TW201704858A - Photo-sensitive resin composition, dry film, and printed wiring board - Google Patents

Abstract

A light-sensitive resin composition contains a carboxyl-group-containing resin (A), an unsaturated compound (B), a photopolymerization initiator (C), an epoxy compound (D), and a component (E) containing at least one compound selected from the group comprising melamine and melamine derivatives. The carboxyl-group-containing resin (A) contains a carboxyl-group-containing resin (A1) having a bisphenol fluorene skeleton.

Description

Photosensitive resin composition, dry film and printed wiring board (1)

The present invention relates to a photosensitive resin composition, a dry film, a printed wiring board having a solder resist layer, and a printed wiring board having an interlayer insulating layer, wherein the dry film is a dried material of the photosensitive resin composition, and the solder resist layer A cured product of the photosensitive resin composition is contained, and the interlayer insulating layer contains a cured product of the photosensitive resin composition.

In the past, an electrically insulating resin composition was used to form an electrically insulating layer such as a solder resist layer, a plating resist layer, an etch resist layer, and an interlayer insulating layer of a printed wiring board. Such a resin composition is, for example, a photosensitive resin composition.

It has been proposed to formulate a carboxyl group-containing resin in a photosensitive resin composition for imparting high heat resistance to a layer formed of a photosensitive resin composition having a bisphenol fluorene skeleton. For example, Japanese Patent No. 4,508, 929 discloses the use of a carboxyl group-containing resin having an anthracene skeleton obtained by reacting a fluorene epoxy (meth) acrylate with a polyvalent carboxylic acid or an anhydride thereof.

A plating layer may be formed on the layer composed of the cured product of the photosensitive resin composition, and the photosensitive resin composition contains a carboxyl group-containing resin having a bisphenol fluorene skeleton. Before forming such a plating layer on the cured product, the surface of the layer of the cured product may be roughened by, for example, an oxidizing agent containing potassium permanganate, thereby bonding the layer of the cured product to the plating layer. Sexual improvement. However, if the oxidizing agent is used to treat the layer of the cured product, the surface of the layer of the cured product is corroded, and the thickness of the layer is thinned. Although the carboxyl group-containing resin having a bisphenol fluorene skeleton has high resistance to the oxidizing agent, even if the photosensitive resin composition contains the carboxyl group-containing resin, the thickness of the layer of the cured product may be reduced due to the oxidizing agent.

The carboxyl group-containing resin having a bisphenol fluorene skeleton may lower the developability of the photosensitive resin composition. When the molecular weight of the carboxyl group-containing resin is reduced in order to improve the developability, the resistance of the layer composed of the cured product to the oxidizing agent is lowered, and the thickness of the layer of the cured product is further reduced by the oxidizing agent. Therefore, it is difficult to roughen the surface of the layer composed of the cured material by the oxidizing agent, so as to improve the adhesion between the cured product and the plating layer.

An object of the present invention is to provide a photosensitive resin composition, a dry film, a printed wiring board having a solder resist layer, and a printed wiring board including an interlayer insulating layer, wherein the dry film is a dried product of the photosensitive resin composition, The solder resist layer contains a cured product of the photosensitive resin composition, and the interlayer insulating layer contains a cured product of the photosensitive resin composition described above, and Further, even if the photosensitive resin composition contains a carboxyl group-containing resin having a bisphenol fluorene skeleton, excellent developability can be obtained, and in the pre-step of the plating treatment, the thickness of the layer of the cured product can be hardly caused by the oxidizing agent. It is thinned and the surface of the cured product can be roughened with an oxidizing agent.

A photosensitive resin composition of one aspect of the present invention, comprising: a carboxyl group-containing resin (A); an unsaturated compound (B) having at least one ethylenically unsaturated bond in one molecule; and a photopolymerization initiator (C); an epoxy compound (D); and, component (E), which contains at least one compound selected from the group consisting of melamine and a melamine derivative; and the carboxyl group-containing resin (A) contains a carboxyl group-containing resin ( A1), the carboxyl group-containing resin (A1) has a bisphenol fluorene skeleton.

A dry film of one aspect of the present invention is a dried product of the photosensitive resin composition.

A printed wiring board according to an aspect of the present invention includes an interlayer insulating layer containing the photosensitive resin composition.

A printed wiring board according to an aspect of the present invention includes a solder resist layer containing the photosensitive resin composition.

According to one aspect of the present invention, even if the photosensitive resin composition contains a carboxyl group-containing resin having a bisphenol fluorene skeleton, excellent developability can be obtained, and in the pre-step of the plating treatment, the layer of the cured product can be obtained. The thickness is not easily thinned by the oxidizing agent, and the surface of the cured product can be roughened with an oxidizing agent.

1‧‧‧ core material

2‧‧‧Insulation

3‧‧‧Conductor line (first conductor line)

4‧‧ ‧ film

5‧‧‧Unexposed parts

6‧‧‧ hole

7‧‧‧Interlayer insulation

8‧‧‧Second conductor line

9‧‧‧Perforated plating

10‧‧‧through holes

11‧‧‧Printed circuit board

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

Hereinafter, one embodiment of the present invention will be described. In the following description, "(meth)acrylic acid" means at least one of "acrylic acid" and "methacrylic acid". For example, (meth) acrylate means at least one of acrylate and methacrylate.

The photosensitive resin composition of the present embodiment, comprising: a carboxyl group-containing resin (A); an unsaturated compound (B) having at least one ethylenically unsaturated bond in one molecule; and a photopolymerization initiator (C); Epoxy compound (D); and, component (E).

The carboxyl group-containing resin (A) contains a carboxyl group-containing resin (A1) having a bisphenol fluorene skeleton.

The carboxyl group-containing resin (A1) is, for example, a reaction product of an intermediate and an acid anhydride, and the intermediate is a reaction product of an epoxy compound (a1) and an unsaturated group-containing carboxylic acid (a2). The epoxy compound (a1) has a bisphenol fluorene skeleton, and the bisphenol fluorene skeleton is represented by the following formula (1), and in the formula (1), R ₁ to R ₈ are each independently hydrogen and have a carbon number of 1 to 5. Alkyl or halogen.

The carboxyl group-containing resin (A1) is synthesized by reacting the epoxy compound (a1) with the unsaturated group-containing carboxylic acid (a2), and reacting the intermediate obtained thereby with an acid anhydride.

R ₁ to R ₈ in the formula (1) may each be hydrogen or may be an alkyl group having 1 to 5 carbon atoms or a halogen. This is because, even if the hydrogen in the aromatic ring is replaced by a low molecular weight alkyl group or a halogen, the carboxyl group-containing resin (A1) is not adversely affected, and the carboxyl group-containing resin (A1) is sometimes promoted. The heat resistance or flame retardancy of the cured product of the photosensitive resin composition.

Component (E) contains at least one compound selected from the group consisting of melamine and melamine derivatives. Thereby, even if the photosensitive resin composition contains a bisphenol fluorene skeleton, the cured product of the photosensitive resin composition can be remarkably hardly corroded by the oxidizing agent containing potassium permanganate. In other words, the photosensitive resin composition-containing component (E) can impart resistance to the oxidizing agent to the cured product of the photosensitive resin composition. Thereby, in the pre-step of the plating treatment, the thickness of the layer of the cured product can be made less difficult to be thinned by the oxidizing agent, and the surface of the cured product can be roughened with an oxidizing agent to make the hardened material and the copper or The adhesion of the plating layer composed of gold or the like is improved.

In the present embodiment, the component (E) may contain only melamine, may contain only a melamine derivative, or may contain a melamine and a melamine derivative. Melamine is 2,4,6-triamino-1,3,5-three And can be obtained from generally commercially available compounds. Further, the melamine derivative may be a compound having one triazine ring and an amine group in one molecule thereof. As the melamine derivative, for example, guanamine; methyl decylamine; phenyl decylamine; 2,4-diamino-6-methylpropenyl oxyethyl-S-triazine, 2 -vinyl-4,6-diamino-S-triazine, 2-vinyl-4,6-diamino-S-triazine/isocyanuric acid adduct, 2,4-diamine S-triazine derivatives such as -6-methacryloyloxyethyl-S-triazine/isocyanuric acid addition; and melamine and anhydride such as melamine-tetrahydrophthalate The reactants. More specific examples of the melamine derivative include the product name VD-1 of Shikoku Chemical Industry Co., Ltd., the product name VD-2, and the product name VD-3. The melamine derivative is preferably a compound having one triazine ring and two or more amine groups in one molecule thereof. At least one of the two or more amine groups is a substituent having no -NH ₂ group. That is, the melamine derivative does not contain melamine. In such a case, the melamine derivative dispersed in the photosensitive resin composition can be coordinate-bonded to a metal element contained in a conductor layer of a plating layer or a core material, and is located in photosensitivity. The contact surface of the resin composition. Therefore, the adhesiveness of the photosensitive resin composition can be improved. Examples of the metal element include gold, silver, copper, and nickel.

When the component (E) is soluble or difficult to dissolve in the photosensitive resin composition, the component (E) having an average particle diameter of 20 μm or less (preferably 15 μm or less) may be dispersed in the photosensitive resin composition. At this time, since the component (E) is uniformly dispersed in the photosensitive resin composition, the component (E) can be further easily coordinate-bonded to the metal element. Thereby, the adhesiveness of the photosensitive resin composition can be further improved. The lower limit of the average particle diameter of the component (E) is not particularly limited, and may be set to 0.01 μm or more. In addition, the average particle diameter of the component (E) is set to D ₅₀ by a laser diffraction type particle size distribution measuring apparatus in a state in which the component (E) is dispersed in the uncured photosensitive resin composition. To carry out the measurement.

The carboxyl group-containing resin (A1) is more specifically described. In order to synthesize the carboxyl group-containing resin (A1), first, an epoxy group (refer to the formula (2)) of at least a part of the epoxy compound (a1) is reacted with the unsaturated group-containing carboxylic acid (a2) to thereby synthesize an intermediate. . The intermediate has a structure (S3) represented by the following formula (3) which is produced by a ring-opening addition reaction of an epoxy group with an unsaturated group-containing carboxylic acid (a2). That is, the intermediate has a secondary hydroxyl group in the structure (S3) which is produced by a ring-opening addition reaction of an epoxy group with an unsaturated group-containing carboxylic acid (a2). In the formula (3), A is an unsaturated group-containing carboxylic acid residue.

The secondary hydroxyl group in the intermediate is then reacted with an anhydride. Thereby, the carboxyl group-containing resin (A1) can be synthesized.

The acid anhydride may contain at least one of acid dianhydride (a3) and monoanhydride (a4). When the acid anhydride contains the acid monoanhydride (a4), the carboxyl group-containing resin (A1) has a bisphenol fluorene skeleton (S1) represented by the formula (1) and a structure (S4) represented by the following formula (4).

The structure (S4) is produced by reacting a secondary hydroxyl group in the structure (S3) of the intermediate with an acid anhydride group in the acid monoanhydride (a4). In the formula (4), A is an unsaturated group-containing carboxylic acid residue, and B is an acid mono-anhydride residue.

When the acid anhydride contains the acid dianhydride (a3), the carboxyl group-containing resin (A1) has a bisphenol fluorene skeleton (S1) and a structure (S5) represented by the following formula (5).

The structure (S5) is produced by reacting two acid anhydride groups in the acid dianhydride (a3) with two secondary hydroxyl groups in the intermediate. That is, the structure (S5) is produced by crosslinking two secondary hydroxyl groups with each other by acid dianhydride (a3). Furthermore, there may be a case where two secondary hydroxyl groups present in one molecule of the intermediate are cross-linked to each other, and two secondary hydroxyl groups respectively present in the intermediate of two molecules are cross-linked to each other. The situation. If two secondary hydroxyl groups respectively present in the intermediate of two molecules are cross-linked to each other, the molecular weight increases. In the formula (5), A is an unsaturated group-containing carboxylic acid residue, and D is an acid dianhydride residue.

The secondary hydroxyl group in the intermediate can be reacted with an acid anhydride to obtain a carboxyl group-containing resin (A1). When the acid anhydride contains acid dianhydride (a3) and acid monoanhydride (a4), a part of the secondary hydroxyl group in the intermediate is reacted with the acid dianhydride (a3), and the secondary hydroxyl group in the intermediate is made. Another part of the reaction with the acid monoanhydride (a4). Thereby, the carboxyl group-containing resin (A1) can be synthesized. At this time, the carboxyl group-containing resin (A1) has a bisphenol fluorene skeleton (S1), a structure (S4), and a structure (S5).

The carboxyl group-containing resin (A1) may further have a structure (S6) represented by the following formula (6). The structure (S6) is produced by reacting only one of the two acid anhydride groups in the acid dianhydride (a3) with the secondary hydroxyl group in the intermediate. In the formula (6), A is an unsaturated group-containing carboxylic acid residue, and D is an acid dianhydride residue.

When the intermediate is synthesized, when a part of the epoxy group in the epoxy compound (a1) is left unreacted, the carboxyl group-containing resin (A1) may have a structure (S2) as shown in the formula (2). base. Further, when a part of the structure (S3) in the intermediate remains without reaction, the carboxyl group-containing resin (A1) may have a structure (S3).

When the acid anhydride contains acid dianhydride (a3), the number of structures (S2) and structures (S6) in the carboxyl group-containing resin (A1) is reduced by optimizing the reaction conditions for synthesizing the carboxyl group-containing resin (A1). Or the structure (S2) and the structure (S6) are substantially removed from the carboxyl group-containing resin (A1).

As described above, the carboxyl group-containing resin (A1) may have a bisphenol fluorene skeleton (S1), and may have a structure (S4) when the acid anhydride contains the acid monoanhydride (a4), and when the acid anhydride contains the acid dianhydride (a3) It may have a structure (S5). Further, when the acid anhydride contains the acid monoanhydride (a4), the carboxyl group-containing resin (A1) sometimes has at least one of the structure (S2) and the structure (S3). Further, when the acid anhydride contains the acid dianhydride (a3), the carboxyl group-containing resin (A1) may have at least one of the structure (S2) and the structure (S6). Further, when the acid anhydride contains the acid monoanhydride (a4) and the acid dianhydride (a3), the carboxyl group-containing resin (A1) sometimes has at least one of (S2), structure (S3), and structure (S6).

Further, when the epoxy compound (a1) itself has a secondary hydroxyl group, that is, for example, when n=1 or more in the following formula (7), the carboxyl group-containing resin (A1) sometimes has an epoxy group. A structure produced by reacting a secondary hydroxyl group in the compound (a1) with an acid anhydride.

Further, the structure of the carboxyl group-containing resin (A1) is rationally derived based on technical common sense, and in reality, the structure of the carboxyl group-containing resin (A1) cannot be specified by analysis. The reason is as follows. When the epoxy compound (a1) itself has a secondary hydroxyl group (for example, when n is 1 or more in the formula (7)), the carboxyl group-containing resin (A1) differs depending on the amount of the secondary hydroxyl group in the epoxy compound (a1). The structure of the ) will vary greatly. Further, when the intermediate is reacted with the acid dianhydride (a3), as described above, there may be a case where the two secondary hydroxyl groups present in one molecule of the intermediate are cross-linked by the acid dianhydride (a3). In the case, the two secondary hydroxyl groups present in the two molecules in the intermediate are crosslinked by the acid dianhydride (a3), respectively. Therefore, the carboxyl group-containing resin (A1) finally obtained contains a plurality of molecules having different structures from each other, and thus even if the carboxyl group-containing resin (A1) is analyzed, the structure cannot be specified.

The carboxyl group-containing resin (A1) has photoreactivity because it has an ethylenically unsaturated group derived from the unsaturated group-containing carboxylic acid (a2). Therefore, the carboxyl group-containing resin (A1) can impart photosensitivity (specifically, ultraviolet curability) to the photosensitive resin composition. Further, the carboxyl group-containing resin (A1) can be composed of a photosensitive resin because it has a carboxyl group derived from an acid anhydride. The material imparts developability based on an aqueous alkaline solution containing at least one of an alkali metal salt and an alkali metal hydroxide. Further, when the acid anhydride contains the acid dianhydride (a3), the molecular weight of the carboxyl group-containing resin (A1) depends on the number of bridging by the acid dianhydride (a3). Therefore, the carboxyl group-containing resin (A1) whose acid value and molecular weight are appropriately adjusted can be obtained. When the acid anhydride contains the acid dianhydride (a3) and the acid monoanhydride (a4), by controlling the amounts of the acid dianhydride (a3) and the acid monoanhydride (a4), and the acid monoanhydride (a4) relative to the acid dianhydride ( The amount of a3) can easily obtain a carboxyl group-containing resin (A1) having a desired molecular weight and acid value.

The weight average molecular weight of the carboxyl group-containing resin (A1) is preferably in the range of 700 to 10,000. When the weight average molecular weight is 700 or more, the viscosity of the film formed of the photosensitive resin composition can be further suppressed, and the insulation reliability and plating resistance of the cured product can be further improved. Moreover, when the weight average molecular weight is 10,000 or less, the developability by the alkaline aqueous solution of the photosensitive resin composition can be particularly improved. The weight average molecular weight is further preferably in the range of 900 to 8,000, particularly preferably in the range of 1,000 to 5,000.

The solid content acid value of the carboxyl group-containing resin (A1) is preferably in the range of 60 to 140 mgKOH/g. In this case, the developability of the photosensitive resin composition can be particularly improved. The solid content acid value is more preferably in the range of 80 to 135 mgKOH/g, still more preferably in the range of 90 to 130 mgKOH/g.

The weight average molecular weight (Mw) of the carboxyl group-containing resin (A1) is determined by colloidal permeation chromatography (Gel Permeation) The results of the molecular weight measurement performed by Chromatography, GPC) were calculated. The molecular weight measurement by colloidal osmosis chromatography can be carried out, for example, under the following conditions.

GPC device: manufactured by Showa Denko, trade name: SHODEX SYSTEM 11; pipe column: SHODEX KF-800P, KF-005, KF-003, KF-001 4 tube series; mobile phase: Tetrahydrofuran (THF); flow : 1 ml / min; column temperature: 45 ° C; detector: refractive index (RI) detector; conversion: polystyrene.

The raw material of the carboxyl group-containing resin (A1) and the reaction conditions when the carboxyl group-containing resin (A1) is synthesized will be described in detail.

The epoxy compound (a1) has a structure (S7) represented by the following formula (7), for example. n in the formula (7) is, for example, a number in the range of 0 to 20. In order to make the molecular weight of the carboxyl group-containing resin (A1) an appropriate value, the average of n is particularly preferably in the range of 0 to 1. If the average of n is in the range of 0 to 1, especially when the acid anhydride contains acid dianhydride (a3), it is easy to suppress an excessive molecular weight increase due to the addition of the acid dianhydride (a3).

The unsaturated carboxylic acid (a2) may contain, for example, a compound having only one ethylenically unsaturated group in one molecule. More specifically, the unsaturated group-containing carboxylic acid (a2) may contain, for example, at least one compound selected from the group consisting of acrylic acid, methacrylic acid, and ω-carboxy-polycaprolactone (n≒). 2) monoacrylate, crotonic acid, cinnamic acid, succinic acid mono(2-propenyl methoxyethyl) ester, succinic acid mono(2-methylpropenyl oxyethyl) ester, phthalic acid mono ( 2-propenyl methoxyethyl) ester, mono(2-methylpropenyl oxyethyl) phthalate, mono(2-propenyl methoxypropyl) phthalate, o-phenyl phthalate Mono(2-methylpropenyloxypropyl)carboxylate, mono(2-propenyloxyethyl) maleate, mono(2-methylpropenyloxyethyl) maleate, Β-carboxyethyl acrylate, mono(2-propenyl methoxyethyl) tetrahydrophthalate, mono(2-methylpropenyl oxyethyl) tetrahydrophthalate, hexahydroortho Mono(2-propenyl methoxyethyl) phthalate, and mono(2-methylpropenyl oxyethyl) hexahydrophthalate. The unsaturated carboxylic acid (a2) preferably contains acrylic acid.

When the epoxy compound (a1) and the unsaturated group-containing carboxylic acid (a2) are reacted, a known method can be employed. For example, an unsaturated group-containing carboxylic acid (a2) is added to a solvent solution of the epoxy compound (a1), and a thermal polymerization inhibitor and a catalyst are further added as needed, and stirred and mixed. A reactive solution is obtained. The reactive solution can be preferably reacted at a temperature of from 60 to 150 ° C by a conventional method, and it is particularly preferred to carry out the reaction at a temperature of from 80 to 120 ° C to obtain an intermediate. The solvent may contain, for example, at least one component selected from the group consisting of ketones such as methyl ethyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene and xylene; ethyl acetate and butyl acetate; , acetic acid such as cellosolve acetate, butyl cyproterone acetate, carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether acetate, etc. Esters; and, dialkyl glycol ethers. The thermal polymerization inhibitor may contain, for example, at least one of hydroquinone and hydroquinone monomethyl ether. The catalyst may contain, for example, at least one component selected from the group consisting of tertiary amines such as benzyldimethylamine and triethylamine; trimethylbenzylammonium chloride, A a quaternary ammonium salt such as triethylammonium chloride; triphenylphosphine; and triphenyl stibine.

In particular, it is preferred that the catalyst contains triphenylphosphine. That is, it is preferred 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 of the epoxy group in the epoxy compound (a1) with the unsaturated group-containing carboxylic acid (a2) can be particularly promoted, and a reaction of 95% or more, 97% or more, or approximately 100% can be achieved. Rate (conversion rate). Therefore, an intermediate having the structure (S3) can be obtained in a high yield. Further, in the layer containing the cured product of the photosensitive resin composition, the occurrence of ion migration can be suppressed, and the insulation reliability of the layer can be further improved.

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) is 1 mol of the epoxy group of the epoxy compound (a1). Preferably, it is in the range of 0.8 to 1.2 moles. At this time, a photosensitive resin composition having excellent photosensitivity and storage stability can be obtained.

It is also preferred to react the epoxy compound (a1) with the unsaturated group-containing carboxylic acid (a2) in a state in which bubbles are generated. At this time, since the addition polymerization reaction of the unsaturated group can be suppressed, the increase in the molecular weight of the intermediate and the gelation of the solution of the intermediate can be suppressed. Further, excessive coloring of the final product, that is, the carboxyl group-containing resin (A1) can be suppressed.

The intermediate obtained in such a manner has a hydroxyl group which is produced by a reaction of an epoxy group of the epoxy compound (a1) with a carboxyl group of the unsaturated group-containing carboxylic acid (a2).

The acid dianhydride (a3) is a compound having two acid anhydride groups. The acid dianhydride (a3) may contain an acid anhydride of a tetracarboxylic acid. The acid dianhydride (a3) may contain, for example, at least one compound selected from the group consisting of 1,2,4,5-benzenetetracarboxylic dianhydride, diphenyl ketone tetracarboxylic dianhydride, methyl Cyclohexene tetracarboxylic dianhydride, tetracarboxylic dianhydride, naphthalene-1,4,5,8-tetracarboxylic dianhydride, ethylene tetracarboxylic dianhydride, 9,9'-bis(3,4-dicarboxyphenyl) Sebacic anhydride, glycerol bis(hydrogen trimellitate) monoacetate, ethylene glycol bis(hydrogen trimellitate), 3,3',4,4'-diphenylphosphonium tetracarboxylic dianhydride 1,3,3a,4,5,9b-hexahydro-5(tetrahydro-2,5-di-oxy-3-furanyl)naphtho[1,2-c]furan-1,3- Diketone, 1,2,3,4-butanetetracarboxylic dianhydride, and 3,3',4,4'-biphenyltetracarboxylic dianhydride. In particular, it is preferably acid The dianhydride (a3) contains 3,3',4,4'-biphenyltetracarboxylic dianhydride. That is, it is preferred that D in the formula (5) and the formula (6) contains a 3,3',4,4'-biphenyltetracarboxylic dianhydride residue. In this case, the good developability of the photosensitive resin composition can be ensured, and the viscosity of the film formed of the photosensitive resin composition can be further suppressed, and the insulation reliability and plating resistance of the cured product can be further improved. The amount of 3,3',4,4'-biphenyltetracarboxylic dianhydride is preferably in the range of 20 to 100 mol%, more preferably 40 to 100, based on the total of the acid dianhydride (a3). Moore% is within the scope, but is not limited to these ranges.

The acid monoanhydride (a4) is a compound having one acid anhydride group. The acid monoanhydride (a4) may contain an acid anhydride of a dicarboxylic acid. The acid monoanhydride (a4) may contain, for example, at least one compound selected from the group consisting of phthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, methyl four. Hydrogen phthalic anhydride, methyl nadic acid anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, succinic anhydride, methyl succinic anhydride, maleic anhydride, lemon Tonic anhydride, glutaric anhydride, cyclohexane-1,2,4-tricarboxylic acid-1,2-anhydride, and itaconic anhydride. In particular, it is preferred that the acid monoanhydride (a4) contains 1,2,3,6-tetrahydrophthalic anhydride. That is, it is preferred that the acid anhydride contains 1,2,3,6-tetrahydrophthalic anhydride. That is, it is preferred that the carboxyl group-containing resin (A1) has a structure (S4), and B in the formula (4) contains a 1,2,3,6-tetrahydrophthalic anhydride residue. In this case, the good developability of the photosensitive resin composition can be ensured, and the viscosity of the film formed of the photosensitive resin composition can be further suppressed, and the insulation reliability and plating resistance of the cured product can be further improved. The amount of 1,2,3,6-tetrahydrophthalic anhydride relative to the acid monoanhydride (a4) as a whole is preferably The range of 20 to 100 mol% is more preferably in the range of 40 to 100 mol%, but is not limited to these ranges.

When the intermediate is reacted with an acid anhydride, a known method can be employed. For example, an acid anhydride is added to a solvent solution of an intermediate, and a thermal polymerization inhibitor and a catalyst are further added as needed, and stirred and mixed, whereby a reactive solution is obtained. The reactive solution can be reacted at a temperature of 60 to 150 ° C by a conventional method, and it is particularly preferable to carry out the reaction at a temperature of 80 to 120 ° C to obtain a carboxyl group-containing resin (A1). ). As the solvent, catalyst, and polymerization inhibitor, a suitable solvent, catalyst, and polymerization inhibitor can be used, and a solvent, a catalyst, and a polymerization inhibitor used in the synthesis of the intermediate can be used as it is.

In particular, it is preferred that the catalyst contains triphenylphosphine. That is, it is preferred to react the intermediate with an acid anhydride in the presence of triphenylphosphine. In this case, the reaction of the secondary hydroxyl group and the acid anhydride in the intermediate can be particularly promoted, and a reaction rate (conversion ratio) of 90% or more, 95% or more, 97% or more, or approximately 100% can be achieved. Therefore, the carboxyl group-containing resin (A1) having at least one of the structures (S4) and (S5) can be obtained in a high yield. Further, in the layer containing the cured product of the photosensitive resin composition, the occurrence of ion migration can be suppressed, and the insulation reliability of the layer can be further improved.

When the acid anhydride contains the acid dianhydride (a3) and the acid monoanhydride (a4), the amount of the acid dianhydride (a3) is preferably 0.05% with respect to 1 mol of the epoxy group of the epoxy compound (a1). Within 0.24 moles. Further, the amount of the acid monoanhydride (a4) is preferably 1 mol of the epoxy group of the epoxy compound (a1). It is in the range of 0.3~0.7 m. At this time, the carboxyl group-containing resin (A1) whose acid value and molecular weight are appropriately adjusted can be easily obtained.

The carboxyl group-containing resin (A) may contain only the carboxyl group-containing resin (A1), and may further contain a carboxyl group-containing resin (hereinafter also referred to as a carboxyl group-containing resin (F)) other than the carboxyl group-containing resin (A1).

The carboxyl group-containing resin (F) may contain, for example, a compound having a carboxyl group but not having photopolymerization (hereinafter referred to as a component (F1)). The component (F1) contains a polymer such as an ethylenically unsaturated monomer, and the ethylenically unsaturated monomer contains an ethylenically unsaturated compound having a carboxyl group. The ethylenically unsaturated compound having a carboxyl group may contain the following compounds: acrylic acid, methacrylic acid, ω-carboxy-polycaprolactone (n≒2) monoacrylate, and the like. The ethylenically unsaturated compound having a carboxyl group may further contain a reaction product with a dibasic acid anhydride such as pentaerythritol triacrylate or pentaerythritol trimethacrylate. The ethylenically unsaturated monomer may further contain the following ethylenically unsaturated compound having no carboxyl group: 2-(meth)acryloxyethyl phthalate, 2-(methyl) propylene phthalate A (meth) acrylate or the like which is a methoxyethyl 2-hydroxyethyl ester, a linear or branched aliphatic or alicyclic group in which a ring may have a part of an unsaturated bond.

The carboxyl group-containing resin (F) may contain a compound having a carboxyl group and an ethylenically unsaturated group (hereinafter referred to as a component (F2)). Further, the carboxyl group-containing resin (F) may contain only the component (F2). a component (F2) containing a resin (hereinafter referred to as a first resin (g)), which is, for example, a reaction product of an intermediate with at least one compound (g3) selected from the group consisting of polycarboxylic acids and anhydrides thereof, The intermediate is an epoxidation having two or more epoxy groups in one molecule. The reactant of the compound (g1) and the ethylenically unsaturated compound (g2). The first resin (g), for example, can be obtained by reacting an epoxy group in the epoxy compound (g1) with a carboxyl group in the ethylenically unsaturated compound (g2), and then adding the compound (g3) to the obtained intermediate. . The epoxy compound (g1) may contain an appropriate epoxy compound: a cresol novolak type epoxy compound, a phenol novolak type epoxy compound, a biphenol novolak type epoxy compound, and the like. In particular, the epoxy compound (g1) preferably contains at least one compound selected from the group consisting of a biphenol novolak type epoxy compound and a cresol novolak type epoxy compound. The epoxy compound (g1) may contain only a biphenol novolak type epoxy compound, or may contain only a cresol novolak type epoxy compound. At this time, since the aromatic ring is contained in the main chain of the epoxy compound (g1), the cured product of the photosensitive resin composition is remarkably hard to be corroded by the oxidizing agent. The epoxy compound (g1) may contain a polymer of the ethylenically unsaturated compound (h). The ethylenically unsaturated compound (h) contains an epoxy group-containing compound (h1) such as glycidyl (meth)acrylate or further contains 2-(methyl)propenyloxyethyl phthalate. The compound (h2) which does not have an epoxy group. The ethylenically unsaturated compound (g2) preferably contains at least one of acrylic acid or methacrylic acid. The compound (g3) contains, for example, one or more compounds selected from the group consisting of polycarboxylic acids such as phthalic acid, tetrahydrophthalic acid, and methyltetrahydrophthalic acid; Anhydrides of these polycarboxylic acids. In particular, the compound (g3) preferably contains at least one polycarboxylic acid selected from the group consisting of phthalic acid, tetrahydrophthalic acid, and methyltetrahydrophthalic acid.

The component (F2) may further contain a resin (referred to as a second resin (i)) which is a reactant of a polymer of an ethylenically unsaturated monomer and an ethylenically unsaturated compound having an epoxy group, the ethylene The unsaturated monomer contains an ethylenically unsaturated compound having a carboxyl group. The ethylenically unsaturated monomer may further contain an ethylenically unsaturated compound having no carboxyl group. The second resin (i) can be obtained by reacting an ethylenically unsaturated compound having an epoxy group with a part of carboxyl groups in the polymer. The ethylenically unsaturated monomer may further contain an ethylenically unsaturated compound having no carboxyl group. An ethylenically unsaturated compound having a carboxyl group, for example, the following compounds: acrylic acid, methacrylic acid, ω-carboxy-polycaprolactone (n≒2) monoacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, etc. . An ethylenically unsaturated compound having no carboxyl group, and containing, for example, the following compound: 2-(methyl)propenyloxyethyl phthalate, 2-(methyl)propenyloxyethyl phthalate- 2-hydroxyethyl ester, a linear or branched aliphatic or alicyclic (wherein the ring may have a part of an unsaturated bond) (meth) acrylate or the like. The ethylenically unsaturated compound having an epoxy group preferably contains glycidyl (meth)acrylate.

The carboxyl group-containing resin (A) contains only the carboxyl group-containing resin (A1) or the carboxyl group-containing resin (A1) and the carboxyl group-containing resin (F). The carboxyl group-containing resin (A) preferably contains 30% by mass or more, more preferably 50% by mass or more, and still more preferably 100% by mass of the carboxyl group-containing resin (A1). In this case, the heat resistance and insulation reliability of the cured product of the photosensitive resin composition can be particularly improved. Also, can be sufficiently reduced by the photosensitive tree The viscosity of the film formed by the lipid composition. Further, the developability based on the alkaline aqueous solution of the photosensitive resin composition can be ensured.

As described above, the photosensitive resin composition contains a carboxyl group-containing resin (A), an unsaturated compound (B) having at least one ethylenically unsaturated bond in one molecule, and a photopolymerization initiator (C). Epoxy compound (D) and component (E).

The unsaturated compound (B) can impart photocurability to the photosensitive resin composition. The unsaturated compound (B) may contain, for example, at least one compound selected from the group consisting of: a monofunctional (meth) acrylate such as 2-hydroxyethyl (meth)acrylate; and, Alcohol di(meth)acrylate, trimethylolpropane di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(methyl) Acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, ε-caprolactone modified pentaerythritol hexaacrylate, tricyclodecane dimethanol di(meth) acrylate, etc. Functional (meth) acrylate.

In particular, the unsaturated compound (B) preferably contains a trifunctional compound, that is, a compound having three unsaturated bonds in one molecule. In this case, when the film formed of the photosensitive resin composition is exposed and developed, the resolution can be improved, and the developability of the photosensitive resin composition based on the alkaline aqueous solution can be particularly improved. The trifunctional compound may contain, for example, at least one compound selected from the group consisting of trimethylolpropane tri(meth)acrylate, EO-modified trimethylolpropane tri(meth)acrylate , pentaerythritol tri(meth) acrylate, ethoxylated Tris(meth)acrylate, ε-caprolactone modified ginseng (2-propenyloxyethyl)isocyanate, and ethoxylated glycerol tri(meth)acrylate .

The unsaturated compound (B) preferably also contains a phosphorus-containing compound (phosphorus-containing unsaturated compound). At this time, the flame retardancy of the cured product of the photosensitive resin composition can be improved. The phosphorus-containing unsaturated compound may contain, for example, at least one compound selected from the group consisting of 2-methylpropenyloxyethyl phosphate (as a specific example, manufactured by Kyoeisha Chemical Co., Ltd.) Product type LIGHT ESTER P-1M, and LIGHT ESTER P-2M), 2-propenyl methoxyethyl phosphate (as a specific example, the product model LIGHT ACRYLATE P-1A manufactured by Kyoeisha Chemical Co., Ltd.), Diphenyl-2-methylpropenyloxyethyl phosphate (as a specific example, the product model MR-260 manufactured by Daihatsu Industrial Co., Ltd.) and the HFA series manufactured by Showa Polymer Co., Ltd. For example, the addition reaction of dipentaerythritol hexaacrylate with HCA (9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide) is also available in the product models HFA-6003 and HFA-6007. The addition reaction of caprolactone-modified dipentaerythritol hexaacrylate with HCA (9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide) is also the product model HFA-3003 and HFA. -6127, etc.).

The unsaturated compound (B) may contain a prepolymer. The prepolymer may contain, for example, at least one compound selected from the group consisting of polymerizing a monomer having an ethylenically unsaturated bond and then adding an ethylenically unsaturated group. And, oligo(meth)acrylic acid Ester prepolymers. The oligomeric (meth) acrylate prepolymer may contain, for example, at least one component selected from the group consisting of epoxy (meth) acrylate, polyester (meth) acrylate, Amine ester (meth) acrylate, alkyd resin (meth) acrylate, oxime resin (meth) acrylate, and spirane resin (meth) acrylate.

The photopolymerization initiator (C) contains, for example, a fluorenylphosphine oxide-based photopolymerization initiator (C1). In other words, the photosensitive resin composition contains, for example, a fluorenylphosphine oxide-based photopolymerization initiator (C1). In this case, although the photosensitive resin composition contains the carboxyl group-containing resin (A1), it is possible to impart high sensitivity to ultraviolet light to the photosensitive resin composition. Further, the occurrence of ion migration is suppressed in the layer containing the cured product of the photosensitive resin composition, and the insulation reliability of the layer is further improved.

Further, the fluorenylphosphine oxide-based photopolymerization initiator (C1) is less likely to interfere with the electrical insulation of the cured product. Therefore, by subjecting the photosensitive resin composition to exposure curing, a cured product excellent in electrical insulating properties can be obtained, and the cured product is suitable as, for example, a solder resist layer, a plating resist layer, an etch resist layer, and an interlayer insulating layer.

The fluorenylphosphine oxide-based photopolymerization initiator (C1) may contain, for example, at least one component selected from the group consisting of 2,4,6-trimethylbenzylidene-diphenyl- Monodecylphosphine oxide photopolymerization initiator such as phosphine oxide, 2,4,6-trimethylbenzimidyl-phenyl-phosphonic acid ethyl ester; and, bis-(2,6-dichlorobenzene) Mercapto) phenylphosphine oxide, bis-(2,6-dichlorobenzhydryl)-2,5-dimethylphenylphosphine oxide, bis-(2,6-dichlorobenzhydryl)- 4-propylphenylphosphine oxide, bis-(2,6-dichlorobenzylidene)-1- Naphthylphosphine oxide, bis-(2,6-dimethoxybenzylidene)phenylphosphine oxide, bis-(2,6-dimethoxybenzylidene)-2,4,4-tri Methyl amyl phosphine oxide, bis-(2,6-dimethoxybenzylidene)-2,5-dimethylphenylphosphine oxide, bis-(2,4,6-trimethylbenzene A bis-indenylphosphine oxide-based photopolymerization initiator such as phenylphosphine oxide or (2,5,6-trimethylbenzylidene)-2,4,4-trimethylpentylphosphine oxide. In particular, it is preferred that the fluorenylphosphine oxide-based photopolymerization initiator (C1) contains 2,4,6-trimethylbenzylidene-diphenyl-phosphine oxide, and is preferably a fluorenylphosphine oxide-based light. The polymerization initiator (C1) contains only 2,4,6-trimethylbenzimidyl-diphenyl-phosphine oxide.

The photopolymerization initiator (C) preferably contains a hydroxyketone-based photopolymerization initiator (C2) in addition to the fluorenylphosphine oxide-based photopolymerization initiator (C1). That is, the photosensitive resin composition preferably contains a hydroxyketone-based photopolymerization initiator (C2). In this case, it is possible to impart further high photosensitivity to the photosensitive resin composition as compared with the case where the hydroxyketone-based photopolymerization initiator (C2) is not contained. As a result, when the coating film formed of the photosensitive resin composition is irradiated with ultraviolet rays to be cured, the coating film can be sufficiently cured from the surface to the deep portion. Examples of the hydroxyketone-based photopolymerization initiator (C2) include 1-hydroxy-cyclohexyl-phenyl-ketone, methyl phenylglyoxylate, and 1-[4-(2-hydroxyethoxy). -phenyl]-2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propenyl)-benzene Methyl]phenyl}-2-methyl-propan-1-one, and 2-hydroxy-2-methyl-1-phenyl-propan-1-one.

The mass ratio of the fluorenylphosphine oxide photopolymerization initiator (C1) to the hydroxyketone photopolymerization initiator (C2) is preferably from 1:0.01 to 1: Within the scope of 10. In this case, the hardenability in the vicinity of the surface of the coating film formed of the photosensitive resin composition and the hardenability in the deep portion can be uniformly adjusted.

The photopolymerization initiator (C) preferably also contains bis(diethylamino)diphenyl ketone (C3). In other words, the photosensitive resin composition preferably contains a fluorenylphosphine oxide-based photopolymerization initiator (C1) and bis(diethylamino)diphenyl ketone (C3), or a photosensitive resin composition. A fluorenylphosphine oxide-based photopolymerization initiator (C1), a hydroxyketone-based photopolymerization initiator (C2), and bis(diethylamino)diphenyl ketone (C3) are contained. At this time, when the coating film formed of the photosensitive resin composition is partially exposed and developed, the hardening of the portion which is not exposed is suppressed, so that the resolution is particularly high. Therefore, it is possible to form a cured product of the photosensitive resin composition having a very fine pattern. In particular, when an interlayer insulating layer of a multilayer printed wiring board is produced from a photosensitive resin composition, and a hole having a small diameter for a through hole is provided in the interlayer insulating layer by photolithography (see FIG. 1) It is possible to form a hole with a small diameter precisely and easily.

The amount of bis(diethylamino)diphenyl ketone (C3) is preferably in the range of 0.5 to 20% by mass based on the fluorenylphosphine oxide-based photopolymerization initiator (C1). When the amount of bis(diethylamino)diphenyl ketone (C3) is 0.5% by mass or more with respect to the fluorenylphosphine oxide-based photopolymerization initiator (C1), the resolution is particularly high. Further, with respect to the fluorenylphosphine oxide-based photopolymerization initiator (C1), if bis(diethylamino)diphenyl ketone (C3) When the amount is 20% by mass or less, bis(diethylamino)diphenyl ketone (C3) is less likely to interfere with the electrical insulating properties of the cured product of the photosensitive resin composition.

The photosensitive resin composition may further contain a known photopolymerization accelerator, a sensitizer, or the like. The photosensitive resin composition may contain, for example, at least one component selected from the group consisting of benzoin and its alkyl ethers; acetophenones such as acetophenone and benzoin dimethyl ketal; - anthracene such as methyl hydrazine; 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, a thioxanthone such as 2,4-diisopropylthioxanthone; a diphenyl ketone such as diphenyl ketone or 4-benzylidene-4'-methyldiphenyl sulfide; , xanthone such as 4-diisopropyldibenzopiperidone; and α-hydroxyl group such as 2-hydroxy-2-methyl-1-phenyl-propan-1-one a ketone; a compound containing a nitrogen atom such as 2-methyl-1-[4-(methylthio)phenyl]-2-(N-morpholinyl)-1-propanone. The photosensitive resin composition may contain, in addition to the photopolymerization initiator (C), ethyl p-dimethylbenzoate, p-dimethylamino benzoic acid isoamyl ester, and 2-dimethylamino benzoate. A known photopolymerization accelerator or sensitizer such as a tertiary amine such as ethyl ester. 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, as needed. The photosensitive resin composition may contain, in addition to the photopolymerization initiator (C), a sensitizer for laser exposure, that is, coumarin such as 7-diethylamino-4-methylcoumarin A derivative, a carbocyanine pigment, a xanthene pigment, or the like.

The epoxy compound (D) can impart thermosetting properties to the photosensitive resin composition. The epoxy compound (D) preferably contains a crystalline epoxy resin. At this time, the developability of the photosensitive resin composition can be improved. Further, the epoxy compound (D) may further contain an amorphous epoxy resin. Here, the "crystalline epoxy resin" is an epoxy resin having a melting point, and the "amorphous epoxy resin" is an epoxy resin having no melting point.

The crystalline epoxy resin preferably contains, for example, one or more components selected from the group consisting of 1,3,5-gin(2,3-epoxypropyl)-1,3,5. - Triazine-2,4,6(1H,3H,5H)-trione, hydroquinone-type crystalline epoxy resin (as a specific example, trade name YDC-1312 manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd.), Biphenyl type crystalline epoxy resin (trade name: YX-4000, manufactured by Mitsubishi Chemical Corporation), and diphenyl ether type crystalline epoxy resin (for specific example, Nippon Steel & Sumitomo Chemical Co., Ltd.) Manufactured product model YSLV-80DE), bisphenol type crystalline epoxy resin (for example, YSLV-80XY, manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd.), bismuth (hydroxyphenyl) ethane type crystallinity An epoxy resin (a specific example, a product model GTR-1800 manufactured by Nippon Kayaku Co., Ltd.) and a bisphenol fluorene-type crystalline epoxy resin (a specific example, an epoxy resin having a structure (S7)).

The crystalline epoxy resin preferably has two epoxy groups in one molecule.

The crystalline epoxy resin preferably has an epoxy equivalent of from 150 to 300 g/eq. The epoxy equivalent is a ring containing 1 gram equivalent The gram weight of the crystalline epoxy resin of the oxy group. The crystalline epoxy resin has a melting point. The melting point of the crystalline epoxy resin is, for example, 70 to 180 °C.

In particular, the epoxy compound (D) preferably contains a crystalline epoxy resin having a melting point of 110 ° C or lower. At this time, the developability based on the alkaline aqueous solution of the photosensitive resin composition is particularly improved. The crystalline epoxy resin having a melting point of 110 ° C or less may contain, for example, at least one component selected from the group consisting of biphenyl type epoxy resins (for example, a product model YX manufactured by Mitsubishi Chemical Corporation) -4000), diphenyl ether type epoxy resin (as a specific example, the product model YSLV-80DE manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd.), and bisphenol type epoxy resin (as a specific example, Nippon Steel & Sumitomo Metal Co., Ltd. The product model YSLV-80XY manufactured by Chemical Co., Ltd., and the bisphenol fluorene-type crystalline epoxy resin (for example, an epoxy resin having a structure (S7)).

The amorphous epoxy resin may contain, for example, at least one component selected from the group consisting of phenol novolak-type epoxy resins (as a specific example, the product model EPICLON N-775 manufactured by DIC Corporation) , a cresol novolak type epoxy resin (a specific example, a product model EPICLON N-695 manufactured by DIC Corporation), and a bisphenol A novolak type epoxy resin (as a specific example, a product model manufactured by DIC Corporation) EPICLON N-865), a bisphenol A type epoxy resin (a specific example, a product model jER1001 manufactured by Mitsubishi Chemical Corporation), and a bisphenol F type epoxy resin (a product manufactured by Mitsubishi Chemical Corporation as a specific example) model jER4004P), bisphenol S-type epoxy resin (as a specific example, product model EPICLON EXA-1514 manufactured by DIC Corporation), bisphenol AD type epoxy resin, and biphenyl novolac type epoxy resin (as a specific example, Nippon Chemical Co., Ltd. product type NC-3000), hydrogenated bisphenol A type epoxy resin (as a specific example, product model ST-4000D manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd.), naphthalene type epoxy resin (As a specific example, the product type EPICLON HP-4032, EPICLON HP-4700, EPICLON HP-4770 manufactured by DIC Corporation), and the tertiary butyl catechol type epoxy resin (as a specific example, DIC Corporation) The manufactured product model EPICLON HP-820), the dicyclopentadiene type epoxy resin (as a specific example, the product model EPICLON HP-7200 manufactured by DIC Corporation), and the adamantane type epoxy resin (as a specific example, Product model: ADAMANTATE XE-201), special bifunctional epoxy resin (as a specific example, the product model YL7175-500 and YL7175-1000 manufactured by Mitsubishi Chemical Corporation; DIC Co., Ltd. EPICLON TSR-960, EPICLON TER-601, EPICLON TSR-250-80BX, EPICLON 1650-75MPX, EPICLON EXA-4850, EPICLON EXA-4816, EPICLON EXA-4822, and EPICLON EXA-9726 manufactured by the company; Product model YSLV-120TE manufactured by Tiejinjin Chemical Co., Ltd., rubber-like core-shell polymer modified bisphenol A epoxy resin (as a specific example, the product model manufactured by Zhonghua Co., Ltd. MX-156), rubbery core-shell polymer modified bisphenol F-type epoxy resin (as a specific example, the product model MX-136 manufactured by Chunghua Co., Ltd.), and bisphenol F-type epoxy containing rubber particles Resin (as a specific example, the product model MX-130 manufactured by Chung Ching Co., Ltd.).

The epoxy compound (D) may contain a phosphorus-containing epoxy resin. At this time, the flame retardancy of the cured product of the photosensitive resin composition can be improved. The crystalline epoxy resin may contain a phosphorus-containing epoxy resin, or the amorphous epoxy resin may contain a phosphorus-containing epoxy resin. Phosphorus-containing epoxy resin, for example, phosphoric acid-modified bisphenol F-type epoxy resin (for example, EPICRON EXA-9726 and EPICRON EXA-9710, manufactured by DIC Corporation), Nippon Steel & Sumitomo Chemical Co., Ltd. The company's product model EPOTORT FX-305 and so on.

The photosensitive resin composition of the present embodiment may contain an organic solvent. The organic solvent is used for liquidification or varnishing of a photosensitive resin composition, adjustment of viscosity, adjustment of coatability, adjustment of film formability, and the like.

The organic solvent may contain, for example, at least one compound selected from the group consisting of: linear, branched, quaternary or polyhydric alcohols such as ethanol, propanol, isopropanol, hexanol, ethylene glycol; Ketones such as methyl ethyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene and xylene; Swasol series (manufactured by Maruzen Petrochemical Co., Ltd.), Solvesso series (manufactured by ExxonMobil Chemical Company), etc. Petroleum aromatic mixed solvent; celluloid, such as celecoxib, butyl acesulfame, etc.; carbitol, carbitol, butyl carbitol, etc. a glycol alkyl ether; a polypropylene glycol alkyl ether such as dipropylene glycol methyl ether; an acetate such as ethyl acetate, butyl acetate, celecoxib acetate or carbitol acetate; and a dioxane Glycol ethers.

In the present embodiment, it is preferred that the photosensitive resin composition contains an inorganic filler (K). At this time, the inorganic filler (K) has a tendency to be less corroded by the oxidizing agent than the cured product of the photosensitive resin composition. That is, the cured product of the photosensitive resin composition has a portion on the outer surface which is easily corroded by the oxidizing agent and a portion which is hard to be corroded. Therefore, when the outer surface of the cured product containing the inorganic filler (K) is roughened by the aforementioned oxidizing agent, the surface of the cured product can be appropriately etched by the aforementioned oxidizing agent. Thereby, it is possible to impart a rough surface suitable for the plating treatment to the cured product, and it is possible to improve the adhesion between the cured product and the plating layer.

The inorganic filler (K) may contain, for example, one or more materials selected from the group consisting of barium sulfate, crystalline cerium oxide, nano cerium oxide, carbon nanotube, talc. , bentonite, hydrotalcite, aluminum hydroxide, magnesium hydroxide, and titanium dioxide. When the inorganic filler (K) contains a white material such as titanium oxide or zinc oxide, the photosensitive resin composition and the cured product thereof can be whitened by the white material.

The amount of the inorganic filler (K) in the photosensitive resin composition can be appropriately set. However, the amount of the inorganic filler (K) relative to the carboxyl group-containing resin (A) is preferably in the range of 1 to 300% by mass. It is preferably in the range of 3 to 200% by mass, more preferably in the range of 5 to 100% by mass.

The inorganic filler (K) preferably contains cerium oxide (k). Cerium oxide (k) has a hydroxyl group. This hydroxyl group is considered to be capable of being modified by the aforementioned oxidizing agent. Therefore, it is also possible to impart a rough surface to the surface of the cerium oxide (k) by using the above oxidizing agent. When the oxidizing agent is used to etch the cured product of the photosensitive resin composition, even if the cerium oxide (k) is located in a hard-to-corrode place on the surface of the cured product, the oxidizing agent can be used to moderately corrode the hardly corrodible local. Thereby, it is possible to impart a rough surface which is more suitable for the plating treatment to the cured product, and it is possible to further improve the adhesion between the cured product and the plating layer.

The cerium oxide (k) preferably has an average particle diameter of 1 μm or less. By setting the average particle diameter of the cerium oxide (k) to 1 μm or less, the roughness of the rough surface formed on the cured product can be made fine. Thereby, the surface area of the cured product increases, and in this case, the fixing effect is increased, and the adhesion between the rough surface and the plating layer can be improved. The lower limit of the average particle diameter of the cerium oxide (k) is not particularly limited, and is, for example, preferably 0.001 μm or more. The average particle diameter was measured by a laser diffraction type particle size distribution measuring apparatus and set to D ₅₀ . The average particle diameter of the cerium oxide (k) is more preferably 0.1 μm or less. At this time, the roughness of the rough surface formed on the cured product can be made particularly fine. Further, in the photosensitive resin composition, scattering at the time of exposure can be suppressed, whereby the resolution of the photosensitive resin composition can be further improved.

The inorganic filler (K) contains only cerium oxide (k) or an inorganic filler other than cerium (k) and cerium (k). The inorganic filler (K) preferably contains 30% by mass or more of cerium oxide (k), more preferably It is contained in an amount of 50% by mass or more, and more preferably 100% by mass or more. In this case, the adhesion between the cured product and the plating layer can be particularly improved.

The photosensitive resin composition preferably contains a decane coupling agent. At this time, the dispersibility of the inorganic filler (K) can be improved. Further, the resolution of the photosensitive resin composition can also be improved.

The decane coupling agent is a compound containing a ruthenium atom and containing 2 to 4 hydrolyzable groups selected from the group consisting of -OCH ₃ group, -OC ₂ H ₅ group, and -OCOCH ₃ group. The decane coupling agent may further contain a reactive group such as an amine group, an epoxy group, an ethylene (allyl) group, a methacryl fluorenyl group, a decyl group, an isocyanate group or a thioether group, in addition to the hydrolyzable group. Or methyl.

As the decane coupling agent, for example, 3-(2-aminoethylamino)propyldimethoxymethylnonane, 3-(2-aminoethylamino)propyltriethoxydecane can be cited. , 3-(2-Aminoethylamino)propyltrimethoxydecane, 3-aminopropyldiethoxymethylnonane, 3-aminopropyltriethoxydecane, 3-Amino Amino compound such as propyltrimethoxydecane; 3-glycidoxypropyltrimethoxydecane, 3-glycidoxypropyltriethoxydecane, 2-(3,4-epoxy ring Epoxy such as hexyl)ethyltrimethoxydecane, 3-glycidoxypropyl(dimethoxy)methylnonane, diethoxy(3-glycidoxypropyl)methyldecane 3-propenyloxypropyltrimethoxydecane, 3-methylpropenyloxypropyltrimethoxydecane, 3-methylpropenyloxypropyltriethoxydecane, 3-methylpropene (meth) acrylates such as methoxypropyl methyl dimethoxy decane, 3-methyl propylene methoxy propyl methyl diethoxy decane; vinyl trimethoxy decane, vinyl triethyl Oxydecane, p-styryltrimethoxydecane, diethoxymethyl Vinyl compounds such as vinyl vinyl hydride, vinyl ginseng (2-methoxyethoxy) decane; allyl compounds such as allyl triethoxy decane and allyl trimethoxy decane; p-styryl trimethoxy a styrene compound such as decane; an isocyanate such as 3-isocyanatopropyltrimethoxydecane or 3-isocyanatopropyltriethoxydecane; 3-ureidopropyltrimethoxydecane, 3- Ureas such as ureidopropyltriethoxydecane; hydrazine compounds such as (3-mercaptopropyl)triethoxydecane and (3-mercaptopropyl)trimethoxydecane; bis(triethoxyindenyl) Sulfide such as propyl) tetrasulfide; tetraethyl ortho-decylate; methyltrimethoxydecane.

In the present embodiment, the oxidizing agent may be an oxidizing agent which can be obtained as a desmear liquid. Such an oxidizing agent may contain, for example, at least one permanganate selected from the group consisting of sodium permanganate and potassium permanganate.

The amount of the component in the photosensitive resin composition is appropriately adjusted so that the photosensitive resin composition has photocurability and can be developed by an alkaline solution.

The amount of the carboxyl group-containing resin (A) is preferably in the range of 5 to 85% by mass, more preferably in the range of 10 to 75% by mass, based on the solid content of the photosensitive resin composition. It is further preferably in the range of 30 to 60% by mass.

The amount of the unsaturated compound (B) is preferably in the range of 1 to 50% by mass based on the carboxyl group-containing resin (A), and more preferably in the range of 10 to 45% by mass. Further preferably, it is in the range of 40% by mass.

The amount of the photopolymerization initiator (C) is preferably in the range of 0.1 to 30% by mass based on the carboxyl group-containing resin (A), and more preferably in the range of 1 to 25% by mass.

The amount of the epoxy compound (D) is preferably 0.7 to 2.5 in terms of the equivalent amount of the epoxy group contained in the epoxy compound (D) with respect to 1 equivalent of the carboxyl group contained in the carboxyl group-containing resin (A). The range is preferably in the range of 0.7 to 2.3, and further preferably in the range of 0.7 to 2.0. In addition, the total amount of the epoxy groups contained in the crystalline epoxy resin is preferably in the range of 0.1 to 2.0, and in the range of 0.2 to 1.9, based on 1 equivalent of the carboxyl group contained in the carboxyl group-containing resin (A). The range is more preferably in the range of 0.3 to 1.5.

The amount of the component (E) is preferably in the range of 0.1 to 10% by mass based on the carboxyl group-containing resin (A), and more preferably in the range of 0.5 to 5% by mass.

When the photosensitive resin composition contains an organic solvent, the amount of the organic solvent is preferably such that the organic solvent can be quickly volatilized and disappeared when the coating film formed of the photosensitive resin composition is dried, that is, The organic solvent is adjusted in such a manner that it does not remain in the dried film. In particular, the amount of the organic solvent is preferably in the range of 0 to 99.5% by mass, and more preferably in the range of 15 to 60% by mass, based on the entire photosensitive resin composition. Further, the appropriate ratio of the organic solvent varies depending on the coating method and the like. Therefore, it is preferred to appropriately adjust the ratio depending on the coating method.

In addition, the solid content amount is a total amount of all the components remaining after the volatile component such as a solvent is removed from the photosensitive resin composition.

The photosensitive resin composition may further contain components other than the above components, within a range that does not impair the effects of the embodiment.

The photosensitive resin composition may contain at least one resin selected from the group consisting of toluene diisocyanate and morpholine diisocyanate which are blocked with caprolactam, hydrazine, malonate or the like. , isophorone diisocyanate and hexamethylene diisocyanate blocked isocyanate; melamine resin, n-butyl melamine resin, isobutylated melamine resin, butylated urea resin, butylated melamine urea co-condensation resin, An amide-based resin such as a benzoguanamine-based co-condensation resin; a thermosetting resin other than the above; an ultraviolet curable epoxy (meth) acrylate; and a (meth)acrylic acid in a bisphenol A type a resin obtained by an epoxy resin such as a phenol novolak type, a cresol novolac type, or an alicyclic type; and a polymer compound such as a diallyl phthalate resin, a phenoxy resin, an amine ester resin, or a fluororesin .

The photosensitive resin composition may contain a curing agent for curing the epoxy compound (D). The hardener may contain, for example, at least one component selected from the group consisting of imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenyl Imidazole derivatives such as imidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-(2-cyanoethyl)-2-ethyl-4-methylimidazole; dicyandiamide, benzene Methyl dimethylamine, 4-(dimethylamino)-N,N-dimethylbenzylamine, 4-methoxy-N,N-dimethylbenzylamine, 4-methyl -N,N-dimethylbenzylamine and other amine compounds; ruthenium compounds such as hexamethylenedifluoride and ruthenium dioxime; phosphorus compounds such as triphenylphosphine; acid anhydride; phenol; thiol; Lewis acid amine And; 鎓 salt. These into For the commercial products, for example, 2MZ-A, 2MZ-OK, 2PHZ, 2P4BHZ, 2P4MHZ (all trade names of imidazole compounds) manufactured by Shikoku Chemicals Co., Ltd.; U manufactured by San-Apro Co., Ltd. -CAT3503N, U-CAT3502T (trade names of blocked isocyanate compounds of dimethylamine); DBU, DBN, U-CATSA102, U-CAT5002 (all of which are bicyclic guanidine compounds and salts thereof).

The photosensitive resin composition may contain at least one component selected from the group consisting of a curing accelerator; a colorant; a copolymer of polyfluorene oxide, acrylate, etc.; a leveling agent; Cohesive imparting agent such as a coupling agent; a thixotropic agent; a polymerization inhibitor; an antihalation agent; a flame retardant; an antifoaming agent; an antioxidant; a surfactant; and a polymer dispersing agent.

The content of the amine compound in the photosensitive resin composition is preferably as small as possible. When it is carried out in this manner, the electrical insulation of the layer composed of the cured product of the photosensitive resin composition is not easily impaired. In particular, the amount of the amine compound is preferably 6% by mass or less based on the carboxyl group-containing resin (A), and more preferably 4% by mass or less.

The photosensitive resin composition can be prepared by blending a raw material of the photosensitive resin composition as described above, and by using, for example, a three-roll mill, a ball mill, and a sand. A well-known kneading method such as a sand mill is used for kneading. When the raw material of the photosensitive resin composition contains a liquid component or a component having a low viscosity, the photosensitive resin composition can be prepared by the following method: A portion other than the liquid component and the component having a low viscosity is kneaded in the raw material, and then a liquid component, a component having a low viscosity, and the like are added to the obtained mixture and mixed.

In consideration of storage stability and the like, the first agent can be prepared by mixing a part of components of the photosensitive resin composition, and the second agent can be prepared by mixing the remaining components. That is, the photosensitive resin composition may have a first agent and a second agent. In this case, for example, the first compound can be prepared by premixing and dispersing the unsaturated compound (B), a part of the organic solvent, and the thermosetting component in the component of the photosensitive resin composition, and sensitizing The remaining components of the components of the resin composition are mixed and dispersed to prepare a second agent. At this time, the required amount of the first agent and the second agent may be mixed at appropriate to prepare a mixed solution, and the mixed solution is hardened to obtain a cured product.

The photosensitive resin composition of this embodiment is suitable for an electrically insulating material used for a printed wiring board. In particular, the photosensitive resin composition is suitable for a material such as a solder resist layer, a plating resist layer, an etch resist layer, or an interlayer insulating layer.

The photosensitive resin composition of the present embodiment preferably has a property of being developed by an aqueous solution of sodium carbonate even in the case of a film having a thickness of 25 μm. In this case, since a sufficiently thick electrically insulating layer can be produced from the photosensitive resin composition by photolithography, the photosensitive resin composition can be widely applied to the production of an interlayer insulating layer in a printed wiring board. Flux layer, etc. Of course, it is also possible to produce an electrically insulating layer thinner than the thickness of 25 μm from the photosensitive resin composition.

Whether or not the film having a thickness of 25 μm can be developed by an aqueous solution of sodium carbonate can be confirmed by the following method. The wet coating film was formed by coating a photosensitive resin composition on a suitable substrate, and then the wet coating film was heated at 80 ° C for 30 minutes to form a film having a thickness of 25 μm. Exposure was carried out by irradiating the film with ultraviolet rays at a condition of 500 mJ/cm ² in a state in which the negative mask was directly adhered to the film, and the negative mask had an exposure portion for blocking ultraviolet rays and shielding. Non-exposure part of ultraviolet light. After the exposure, the following treatment was carried out: a 1% sodium carbonate (Na ₂ CO ₃ ) aqueous solution at 30 ° C was sprayed on the film at an injection pressure of 0.2 MPa for 90 seconds, and then pure water was sprayed at a spray pressure of 0.2 MPa for 90 seconds. . When the film was observed after the treatment, and the portion corresponding to the non-exposed portion in the film was removed and the residue could not be confirmed, it was confirmed that the film having a thickness of 25 μm can be developed by an aqueous solution of sodium carbonate.

Hereinafter, an example of a method of manufacturing a printed wiring board having an interlayer insulating layer formed of the photosensitive resin composition of the present embodiment will be described with reference to FIG. 1 to FIG. In the method, a through hole is formed on the interlayer insulating layer by photolithography.

First, as shown in FIG. 1A, the core material 1 is prepared. The core material 1 is provided with, for example, at least one insulating layer 2 and at least one conductor line 3. The conductor line 3 provided on one side of the core material 1 is hereinafter referred to as a first conductor line 3. As shown in Fig. 1B, a film 4 is formed on one surface of the core material 1 from a photosensitive resin composition. The method of forming the film 4 includes, for example, a coating method and a dry film method.

In the coating method, for example, a photosensitive resin composition is applied onto the core material 1 to form a wet film. The coating method of the photosensitive resin composition may be selected from known methods, for example, a group consisting of a dipping method, a spray method, a spin coating method, a roll coating method, and a curtain coating method. (curtain coating), and screen printing. Then, in order to volatilize the organic solvent in the photosensitive resin composition, for example, the wet coating film is dried at a temperature in the range of 60 to 120 ° C, whereby the film 4 can be obtained.

In the dry film method, first, a photosensitive resin composition is applied onto a suitable support made of polyester or the like, and dried, whereby a dried product of a photosensitive resin composition is formed on the support, that is, dried. membrane. Thereby, a laminated body having a dry film and a support for supporting the dry film is obtained. First, the dry film in the laminate is superposed on the core material 1, and then the dry film is pressed against the core material 1, and then the support is peeled off from the dry film, thereby transferring the dry film to the core from the support. On the material 1. Thereby, the film 4 composed of the dry film is provided on the core material 1.

As shown in Fig. 1C, the film 4 is partially cured by exposure to the film 4. Therefore, for example, the negative mask is attached to the film 4, and the film 4 is irradiated with ultraviolet rays. The negative photomask includes an exposure portion that allows ultraviolet rays to pass through, and a non-exposure portion that blocks ultraviolet rays, and the non-exposed portion is provided at a position that coincides with the position of the through hole 10. The negative mask is, for example, a photo tool such as a mask film or a dry plate. The source of ultraviolet light can be selected, for example, from the group consisting of: chemical lamp, low pressure mercury lamp, medium Pressure mercury lamp, high pressure mercury lamp, ultra high pressure mercury lamp, xenon lamp, and metal halide lamp.

Further, the exposure method may be a method other than the method using a negative mask. For example, the film 4 can be exposed by a direct drawing method in which ultraviolet rays emitted from a light source are irradiated only on the portion of the film 4 to be exposed. A light source suitable for the direct drawing method may be selected, for example, from the group consisting of a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a metal halide lamp, a g line (436 nm), an h line (405 nm), an i line (365 nm); A combination of two or more of the g line, the h line, and the i line.

Further, in the dry film method, the dry film of the laminate may be laminated on the core material 1, and then the film 4 composed of the dry film may be irradiated with ultraviolet rays through the support without peeling off the support. Thereby, the film 4 is exposed, and then the support is peeled off from the film 4 before the development process.

Then, by performing development processing on the film 4, the unexposed portion 5 of the film 4 shown in Fig. 1C is removed, whereby the through hole 10 is formed in the manner shown in Fig. 1D. Set the hole 6 on it. In the development treatment, an appropriate developer can be used depending on the composition of the photosensitive resin composition. The developing solution is, for example, an alkaline aqueous solution or an organic amine containing at least one of an alkali metal salt and an alkali metal hydroxide. The alkaline aqueous solution, more specifically, contains, for example, at least one component selected from the group consisting of sodium carbonate, potassium carbonate, ammonium carbonate, sodium hydrogencarbonate, potassium hydrogencarbonate, ammonium hydrogencarbonate, sodium hydroxide , potassium hydroxide, ammonium hydroxide, tetramethylammonium hydroxide, and lithium hydroxide. The solvent in the alkaline aqueous solution may be only water or a mixture of water and a hydrophilic organic solvent such as a lower alcohol. Things. The organic amine may contain, for example, at least one component selected from the group consisting of monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, and triisopropanolamine.

The developer is preferably an aqueous alkaline solution containing at least one of an alkali metal salt and an alkali metal hydroxide, and particularly preferably an aqueous sodium carbonate solution. At this time, it is possible to achieve an increase in the working environment and a reduction in the burden of waste disposal.

Then, the film 4 is hardened by heating it. The heating conditions, for example, the heating temperature is in the range of 120 to 200 ° C, and the heating time is in the range of 30 to 120 minutes. When the film 4 is thermally cured in this manner, the properties such as strength, hardness, and chemical resistance of the interlayer insulating layer 7 can be improved.

The film 4 is further irradiated with ultraviolet rays before or after heating, or before and after heating, as needed. At this time, the photocuring of the film 4 can be further performed.

According to the above, the interlayer insulating layer 7 can be provided on the core material 1, and the interlayer insulating layer 7 is composed of a cured product of a photosensitive resin composition. The second conductor line 8 and the perforated plating 9 may be provided on the interlayer insulating layer 7 by a known method such as an additive method. Thereby, as shown in FIG. 1E, a printed wiring board 11 having the first conductor line 3, the second conductor line 8, and the interlayer insulating layer 7 interposed between the first conductor line 3 and the second conductor can be obtained. Between the lines 8; and the through hole 10, the first conductor line 3 and the second conductor line 8 are electrically connected. Furthermore, in Figure 1E, The perforated plating 9 has a tubular shape in which the inner surface of the hole 6 is covered, but a perforated plating 9 may be entirely filled inside the hole 6.

Further, before the perforated plating 9 as in FIG. 1E is provided, the entire inner surface of the hole 6 and a part of the outer surface of the interlayer insulating layer 7 can be roughened. In such a manner, a part of the outer surface of the interlayer insulating layer 7 and the inner surface of the hole 6 are roughened, whereby the adhesion of the core material 1 to the perforated plating 9 can be improved.

When the outer surface of a part of the interlayer insulating layer 7 and the inner surface of the hole 6 are roughened as a whole, it can be carried out in the same order as the general desmear treatment, which is commercially available for degumming. Swelling liquid of slag and degreasing liquid. However, the present invention is not limited to this, and the following method capable of imparting a rough surface to the cured product may be suitably employed: plasma treatment, UV treatment, ozone treatment, and the like.

When the perforated plating 9 is provided, an electroless metal plating treatment may be performed on the outer surface of the roughened portion and the inner surface of the hole 6 to form an initial line. Thereafter, the metal in the electrolyte plating solution is deposited on the starting line by electrolytic metal plating treatment, whereby the perforated plating 9 can be formed.

An example of a method of manufacturing a printed wiring board comprising a solder resist layer formed of the photosensitive resin composition of the present embodiment will be described.

First, prepare the core material. The core material is provided with, for example, at least one insulating layer and at least one conductor line. A film is formed from a photosensitive resin composition on a surface of the core material on which the conductor line is provided. As a method of forming a film, The coating method and the dry film method are listed. As the coating method and the dry film method, the same method as in the case of forming the interlayer insulating layer described above can be employed. The portion is hardened by exposing the film. The exposure method may be the same as the above-described method of forming the interlayer insulating layer. Then, the unexposed portion of the film is removed by subjecting the film to development treatment, whereby the exposed portion of the film remains on the core material. Then, the film on the core material is thermally hardened by heating it. The developing method and the heating method may be the same as those in the case of forming the interlayer insulating layer described above. The film is further irradiated with ultraviolet rays before or after heating, or before and after heating. At this time, the photocuring of the film can be further performed.

According to the above, the solder resist layer can be provided on the core material, and the solder resist layer is composed of a cured product of the photosensitive resin composition. Thereby, it is possible to obtain a printed wiring board comprising: a core material having an insulating layer and a conductor line thereon; and a solder resist layer partially covering the surface of the core material on which the conductor line is provided.

[Examples]

Hereinafter, the present invention will be specifically described by way of examples.

(1) Synthesis Example A-1 to Synthesis Example A-7, and Synthesis Example B-1 and Synthesis Example B-3 to Synthesis Example B-4

In a four-necked flask equipped with a reflux condenser, a thermometer, an air blowing tube, and a stirrer, the raw material components shown in the "First Reaction" column in Tables 1 and 2 were added, and stirred in the presence of bubbles. These raw material ingredients are used to formulate the mixture. In the four-necked flask, the mixture was stirred while the bubbles were present, and the reaction was carried out in the "first reaction" column. Heating is carried out by the reaction temperature and the reaction time shown in the Conditions column. Thereby, a solution of the intermediate is formulated.

Then, the raw material components shown in the "second reaction" column of Tables 1 and 2 were charged into the solution of the intermediate in the four-necked flask, and the solution in the four-necked flask was stirred while the bubbles were generated. The heating was carried out by the reaction temperature and the reaction time shown in the column of "Reaction conditions (1)" in the "second reaction" column. Then, in addition to the synthesis examples B-1 and B-3 and the synthesis example B-4, the solution in the four-necked flask was stirred while the bubbles were generated, and the reaction conditions in the "second reaction" column were used. The reaction temperature and reaction time shown in the column (2) are heated. Thereby, a 65 mass% solution of the carboxyl group-containing resin was obtained. The weight average molecular weight and acid value of the carboxyl group-containing resin are shown in Tables 1 and 2. The molar ratio between the components is also shown in Tables 1 and 2.

Further, the details of the components shown in the column (a1) in Tables 1 and 2 are as follows.

‧Epoxy compound 1: A bisphenol fluorene type epoxy compound having an epoxy equivalent of 250 g/eq, which is represented by the formula (7), and all of R ₁ to R ₈ in the formula (7) are hydrogen.

‧Epoxy compound 2: a bisphenol fluorene type epoxy compound having an epoxy equivalent of 279 g/eq, which is represented by the formula (7), and R ₁ and R ₅ in the formula (7) are each a methyl group, R ₂ ~ R ₄ and R ₆ to R ₈ are all hydrogen.

The details of the components shown in the column (g1) in Tables 1 and 2 are as follows.

‧Epoxy compound A: a biphenol novolak type epoxy resin (trade name: NC-3000-H, manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent: 288 g/eq).

‧Epoxy compound B: cresol novolac type epoxy resin (trade name YDC-700-5, manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd., epoxy equivalent: 203 g/eq).

Further, the details of the components shown in the column (a2) in Tables 1 and 2 are as follows.

‧ ω-carboxy-polycaprolactone (n≒2) monoacrylate: manufactured by Toagosei Co., Ltd., trade name ARONIX M-5300 (number average molecular weight 290).

(2) Synthesis Example B-2

75 parts by mass of methacrylic acid, 85 parts by mass of methyl methacrylate, 20 parts by mass of styrene, and 20 parts were placed in a four-necked flask equipped with a reflux condenser, a thermometer, a glass tube for nitrogen replacement, and a stirrer. Butyl methacrylate, 430 parts by mass of dipropylene glycol monomethyl ether, and 5 parts by mass of azobisisobutyronitrile. The solution in the four-necked flask was heated at 75 ° C for 5 hours under a nitrogen gas stream to carry out a polymerization reaction, whereby a copolymer solution having a concentration of 32% was obtained.

0.1 parts by mass of hydroquinone, 50 parts by mass of glycidyl methacrylate, and 0.8 parts by mass of dimethylbenzylamine were added to the copolymer solution, and heated at 80 ° C for 24 hours. The addition reaction is carried out. Thereby, a 37% solution of the carboxyl group-containing resin (B-1) was obtained. The weight average molecular weight of the carboxyl group-containing resin (B-1) was 31,790, and the acid value of the solid content was 120 mgKOH/g.

[Table 1]

[Table 2]

A part of the components shown in the "Composition" column of Tables 3 to 7 described later were mixed by a three-roll mill. The kneaded product is then transferred to the flask, The photosensitive resin compositions of the examples and the comparative examples other than Example 8 were obtained by stirring and mixing all the components shown in Tables 3 to 7 described later. At the time of producing a photosensitive resin composition, at least one of a group of melamine and a melamine derivative is uniformly dispersed in a photosensitive resin composition. Further, the details of the components shown in Tables 3 to 7 are as follows.

‧ Unsaturated compound (TMPTA): Trimethylolpropane triacrylate.

‧ Unsaturated compound (DPHA): dipentaerythritol hexaacrylate.

‧ Photopolymerization initiator (TPO): 2,4,6-trimethylbenzimidyl-diphenyl-phosphine oxide (manufactured by BASF Corporation, trade name Irgacure TPO).

‧ Photopolymerization initiator (IC819): bis(2,4,6-trimethylbenzylidene)phenylphosphine oxide (manufactured by BASF Corporation, trade name Irgacure 819).

‧ Photopolymerization initiator (IC184): 1-hydroxy-cyclohexyl-phenyl-ketone (manufactured by BASF Corporation, trade name Irgacure 184).

‧ Photopolymerization initiator (IC1173): 2-hydroxy-2-methyl-1-phenyl-propan-1-one (manufactured by BASF Corporation, trade name Irgacure 1173).

‧ Photopolymerization initiator (EAB): 4,4'-bis(diethylamino)diphenyl ketone.

‧Photopolymerization initiator (IC907): 2-methyl-1-(4-methylthiophenyl)-2-(N-morpholinyl)propan-1-one (manufactured by BASF Corporation, product type Irgacure 907 ).

‧ Photopolymerization initiator (DETX): 2,4-diethyl 2,4-diethyl thioxanthene-9-one.

‧ Crystalline epoxy resin (YX4000): biphenyl type crystalline epoxy resin (trade name YX-4000, manufactured by Mitsubishi Chemical Corporation, melting point 105 ° C, epoxy equivalent: 187 g/eq).

‧ Crystalline epoxy resin (YSLV80XY): bisphenol-type crystalline epoxy resin (trade name: YSLV-80XY, manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd., melting point: 75-85 ° C, epoxy equivalent: 192 g/eq)

‧Amorphous epoxy resin (MX-130): Bisphenol F-type epoxy resin containing rubber particles (manufactured by Chunghua Co., Ltd., product model Kane Ace MX-130)

‧Amorphous epoxy resin (EXA-4816): Amorphous epoxy resin solution, bisphenol A type epoxy resin containing long chain carbon chain (DIC Co., Ltd.) in a solid content of 90% Manufactured, product model EPICLON EXA-4816, liquid resin, epoxy equivalent 410 g / eq) dissolved in diethylene glycol monoethyl ether acetate solution (the epoxy equivalent in terms of solid content of 90% is 455.56g/eq).

‧ Melamine: Made of Nissan Chemical Industry Co., Ltd., melamine fine powder, dispersed in a photosensitive resin composition in an average particle diameter of 8 μm.

‧ Melamine derivative: a reaction product of melamine and 1,2,3,6-tetrahydrophthalic anhydride, that is, melamine-tetrahydrophthalic acid salt, dispersed in a photosensitive resin in an average particle diameter of 6 μm In the composition.

‧Antioxidant: A hindered phenolic antioxidant, manufactured by BASF, under the trade designation IRGANOX 1010.

‧Inorganic filler (PMA-ST): dispersion of inorganic filler, nano sol (produced by Nissan Chemical Co., Ltd., product model PMA-ST: propylene glycol monomethyl ether acetate, SiO ₂ content 30%, average Particle size 10~15nm).

‧ Inorganic filler (A-8): Crystalline cerium oxide (IMSIL A-8 manufactured by Unimin Co., Ltd., average particle diameter 2 to 3 μm).

‧ Inorganic filler (B30): Barium sulfate (manufactured by Dai Chemical Industry Co., Ltd., product model BARIACE B30, average particle diameter 0.3 μm).

‧ Inorganic filler (B31): Barium sulfate (manufactured by Dai Chemical Industry Co., Ltd., product model BARIACE B31, average particle diameter 0.3 μm).

‧ Defoamer: manufactured by Shin-Etsu Lee Co., Ltd., product model KS-66.

‧ Surfactant (F-477): Manufactured by DIC Corporation, product model MEGAFACE F-477.

‧ Surfactant (F-470): Manufactured by DIC Corporation, product model MEGAFACE F-470.

‧ Rheology regulator: manufactured by BYK Japan Co., Ltd., product model BYK-430.

‧ decane coupling agent: 3-glycidoxypropyltrimethoxydecane.

‧ Solvent (EDGAC): Diethylene glycol monoethyl ether acetate.

‧ Solvent (MEK): methyl ethyl ketone.

[Examples 1 to 9 and Comparative Examples 1 to 2]

[production test piece]

Test pieces of each of Examples 1 to 9 and Comparative Examples 1 and 2 were produced in the following order.

<Examples 1 to 7, 9 and Comparative Examples 1 to 2>

A glass epoxy copper clad laminate (FR-4 type) having a copper foil having a thickness of 35 μm was prepared. On the glass epoxy-clad laminate, a comb-shaped electrode as a conductor line was formed by a subtractive method, thereby obtaining a printed wiring board having a line width/space of 50 μm/50 μm. A conductor portion CZ-8100 manufactured by MEC Co., Ltd. was used to dissolve and remove the surface portion of the conductor wiring of the printed wiring board having a thickness of about 1 μm, thereby roughening the conductor wiring. A photosensitive resin composition is applied on the entire surface of one side of the printed wiring board by a screen printing method, thereby forming a wet coating film. The wet coating film was heated at 80 ° C for 30 minutes to carry out preliminary drying to form a film having a film thickness of 25 μm. Exposure was carried out by irradiating the film with ultraviolet rays under conditions of 500 mJ/cm ² in a state where the negative mask having the non-exposed portion was directly in contact with the film, and the non-exposed portion had a circular shape including a diameter of 50 μm. The developed film is subjected to development treatment. At the time of development processing, a 1% sodium carbonate aqueous solution of 30 ° C was sprayed on the film at an ejection pressure of 0.2 MPa for 90 seconds. Then, the film was washed by spraying pure water on the film at an ejection pressure of 0.2 MPa for 90 seconds. Thereby, the unexposed portion of the film is removed, and a hole is formed in the film. Then, the film was irradiated with ultraviolet rays at a condition of 1000 mJ/cm ² . Further, the film was heated at 150 ° C for 60 minutes. Thereby, a layer composed of a photosensitive resin composition is formed on the printed wiring board (core material). Thereby a test piece is obtained.

<Example 8>

The components shown in the "composition" column of Table 4, which will be described later, were kneaded by a three-roll mill to obtain a photosensitive resin composition. When the photosensitive resin composition is produced, melamine is uniformly dispersed in the photosensitive resin composition.

First, the photosensitive resin composition is applied onto a film made of polyethylene terephthalate by an applicator, and then dried by heating at 80 to 110 ° C. A dry film having a thickness of 25 μm was formed on the film.

The dry film was heated and laminated on the same printed wiring board as in Examples 1 to 7, 9 and Comparative Examples 1 and 2. The heating lamination was carried out by a vacuum laminator at a condition of 0.5 MPa, 80 ° C, and 1 minute. Thereby, a film having a thickness of 25 μm was formed on the printed wiring board. By performing the same treatments as in Examples 1 to 7 and 9 and Comparative Examples 1 and 2 on the film, a cured product of a photosensitive resin composition (also referred to as dry) is formed on a printed wiring board (core material). The layer formed by the cured film of the film. Further, the film made of polyethylene terephthalate was peeled off from the film before the development step. Thereby a test piece is obtained.

[evaluation test]

The test pieces of each of Examples 1 to 9 and Comparative Examples 1 and 2 were evaluated in the following order. The results are shown in Tables 3 and 4 below.

(1) Viscosity

In the preparation of the test pieces of the respective Examples and Comparative Examples, the degree of stickiness of the film when the negative mask was removed from the film after exposure of the film was evaluated in the following manner.

A: There was no feeling of resistance when the negative mask was removed from the film, and no trace of adhesion was observed on the film after the negative mask was removed.

B: A feeling of resistance was obtained when the negative mask was removed from the film, and a mark of adhesion was confirmed on the film after the negative mask was removed.

C: It is difficult to remove the negative mask from the film, and if the negative mask is forcibly removed, the film is broken.

Further, with respect to Comparative Example 2 in which the viscosity evaluation was C, the following evaluations other than the viscosity were not performed. Further, in Example 8, since the film was formed from the dry film, the evaluation of the viscosity was not performed.

(2) Resolution

The pores formed on the layer composed of the cured product in the test pieces of the respective Examples and Comparative Examples were observed, and the results were evaluated in the following manner.

A: The diameter of the bottom of the hole is 40 μm or more.

B: The diameter of the bottom of the hole is 25 μm or more but less than 40 μm.

C: The diameter of the bottom of the hole is less than 25 μm, or a clear hole is not formed.

(3) Plating resistance

First, a nickel-plated layer was formed on a layer composed of a cured product in the test pieces of the respective Examples and Comparative Examples using a commercially available electroless nickel plating bath, and a gold-plated layer was formed using a commercially available electroless gold plating bath. Thereby, a metal layer composed of a nickel plating layer and a gold plating layer is formed on the layer composed of the cured product. The layer composed of the cured material and the metal layer were visually observed. Further, a cellophane adhesive tape peeling test was performed on the metal layer. The results were evaluated in the following manner.

A: The appearance of the layer composed of the cured product and the metal layer was not confirmed to be abnormal, and the peeling of the metal layer due to the cellophane adhesive tape peeling test did not occur.

B: Discoloration was confirmed in the layer composed of the cured product, but the peeling of the metal layer due to the cellophane adhesive tape peeling test did not occur.

C: It was confirmed that the layer composed of the cured product floated, and the peeling of the metal layer due to the peeling test of the cellophane adhesive tape occurred.

(4) Insulation between wires

A bias voltage of direct current (DC) of 30 V was applied to the conductor line (comb electrode) in the test piece of each of the examples and the comparative examples, and the printed wiring board was exposed to 121 ° C and a relative humidity of 97%. (relative humidity, RH) test environment for 100 hours. The resistance value between the comb-shaped electrodes of the layer composed of the cured product was continuously measured in this test environment, and the results were evaluated in accordance with the following evaluation criteria.

A: The resistance value is maintained at 10 ⁶ Ω or more from the start of the test to the lapse of 100 hours.

B: The resistance value was maintained at 10 ⁶ Ω or more from the start of the test to the lapse of 80 hours, but the resistance value was less than 10 ⁶ Ω from the start of the test to 100 hours before the test.

C: The resistance value was maintained at 10 ⁶ Ω or more from the start of the test to the lapse of 60 hours, but the resistance value was less than 10 ⁶ Ω from the start of the test to 80 hours before the test.

D: The resistance value was less than 10 ⁶ Ω from the start of the test until 60 hours passed.

(5) interlayer insulation

A conductive tape was adhered to the layer composed of the cured material in the test pieces of the respective Examples and Comparative Examples. While applying a bias voltage of DC 100 V to the conductive tape, the printed wiring board was exposed to a test environment of 121 ° C and 97% R.H. for 50 hours. The resistance value between the conductor wiring of the layer composed of the cured product and the conductive tape was continuously measured in this test environment, and the results were evaluated in accordance with the following evaluation criteria.

A: The resistance value was maintained at 10 ⁶ Ω or more from the start of the test until 50 hours passed.

B: The resistance value was maintained above 10 ⁶ Ω from the start of the test to 35 hours, but the resistance value was less than 10 ⁶ Ω from the start of the test until 50 hours passed.

C: The resistance value was maintained above 10 ⁶ Ω from the start of the test to the lapse of 20 hours, but the resistance value was less than 10 ⁶ Ω from the start of the test to 35 hours before the test.

D: The resistance value was less than 10 ⁶ Ω from the start of the test until 20 hours passed.

(6) Glass transition temperature

A layer composed of a cured product is formed on a member made of Teflon (registered trademark). The method of forming the layer composed of the cured product is the same as that in the case of forming a layer composed of a cured product in the test piece. The layer composed of the cured material was first peeled off from the member, and the glass transition temperature of the layer was measured by Thermal Mechanical Analysis (TMA).

(7) Copper plating adhesion test

(7-1) Roughness tolerance

The outer surfaces of the layers composed of the cured materials in the test pieces of the respective examples and comparative examples were roughened in the following order according to the general desmear treatment. The swelling liquid (Swelling Dip Securiganth P manufactured by Ato Technology Co., Ltd., Japan, which is sold as a swelling liquid for desmear) was subjected to a swelling treatment at 60 ° C for 5 minutes to swell the surface of the cured product. Further, hot water washing is performed on the swollen surface. Then, an oxidizing agent (Concentrate Compact CP manufactured by Ato Technology Co., Ltd.) containing potassium permanganate and sold as a desmear liquid was used, and roughening treatment was carried out at 80 ° C for 10 minutes to clean the hot water. The surface is roughened. For the surface roughened in this manner, hot water washing is performed, and further, using a neutralizing liquid (Reduction solution Securiganth P manufactured by Ato Technology Co., Ltd., Japan), the desmear on the surface is removed at 40 ° C. The residue of the liquid was 5 minutes. Also, the surface after neutralization is cleaned. The film thickness of the rough surface-coated film (the layer composed of the cured product of the photosensitive resin composition) was measured in such a manner, and the roughening resistance of the cured product to the desmear liquid was evaluated in accordance with the following evaluation criteria. .

A: The reduction in film thickness due to roughening is more than 0 μm but less than 3.5 μm.

B: The amount of reduction in film thickness due to roughening is 3.5 μm or more but less than 10 μm.

C: The amount of reduction in film thickness due to roughening is 10 μm or more.

(7-2) Adhesion of copper plating layer

The layer composed of the cured product in the test pieces of the respective Examples and Comparative Examples was subjected to a rough surface by the method of the above (7-1), and then a commercially available chemical liquid was used to be treated with electroless copper plating. The starting line is formed on the rough surface of the sheet. The starting line was heated with the hardened material at 150 ° C for 1 hour. Further, by electroplating copper treatment, copper having a thickness of 33 μm was directly deposited on the starting line from a commercially available chemical solution at a current density of ² A/dm ² . Then, the test piece in which copper was deposited was heated at 180 ° C for 30 minutes to form a copper plating layer. The adhesion of the copper plating layer formed in such a manner to the cured product in the test piece was evaluated in accordance with the following evaluation criteria. Here, if blistering was not confirmed on the test piece after the electroless copper plating treatment and the heating after the electroplating copper treatment, the adhesion strength between the copper plating layer and the cured product was evaluated in the following order. The adhesive strength was measured in accordance with Japanese Industrial Standard (JIS)-C6481.

S: No foaming was observed at the time of heating after the electroless copper plating treatment, and no foaming was observed even during heating after the electroplating copper treatment. Further, the bonding strength of copper is 0.4 kN/m or more.

A: No foaming was observed at the time of heating after the electroless copper plating treatment, and no foaming was observed even during heating after the electroplating copper treatment. Further, the bonding strength of copper is 0.3 kN/m or more but less than 0.4 kN/m.

B: No foaming was observed at the time of heating after the electroless copper plating treatment, and no foaming was observed even during heating after the electroplating copper treatment. Further, the bonding strength of copper is less than 0.3 kN/m.

C: Foaming was confirmed at the time of heating after electroless copper plating treatment or heating after electroplating copper treatment.

The evaluation results of Examples 1 to 9 and Comparative Examples 1 and 2 are shown in Tables 3 to 4 below.

[table 3]

[Table 4]

[Examples 10 to 21 and Comparative Examples 3 to 6]

[production test piece]

First, the photosensitive resin compositions of Examples 10 to 21 and Comparative Examples 3 to 6 were applied onto a film made of polyethylene terephthalate by an applicator, and further heated at 95 ° C for 25 minutes. To dry it, a dry film having a thickness of 25 μm was formed on the film.

Test pieces of each of Examples 10 to 21 and Comparative Examples 3 to 6 were produced in the same manner as in Example 8. Here, immediately after the dry film was heated and laminated on the printed wiring board, the intensity of the ultraviolet ray at the time of the first exposure was set to 250 mJ/cm ² . Further, after the film was irradiated with ultraviolet rays under the conditions of 1000 mJ/cm ² , the temperature at which the film was heated was also set to 160 °C.

[evaluation test]

The test pieces of each of Examples 10 to 21 and Comparative Examples 3 to 6 were evaluated in the following order. The results are shown in Tables 5 to 7 below.

(8) developability

For each of the examples and comparative examples, after the development processing described above, the non-exposed portion of the printed wiring board was observed, and the results were evaluated in the following manner.

Good: The unexposed film has been completely removed.

Inappropriate: A portion of the unexposed film remains on the printed wiring board.

(9) Resolution

The resolution of the test pieces of the respective examples and comparative examples was evaluated in the same order as the test pieces of Examples 1 to 9 and Comparative Examples 1 and 2, and the same evaluation criteria.

(10) Plating resistance

The plating resistance of the test pieces of the respective examples and comparative examples was evaluated in the same order as the test pieces of Examples 1 to 9 and Comparative Examples 1 and 2, and the same evaluation criteria.

(11) Insulation between wires

The exposure time was set to 150 hours, and the resistance between the comb electrodes in the test pieces of the respective examples and comparative examples was continuously measured in the same order as the test pieces of Examples 1 to 9 and Comparative Examples 1 and 2. value. The results were evaluated according to the following evaluation criteria.

A: The resistance value was maintained at 10 ⁶ Ω or more from the start of the test to 150 hours.

B: The resistance value was maintained above 10 ⁶ Ω from the start of the test to the elapse of 100 hours, but the resistance value was less than 10 ⁶ Ω from the start of the test to 150 hours before the test.

C: The resistance value was less than 10 ⁶ Ω from the start of the test until 100 hours passed.

(12) interlayer insulation

The test environment was set to 85 ° C, 85% RH, and the exposure time was set to 2000 hours. Further, the examples were continuously measured in the same order as the test pieces of Examples 1 to 8 and Comparative Examples 1 to 3. The resistance value between the conductor line and the conductive tape in the test piece of the comparative example. The results were evaluated according to the following evaluation criteria.

A: The resistance value was maintained above 10 ⁸ Ω from the start of the test to 2000 hours.

B: The resistance value was maintained above 10 ⁸ Ω from the start of the test to 1000 hours, but the resistance value was less than 10 ⁶ Ω from the start of the test to 2000 hours.

C: The resistance value is less than 10 ⁸ Ω from the start of the test to 1000 hours before the test.

(13) Pressure cooker test (PCT)

The test pieces of the respective examples and comparative examples were placed in an environment of 121 ° C and 100% R.H. for 120 hours, and then the appearance of the layer composed of the cured product was evaluated in accordance with the following evaluation criteria.

A: No abnormality was observed in the layer composed of the cured product.

B: Discoloration was observed in the layer composed of the cured product.

C: A large discoloration was observed in the layer composed of the cured product, and a part of the expansion occurred.

(14) Copper plating adhesion test

The photosensitive resin composition of each of the examples and the comparative examples was applied onto a film made of polyethylene terephthalate by an applicator, and then dried by heating at 95 ° C for 25 minutes. Thereby, a dry film having a thickness of 30 μm was formed on the film.

The dry film was used, and a test piece was obtained by the same method as described above.

(14-1) Roughness tolerance

The outer surfaces of the test pieces of the respective examples and comparative examples were given a rough surface in the same order as in the examples 1 to 9 and the comparative examples 1 and 2, and the roughening resistance of the cured product to the desmear liquid was evaluated.

(14-2) Adhesion of copper plating layer

In the same order as in Examples 1 to 9 and Comparative Examples 1 and 2, a copper plating layer was formed on the layer composed of the cured material in the test pieces of the respective Examples and Comparative Examples, and the copper plating layer and the hardened layer were evaluated. The bonding strength of the object.

The evaluation results of Examples 10 to 21 and Comparative Examples 3 to 6 are shown in Tables 5 to 7 below.

[table 5]

[Table 6]

[Table 7]

According to the above embodiment, the photosensitive resin composition of the first aspect of the present invention contains: a carboxyl group-containing resin (A); and an unsaturated compound (B) having at least one ethylenic unsaturation in one molecule. key; Photopolymerization initiator (C); epoxy compound (D); and component (E) containing at least one compound selected from the group consisting of melamine and melamine derivatives; and, the aforementioned carboxyl group-containing resin (A) The carboxyl group-containing resin (A1) is contained, and the carboxyl group-containing resin (A1) has a bisphenol fluorene skeleton.

According to the first aspect, even if the photosensitive resin composition contains a carboxyl group-containing resin having a bisphenol fluorene skeleton, excellent developability can be obtained, and in the pre-plating step, the photosensitive resin composition can be contained. The thickness of the layer of the cured product is not easily thinned by the oxidizing agent, and the surface of the cured product can be roughened with an oxidizing agent.

In the photosensitive resin composition of the second aspect, in the first aspect, the carboxyl group-containing resin (A1) may be a reaction product of an intermediate and an acid anhydride, and the intermediate is an epoxy compound having a bisphenol fluorene skeleton ( A1) a reactant with an unsaturated carboxylic acid (a2).

According to the second aspect, excellent developability can be imparted to the photosensitive resin composition.

In the photosensitive resin composition of the third aspect, the epoxy compound (D) may contain a crystalline epoxy resin in the first or second aspect.

According to the third aspect, the developability of the photosensitive resin composition can be improved.

The photosensitive resin composition of the fourth aspect may further contain an inorganic filler (K) in any of the first to third aspects.

According to the fourth aspect, it is possible to impart a rough surface suitable for the plating treatment to the cured product of the photosensitive resin composition, and it is possible to improve the adhesion between the cured product and the plating layer.

In the photosensitive resin composition of the fifth aspect, the inorganic filler (K) may contain cerium oxide (k) in the fourth aspect.

According to the fifth aspect, even if the cerium oxide (k) is located on a surface of the cured product of the photosensitive resin composition which is hard to corrode, the hardly corroded portion can be moderately corroded. Thereby, it is possible to impart a rough surface which is more suitable for the plating treatment to the cured product, and it is possible to further improve the adhesion between the cured product and the plating layer.

In the photosensitive resin composition of the sixth aspect, the cerium oxide (k) may have an average particle diameter of 1 μm or less in the fifth aspect.

According to the sixth aspect, the roughness of the rough surface formed on the cured product of the photosensitive resin composition can be made fine. Thereby, the surface area of the cured product increases, and in this case, the fixing effect is increased, and the adhesion between the rough surface and the plating layer can be improved.

In the photosensitive resin composition of the seventh aspect, the photopolymerization initiator (C) may contain a mercaptophosphine oxide-based photopolymerization initiator for any of the first to sixth aspects ( C1).

According to the seventh aspect, the photosensitive resin composition contains the carboxyl group-containing resin (A1), and when the photosensitive resin composition is exposed to ultraviolet light, high sensitivity can be imparted to the photosensitive resin composition. Moreover, a cured product excellent in electrical insulating properties can be obtained.

In the photosensitive resin composition of the eighth aspect, the photopolymerization initiator (C) may contain a hydroxyketone photopolymerization initiator (C2) for any of the first to seventh aspects. .

According to the eighth aspect, it is possible to impart further high photosensitivity to the photosensitive resin composition as compared with the case where the hydroxyketone-based photopolymerization initiator (C2) is not contained.

In the photosensitive resin composition of the ninth aspect, the photopolymerization initiator (C) may contain bis(diethylamino)diphenyl group in any of the first to eighth aspects. Ketone (C3).

According to the ninth aspect, when the coating film formed of the photosensitive resin composition is partially exposed and developed, the hardening of the portion not exposed is suppressed, whereby the resolution is particularly high. Therefore, a very fine pattern can be formed with the cured product of the photosensitive resin composition.

The dry film of the tenth aspect is a dried product of the photosensitive resin composition of any of the first to ninth aspects.

According to the tenth aspect, even if the photosensitive resin composition contains a carboxyl group-containing resin having a bisphenol fluorene skeleton, excellent developability can be obtained, and in the pre-step of the plating treatment, a cured product containing a dry film can be obtained. The thickness of the layer is not easily thinned by the oxidizing agent, and the surface of the cured product can be roughened with an oxidizing agent.

A printed wiring board according to an eleventh aspect, comprising: an interlayer insulating layer comprising a cured product of the photosensitive resin composition of any one of the first to ninth aspects.

According to the eleventh aspect, it is possible to obtain a printed wiring board which is provided with an excellent interlayer insulating layer.

A printed wiring board according to a twelfth aspect, comprising a solder resist layer comprising a cured product of the photosensitive resin composition of any one of the first to ninth aspects.

According to the twelfth aspect, it is possible to obtain a printed wiring board which is provided with an excellent solder resist layer.

A method for producing a photosensitive resin composition according to a thirteenth aspect, which comprises the steps of: reacting an epoxy compound (a1) having a bisphenol fluorene skeleton with an unsaturated group-containing carboxylic acid (a2) to obtain an intermediate a step of synthesizing the intermediate and the acid anhydride to synthesize the carboxyl group-containing resin (A1); and, the carboxyl group-containing resin (A) containing the carboxyl group-containing resin (A1), having at least one ethylene in one molecule a step of obtaining a photosensitive resin composition by mixing an unsaturated compound (B) having an unsaturated bond, a photopolymerization initiator (C), an epoxy compound (D), and a component (E); (E) at least one compound containing a group selected from the group consisting of melamine and melamine derivatives.

According to the thirteenth aspect, even if a carboxyl group-containing resin having a bisphenol fluorene skeleton is contained, a photosensitive resin composition having excellent developability can be obtained. Further, when a rough surface is applied to the cured product of the photosensitive resin composition in the pre-step of the plating treatment, the thickness of the layer of the cured product including the dry film can be prevented from being thinned by the oxidizing agent.

1‧‧‧ core material

2‧‧‧Insulation

3‧‧‧Conductor line (first conductor line)

4‧‧ ‧ film

5‧‧‧Unexposed parts

6‧‧‧ hole

7‧‧‧Interlayer insulation

8‧‧‧Second conductor line

9‧‧‧Perforated plating

10‧‧‧through holes

11‧‧‧Printed circuit board

Claims (12)

A photosensitive resin composition comprising: a carboxyl group-containing resin (A); an unsaturated compound (B) having at least one ethylenically unsaturated bond in one molecule; a photopolymerization initiator (C); an epoxy compound (D); and, component (E), which contains at least one compound selected from the group consisting of melamine and a melamine derivative; and the carboxyl group-containing resin (A) contains a carboxyl group-containing resin (A1), the carboxyl group-containing resin (A1) has a bisphenol fluorene skeleton. The photosensitive resin composition according to claim 1, wherein the carboxyl group-containing resin (A1) is a reaction product of an intermediate and an acid anhydride, and the intermediate is an epoxy compound (a1) having a bisphenol fluorene skeleton and containing The reactant of the saturated carboxylic acid (a2). The photosensitive resin composition according to claim 1 or 2, wherein the epoxy compound (D) contains a crystalline epoxy resin. The photosensitive resin composition according to claim 1 or 2, wherein the photosensitive resin composition further contains an inorganic filler (K). The photosensitive resin composition according to claim 4, wherein the inorganic filler (K) contains cerium oxide (k). The photosensitive resin composition according to claim 5, wherein the cerium oxide (k) has an average particle diameter of 1 μm or less. The photosensitive resin composition according to claim 1 or 2, wherein the photopolymerization initiator (C) contains a fluorenylphosphine oxide-based photopolymerization initiator (C1). The photosensitive resin composition according to claim 1 or 2, wherein the photopolymerization initiator (C) contains a hydroxyketone photopolymerization initiator (C2). The photosensitive resin composition according to claim 1 or 2, wherein the photopolymerization initiator (C) contains bis(diethylamino)diphenyl ketone (C3). A dry film which is a dried product of the photosensitive resin composition according to any one of claims 1 to 9. A printed wiring board comprising an interlayer insulating layer comprising a cured product of the photosensitive resin composition according to any one of claims 1 to 9. A printed wiring board comprising a solder resist layer, the solder resist layer comprising a cured product of the photosensitive resin composition according to any one of claims 1 to 9.