the carboxyl group-containing resin ( It contains silica (E) having a percentage of 50% by mass or more and 300% by mass or less with respect to A), and a blocked isocyanate compound (F) having a percentage of 21% by mass or more and 100% by mass or less with respect to the carboxyl group-containing resin (A).

The dry film according to one aspect of the present invention contains the photosensitive resin composition.

The cured product according to one aspect of the present invention is obtained by curing the photosensitive resin composition.

The printed wiring board according to one aspect of the present invention includes an interlayer insulating layer containing the cured product.

The printed wiring board according to one aspect of the present invention includes a solder resist layer containing the cured product.

According to one aspect of the present invention, it contains a carboxyl group-containing resin, it is easy to reduce the dielectric adjacency of the cured product, it is easy to maintain the flexibility of the cured product, and it is excessive even if the cured product is treated with an oxidizing agent. A printed wiring board provided with a photosensitive resin composition that is not easily corroded, a dry film containing the photosensitive resin composition, a cured product of the photosensitive resin composition, and a solder resist layer or an interlayer insulating layer containing the cured product. Can be provided.

1A to 1E are cross-sectional views showing a process of manufacturing a printed wiring board according to an embodiment of the present invention.

Hereinafter, an embodiment of the present invention will be described. The following embodiment is only one of various embodiments of the present invention. The following embodiments can be variously modified according to the design as long as the object of the present invention can be achieved.

The photosensitive resin composition according to the present embodiment is for a carboxyl group-containing resin (A), a photopolymerization initiator (B), a photopolymerizable compound (C), an epoxy compound (D), and a carboxyl group-containing resin (A). It contains silica (E) having a percentage ratio of 50% by mass or more and 300% by mass or less, and a blocked isocyanate compound (F) having a percentage ratio of 21% by mass or more and 100% by mass or less with respect to the carboxyl group-containing resin (A).

According to this embodiment, it is easy to reduce the dielectric loss tangent of the cured product of the photosensitive resin composition. Therefore, the high frequency characteristics of the printed wiring board containing the cured product of the photosensitive resin composition are likely to be improved. Further, it is easy to maintain the flexibility of the cured product, and even if the cured product is treated with an oxidizing agent, it can be prevented from being excessively corroded. The reason is presumed to be as follows. However, this embodiment is not bound by the explanation of the following reasons.

When the photosensitive resin composition contains silica (E) and the percentage of silica (E) to the carboxyl group-containing resin (A) is 50% by mass or more, the silica (E) has a dielectric loss tangent of the cured product. Can be reduced. Further, the photosensitive resin composition contains the blocked isocyanate compound (F), and the percentage of the blocked isocyanate compound (F) is 21% by mass or more and 100% by mass or less with respect to the carboxyl group-containing resin (A). In the process of curing the photosensitive resin composition, the blocked isocyanate compound (F) reacts with the hydroxyl groups, so that the hydroxyl groups in the cured product (X) are reduced, which further reduces the dielectric tangent of the cured product. In addition, the urethane bond generated by this reaction enhances the flexibility of the cured product. Further, the blocked isocyanate compound (F) is likely to bond with the hydroxyl group on the surface of the silica (E), so that the particles of the silica (E) are less likely to fall off from the cured product even if the surface of the cured product is treated with an oxidizing agent. ..

Further, the blocked isocyanate compound (F) can enhance the developability when forming a film such as a solder resist layer and an interlayer insulating layer from a photosensitive resin composition by a photolithography method. The reason is not sufficiently clear, but if the percentage of the blocked isocyanate compound (F) in the photosensitive resin composition is 21% by mass or more and 100% by mass or less with respect to the carboxyl group-containing resin (A), the block is blocked. Since the isocyanate compound (F) acts as a plasticizer, the photosensitive resin composition becomes easily compatible with a developing solution such as an alkaline aqueous solution, and thus the photosensitive resin composition is easily dissolved or dispersed in the developing solution. It is inferred that. Further, since the blocked isocyanate compound (F) is protected by a blocking agent, a reaction is unlikely to occur in the process of forming a film by the photolithography method. It is presumed that this also contributes to the improvement of developability.

The components of the photosensitive resin composition will be described in more detail.

The carboxyl group-containing resin (A) can contain a component having a carboxyl group having an ethylenically unsaturated group. In this case, the carboxyl group-containing resin (A) can impart photosensitive property, specifically, photocurability to the photosensitive resin composition.

The carboxyl group-containing resin (A) preferably contains a carboxyl group-containing resin (A1) having an aromatic ring. In this case, the heat resistance and electrical insulation of the cured product of the photosensitive resin composition tend to increase. It is more preferable that the carboxyl group-containing resin (A1) has a polycyclic aromatic ring of any one of a biphenyl skeleton, a naphthalene skeleton, a fluorene skeleton, and an anthracene skeleton. In this case, the heat resistance and electrical insulation of the cured product are likely to increase.

It is particularly preferable that the carboxyl group-containing resin (A) contains a carboxyl group-containing resin (A11) having a bisphenol fluorene skeleton. In this case, the heat resistance and electrical insulation of the cured product are particularly likely to increase.

The bisphenol fluorene skeleton is represented by the following formula (1).

In the formula (1), R ₁ to R ₈ are independently hydrogen, an alkyl group having 1 to 5 carbon atoms, or a halogen. That is, each of R ₁ to R ₈ in the formula (1) may be hydrogen, or may be an alkyl group having 1 to 5 carbon atoms or a halogen. Even if hydrogen in the aromatic ring is substituted with a low molecular weight alkyl group or halogen, the physical properties of the carboxyl group-containing resin (A11) are not adversely affected, but rather the substitution causes the carboxyl group-containing resin (A11) to be contained. This is because the heat resistance or flame retardancy of the cured product of the photosensitive resin composition may be improved.

The carboxyl group-containing resin (A11) is obtained by reacting, for example, an epoxy compound (a1) having a bisphenol fluorene skeleton represented by the formula (1) with an unsaturated group-containing carboxylic acid (a2), and an intermediate obtained thereby. It is synthesized by reacting the body with an acid anhydride (a3).

The epoxy compound (a1) has, for example, a structure represented by the following formula (2). N in the equation (2) is, for example, an integer in the range of 0 to 20. In order to appropriately control the molecular weight of the carboxyl group-containing resin (A11), the average of n is more preferably in the range of 0 to 1. When the average of n is in the range of 0 to 1, the excessive increase in the molecular weight of the carboxyl group-containing resin (A11) is likely to be suppressed. Further, in the formula (2), R ₁ to R ₈ are independently hydrogen, an alkyl group having 1 to 5 carbon atoms, or a halogen.

The unsaturated group-containing carboxylic acid (a2) contains, for example, a compound having only one ethylenically unsaturated group in one molecule. More specifically, the unsaturated group-containing carboxylic acid (a2) includes, for example, acrylic acid, methacrylic acid, ω-carboxy-polycaprolactone (n≈2) monoacrylate, crotonic acid, cinnamic acid, 2-acryloyloxyethyl succinate. Acid, 2-methacryloyloxyethyl succinic acid, 2-acryloyloxyethylphthalic acid, 2-methacryloyloxyethylphthalic acid, 2-acryloyloxypropylphthalic acid, 2-methacryloyloxypropylphthalic acid, 2-acryloyloxyethylmaleic acid, 2-methacryloyloxyethyl maleic acid, β-carboxyethyl acrylate, 2-acryloyloxyethyl tetrahydrophthalic acid, 2-methacryloyloxyethyl tetrahydrophthalic acid, 2-acryloyloxyethyl hexahydrophthalic acid, and 2-methacryloyloxyethyl hexahydro Contains at least one compound selected from the group consisting of phthalic acids. Preferably, the unsaturated group-containing carboxylic acid (a2) contains acrylic acid. When the unsaturated group-containing carboxylic acid (a2) contains acrylic acid, the acrylic acid is preferably contained in an amount of 50 mol% or more, preferably 80 mol% or more, of the unsaturated group-containing carboxylic acid (a2). Is more preferable, and it is more preferably contained in an amount of 85 mol% or more, and particularly preferably contained in an amount of 90 mol% or more.

The epoxy compound (a1) and the unsaturated group-containing carboxylic acid (a2) can be reacted by an appropriate method. For example, an unsaturated group-containing carboxylic acid (a2) is added to a solvent solution of the epoxy compound (a1), and if necessary, a thermal polymerization inhibitor and a catalyst are added and mixed by stirring to obtain a reactive solution. An intermediate can be obtained by reacting this reactive solution by a conventional method at a temperature of preferably 60 ° C. or higher and 150 ° C. or lower, more preferably 80 ° C. or higher and 120 ° C. or lower. The solvent in this case is, for example, ketones such as methyl ethyl ketone and cyclohexanone, aromatic hydrocarbons such as toluene and xylene, and ethyl acetate, butyl acetate, cellosolve acetate, butyl cellosolve acetate, carbitol acetate, butyl carbitol acetate and propylene. It can contain at least one component selected from the group consisting of acetic acid esters such as glycol monomethyl ether acetate and dialkyl glycol ethers. The thermal polymerization inhibitor can contain at least one component selected from the group consisting of, for example, hydroquinone, methylhydroquinone, and hydroquinone monomethyl ether. The catalyst is selected from the group consisting of, for example, tertiary amines such as benzyldimethylamine and triethylamine, quaternary ammonium salts such as trimethylbenzylammonium chloride and methyltriethylammonium chloride, triphenylphosphine, and triphenylstibine. It can contain at least one component.

It is preferred that the catalyst particularly contains triphenylphosphine. That is, it is preferable to react the epoxy compound (a1) with the unsaturated group-containing carboxylic acid (a2) in the presence of triphenylphosphine. In this case, the ring-opening addition reaction between the epoxy group and the unsaturated group-containing carboxylic acid (a2) in the epoxy compound (a1) is particularly promoted, and the reaction rate (conversion) is 95% or more, 97% or more, or almost 100%. Rate) can be achieved.

It is also preferable to react the epoxy compound (a1) with the unsaturated group-containing carboxylic acid (a2) under air bubbling. In this case, the addition polymerization reaction of the unsaturated group can be suppressed, and the increase in the molecular weight of the intermediate and the gelation of the solution of the intermediate can be suppressed. In addition, excessive coloring of the final product, the carboxyl group-containing resin (A11), can be suppressed.

When the epoxy compound (a1) is reacted with the unsaturated group-containing carboxylic acid (a2), the amount of the unsaturated group-containing carboxylic acid (a2) with respect to 1 mol of the epoxy group of the epoxy compound (a1) is 0.8 mol. It is preferably 1.2 mol or more. In this case, a photosensitive resin composition having excellent photosensitivity and stability can be obtained.

The intermediate thus obtained comprises a hydroxyl group generated by the reaction of the epoxy group of the epoxy compound (a1) with the carboxyl group of the unsaturated group-containing carboxylic acid (a2).

Next, the intermediate is reacted with the acid anhydride (a3). The acid anhydride (a3) contains, for example, an acid dianhydride (a4).

The acid anhydride (a4) is a compound having two acid anhydride groups. The acid dianhydride (a4) can contain an anhydride of tetracarboxylic acid. The acid dianhydride (a4) includes, for example, 1,2,4,5-benzenetetracarboxylic acid dianhydride, benzophenone tetracarboxylic acid dianhydride, methylcyclohexene tetracarboxylic acid dianhydride, tetracarboxylic acid dianhydride, and the like. Naphthalene-1,4,5,8-tetracarboxylic acid dianhydride, ethylenetetracarboxylic acid dianhydride, 9,9'-bis (3,4-dicarboxyphenyl) fluorene dianhydride, glycerin bisanhydrotri Meritate Monoacetate, Ethylene Glycolbisan HydroTrimeritate, 3,3', 4,4'-Diphenylsulfone Tetracarboxylic Acid Dianide, 1,3,3a, 4,5,9b-Hexahydro-5 (Tetrahydro) -2,5-dioxo-3-furanyl) naphtho [1,2-c] furan-1,3-dione, 1,2,3,4-butanetetracarboxylic acid dianhydride, and 3,3', 4 , 4'-Biphenyltetracarboxylic acid dianhydride can contain at least one compound selected from the group consisting of dianhydride. In particular, the acid dianhydride (a4) preferably contains 3,3', 4,4'-biphenyltetracarboxylic acid dianhydride. In this case, while ensuring good developability of the photosensitive resin composition, it is possible to suppress the tackiness of the film produced from the photosensitive resin composition and improve the insulation reliability and plating resistance of the cured product.

The acid anhydride (a3) may contain an acid anhydride (a5). The acid anhydride (a5) is a compound having one acid anhydride group. The acid monoanhydride (a5) can contain an anhydride of a dicarboxylic acid. The acid monoanhydride (a5) is, for example, phthalic anhydride, 1,2,3,6-tetrahydroanhydride, methyltetrahydrophthalic anhydride, methylnadic acid anhydride, hexahydrophthalic anhydride, methylhexa. Hydrophthalic anhydride, succinic anhydride, methylsuccinic anhydride, maleic anhydride, citraconic anhydride, glutaric anhydride, cyclohexane-1,2,4-tricarboxylic acid-1,2-anhydride, and It can contain one or more compounds selected from the group consisting of itaconic anhydride. In particular, the acid monoanhydride (a5) preferably contains 1,2,3,6-tetrahydrophthalic anhydride. That is, it is preferable that the acid anhydride (a3) contains 1,2,3,6-tetrahydrophthalic anhydride. In this case, while ensuring good developability of the photosensitive resin composition, the tackiness of the film formed from the photosensitive resin composition can be further suppressed, and the insulation reliability and plating resistance of the cured product can be further improved. .. 1,2,3,6-tetrahydrophthalic anhydride is preferably in the range of 20 mol% or more and 100 mol% or less, and 40 mol% or more and 100 mol% or less, based on the whole acid monoanhydride (a5). It is more preferable, but not limited to.

An appropriate method can be adopted for reacting the intermediate with the acid anhydride (a3). For example, an acid anhydride (a3) is added to a solvent solution of the intermediate, and if necessary, a thermal polymerization inhibitor and a catalyst are added and mixed by stirring to obtain a reactive solution. By reacting this reactive solution at a temperature of preferably 60 ° C. or higher and 150 ° C. or lower, particularly preferably 80 ° C. or higher and 120 ° C. or lower by a conventional method, a carboxyl group-containing resin (A11) having a bisphenol fluorene skeleton can be obtained. As the solvent, catalyst and polymerization inhibitor, appropriate ones can be used, and the solvent, catalyst and polymerization inhibitor used at the time of synthesizing the intermediate can also be used as they are.

It is preferred that the catalyst particularly contains triphenylphosphine. That is, it is preferable to react the intermediate with the acid anhydride (a3) in the presence of triphenylphosphine. In this case, the reaction between the intermediate and the acid anhydride (a3) is particularly promoted, and a reaction rate (conversion rate) of 90% or more, 95% or more, 97% or more, or almost 100% can be achieved.

When the acid anhydride (a3) contains the acid dianhydride (a4), the amount of the acid dianhydride (a4) is 0.05 mol or more and 0 with respect to 1 mol of the epoxy group of the epoxy compound (a1). It is preferably .24 mol or less. In this case, a carboxyl group-containing resin (A11) having a bisphenol fluorene skeleton in which the acid value and the molecular weight are appropriately adjusted can be easily obtained.

When the acid anhydride (a3) further contains the acid anhydride (a5), the amount of the acid anhydride (a5) is 0.3 mol with respect to 1 mol of the epoxy group of the epoxy compound (a1). It is preferably 0.7 or more and 0.7 or less. In this case, a carboxyl group-containing resin (A11) having a bisphenol fluorene skeleton in which the acid value and the molecular weight are appropriately adjusted can be easily obtained.

It is also preferable to react the intermediate with the acid anhydride (a3) under air bubbling. In this case, by suppressing an excessive increase in the molecular weight of the carboxyl group-containing resin (A11) having a bisphenol fluorene skeleton to be produced, the developability of the photosensitive resin composition with an alkaline aqueous solution is particularly improved.

The carboxyl group-containing resin (A) may contain a carboxyl group-containing resin having no bisphenol fluorene skeleton (hereinafter, also referred to as a carboxyl group-containing resin (A2)). The carboxyl group-containing resin (A) may contain at least one of the carboxyl group-containing resin (A11) and the carboxyl group-containing resin (A2).

The carboxyl group-containing resin (A2) can contain, for example, a carboxyl group-containing resin having a carboxyl group and no photopolymerizability (hereinafter, referred to as a carboxyl group-containing resin (A2-1)). The carboxyl group-containing resin (A2-1) contains, for example, a polymer of an ethylenically unsaturated monomer containing an ethylenically unsaturated compound having a carboxyl group. The ethylenically unsaturated compound having a carboxyl group can contain a compound such as acrylic acid, methacrylic acid, and ω-carboxy-polycaprolactone (n≈2) monoacrylate. The ethylenically unsaturated compound having a carboxyl group can also contain a reaction product of pentaerythritol triacrylate, pentaerythritol trimethacrylate and the like with dibasic acid anhydride. The ethylenically unsaturated monomer is 2- (meth) acryloyloxyethyl phthalate, 2- (meth) acryloyloxyethyl-2-hydroxyethyl phthalate, linear or branched aliphatic or alicyclic group (however, It may further contain an ethylenically unsaturated compound having no carboxyl group, such as a (meth) acrylic acid ester (which may have a partially unsaturated bond in the ring).

The carboxyl group-containing resin (A2) may contain a carboxyl group-containing resin having a carboxyl group and an ethylenically unsaturated group (hereinafter, referred to as a carboxyl group-containing resin (A2-2)). The carboxyl group-containing resin (A2-2) can impart photosensitivity, specifically, photocurability, to the photosensitive resin composition. The carboxyl group-containing resin (A2) may contain only the carboxyl group-containing resin (A2-2).

The carboxyl group-containing resin (A2-2) is polyvalent, for example, an intermediate which is a reaction product of an epoxy compound (x1) having two or more epoxy groups in one molecule and an ethylenically unsaturated compound (x2). It contains a resin (hereinafter, also referred to as the first resin (x)) which is a reaction product with at least one compound (x3) selected from the group of carboxylic acid and its anhydride. In the first resin (x), for example, the compound (x3) is added to an intermediate obtained by reacting an epoxy group in an epoxy compound (x1) with a carboxyl group in an ethylenically unsaturated compound (x2). You can get it.

The epoxy compound (x1) can contain an appropriate epoxy compound such as a cresol novolac type epoxy compound, a phenol novolac type epoxy compound, and a biphenyl novolac type epoxy compound. In particular, the epoxy compound (x1) preferably contains at least one compound selected from the group of biphenyl novolac type epoxy compounds and cresol novolac type epoxy compounds. In this case, the resin contained in the above-mentioned carboxyl group-containing resin (A1) having an aromatic ring can be obtained. The epoxy compound (x1) may contain only the biphenyl novolac type epoxy compound, or may contain only the cresol novolac type epoxy compound.

The epoxy compound (x1) may contain a polymer of the ethylenically unsaturated compound (z). The ethylenically unsaturated compound (z) contains a compound (z1) having an epoxy group such as glycidyl (meth) acrylate, or further has no epoxy group such as 2- (meth) acryloyloxyethyl phthalate. Contains compound (z2). The ethylenically unsaturated compound (x2) preferably contains at least one of acrylic acid and methacrylic acid. The compound (x3) contains one or more compounds selected from the group consisting of polyvalent carboxylic acids such as phthalic acid, tetrahydrophthalic acid, and methyltetrahydrophthalic acid, and anhydrides of these polyvalent carboxylic acids. .. In particular, the compound (x3) preferably contains at least one polyvalent carboxylic acid selected from the group of phthalic acid, tetrahydrophthalic acid and methyltetrahydrophthalic acid.

The carboxyl group-containing resin (A2-2) is a resin which is a reaction product of a polymer of an ethylenically unsaturated monomer containing an ethylenically unsaturated compound having a carboxyl group and an ethylenically unsaturated compound having an epoxy group. It may contain (referred to as a second resin (y)). The ethylenically unsaturated monomer may further contain an ethylenically unsaturated compound having no carboxyl group. The second resin (y) is obtained by reacting an ethylenically unsaturated compound having an epoxy group with a part of the carboxyl groups in the polymer. The ethylenically unsaturated monomer may further contain an ethylenically unsaturated compound having no carboxyl group. The ethylenically unsaturated compound having a carboxyl group contains, for example, a compound such as acrylic acid, methacrylic acid, ω-carboxy-polycaprolactone (n≈2) monoacrylate, pentaerythritol triacrylate, and pentaerythritol trimethacrylate. Ethyl unsaturated compounds having no carboxyl group include, for example, 2- (meth) acryloyloxyethyl phthalate, 2- (meth) acryloyloxyethyl-2-hydroxyethyl phthalate, linear or branched aliphatic or fat. It contains a compound such as a cyclic (but may have a partially unsaturated bond in the ring) (meth) acrylic acid ester. The ethylenically unsaturated compound having an epoxy group preferably contains glycidyl (meth) acrylate.

The carboxyl group-containing resin (A) preferably contains the carboxyl group-containing resin (A1) in an amount of 25% by mass or more, more preferably 40% by mass or more, further preferably 60% by mass or more, and 100%. It is particularly preferable to contain it in mass%. In this case, the heat resistance and insulation reliability of the cured product of the photosensitive resin composition can be particularly improved.

The carboxyl group-containing resin (A) preferably contains the carboxyl group-containing resin (A11) in an amount of 25% by mass or more, more preferably 40% by mass or more, further preferably 60% by mass or more, and 100%. It is particularly preferable to contain it in mass%. In this case, excellent photosensitivity of the photosensitive resin composition and developability with an alkaline aqueous solution can be ensured. In addition, the heat resistance and insulation reliability of the cured product of the photosensitive resin composition can be particularly improved, and the dielectric constant can be reduced. Further, the tackiness of the film formed from the photosensitive resin composition can be sufficiently reduced.

The weight average molecular weight of the carboxyl group-containing resin (A) is preferably 700 or more and 100,000 or less. When the weight average molecular weight of the carboxyl group-containing resin (A) is 700 or more, the tackiness of the film formed from the photosensitive resin composition is easily suppressed, and the insulation reliability of the cured product of the photosensitive resin composition and the insulation reliability and Plating resistance can be improved. When the weight average molecular weight of the carboxyl group-containing resin (A) is 100,000 or less, the developability of the photosensitive resin composition with an alkaline aqueous solution tends to be good. The weight average molecular weight of the carboxyl group-containing resin (A) is more preferably 900 or more and 60,000 or less, further preferably 1200 or more and 10000 or less, and particularly preferably 1400 or more and 5000 or less. The weight average molecular weight of the carboxyl group-containing resin (A) is calculated, for example, from the measurement results under the following conditions by gel permeation chromatography.

GPC device: Showa Denko SHODEX SYSTEM 11,
Column: 4 series of SHODEX KF-800P, KF-005, KF-003, KF-001,
Mobile phase: THF,
Flow rate: 1 ml / min,
Column temperature: 45 ° C,
Detector: RI,
Conversion: Polystyrene.

The carboxyl group-containing resin (A) preferably contains a component having an acid value of 65 mgKOH / g or more and 150 mgKOH / g or less. In this case, the developability of the photosensitive resin composition with an alkaline aqueous solution is particularly likely to be improved. The acid value is more preferably 70 mgKOH / g or more and 145 mgKOH / g or less, further preferably 75 mgKOH / g or more and 140 mgKOH / g or less, and particularly preferably 85 mgKOH / g or more and 135 mgKOH / g or less.

The percentage of the carboxyl group-containing resin (A) to the solid content of the photosensitive resin composition is preferably 5% by mass or more and 85% by mass or less. This percentage is more preferably 10% by mass, and even more preferably 20% by mass or more. Further, this percentage is more preferably 75% by mass or less, and further preferably 50% by mass or less.

The percentage of the carboxyl group-containing resin (A1) to the solid content of the photosensitive resin composition is preferably 5% by mass or more and 85% by mass or less. This percentage is more preferably 10% by mass, and even more preferably 20% by mass or more. Further, this percentage is more preferably 75% by mass or less, and further preferably 50% by mass or less.

The percentage of the carboxyl group-containing resin (A11) to the solid content of the photosensitive resin composition is preferably 5% by mass or more and 85% by mass or less. This percentage is more preferably 10% by mass, and even more preferably 20% by mass or more. Further, this percentage is more preferably 75% by mass or less, and further preferably 50% by mass or less.

The photopolymerization initiator (B) will be described.

The photopolymerization initiator (B) is a component that can improve the photosensitivity of the photosensitive resin composition. The photopolymerization initiator (B) is at least one selected from the group consisting of, for example, an α-aminoalkylphenone-based photopolymerization initiator, an acylphosphine oxide-based photopolymerization initiator, and an oxime ester-based photopolymerization initiator. It is preferable to include it. In this case, when the photosensitive resin composition is exposed by irradiating it with light such as ultraviolet rays, it is possible to impart high photosensitive property to the photosensitive resin composition. It is more preferable that the photopolymerization initiator (B) contains an acylphosphine oxide-based photopolymerization initiator (B1). In this case, high photosensitivity can be imparted to the photosensitive resin composition, and the insulation reliability of the cured product of the photosensitive resin composition can be particularly improved.

The α-aminoalkylphenone-based photopolymerization initiator is, for example, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane-1-one, 2-benzyl-2-dimethylamino-1- (4-morpho). Selected from the group consisting of linophenyl) -butanone-1,2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone. It can contain at least one component.

The acylphosphine oxide-based photopolymerization initiator (B1) is a monoacyl such as 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide or 2,4,6-trimethylbenzoyl-ethyl-phenyl-phosphinate. Phosphine oxide-based photopolymerization initiator, and bis- (2,6-dichlorobenzoyl) phenylphosphine oxide, bis- (2,6-dichlorobenzoyl) -2,5-dimethylphenylphosphine oxide, bis- (2) , 6-Dichlorobenzoyl) -4-propylphenylphosphine oxide, bis- (2,6-dichlorobenzoyl) -1-naphthylphosphine oxide, bis- (2,6-dimethoxybenzoyl) phenylphosphine oxide, bis- (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, bis- (2,6-dimethoxybenzoyl) -2,5-dimethylphenylphosphine oxide, bis- (2,4,6) -Selected from the group consisting of bisacylphosphine oxide-based photopolymerization initiators such as (trimethylbenzoyl) phenylphosphine oxide and (2,5,6-trimethylbenzoyl) -2,4,4-trimethylpentylphosphine oxide. It can contain at least one component.

Oxime ester-based photopolymerization initiators include, for example, 1,2-octanedione, 1- [4- (phenylthio)-, 2- (О-benzoyloxime)], etanone, 1- [9-ethyl-6- (2). -Methylbenzoyl) -9H-carbazole-3-yl]-, can include at least one component selected from the group consisting of 1- (O-acetyloxime).

The photosensitive resin composition may further contain an appropriate photopolymerization accelerator, a sensitizer, and the like. For example, the photosensitive resin composition includes 1-hydroxy-cyclohexyl-phenyl-ketone, phenylglycoxyacid methyl ester, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1. -Propane-1-one, 2-hydroxy-1-{4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] phenyl} -2-methyl-propane-1-one, 2-hydroxy- Hydroxyketones such as 2-methyl-1-phenyl-propane-1-one; benzoins and their alkyl ethers; acetophenones such as acetophenone and benzyl dimethyl ketal; anthraquinones such as 2-methylanthraquinone; 2,4-dimethyl Thioxanthones such as thioxanthone, 2,4-diethylthioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diisopropylthioxanthone; benzophenone, 4-benzoyl-4'-methyldiphenylsulfide, bis (diethylamino) benzophenone and the like. Benzophenones; Xanthones such as 2,4-diisopropylxanthone; α-Hydroxyketones such as 2-hydroxy-2-methyl-1-phenyl-propan-1-one; and 2-Methyl-1- [4-( It can contain at least one component selected from the group consisting of compounds containing a nitrogen atom such as methylthio) phenyl] -2-morpholino-1-propanone. The photosensitive resin composition, together with the photopolymerization initiator (B), is appropriately prepared from a tertiary amine system such as p-dimethylbenzoic acid ethyl ester, p-dimethylaminobenzoic acid isoamyl ester, and 2-dimethylaminoethylbenzoate. It may contain a photopolymerization accelerator, a sensitizer and the like. The photosensitive resin composition may contain at least one of a photopolymerization initiator for visible light exposure and a photopolymerization initiator for near-infrared exposure, if necessary. The photosensitive resin composition contains a photopolymerization initiator (B), a coumarin derivative such as 7-diethylamino-4-methylcoumarin, which is a sensitizer for a laser exposure method, a carbocyanine dye system, a xanthene dye system, and the like. You may.

The photopolymerization initiator (B) preferably contains a hydroxyketone-based photopolymerization initiator (B2) in addition to the acylphosphine oxide-based photopolymerization initiator (B1). That is, the photosensitive resin composition preferably contains a hydroxyketone-based photopolymerization initiator (B2). In this case, higher photosensitivity can be imparted to the photosensitive resin composition as compared with the case where the hydroxyketone-based photopolymerization initiator (B2) is not contained. As a result, when the coating film formed from the photosensitive resin composition is cured by irradiating it with ultraviolet rays, the coating film can be sufficiently cured from its surface to a deep portion. Examples of the hydroxyketone-based photopolymerization initiator (B2) include 1-hydroxy-cyclohexyl-phenyl-ketone, phenylglycoxyacid methyl ester, and 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy. -2-Methyl-1-propane-1-one, 2-hydroxy-1-{4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] phenyl} -2-methyl-propane-1- On, 2-hydroxy-2-methyl-1-phenyl-propane-1-one and the like can be mentioned.

The mass ratio ((B1) :( B2)) of the acylphosphine oxide-based photopolymerization initiator (B1) to the hydroxyketone-based photopolymerization initiator (B2) is in the range of 1: 0.01 to 1:10. Is preferable. In this case, the curability near the surface of the film formed from the photosensitive resin composition and the curability in the deep part can be improved in a well-balanced manner.

The photopolymerization initiator (B) also preferably contains a bis (diethylamino) benzophenone (B3). That is, the photosensitive resin composition contains an acylphosphine oxide-based photopolymerization initiator (B1) and a bis (diethylamino) benzophenone (B3), or an acylphosphine oxide-based photopolymerization initiator (B1), a hydroxyketone-based. It preferably contains a photopolymerization initiator (B2) and a bis (diethylamino) benzophenone (B3). In this case, when the coating film formed from the photosensitive resin composition is partially exposed and then developed, the unexposed portion is suppressed from being cured, so that the resolution is particularly high. Therefore, it is possible to form a very fine pattern with the cured product of the photosensitive resin composition. In particular, when an interlayer insulating layer of a multilayer printed wiring board is prepared from a photosensitive resin composition and a small diameter hole for a through hole is provided in the interlayer insulating layer by a photolithography method, the small diameter hole is formed precisely and easily. It becomes possible to do.

The percentage of bis (diethylamino) benzophenone (B3) to the acylphosphine oxide-based photopolymerization initiator (B1) is preferably 0.5% by mass or more and 20% by mass or less. When the bis (diethylamino) benzophenone (B3) is 0.5% by mass or more, the resolution is particularly high. Further, when the bis (diethylamino) benzophenone (B3) is 20% by mass or less, the bis (diethylamino) benzophenone (B3) is less likely to inhibit the electrical insulating property of the cured product of the photosensitive resin composition.

The percentage of the photopolymerization initiator (B) to the carboxyl group-containing resin (A) is preferably 0.1% by mass or more and 30% by mass or less, and more preferably 1% by mass or more and 25% by mass or less.

The percentage of the photopolymerization initiator (B) with respect to the entire photosensitive resin composition (solid content) is preferably 0.001% by mass or more and 6% by mass or less, and is 0.01% by mass or more and 3% by mass or less. Is more preferable.

The photopolymerizable compound (C) will be described.

The photopolymerizable compound (C) can impart photosensitivity, specifically, photocurability, to the photosensitive resin composition. The compound contained in the above-mentioned carboxyl group-containing resin (A) is excluded from the photopolymerizable compound (C).

The photopolymerizable compound (C) contains, for example, a compound having an ethylenically unsaturated bond. More specifically, the photopolymerizable compound (C) is a monofunctional (meth) acrylate such as 2-hydroxyethyl (meth) acrylate; as well as diethylene glycol di (meth) acrylate, trimethylpropandi (meth) acrylate, and the like. Trimethylol propantri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, ε-caprolactone-modified pentaeristol It contains at least one compound selected from the group consisting of polyfunctional (meth) acrylates such as hexaacrylate and tricyclodecanedimethanol di (meth) acrylate.

The photopolymerizable compound (C) preferably contains a compound (C1) having a tricyclodecane skeleton. The compound (C1) having a tricyclodecane skeleton contains, for example, tricyclodecanedimethanol di (meth) acrylate. In this case, the dielectric loss tangent of the cured product can be further reduced. The percentage of the compound (C1) having a tricyclodecane skeleton to the photopolymerizable compound (C) is preferably 20% by mass or more, more preferably 40% by mass or more, and further preferably 60% by mass or more. preferable.

The photopolymerizable compound (C) also preferably contains a trifunctional compound, that is, a compound having three unsaturated bonds in one molecule. In this case, the developability and resolvability when forming a film from the photosensitive resin composition by a photolithography method are further improved. Trifunctional compounds include, for example, trimethylolpropane tri (meth) acrylate, EO-modified trimethylolpropane tri (meth) acrylate, pentaeristoltri (meth) acrylate, ethoxylated isocyanurate tri (meth) acrylate and ε-caprolactone-modified. It can contain at least one compound selected from the group consisting of tris- (2-acryloxyethyl) isocyanurate and ethoxylated glycerin tri (meth) acrylate.

The photopolymerizable compound (C) also preferably contains a phosphorus-containing compound (phosphorus-containing unsaturated compound). In this case, the flame retardancy of the cured product of the photosensitive resin composition is improved. The phosphorus-containing unsaturated compounds include, for example, 2-methacryloyloxyethyl acid phosphate (specific examples, part numbers light ester P-1M and light ester P-2M manufactured by Kyoeisha Chemical Co., Ltd.) and 2-acryloyloxyethyl acid phosphate. (Specific example, product number light acrylate P-1A manufactured by Kyoeisha Chemical Co., Ltd.), diphenyl-2-methacryloyloxyethyl phosphate (specific example, product number MR-260 manufactured by Daihachi Kogyo Co., Ltd.), and Showa Polymer Co., Ltd. HFA series (for example, part number HFA-6003 which is an addition reaction product of dipentaerystol hexaacrylate and HCA (9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide), and HFA-6007, part number HFA-3003, which is an addition reaction product of caprolactone-modified dipentaerystol hexaacrylate and HCA (9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide), and HFA- It can contain at least one compound selected from the group consisting of 6127 etc.).

The photopolymerizable compound (C) may contain a prepolymer. The prepolymer is at least one selected from the group consisting of, for example, a prepolymer obtained by polymerizing a monomer having an ethylenically unsaturated bond and then adding an ethylenically unsaturated group, and oligo (meth) acrylate prepolymers. Can contain the compounds of. Oligo (meth) acrylate prepolymers include, for example, epoxy (meth) acrylate, polyester (meth) acrylate, urethane (meth) acrylate, alkyd resin (meth) acrylate, silicone resin (meth) acrylate, and spirane resin (meth) acrylate. It can contain at least one component selected from the group consisting of.

The percentage of the photopolymerizable compound (C) to the carboxyl group-containing resin (A) is preferably 1% by mass or more and 50% by mass or less. This percentage is more preferably 10% by mass or more, and even more preferably 21% by mass or more. Further, this percentage is more preferably 45% by mass or less, and further preferably 40% by mass or less.

The epoxy compound (D) will be described.

Since the epoxy compound (D) can react with the carboxyl group in the carboxyl group-containing resin (A), it is possible to impart thermosetting property to the photosensitive resin composition.

The epoxy compound (D) preferably contains a crystalline epoxy compound (D1). In this case, the developability is likely to be improved. Further, when the organic filler (G) described later contains an organic filler having a carboxyl group, the carboxyl group in the organic filler facilitates the dissolution of the crystalline epoxy compound (D1) in the photosensitive resin composition. This makes it difficult to recrystallize the crystalline epoxy compound (D1).

The epoxy compound (D) may further contain an amorphous epoxy compound (D2). The "crystalline epoxy compound" is an epoxy compound having a melting point, and the "amorphous epoxy compound" is an epoxy compound having no melting point.

The crystalline epoxy compound (D1) is, for example, 1,3,5-tris (2,3-epoxypropyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, Hydroquinone type crystalline epoxy compound (specific example, product name YDC-1312 manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd.), biphenyl type crystalline epoxy compound (specific example, product name YX-4000 manufactured by Mitsubishi Chemical Co., Ltd.), diphenyl ether type crystalline epoxy Compound (specific example, product number YSLV-80DE manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.), bisphenol type crystalline epoxy compound (specific example, product name YSLV-70XY, YSLV-80XY manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.), tetrakisphenol ethane type crystal. One or more selected from the group consisting of a sex epoxy compound (specific example, product number GTR-1800 manufactured by Nippon Kayaku Co., Ltd.) and a bisphenol fluorene type crystalline epoxy compound (specific example, an epoxy resin having a structure (S7)). It preferably contains an ingredient.

The crystalline epoxy compound (D1) preferably has two epoxy groups in one molecule. In this case, it is possible to make the cured product less likely to crack as the temperature changes repeatedly.

The epoxy equivalent of the crystalline epoxy compound (D1) is preferably 150 g / eq or more and 300 g / eq or less. This epoxy equivalent is the gram weight of the crystalline epoxy compound (D1) containing 1 gram equivalent of an epoxy group. The crystalline epoxy compound (D1) has a melting point. The melting point of the crystalline epoxy compound (D1) is, for example, 70 ° C. or higher and 180 ° C. or lower.

In particular, the epoxy compound (D) preferably contains a crystalline epoxy compound (D1-1) having a melting point of 110 ° C. or lower. In this case, the developability of the photosensitive resin composition with an alkaline aqueous solution is particularly likely to be improved. Examples of the crystalline epoxy compound (D1-1) having a melting point of 110 ° C. or lower include a biphenyl type epoxy resin (specific example, product number YX-4000 manufactured by Mitsubishi Chemical Corporation) and a biphenyl ether type epoxy resin (specific example, Nippon Steel & Sumikin Chemical Co., Ltd.). At least one selected from the group consisting of company part number YSLV-80DE), bisphenol type epoxy resin (specific example, part number YSLV-70XY, YSLV-80XY manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.), and bisphenol fluorene type crystalline epoxy compound. Can contain ingredients.

Examples of the amorphous epoxy compound (D2) include a phenol novolac type epoxy resin (specific example, product number EPICLON N-775 manufactured by DIC Co., Ltd.) and a cresol novolac type epoxy resin (specific example, product number EPICLONN-manufactured by DIC Co., Ltd.). 695), bisphenol A novolak type epoxy resin (specific example, product number EPICLON N-865 manufactured by DIC Co., Ltd.), bisphenol A type epoxy resin (specific example, product number jER1001 manufactured by Mitsubishi Chemical Corporation), bisphenol F type epoxy resin (specific example). Specific examples include product number jER4004P manufactured by Mitsubishi Chemical Co., Ltd.), bisphenol S type epoxy resin (specific example, product number EPICLON EXA-1514 manufactured by DIC Co., Ltd.), bisphenol AD type epoxy resin, biphenyl novolac type epoxy resin (specific example, Japan). Chemicals Co., Ltd. part number NC-3000), hydrogenated bisphenol A type epoxy resin (specific example, Nippon Steel & Sumitomo Metal Chemical Co., Ltd. part number ST-4000D), naphthalene type epoxy resin (specific example, DIC Co., Ltd. part number) EPICLON HP-4032, EPICLON HP-4700, EPICLONHP-4770), tertiary butyl catechol type epoxy resin (specific example, product number EPICLON HP-820 manufactured by DIC Co., Ltd.), dicyclopentadiene type epoxy resin (specific example, manufactured by DIC) EPICLONHP-7200), Adamantane type epoxy resin (specific example, product number ADAMANTATEX-E-201 manufactured by Idemitsu Kosan Co., Ltd.), special bifunctional epoxy resin (specific example, product number YL7175-500 manufactured by Mitsubishi Chemical Corporation). , And YL7175-1000; part numbers EPICLON TSR-960, EPICLON TER-601, EPICLON TSR-250-80BX, EPICLON 1650-75MPX, EPICLON EXA-4850, EPICLON EXA-4816, EPICLON EXA-48, manufactured by DIC Co., Ltd. -9726; Nippon Steel & Sumitomo Metal Chemical Co., Ltd. product number YSLV-120TE), rubber-like core-shell polymer-modified bisphenol A type epoxy resin (specific example, Kaneka Co., Ltd. product number MX-156), rubber-like core-shell polymer-modified bisphenol F-type epoxy Resin (as a specific example, a product manufactured by Kaneka Co., Ltd.) It is preferable to contain at least one component selected from the group consisting of No. MX-136) and a rubber particle-containing bisphenol F type epoxy resin (specific example, product No. Kaneka MX-130 manufactured by Kaneka Corporation).

The epoxy compound (D) may contain a phosphorus-containing epoxy resin. In this case, the flame retardancy of the cured product of the photosensitive resin composition is improved. The phosphorus-containing epoxy resin may be contained in the crystalline epoxy compound (D1) or may be contained in the amorphous epoxy compound (D2). Phosphorus-containing epoxy resins include, for example, phosphoric acid-modified bisphenol F-type epoxy resin (specific examples, product numbers EPICLON EXA-9726 and EPICLON EXA-9710 manufactured by DIC Corporation) and Epototo FX-305 manufactured by Nippon Steel & Sumitomo Metal Chemical Corporation. And so on.

Regarding the amount of the epoxy compound (D) in the photosensitive resin composition, the equivalent of the epoxy group of the epoxy compound (D) is 0.1 or more and 1 or more with respect to 1 equivalent of the carboxyl group of the carboxyl group-containing resin (A). It is preferably less than. In this case, the dielectric loss tangent of the cured product is likely to be reduced while maintaining the thermosetting property of the photosensitive resin composition. Therefore, the cured product tends to have more excellent dielectric properties. The equivalent of the epoxy group is more preferably 0.9 or less, and even more preferably 0.8 or less. Further, the equivalent of the epoxy group is more preferably 0.5 or more, and further preferably 0.7 or more.

Silica (E) will be described.

As described above, when the photosensitive resin composition contains silica (E) and the percentage of silica (E) is 50% by mass or more with respect to the carboxyl group-containing resin (A), the dielectric loss tangent of the cured product is formed. Is easy to reduce. Further, the silica (E) can reduce the coefficient of linear expansion of the cured product so that the printed wiring board provided with the layer made from the cured product is less likely to warp. Further, when the percentage of silica (E) is 300% by mass or less, the flexibility of the cured product is easily maintained. The percentage of silica (E) is more preferably 100% by mass or more, and even more preferably 130% by mass or more. Further, this percentage is more preferably 250% by mass or less, and further preferably 220% by mass or less.

The silica (E) preferably contains silica (E1) having an average particle size of 0.1 μm or more and 5 μm or less. In this case, when the surface of the cured product is treated with an oxidizing agent, fine irregularities are likely to be formed on the cured product, which tends to increase the surface area of the cured product. Therefore, when a conductor is produced on the surface of the cured product by plating, the adhesion between the cured product and the conductor tends to be high. Further, it is possible to improve the resolution by making it difficult for light to be scattered by the silica (E). The average particle size of silica (E1) is more preferably 3 μm or less, and even more preferably 2 μm or less. Further, the average particle size is more preferably 0.2 μm or more, and further preferably 0.4 μm or more. The average particle size of silica (E1) is a cumulative 50% diameter (median diameter D50) calculated from the particle size distribution obtained by the laser diffraction / scattering method.

The silica (E) may contain silica (E2) having an average particle size of 1 nm or more and 150 nm or less. In this case, when the cured product is treated with an oxidizing agent, the cured product is less likely to be excessively corroded, and particularly fine irregularities are likely to be formed on the surface of the cured product. The average particle size of silica (E2) is more preferably 5 nm or more, further preferably 20 nm or more, and particularly preferably 25 nm or more. The average particle size of silica (E2) is more preferably 120 nm or less, further preferably 85 nm or less, and particularly preferably 65 nm or less. The average particle size of silica (E2) is a cumulative 50% diameter (median diameter D50) calculated from the particle size distribution obtained by the dynamic light scattering method.

The silica (E2) may contain two or more types of silica having different average particle sizes. In this case, the resolvability is more likely to be improved, and when the surface of the cured product is treated with an oxidizing agent, fine irregularities are more likely to be formed on the surface of the cured product.

The silica (E2) can contain, for example, at least two types of silica (E21) and silica (E22) having different average particle sizes. The average particle size of silica (E21) having a larger average particle size is, for example, 20 nm or more and 100 nm or less, and the average particle size of silica (E22) having a smaller average particle size is, for example, 1 nm or more and less than 20 nm. The average particle size of silica (E21) is more preferably 20 nm or more, and even more preferably 30 nm or more. The average particle size of silica (E21) is more preferably less than 70 nm, and even more preferably 60 nm or less. The average particle size of silica (E22) is preferably 1 nm or more and 15 nm or less when the average particle size of silica (E21) is 20 nm or more and 100 nm or less, and more preferably 10 nm or more and 15 nm or less. The mass ratio of silica (E21) to silica (E22) is preferably 20:80 to 80:20. In this case, the coefficient of thermal expansion of the cured product can be further reduced, and the dielectric loss tangent can be further reduced.

The silica (E2) preferably contains silica particles derived from silica sol. In this case, the transparency of the photosensitive resin composition can be improved. Therefore, silica (E) can contribute to the improvement of resolution. Examples of silica sol include spherical silica sol and chain silica sol. As a specific example of the silica sol, an organosilica sol manufactured by Nissan Chemical Industry Co., Ltd .: Part numbers MA-ST-M, MA-ST-L, IPA-ST, IPA-ST-ZL, IPA-ST-UP, EG-ST, NPC -ST-30, PGM-ST, DMAC-ST, MEK-ST-40, MIBK-ST, MIBK-ST-L, CHO-ST-M, EAC-ST, TOR-ST, MEK-AC-4130Y, MEK -AC-5140Z, PGM-AC-2140Y, PGM-AC-4130Y, MIBK-AC-2140Z, MIKB-SD-L, MEK-EC-6150P, MEK-EC-7150P, EP-F2130Y, EP-F6140P, EP -F7150P, PMA-ST, MEK-EC-2130Y, MEK-AC-2140Z, MEK-ST-L, MEK-ST-ZL, MEK-ST-UP; NANOCRYL manufactured by Hanse-Chemie: Part numbers XP0396, XP0596, XP0733, XP0746, XP0765, XP0768, XP0953, XP0954, XP1045; NANOPOX manufactured by Hanse-Chemie: Part Nos. XP0516, XP0525, XP0314 and the like can be mentioned.

The silica (E) may contain silica (E1) and silica (E2). The mass ratio of silica (E1) to silica (E2) in this case is, for example, 50: 1 to 2: 1.

The photosensitive resin composition may contain an inorganic filler other than silica (E). The inorganic filler contains at least one selected from the group consisting of, for example, barium sulfate, carbon nanotubes, talc, bentonite, aluminum hydroxide, magnesium hydroxide, titanium oxide and the like. The total percentage of the silica (E) in the photosensitive resin composition and the other inorganic fillers is preferably 50% by mass or more and 300% by mass or less with respect to the carboxyl group-containing resin (A).

The silica (E) is preferably surface-treated with a silane coupling agent. In this case, the dispersibility of silica (E) in the photosensitive resin composition and the cured product tends to increase. Further, the silica (E) particles are easily retained in the cured product, and when the surface of the cured product is treated with an oxidizing agent, the silica (E) particles are less likely to fall off from the cured product. Therefore, the surface of the cured product is less likely to be excessively corroded by the oxidizing agent.

Examples of the silane coupling agent include tetraethoxysilane, tetramethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinylmethyldiethoxysilane, vinylmethyldimethoxysilane, 2- (3,4 epoxycyclohexyl) ethyltrimethoxysilane, and the like. 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldimethoxysilane , P-styryltrimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropylmethyldimethoxysilane, 3-Aminopropylmethyldiethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3- (2-aminoethylamino) propyltriethoxysilane, N, N-dimethyl-3- (trimethoxy) Cyril) propylamine, 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine, N-phenyl-3-aminopropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltri Methoxysilane, 3-mercaptopropyltriethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, allyltri Ethoxysilane, allyltrimethoxysilane, allylchlorodimethylsilane, 3-chloropropyltrimethoxysilane, 3-chloropropyltriethoxysilane, 3-chloropropyldimethoxymethylsilane, chloromethyltriethoxysilane, chloromethyltrimethoxysilane, 3 -Chloropropylmethyldiethoxysilane, 3-isocyanoxidetriethoxysilane, 3-acryloxypropyltrimethoxysilane, bis (triethoxysilylpropyl) tetrasulfide, cyclohexyltrimethoxysilane, methyltriethoxysilane, methyltrimethoxysilane, Ethyltriethoxysilane, ethyltrimethoxysilane, hexyltrimethoxysilane, hexyltriet Xysilane, hexadecyltrimethoxysilane, octadecyltriethoxysilane, octadecyltrimethoxysilane, n-octyltriethoxysilane, n-octyltrimethoxysilane, dodecyltriethoxysilane, dodecyltrimethoxysilane, propyltrimethoxysilane, propyltriethoxy Silane, benzyltriethoxysilane, methylphenyldimethoxysilane, methylphenyldiethoxysilane, phenyltriethoxysilane, phenyltrimethoxysilane, p-tolyltrimethoxysilane, 4-vinylphenyltrimethoxysilane, 1-naphthyltrimethoxysilane, 3,3,3-Trifluoropropyltrimethoxysilane, 11-pentafluorophenoxyundecyltrimethoxysilane, pentafluorophenyltrimethoxysilane, 11-azidoundecyltrimethoxysilane, 2-cyanoethyltriethoxysilane, vinyltriacetoxy It contains at least one selected from the group consisting of silane and the like.

The silane coupling agent preferably has a phenyl skeleton. In this case, the particles of silane (E) are less likely to fall off. Further, when the carboxyl group-containing resin (A) contains a carboxyl group-containing resin (A1) having an aromatic ring or a carboxyl group-containing resin (A11) having a bisphenol fluorene skeleton, the particles of the silane (E) are particularly difficult to fall off. Become.

Only a part of silica (E) may be surface-treated with a silane coupling agent. For example, when silica (E) contains silica (E1) and silica (E2), only silica (E1) may be surface-treated with a silane coupling agent.

The blocked isocyanate compound (F) will be described.

As described above, the blocked isocyanate compound (F) can lower the dielectric loss tangent of the cured product, increase the flexibility of the cured product, and further, when the surface of the cured product is treated with an oxidizing agent, the cured product Can be prevented from being excessively corroded.

As described above, it is presumed that the above action can be obtained by reacting the blocked isocyanate compound (F) with the hydroxyl group. The hydroxyl groups capable of reacting with the blocked isocyanate compound (F) include the hydroxyl group of the carboxyl group-containing resin (A), the hydroxyl group generated by the reaction of the carboxyl group-containing resin (A) with the epoxy compound (D), and the silica (E). Examples thereof include hydroxyl groups existing on the surface of. The hydroxyl group of the carboxyl group-containing resin (A) is, for example, a carboxyl group-containing resin (A) carboxylic to a secondary hydroxyl group in an intermediate obtained by reacting an epoxy compound with an unsaturated compound having a carboxyl group. When a compound obtained by reacting an acid or a carboxylic acid anhydride is contained, an unreacted secondary hydroxyl group derived from an intermediate in this compound can be mentioned. The above-mentioned carboxyl group-containing resin (A11) and the second resin (y) may have such a hydroxyl group.

Further, as described above, the blocked isocyanate compound (F) can enhance the developability when forming a film from the photosensitive resin composition by a photolithography method.

As described above, the percentage of the blocked isocyanate compound (F) to the carboxyl group-containing resin (A) is 21% by mass or more and 100% by mass or less, whereby the above-mentioned action of the blocked isocyanate compound (F) can be obtained. That is, when this percentage is 21% by mass or more, the dielectric loss tangent of the cured product can be lowered, the flexibility of the cured product can be increased, and the surface of the cured product treated with the oxidizing agent is excessively corroded. It can be made less likely to be corroded, and the developability can be further improved. Further, when the percentage is 100% by mass or less, the developability can be improved. This percentage is more preferably 24% by mass or more, and even more preferably 40% by mass or more. Further, this percentage is more preferably 90% by mass or less, and further preferably 80% by mass or less.

The details of the blocked isocyanate compound (F) will be further described. The blocked isocyanate compound (F) is a compound obtained by blocking the isocyanate compound with a blocking agent.

The number of isocyanate groups in one molecule of an isocyanate compound is, for example, 2 or more and 6 or less. The isocyanate compound may be an aliphatic, alicyclic or aromatic polyisocyanate. The isocyanate compound includes, for example, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, isophorone diisocyanate, 1,6-hexamethylene diisocyanate, 1,3-trimethylene diisocyanate, 1,4-tetramethylene diisocyanate, 2, 2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, 1,9-nonamethylene diisocyanate, 1,10-decamethylene diisocyanate, 1,4-cyclohexanediisocyanate, 2,2'-diethyl ether Diisocyanate, diphenylmethane-4,4'-diisocyanate, o-ximethylene diisocyanate, m-ximethylene diisocyanate, p-xamethylene diisocyanate, methylene bis (cyclohexamethylene diisocyanate), cyclohexane-1,3-dimethylene diisocyanate, cyclohexane-1,4-dimethylerene Diisocyanate, 1,5-naphthalenediocyanate, p-phenylenediocyanate, 3,3'-methylene dithrylene-4,4'-diisocyanate, 4,4'-diphenyl ether diisocyanate, tetrachlorophenylenediisocyanate, norbornan diisocyanate, hydrogenated 1, It contains an isocyanate compound such as 3-xylylene diisocyanate and 1,4-xylylene diisocyanate hydride, and at least one selected from the group consisting of multimers thereof. In particular, the isocyanate compound preferably contains at least one compound selected from the group consisting of tolylene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, and multimers thereof. Examples of the multimer include a biuret form, an isocyanurate form, an adduct form, and the like, and the biuret form is preferable.

Examples of the blocking agent in the blocked isocyanate compound (F) include oxime compounds, lactam compounds, phenol compounds, alcohol compounds, amine compounds, active methylene compounds, pyrazole compounds, mercaptan compounds, imidazole compounds, and imide compounds. .. In particular, the blocking agent preferably contains at least one compound selected from the group consisting of oxime compounds, lactam compounds, phenol compounds, alcohol compounds, amine compounds, active methylene compounds, and pyrazole compounds. Examples of the oxime compound include oxime and ketooxime, and specific examples thereof include acetone oxime, formaldoxime, cyclohexanone oxime, methyl ethyl ketone oxime, cyclohexanone oxime, and benzophenone oxime. Examples of the lactam compound include ε-caprolactam and γ-butyrolactam. Examples of the phenol compound include phenol, naphthol, cresol, xylenol, and halogen-substituted phenol. Examples of the alcohol compound include methanol, ethanol, propanol, butanol, cyclohexanol, ethylene glycol monoalkyl ether, propylene glycol monoalkyl ether, alkyl lactate and the like. Examples of the amine compound include primary amines and secondary amines, and examples thereof include aniline, diphenylamine, ethyleneimine, and polyethyleneimine. Examples of the active methylene compound include diethyl malonate, dimethyl malonate, ethyl acetoacetate, and methyl acetoacetate. Examples of the pyrazole compound include pyrazole, methylpyrazole, and dimethylpyrazole. Examples of the mercaptan compound include alkyl mercaptans and aryl mercaptans.

The photosensitive resin composition may further contain an organic filler (G). The organic filler (G) improves the storage stability of the photosensitive resin composition by imparting thixophilicity to the photosensitive resin composition. Further, the organic filler (G) can further improve the adhesion between the cured product and the conductor.

The organic filler (G) preferably has a reactive group. In this case, the organic filler (G) has high compatibility in the photosensitive resin composition, and by imparting stronger thixo property to the photosensitive resin composition), the storage stability of the photosensitive resin composition can be improved. Can be improved further. In addition, the adhesion between the cured product and the conductor is further improved. The reactive group contained in the organic filler (G) more preferably contains at least one group selected from the group consisting of, for example, a carboxyl group, an amino group, an epoxy group, a vinyl group, and a hydroxyl group, and more preferably contains a carboxyl group and an amino group. It is more preferable to contain at least one of the groups. In this case, the storage stability of the photosensitive resin composition is further improved. In addition, the adhesion between the cured product and the conductor is further improved.

It is particularly preferable that the reactive group contains a carboxyl group. In this case, the developability of the photosensitive resin composition is improved. Further, the carboxyl group of the organic filler (G) can react with the epoxy compound (D) in the photosensitive resin composition. As a result, the organic filler (G) is likely to be uniformly dispersed inside the cured product. Further, the carboxyl group of the organic filler (G) can enhance the adhesion between the cured product and the conductor. When the photosensitive resin composition contains the crystalline epoxy compound (D1), the compatibility of the crystalline epoxy compound (D1) in the photosensitive resin composition is improved to improve the compatibility of the crystalline epoxy compound (D1). ) Can be difficult to crystallize. Further, when the photosensitive resin composition flows to form a coating film, the coating film is less likely to become non-uniform, so that a solder resist layer, an interlayer insulating layer, etc. produced from the photosensitive resin composition can be used. It becomes easy to make the thickness of the layer uniform.

It is also preferable that the reactive group contains a hydroxyl group. In this case as well, it is easy to further improve the adhesion between the cured product of the composition and the conductor. The reactive group may contain both a carboxyl group and a hydroxyl group.

When the organic filler (G) has a carboxyl group, the carboxyl group is produced by polymerizing or cross-linking a carboxylic acid monomer such as acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid, and itaconic acid. Formed as a side chain in an object. The carboxylic acid monomer has a carboxyl group and a polymerizable unsaturated double bond.

When the organic filler (G) has a carboxyl group, the acid value of the organic filler (G) is preferably 1 mgKOH / g or more and 60 mgKOH / g or less. When the acid value is 1 mgKOH / g or more, the stability of the photosensitive resin composition and the developability of the cured product tend to be particularly high. When the acid value is 60 mgKOH / g or less, the moisture resistance reliability of the cured product tends to be improved. The acid value of the organic filler (G) is more preferably 3 mgKOH / g or more. Further, the acid value is more preferably 40 mgKOH / g or less.

The organic filler (G) preferably contains rubber particles. It is also preferable that the organic filler (G) contains only rubber particles. The rubber particles can further increase the flexibility of the cured product. The rubber particles may have a crosslinked structure. The rubber particles include, for example, at least one polymer selected from the group consisting of crosslinked acrylic rubber, crosslinked acrylonitrile-butadiene rubber (NBR), crosslinked methyl methacrylate-butadiene-styrene (MBS) and crosslinked styrene-butadiene rubber (SBR). .. In this case, the flexibility of the cured product is particularly likely to be improved. Further, when the surface of the cured product is treated with an oxidizing agent, the surface is more likely to be roughened more appropriately.

Specific examples of the rubber particles include product number XER-91-MEK manufactured by JSR Corporation, product number XER-32-MEK manufactured by JSR Corporation, and product number XSK-500 manufactured by JSR Corporation. XER-91-MEK is a crosslinked rubber (NBR) having a carboxyl group having an average primary particle diameter of 0.07 μm, and is provided as a methyl ethyl ketone dispersion having a content of the crosslinked rubber of 15% by weight, and has an acid value of 10. It is 0 mgKOH / g. XER-32-MEK is a dispersion in which a polymer (linear particles) of a carboxyl group-modified hydrogenated nitrile rubber is dispersed in methyl ethyl ketone at a content of 17% by weight based on the total amount of the dispersion. Further, XSK-500 is a crosslinked rubber (SBR) having a carboxyl group and a hydroxyl group having an average primary particle diameter of 0.07 μm, and is provided as a methyl ethyl ketone dispersion having a content ratio of the crosslinked rubber of 15% by weight. As described above, the organic filler (G) is a dispersion liquid and may be blended in the photosensitive resin composition. That is, the rubber particles are a dispersion liquid and can be blended in the photosensitive resin composition. In addition to the above, specific examples of the organic filler (G) include product number XER-92 manufactured by JSR Corporation.

The average particle size of the organic filler (G) is preferably 1 μm or less. In this case, the developability of the photosensitive resin composition is likely to be improved. Further, when the surface of the cured product is treated with an oxidizing agent, fine irregularities are likely to be formed on the cured product, which tends to increase the surface area of the cured product. Therefore, the adhesion between the cured product and the conductor tends to be higher. The average particle size of the organic filler (G) is more preferably 0.5 μm or less, and further preferably 0.3 μm or less. In this case, the scattering of light in the photosensitive resin composition can be suppressed, which makes it easier to further improve the resolution. In addition, the unevenness formed by roughening the surface of the cured product tends to become finer. The average particle size of the organic filler (G) is, for example, 0.001 μm or more. The average particle size of the organic filler (G) is a cumulative 50% diameter (median diameter% D50) calculated from the particle size distribution measured by the dynamic light scattering method.

The organic filler (G) may contain particles other than rubber particles. In this case, the organic filler (G) can contain at least one particle selected from the group consisting of, for example, acrylic resin particles having a carboxyl group and cellulose particles having a carboxyl group. The acrylic resin particles having a carboxyl group can contain at least one particle component selected from the group consisting of non-crosslinked styrene / acrylic resin particles and crosslinked styrene / acrylic resin particles. Specific examples of the non-crosslinked styrene / acrylic resin particles include product number FS-201 (average primary particle diameter 0.5 μm) manufactured by Nippon Paint Industrial Coatings Co., Ltd. Specific examples of the crosslinked styrene / acrylic resin particles are product number MG-351 (average primary particle diameter 1.0 μm) and product number BGK-001 (average primary particle diameter 1.0 μm) manufactured by Nippon Paint Industrial Coatings Co., Ltd. Can be mentioned. Further, the organic filler (G) may contain particles other than the above-mentioned particles selected from the rubber particles, the acrylic resin particles, and the cellulose particles. In this case, the organic filler (G) can contain particles having a carboxyl group. That is, the particles having a carboxyl group may be different from the particles selected from the rubber particles, the acrylic resin particles, and the cellulose particles.

The percentage of the organic filler (G) to the carboxyl group-containing resin (A) is preferably 1% by mass or more and 60% by mass or less. In this case, the thixophilicity of the photosensitive resin composition is particularly likely to increase, and the stability is improved. In addition, the surface of the cured product is more likely to be moderately roughened by the oxidizing agent, and the adhesion between the cured product and the conductor is more likely to be improved. This percentage is more preferably 3% by mass or more, and further preferably 5% by mass or more. Further, this percentage is more preferably 30% by mass or less, and further preferably 17% by mass or less.

The photosensitive resin composition may contain a coupling agent. The coupling agent can further improve the dispersibility of the silica (E), and when the photosensitive resin composition contains the organic filler (G), the dispersibility of the organic filler (G) can also be improved. .. Further, the resolution can be improved. The coupling agent has at least one atom selected from the group consisting of, for example, a silicon atom, an aluminum atom, a titanium atom, and a zirconium atom. Further, the coupling agent further has a functional group selected from the group consisting of, for example, an alkoxy group, an acyloxy group and an alkoxide. The coupling agent preferably has a silicon atom, that is, the coupling agent preferably contains a silane coupling agent.

The percentage of the coupling agent to the total of the silica (C) and the organic filler (G) is more preferably 0.05% by mass or more and 5% by mass or less.

The photosensitive resin composition may contain melamine. In this case, when the cured product of the photosensitive resin composition is treated with an oxidizing agent, the cured product can be prevented from being excessively corroded. Melamine is 2,4,6-triamino-1,3,5-triazine and is generally commercially available. The average particle size of melamine is preferably 20 μm or less, more preferably 15 μm or less. Since the melamine is uniformly dispersed in the photosensitive resin composition, the melamine is more easily coordinated and bonded to the metal element. Thereby, the adhesion of the photosensitive resin composition can be further improved. The lower limit of the average particle size of melamine is not particularly limited, but can be 0.01 μm or more. The average particle size of melamine is a cumulative 50% diameter (median diameter D50) calculated from a particle size distribution measured by a laser diffraction / scattering method in a state where melamine is dispersed in a photosensitive resin composition. ..

When the photosensitive resin composition contains melamine, the percentage of melamine to the carboxyl group-containing resin (A) is preferably 0.1% by mass or more and 10% by mass or less. In this case, excessive corrosion when the cured product is treated with an oxidizing agent is more likely to be suppressed. This percentage is more preferably 0.3% by mass or more, further preferably 0.5% by mass or more, and particularly preferably 1% by mass or more. Further, the percentage is more preferably 9% by mass or less, further preferably 8% by mass or less, and particularly preferably 6% by mass or less.

The photosensitive resin composition may contain an organic solvent. The organic solvent is used for the purpose of liquefaction or varnishing of the photosensitive resin composition, adjusting the viscosity, adjusting the coatability, adjusting the film-forming property, and the like.

Organic solvents include linear, branched, secondary or polyhydric alcohols such as ethanol, propyl alcohol, isopropyl alcohol, hexanol and ethylene glycol; ketones such as methyl ethyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene and xylene. Kind: Petroleum-based aromatic mixed solvents such as Swazol series (manufactured by Maruzen Petrochemical Co., Ltd.) and Solbesso series (manufactured by Exxon Chemical Co., Ltd.) Thor; propylene glycol alkyl ethers such as propylene glycol methyl ether; polypropylene glycol alkyl ethers such as dipropylene glycol methyl ether; acetate esters such as ethyl acetate, butyl acetate, cellosolve acetate, carbitol acetate; and dialkyl glycol ethers. It can contain one or more compounds selected from the group consisting of classes.

When the photosensitive resin composition contains an organic solvent, the amount of the organic solvent is such that the organic solvent volatilizes rapidly when the coating film formed from the photosensitive resin composition is dried, that is, the organic solvent is dried. It is preferable to adjust so that it does not remain on the film. In particular, the proportion of the organic solvent with respect to the entire photosensitive resin composition is preferably 0% by mass or more and 99.5% by mass or less, and more preferably 15% by mass or more and 60% by mass or less. Since the preferable ratio of the organic solvent differs depending on the coating method and the like, it is preferable that the ratio is appropriately adjusted according to the coating method.

The photosensitive resin composition may further contain components other than the above components as long as the effects of the present embodiment are not impaired.

The photosensitive resin composition includes tolylene diisocyanate-based, morpholini diisocyanate-based, isophorone diisocyanate-based and hexamethylene diisocyanate-based blocked isocyanates blocked with caprolactam, oxime, malonic acid ester and the like; butylated urea resins; various other than the above. Thermocurable resin; UV curable epoxy (meth) acrylate; Resin obtained by adding (meth) acrylic acid to epoxy resins such as bisphenol A type, phenol novolac type, cresol novolac type, and alicyclic type; and diallyl phthalate. It may contain at least one resin selected from the group consisting of polymer compounds such as resins, phenoxy resins, urethane resins, melamine resins, and fluororesins.

The photosensitive resin composition may contain a curing agent for curing the epoxy compound (D). The curing agent is, for example, imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, 1- (2). Imidazole derivatives such as -cyanoethyl) -2-ethyl-4-methylimidazole; dicyandiamide, benzyldimethylamine, 4- (dimethylamino) -N, N-dimethylbenzylamine, 4-methoxy-N, N-dimethylbenzylamine, Amine compounds such as 4-methyl-N, N-dimethylbenzylamine; hydrazine compounds such as adipate hydrazide and sebacic acid hydrazide; phosphorus compounds such as triphenylphosphine; acid anhydrides; phenols; mercaptans; amine amine complexes; And can contain at least one component selected from the group consisting of onium salts. Commercially available products of these components include, for example, 2MZ-A, 2MZ-OK, 2PHZ, 2P4BHZ, 2P4MHZ (both are trade names of imidazole compounds) manufactured by Shikoku Kasei Co., Ltd., U-CAT3503N and UCAT3502T manufactured by San Apro Co., Ltd. (All are trade names of blocked isocyanate compounds of dimethylamine), DBU, DBN, U-CATSA102, U-CAT5002 (all are bicyclic amidine compounds and salts thereof).

The photosensitive resin composition may contain an adhesion imparting agent. Examples of the adhesion-imparting agent include acetguanamine (2,4-diamino-6-methyl-1,3,5-triazine) and benzoguanamine (2,4-diamino-6-phenyl-1,3,5-triazine). ) And other guanamine derivatives, as well as 2,4-diamino-6-methacryloyloxyethyl-S-triazine, 2-vinyl-4,6-diamino-S-triazine, 2-vinyl-4,6-diamino-S-triazine. Examples thereof include isocyanuric acid adducts, S-triazine derivatives such as 2,4-diamino-6-methacryloyloxyethyl-S-triazine and isocyanuric acid adducts, silane coupling agents, and melamine derivatives.

The photosensitive resin composition may contain a rheology control agent. The rheology control agent makes it easier to optimize the viscosity of the photosensitive resin composition. Examples of the rheology control agent include urea-modified medium-polar polyamide (product number BYK-430 and BYK-431 manufactured by Big Chemie Japan Co., Ltd.), polyhydroxycarboxylic acid amide (product number BYK-405 manufactured by Big Chemie Japan Co., Ltd.), and the like. Modified urea (part number BYK-410, BYK-411, BYK-420 manufactured by Big Chemie Japan Co., Ltd.), high molecular weight urea derivative (part number BYK-415 manufactured by Big Chemie Japan Co., Ltd.), urea modified urethane (part number BYK-415 manufactured by Big Chemie Japan Co., Ltd.) Company-made part number BYK-425), polyurethane (Big Chemy Japan Co., Ltd. part number BYK-428), castor oil wax, polyethylene wax, polyamide wax, bentonite, kaolin, clay.

The photosensitive resin composition is a curing accelerator; a colorant; a copolymer such as silicone or acrylate; a leveling agent; a thixotropy agent; a polymerization inhibitor; an antihalation agent; a flame retardant; an antifoaming agent; an antioxidant; a surfactant. Agents; as well as at least one component selected from the group consisting of polymeric dispersants.

The photosensitive resin composition of the present embodiment can be prepared by an appropriate method. For example, the photosensitive resin composition can be prepared by mixing the raw materials of the photosensitive resin composition and stirring the mixture. Further, the photosensitive resin composition may be prepared by kneading by an appropriate kneading method using, for example, a three-roll, a ball mill, a sand mill or the like. When the raw material contains a liquid component, a low-viscosity component, etc., the portion of the raw material excluding the liquid component, the low-viscosity component, etc. is first kneaded to prepare a mixture, and then the obtained mixture is added. A photosensitive resin composition may be prepared by adding a liquid component, a component having a low viscosity, or the like and mixing them. When the photosensitive resin composition contains a solvent, a part or all of the solvent among the raw materials may be mixed first, and then mixed with the rest of the raw materials.

A printed wiring board containing a cured product of the photosensitive resin composition and a method for producing the printed wiring board will be described.

The printed wiring board includes at least one of an interlayer insulating layer containing a cured product of the photosensitive resin composition and a solder resist layer containing a cured product of the photosensitive resin composition.

The printed wiring board 11 including the interlayer insulating layer 7 containing the cured product of the photosensitive resin composition will be described in detail with reference to FIGS. 1A to 1E.

When manufacturing the printed wiring board 11, for example, a photosensitive resin composition and a base material 1 are prepared. The base material 1 includes an insulating layer 2 and a second conductor layer 3 that overlaps the insulating layer 2. An interlayer insulating layer 7 is produced from the photosensitive resin composition on the base material 1 by a photolithography method. That is, the film 4 prepared from the photosensitive resin composition is overlaid on the base material 1 so as to cover the second conductor layer 3, and the negative pattern-like region of the film 4 including the pattern of the via holes 6 is exposed. Then, the development treatment is performed using an alkaline aqueous solution. As a result, the interlayer insulating layer 7 and the via hole 6 penetrating the interlayer insulating layer 7 are produced.

Specifically, for example, first, as shown in FIG. 1A, the base material 1 is prepared. The base material 1 includes an insulating layer 2 and a second conductor layer 3. The second conductor layer 3 is a conductor wiring.

By applying the photosensitive resin composition on the base material 1 and further drying it if necessary, a film 4 covering the second conductor layer 3 is produced as shown in FIG. 1B. The method for applying the photosensitive resin composition is selected from the group consisting of, for example, a dipping method, a spray method, a spin coating method, a roll coating method, a curtain coating method, a screen printing method, and the like. When the photosensitive resin composition is dried, the photosensitive resin composition is heated at a temperature of, for example, 60 ° C. or higher and 130 ° C. or lower.

The film 4 may be formed by superimposing a dry film containing a photosensitive resin composition on the substrate 1. The dry film is formed on the support by applying the photosensitive resin composition on an appropriate support such as made of polyester and then drying the dry film. As a result, a dry film with a support including a dry film and a support for supporting the dry film can be obtained. The dry film in the dry film with a support is superposed on the base material 1 so as to cover the second conductor layer 3, and then pressure is applied to the dry film and the base material 1. As a result, the film 4 made of a dry film is overlaid on the base material 1.

Next, the film 4 is exposed. For example, the negative pattern-like region of the film 4 including the pattern of the via holes 6 is exposed. In this case, for example, the film 4 is irradiated with ultraviolet rays via a negative mask. The negative mask includes an exposed portion that transmits ultraviolet rays and a non-exposed portion that shields ultraviolet rays, and the pattern of the non-exposed portion includes a pattern of via holes 6. The negative mask is, for example, a photo tool such as a mask film or a dry plate. The ultraviolet light source is selected from the group consisting of, for example, a chemical lamp, a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a YAG laser, an LED, a xenon lamp and a metal halide lamp.

When the film 4 is prepared from a dry film, when the film 4 is exposed, for example, the support is peeled from the film 4 in advance, and then the film 4 is exposed. The film 4 may be exposed by irradiating the film 4 with ultraviolet rays while allowing the support to pass through the film 4 while the support is overlapped with the film 4, and then the support may be peeled off from the exposed film 4.

As the exposure method, a method other than the method using a negative mask may be adopted. For example, the film 4 may be exposed by a direct drawing method in which ultraviolet rays emitted from a light source are applied only to a portion of the film 4 to be exposed. The light sources applied to the direct drawing method are, for example, high-pressure mercury lamp, ultra-high pressure mercury lamp, metal halide lamp, YAG laser, LED, g-line (436 nm), h-line (405 nm), i-line (365 nm), and g-line and h-line. And i-rays are selected from the group consisting of two or more combinations.

Next, the film 4 is developed with an alkaline aqueous solution to prepare an interlayer insulating layer 7 having via holes 6. By applying a developing treatment to the film 4, the uncured portion 5 of the film 4 shown in FIG. 1C is removed, thereby providing a via hole 6 as shown in FIG. 1D. In the developing process, an appropriate developing solution can be used according to the composition of the photosensitive resin composition. The developing solution is, for example, an alkaline aqueous solution containing at least one of an alkali metal salt and an alkali metal hydroxide, or an organic amine. More specifically, the alkaline aqueous solution includes, for example, sodium carbonate, potassium carbonate, ammonium carbonate, sodium hydrogencarbonate, potassium hydrogencarbonate, ammonium hydrogencarbonate, sodium hydroxide, potassium hydroxide, ammonium hydroxide, tetramethylammonium hydroxide and water. It contains at least one component selected from the group consisting of lithium oxide. The solvent in the alkaline aqueous solution may be water alone or a mixture of water and a hydrophilic organic solvent such as lower alcohols. The organic amine contains, for example, at least one component selected from the group consisting of monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine and triisopropanolamine.

The alkaline aqueous solution preferably contains at least one of an alkali metal salt and an alkali metal hydroxide, and particularly preferably contains sodium carbonate. In this case, it is possible to improve the working environment and reduce the burden of waste treatment.

Since the photosensitive resin composition according to the present embodiment has good developability, the residue of the uncured photosensitive resin composition after development is unlikely to remain at the bottom of the via holes 6.

Subsequently, the developed film 4 may be thermally cured by heating. The heating conditions are, for example, a heating temperature in the range of 120 ° C. or higher and 200 ° C. or lower, and a heating time in the range of 20 minutes or more and 300 minutes or less. When the film 4 is thermoset in this way, the performance such as strength, hardness, and chemical resistance of the interlayer insulating layer 7 is improved.

If necessary, the film 4 may be further irradiated with ultraviolet rays before or after heating. In this case, the photocuring of the film 4 can be further advanced.

As described above, the interlayer insulating layer 7 made of a cured product of the photosensitive resin composition is provided on the base material 1.

Subsequently, the first conductor layer 8 and the via conductor 9 are produced, but before that, it is preferable to roughen the inner surface of the via hole 6 and the outer surface of the interlayer insulating layer 7 by treating with an oxidizing agent. .. As the oxidizing agent, a desmear solution used in general desmear treatment can be used. Such an oxidizing agent contains, for example, at least one permanganate selected from the group of sodium permanganate and potassium permanganate.

Subsequently, a first conductor layer 8 which is a conductor wiring can be produced on the interlayer insulating layer 7 and a via conductor 9 can be produced in the via hole 6 by a known method such as an additive method. As a result, as shown in FIG. 1E, a printed wiring board 11 having a first conductor layer 8, a second conductor layer 3, an interlayer insulating layer 7, a via hole 6, and a via conductor 9 is obtained. In FIG. 1E, the via conductor 9 is a film that covers the internal life of the via hole 6, but the via conductor 9 may be filled in the entire via hole 6.

In the present embodiment, when the interlayer insulating layer 7 is surface-treated with an oxidizing agent, the surface of the interlayer insulating layer 7 is not excessively corroded, and fine irregularities are likely to be formed. Therefore, the adhesion between the interlayer insulating layer 7 and the first conductor layer 8 and the via conductor 9 can be improved.

A printed wiring board including a solder resist layer containing a cured product of the photosensitive resin composition will be described in detail.

When manufacturing a printed wiring board, for example, first, a core material is prepared. The core material includes, for example, at least one insulating layer and at least one conductor wiring. A solder resist layer is prepared from the photosensitive resin composition on the core material by a photolithography method. That is, a film is formed from the photosensitive resin composition on the surface of the core material on which the conductor wiring is provided. Examples of the film forming method include a coating method and a dry film method. As the coating method and the dry film method, the same method as in the case of forming the above-mentioned interlayer insulating layer can be adopted. The film is partially cured by exposing it. As the exposure method, the same method as in the case of forming the interlayer insulating layer can be adopted. Subsequently, the film is developed to remove the unexposed portion of the film, whereby the exposed portion of the film remains on the core material. Subsequently, the film on the core material is thermoset by heating. As the developing method and the heating method, the same method as in the case of forming the interlayer insulating layer can be adopted. If necessary, the film may be further irradiated with ultraviolet light before or after heating. In this case, the photocuring of the film can be further promoted.

The thickness of the solder resist layer is not particularly limited, but may be 3 μm or more and 50 μm or less.

As described above, a solder resist layer made of a cured product of the photosensitive resin composition is provided on the core material. As a result, a printed wiring board including a core material including an insulating layer and a conductor wiring on the core material, and a solder resist layer partially covering a surface of the core material on which the conductor wiring is provided can be obtained. The surface of the solder resist layer may be roughened by subjecting the solder resist layer to a surface treatment with an oxidizing agent, as in the case of the interlayer insulating layer. As a result, the adhesion between the solder resist layer and the conductor constituting the conductor wiring, solder, or the like can be improved.

Hereinafter, specific examples of this embodiment will be presented. However, this embodiment is not limited to the following examples.

1. 1. Synthesis of carboxyl group-containing resin (1) Synthesis example A-1: Synthesis of resin having a bisphenol fluorene skeleton A bisphenol fluorene type epoxy compound is placed in a four-necked flask equipped with a reflux cooler, a thermometer, an air blow tube and a stirrer. (Epoxy compound represented by the formula (2), in which R ₁ to R ₈ in the formula (2) are all hydrogen, epoxy equivalent 250 g / eq) 250 parts by mass, 72 parts by mass of acrylic acid, triphenylphosphine 1 .5 parts by mass, 0.2 parts by mass of methylhydroquinone, 60 parts by mass of propylene glycol monomethyl ether acetate, and 140 parts by mass of diethylene glycol monoethyl ether acetate were added. A mixture was prepared by stirring these under air bubbling. The mixture was heated at 115 ° C. for 12 hours with stirring in the flask under air bubbling. This prepared a solution of the intermediate. Subsequently, 60.8 parts by mass of 1,2,3,6-tetrahydrophthalic anhydride and 58.8 parts by mass of 3,3', 4,4'-biphenyltetracarboxylic acid dianhydride were added to the solution of the intermediate in the flask. 38.7 parts by mass and 38.7 parts by mass of propylene glycol monomethyl ether acetate were added. These were heated at 115 ° C. for 6 hours with stirring under air bubbling, and further heated at 80 ° C. for 1 hour with stirring under air bubbling. As a result, a solution of the carboxyl group-containing resin A-1 (solid content: 65% by mass) was obtained. The degree of polydispersity (Mw / Mn) of the carboxyl group-containing resin A-1 was 2.15, the weight average molecular weight (Mw) was 3096, and the acid value was 105 mgKOH / g.

(2) Synthesis Example A-2: Synthesis of resin having a biphenyl novolac skeleton A biphenyl novolac type epoxy resin (Nippon Kayaku Co., Ltd.) was placed in a four-necked flask equipped with a reflux condenser, a thermometer, an air blow tube and a stirrer. Manufactured, Part No. NC-3000-H, Epoxy equivalent 288 g / eq) 288 parts by mass, diethylene glycol monoethyl ether acetate 155 parts by mass, methyl hydroquinone 0.2 parts by mass, acrylic acid 72 parts by mass, and triphenylphosphine 3 parts by mass Was added to prepare a mixture. The mixture was heated in a flask at a temperature of 115 ° C. for 12 hours with stirring under air bubbling. This prepared a solution of the intermediate.

Subsequently, 91.2 parts by mass of tetrahydrophthalic anhydride and 90 parts by mass of diethylene glycol monoethyl ether acetate were added to the solution of the intermediate in the flask, and the mixture was heated at 90 ° C. for 4 hours while stirring under air bubbling. .. As a result, a solution of the carboxyl group-containing resin A-2 (solid content: 65% by mass) was obtained. The weight average molecular weight of the carboxyl group-containing resin A-2 was 8120, and the acid value was 76 mgKOH / g.

2. Preparation of photosensitive resin composition Of the raw materials, a powdery raw material and a carboxyl group-containing resin are kneaded in advance using three rolls, and then the remaining raw materials are mixed and mixed in a flask at 35 ° C. A photosensitive resin composition was obtained.

"Raw material (solid content) / parts by mass" in the table indicates the blending amount of the raw material. When the raw material contains a solvent, the blending amount of the raw material is the amount of the solid content excluding the solvent in the raw material. The details of the raw materials are as follows. Further, "E / A" in the table indicates the equivalent of the epoxy group of the epoxy compound to the equivalent of 1 equivalent of the carboxyl group of the carboxyl group-containing resin in the raw material.
-Photopolymerization Initiator A: 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, manufactured by BASF, product number Irgacure TPO.
-Photopolymerization Initiator B: 1-Hydroxy-cyclohexyl-phenyl-ketone, manufactured by BASF, product number Irgacure 184.
-Photopolymerization initiator C: 4,4'-bis (diethylamino) benzophenone.
-Photopolymerization Initiator D: 2-Methyl-1- (4-methylthiophenyl) -2-morpholinopropane-1-one, manufactured by BASF, product number Irgacure 907.
-Photopolymerizable compound A: Tricyclodecanedimethanol diacrylate.
-Photopolymerizable compound B: Trimethylolpropane triacrylate.
-Epoxy compound A: Biphenyl type crystalline epoxy resin, product number YX-4000 manufactured by Mitsubishi Chemical Corporation, melting point 105 ° C., epoxy equivalent 187 g / eq.
-Epoxy compound B: Bisphenol type crystalline epoxy resin, manufactured by Nittetsu Chemical & Materials Co., Ltd., product number YSLV-80XY, melting point 75-85 ° C., epoxy equivalent 192 g / eq.
-Blocked isocyanate compound A: Part number Duranate MF-B60B manufactured by Asahi Kasei Corporation. A solution of n-butyl n butanol acetate of a hexamethylene diisocyanate type methyl ethyl ketone oxime block isocyanate compound. Solid content 60% by mass. Curing temperature 120 ° C or higher.
-Blocked isocyanate compound B: Part number Duranate SBB-70P manufactured by Asahi Kasei Corporation. A propylene glycol monomethyl ether acetate solution of a blocked isocyanate compound having a biuret structure as a mother structure and a block structure having a 1,3-dimethylpyrazole skeleton. Solid content 70% by mass. Curing temperature 110 ° C or higher.
-Blocked isocyanate compound C: Part number Duranate SBN-70D manufactured by Asahi Kasei Corporation. A dipropylene glycol monomethyl ether solution of a pyrazole derivative blocked isocyanate of 1,6-hexamethylene diisocyanate. Solid content 70% by mass. Curing temperature 110 ° C or higher.
-Blocked isocyanate compound D: Part number Duranate 17B-60P manufactured by Asahi Kasei Corporation. A propylene glycol monomethyl ether acetate solution of a blocked isocyanate compound having a biuret structure as a mother structure and an oxime ester structure as a block structure. Solid content 60% by mass. Curing temperature 130 ° C or higher.
-Isocyanate compound: Part number Duranate TPA-100 manufactured by Asahi Kasei Corporation. An isocyanate prepolymer having an isocyanurate structure. Solid content 100% by mass. Isocyanate group content 23% by mass.
-Silica A dispersion: Part number SSP-CM1 manufactured by Admatex Co., Ltd. A slurry containing silica having an average particle size of 0.5 μm treated with phenylsilane and methylethylketone. Solid content 70% by mass.
-Silica B dispersion: Part number SC2050-MTX manufactured by Admatex Co., Ltd. A slurry containing silica having an average particle size of 0.5 μm treated with phenylaminosilane (product number KBM-573 manufactured by Shin-Etsu Chemical Co., Ltd.) and methyl ethyl ketone. Solid content 70% by mass.
-Silica C dispersion: Part number SC2050-MNU manufactured by Admatex Co., Ltd. A slurry containing silica having an average particle size of 0.5 μm treated with vinylsilane and methyl ethyl ketone. Solid content 70% by mass.
-Silica D dispersion: Part number SC2050-MB manufactured by Admatex Co., Ltd. A slurry containing silica having an average particle size of 0.5 μm treated with epoxy silane and methyl ethyl ketone. Solid content 70% by mass.
-Silica E dispersion: Part No. 5SQ-CM2 manufactured by Admatex Co., Ltd. A slurry containing silica having an average particle size of 0.5 μm without surface treatment and methyl ethyl ketone. Solid content 70% by mass.
-Solvent dispersion of silica sol A: Part number MEK-EC-2130Y manufactured by Nissan Chemical Industries, Ltd. A dispersion liquid containing a silica sol having an average particle size of 12 nm and methyl ethyl ketone. Solid content 30% by mass.
-Solvent dispersion of silica sol B: Part number MEK-AC-4130Y manufactured by Nissan Chemical Industries, Ltd. A dispersion liquid containing a silica sol having an average particle size of 45 nm and methyl ethyl ketone. Solid content 30% by mass.
-Dispersion liquid of organic filler A: Part number XER-91-MEK manufactured by JSR Corporation. A dispersion containing crosslinked rubber (NBR) having an average particle size of 0.07 μm and an acid value of 10.0 mgKOH / g and methyl ethyl ketone. Solid content 15% by mass.
-Dispersion liquid of organic filler B: Part number OPE-2St 1200 manufactured by Mitsubishi Gas Chemical Company. A dispersion liquid containing a vinylbenzyl-modified polyphenylene ether oligomer having a number average molecular weight of 1187 and a vinyl group equivalent of 590 g / eq, and toluene. Solid content 65% by mass.
-Antioxidant: Part number Irganox 1010 manufactured by BASF Japan Ltd.
-Melamine: 2,4,6-triamino-1,3,5-triazine. Average particle size 5 μm.
-Coupling agent: 3-glycidoxypropyltrimethoxysilane.
-Surfactant: Part number Megafuck F-477 manufactured by DIC Corporation.
-Solvent: Methyl ethyl ketone.

3. 3. Preparation of test piece (1) Preparation of test piece 1
Test pieces for performing the tests (1) to (8) of the following "4. Evaluation test" were prepared as follows.

The photosensitive resin composition was applied to a film made of polyethylene terephthalate with an applicator and then dried by heating at 90 ° C. for 30 minutes to form a dry film having a thickness of 30 μm on the film. A glass epoxy copper-clad laminate (FR-4 type) provided with a copper foil having a thickness of 17.5 μm was prepared. A comb-shaped electrode having a line width / space width of 30 μm / 30 μm was formed as a conductor wiring on this glass epoxy copper-clad laminate by a subtractive method, thereby obtaining a core material. The conductor wiring was roughened by dissolving and removing the surface portion of the conductor wiring of the core material having a thickness of about 1 μm with an etching agent (product number CZ-8101 manufactured by MEC COMPANY Ltd.). A dry film was heat-laminated on this core material with a vacuum laminator so as to cover the conductor wiring while the film was still overlapped. The conditions for heat laminating were 0.5 MPa, 80 ° C., and 1 minute. As a result, a film made of the above dry film was formed on the core material. Next, when exposing the film, a negative mask having a non-exposed portion having a pattern including a circular shape having a diameter of 100 μm, 80 μm, and 60 μm was directly applied to the film overlapping the film, and the condition of 300 mJ / cm ² was applied to the film. I irradiated the film with ultraviolet rays. After peeling the film from the dry film (film) after exposure, the film was developed. In the development treatment, a 1% Na ₂ CO ₃ aqueous solution at 30 ° C. was sprayed onto the film at an injection pressure of 0.2 MPa for 90 seconds. Subsequently, pure water was sprayed onto the film at an injection pressure of 0.2 MPa for 90 seconds. As a result, the unexposed portion of the film was removed to form via holes in the film. Subsequently, the film was heated at 180 ° C. for 120 minutes. As a result, a layer made of a cured product of the photosensitive resin composition (which can be said to be a cured product of the dry film) was formed on the core material. This gave a test piece.

(2) Preparation of test piece 2
Test pieces for performing the tests (9) and (10) of the following "4. Evaluation test" were prepared as follows.

The photosensitive resin composition was applied to a film made of polyethylene terephthalate with an applicator and then dried by heating at 90 ° C. for 30 minutes to form a dry film having a thickness of 50 μm on the film. This dry film was heat-laminated with a vacuum laminator on the entire surface of a Teflon (registered trademark) film while being overlapped with the film. The conditions for heat laminating are 0.5 MPa, 80 ° C., and 1 minute. As a result, a film having a film thickness of 50 μm made of a dry film was formed on the Teflon film. Next, when exposing the film, a mask having a rectangular exposed portion of 3 mm × 85 mm is directly applied to the film overlapping the film, and the film is exposed to the film through the mask under the condition of 300 mJ / cm ² . Irradiated with ultraviolet rays. After the exposure, the film was peeled off from the dry film (film). Subsequently, in developing the film, a 1% Na ₂ CO ₃ aqueous solution at 30 ° C. was sprayed onto the film at an injection pressure of 0.2 MPa for 90 seconds. Subsequently, the film was washed by injecting pure water at an injection pressure of 0.2 MPa for 90 seconds. Subsequently, the film was heated at 180 ° C. for 120 minutes. As a result, a cured product of the photosensitive resin composition (cured product of the dry film) was formed on the Teflon film. This cured product was peeled off from a Teflon film to obtain a test piece.

4. Evaluation test (1) Developability In the process of producing the test piece, the unexposed part of the film after the development treatment was observed, and the result was evaluated as follows.
A: All unexposed parts of the film have been removed.
B: A part of the unexposed portion of the film remained on the core material. Further development for 30 seconds (1% Na ₂ CO ₃ aqueous solution, 0.2 MPa) was carried out to remove all unexposed areas.
C: A part of the unexposed portion of the film remained on the core material. Even after additional 30-second development (1% Na ₂ CO ₃ aqueous solution, 0.2 MPa), a part of the unexposed portion remained in the core material.
D: Could not develop.

If the evaluation was "D", the tests after (2) below were not performed.

(2) Openness A commercially available swelling treatment liquid (Swelling Dip Security Guns P manufactured by Atotech Japan Co., Ltd.) was prepared as a swelling liquid for desmear. The cured product of the test piece was immersed in this swelling treatment liquid at 60 ° C. for 5 minutes, and then the cured product was washed with hot water. Subsequently, a desmear solution containing potassium permanganate (Concentrate Compact CP manufactured by Atotech Japan Co., Ltd.) was prepared as an oxidizing agent, and the cured product was immersed in the oxidizing agent at 80 ° C. for 10 minutes to cure. The surface of the object was roughened. Subsequently, the cured product is washed with hot water, and then the cured product is immersed in a neutralizing solution (Reduction Solution Securigant P manufactured by Atotech Japan Co., Ltd.) at 40 ° C. for 5 minutes to oxidize the surface of the cured product. Residue was removed. Subsequently, the cured product was washed with water.

In the cured product of the test piece after the above treatment, holes corresponding to the respective patterns of diameters of 100 μm, 80 μm, and 60 μm in the mask at the time of producing the cured product were observed, and the results were evaluated as follows.
A: A hole corresponding to a pattern having a diameter of 100 μm, a hole corresponding to a pattern having a diameter of 80 μm, and a hole corresponding to a pattern having a diameter of 60 μm are all opened.
B: The hole corresponding to the pattern having a diameter of 100 μm and the hole corresponding to the pattern having a diameter of 80 μm were opened, but the hole corresponding to the pattern having a diameter of 60 μm was not opened.
C: The hole corresponding to the pattern having a diameter of 100 μm was opened, but the hole corresponding to the pattern having a diameter of 80 μm and the hole corresponding to the pattern having a diameter of 60 μm were not opened.
D: The hole corresponding to the pattern having a diameter of 100 μm, the hole corresponding to the pattern having a diameter of 80 μm, and the hole corresponding to the pattern having a diameter of 60 μm were not opened.

(3) Plating resistance When manufacturing the test piece, a part of the conductor wiring was prevented from being covered with a layer made of a cured product. A nickel-plated layer was formed on a part of the conductor wiring in this test piece using a commercially available electroless nickel-plated bath, and then a gold-plated layer was formed using a commercially available electroless gold-plated bath. As a result, a metal layer composed of a nickel-plated layer and a gold-plated layer was formed. The layer made of the cured product and the metal layer were visually observed. In addition, a cellophane adhesive tape peeling test was performed on the layer made of the cured product. The results were evaluated as follows.
A: No abnormality was observed in the appearance of the cured product layer and the metal layer, and the cured product layer was not peeled off by the cellophane adhesive tape peeling test.
B: Discoloration was observed in the layer made of the cured product, but the layer made of the cured product was not peeled off by the cellophane adhesive tape peeling test.
C: A large discoloration was observed in the layer made of the cured product, but the layer made of the cured product was not peeled off by the cellophane adhesive tape peeling test.
D: Lifting of the layer made of the cured product was observed, and the layer made of the cured product was peeled off by the cellophane adhesive tape peeling test.

(4) Insulation While applying a bias voltage of DC5V to the conductor wiring (comb-shaped electrode) in the test piece, the printed wiring board was heated at 130 ° C. and 85% R. H. Was exposed for 200 hours in the test environment of. Under this test environment, the electrical resistance values between the comb-shaped electrodes of the cured product layer were constantly measured, and the results were evaluated according to the following evaluation criteria.
A: From the start of the test to the elapse of 200 hours, the electrical resistance value was always maintained at ¹⁰⁶ Ω or higher.
B: The electric resistance value was always maintained at ¹⁰⁶ Ω or more from the start of the test until 150 hours passed, but the electric resistance value became less than ¹⁰⁶ Ω before 200 hours passed from the start of the test.
C: The electric resistance value was always maintained at ¹⁰⁶ Ω or more from the start of the test until 100 hours passed, but the electric resistance value became less than ¹⁰⁶ Ω before 150 hours passed from the start of the test.
D: The electrical resistance value became less than ¹⁰⁶ Ω before 100 hours had passed from the start of the test.

(5) PCT (Pressure Cooker Test)
After the test piece was left to stand in an environment of 121 ° C. and 100% RH for 100 hours, the appearance of the layer made of the cured product was evaluated according to the following evaluation criteria.
A: No abnormality was found in the layer made of the cured product.
B: Slight discoloration was observed in the layer made of the cured product.
C: A large discoloration was observed in the layer composed of the cured product.
D: A large discoloration was observed in the layer made of the cured product, and swelling was partially generated.

(6) Thermal shock resistance A water-soluble flux (manufactured by London Chemical Co., Ltd., product number LONCO 3355-11) is applied to a layer made of a cured product of the test piece, and then the test piece is immersed in a molten solder bath at 280 ° C. for 30 seconds. Then, after immersing in water at 25 ° C. for 30 seconds, the appearance of the layer made of the cured product was observed. This treatment was repeated 5 times and the thermal shock resistance was evaluated as shown below.
A: Even after 5 treatments, no abnormalities such as swelling, peeling, and cracks were observed in the layer made of the cured product.
B: After 5 treatments, abnormalities such as swelling, peeling, and cracks were observed in the layer made of the cured product, but after 4 treatments, abnormalities such as swelling, peeling, and cracks were observed in the layer made of the cured product. I was not able to admit.
C: After 4 treatments, abnormalities such as swelling, peeling, and cracks were observed in the layer made of the cured product, but after 3 treatments, abnormalities such as swelling, peeling, and cracks were observed in the layer made of the cured product. I was not able to admit.
D: Within 3 treatments, abnormalities such as swelling, peeling, and cracks were observed in the layer made of the cured product.

(7) Roughing resistance (evaluation of the thickness of the cured product layer after roughening)
The surface of the cured product in the test piece was roughened by treating it with a swelling treatment liquid, an oxidizing agent and a neutralizing agent in the same manner as in the above-mentioned "(2) Opening property".

The surface of the layer made of this cured product was observed. Subsequently, the layer made of the cured product was ultrasonically cleaned (42 kHz, 30 seconds) and then observed again.

From the results, the resistance of the cured product to the oxidizing agent was evaluated according to the following evaluation criteria.
A: No whitening phenomenon was observed on the surface of the layer made of the cured product, and no significant change was observed in the uneven shape of the surface even after ultrasonic cleaning.
B: No whitening phenomenon was observed on the surface of the layer made of the cured product, but a little desorption of silica from the surface was confirmed after ultrasonic cleaning.
C: A slight whitening phenomenon was observed on the surface of the layer made of the cured product, and desorption of silica from the surface was confirmed after ultrasonic cleaning.
D: The surface of the layer made of the cured product was strongly whitened, and desorption of silica from the surface was confirmed after ultrasonic cleaning.

(8) Adhesion to the copper-plated layer By treating the layer made of the cured product in the test piece with a swelling treatment liquid, an oxidizing agent and a neutralizing agent in the same manner as in the above-mentioned "(2) Opening property". , The surface of this layer was roughened.

Subsequently, an initial wiring was prepared by electroless copper plating treatment using a commercially available chemical solution on a layer made of a cured product, and then the test piece was heated at 150 ° C. for 1 hour. Next, a copper-plated layer was prepared by depositing 33 μm-thick copper on the initial wiring by electrolytic copper plating under the condition of a current density of 2 A / dm ² using a commercially available chemical solution. Subsequently, the test piece was heated at 180 ° C. for 30 minutes.

In the process of producing the above-mentioned copper plating layer, it was confirmed whether or not blisters were generated at the time of heating after the electrolytic copper plating treatment and at the time of heating after the electrolytic copper plating treatment. Further, the adhesion strength between the copper plating layer and the cured product was measured according to JIS C6481. The measurement was performed four times, and the average value was calculated. The results were evaluated as follows.
A: No blister was confirmed during heating after the electrolytic copper plating treatment and during heating after the electrolytic copper plating treatment, and the average value of the adhesion strength was 0.40 kN / m or more.
B: No blister was confirmed during heating after the electrolytic copper plating treatment and during heating after the electrolytic copper plating treatment, and the average value of the adhesion strength was 0.30 kN / m or more and less than 0.4 kN / m.
C: No blister was confirmed during heating after the electrolytic copper plating treatment and during heating after the electrolytic copper plating treatment, and the average value of the adhesion strength was less than 0.3 kN / m.
D: Blister was confirmed during heating after the electrolytic copper plating treatment or during heating after the electrolytic copper plating treatment.

(9) Relative Permittivity The relative permittivity of the test piece was measured under the condition of a frequency of 10 GHz by a cavity resonator method based on JIS C2565 using a permittivity measuring device (ADMS01O manufactured by AET Co., Ltd.). .. The results were evaluated as follows.
A: The relative permittivity is less than 3.2.
B: The relative permittivity is 3.2 or more and less than 3.5.
C: The relative permittivity is 3.5 or more and less than 3.8.
D: The relative permittivity is 3.8 or more.

(10) Dielectric Dissipation Factor The dielectric loss tangent (tan δ) of the test piece is measured by the cavity resonator method at a frequency of 10 GHz using a dielectric constant measuring device (ADMS01O, manufactured by AET Co., Ltd.) in accordance with JIS C2565. It was measured. The results were evaluated as follows.
A: The dielectric loss tangent is less than 0.008.
B: The dielectric loss tangent is 0.008 or more and less than 0.01.
C: The dielectric loss tangent is 0.01 or more and less than 0.012.
D: The dielectric loss tangent is 0.012 or more.

Claims (18)

Carboxyl group-containing resin (A),
Photopolymerization initiator (B),
Photopolymerizable compound (C),
Epoxy compound (D),
Silica (E) having a percentage of 50% by mass or more and 300% by mass or less with respect to the carboxyl group-containing resin (A), and a blocked isocyanate compound having a percentage of 21% by mass or more and 100% by mass or less with respect to the carboxyl group-containing resin (A). F) is contained,
Photosensitive resin composition. The carboxyl group-containing resin (A) contains a carboxyl group-containing resin (A1) having an aromatic ring.
The photosensitive resin composition according to claim 1. The carboxyl group-containing resin (A) contains a carboxyl group-containing resin (A11) having a bisphenol fluorene skeleton.
The photosensitive resin composition according to claim 1 or 2. The photopolymerization initiator (B) contains an acylphosphine oxide-based photopolymerization initiator (B1).
The photosensitive resin composition according to any one of claims 1 to 3. The photopolymerizable compound (C) contains a compound (C1) having a tricyclodecane skeleton.
The photosensitive resin composition according to any one of claims 1 to 4. The equivalent of the epoxy group of the epoxy compound (D) is 0.1 or more and less than 1 with respect to 1 equivalent of the carboxyl group of the carboxyl group-containing resin (A).
The photosensitive resin composition according to any one of claims 1 to 5. The epoxy compound (D) contains a crystalline epoxy compound (D1).
The photosensitive resin composition according to any one of claims 1 to 6. The blocked isocyanate compound (F) is a compound obtained by blocking an isocyanate compound with a blocking agent, and the isocyanate compound is selected from the group consisting of tolylene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, and multimers thereof. Contains at least one compound that is
The photosensitive resin composition according to any one of claims 1 to 7. The blocking agent contains at least one compound selected from the group consisting of oxime compounds, lactam compounds, phenol compounds, alcohol compounds, amine compounds, active methylene compounds, and pyrazole compounds.
The photosensitive resin composition according to claim 8. The silica (E) is surface-treated with a silane coupling agent.
The photosensitive resin composition according to any one of claims 1 to 9. The silane coupling agent has a phenyl skeleton.
The photosensitive resin composition according to claim 10. The silica (E) contains silica (E1) having an average particle size of 0.1 μm or more and 5 μm or less.
The photosensitive resin composition according to any one of claims 1 to 11. Further containing an organic filler (G),
The photosensitive resin composition according to any one of claims 1 to 12. The organic filler (G) has a reactive group.
The photosensitive resin composition according to claim 13. The photosensitive resin composition according to any one of claims 1 to 14 is contained.
Dry film. It is obtained by curing the photosensitive resin composition according to any one of claims 1 to 14.
Hardened product. The interlayer insulating layer containing the cured product according to claim 16 is provided.
Printed wiring board. A solder resist layer containing the cured product according to claim 16.
Printed wiring board.

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