TW201716856A - Photo-sensitive resin composition, dry film, and printed wiring board (2) - Google Patents

Abstract

The objective of the present invention is to have a photosensitive resin composition achieve excellent developability even if a carboxyl group-containing resin having a bisphenol fluorene skeleton is contained therein and to have a cured product of the photosensitive resin composition less susceptible to the occurrence of cracks during repeated temperature changes. A photosensitive resin composition according to the present invention contains a carboxyl group-containing resin (A), an unsaturated compound, a photopolymerization initiator and an epoxy compound. The carboxyl group-containing resin (A) contains a carboxyl group-containing resin (A1) which is a reaction product of an acid anhydride and an intermediate that is a reaction product of an unsaturated group-containing carboxylic acid and an epoxy compound having a bisphenol fluorene skeleton represented by formula (1). The epoxy compound contains a crystalline epoxy resin and an amorphous epoxy resin.

Description

Photosensitive resin composition, dry film and printed wiring board (2)

The present invention relates to a photosensitive resin composition, a dry film, and a printed wiring board. More specifically, the present invention relates to a photosensitive resin composition suitable for forming a solder resist layer and a plating resist layer on a printed wiring board. An electrically insulating layer such as an etch resist layer or an interlayer insulating layer.

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.

However, since the photosensitive resin composition contains a carboxyl group-containing resin having a bisphenol fluorene skeleton, developability is low, and it is difficult to use such a sensitization. An electrically insulating layer such as a solder resist layer and an interlayer insulating layer having a sufficient thickness is formed by photolithography. Moreover, even if the heat resistance of the layer formed of the photosensitive resin composition can be improved, such a layer may be cracked even when the temperature change including temperature rise and temperature drop is repeated.

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, a printed wiring board including an interlayer insulating layer, and a method for producing the photosensitive resin composition, wherein the dry film is the aforementioned a dried product of the photosensitive resin composition, wherein 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, and the photosensitive resin composition contains The carboxyl group-containing resin of the bisphenol fluorene skeleton can still obtain excellent developability, and can still cause the cured product to be less likely to crack during temperature change.

An exemplary photosensitive resin composition 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 ( And an epoxy compound (D); and the carboxyl group-containing resin (A) contains a carboxyl group-containing resin (A1) which is a reactant of an intermediate and an acid anhydride, and the intermediate is a ring a reactant of the oxygen compound (a1) and the unsaturated group-containing carboxylic acid (a2); the epoxy compound (a1) has a bisphenol fluorene skeleton represented by the following formula (1), and in the formula (1), R ₁ ~R ₈ are each independently hydrogen, an alkyl group having 1 to 5 carbon atoms, or a halogen; and the epoxy compound (D) contains a crystalline epoxy resin and an amorphous epoxy resin, and is furthermore than the above-mentioned carboxyl group-containing resin. The total amount of the equivalent weight of the carboxyl group contained in the crystalline epoxy resin and the amorphous epoxy resin is in the range of 0.7 to 2.5,

A dry film according to an aspect of the present invention contains the photosensitive resin composition.

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

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

1‧‧‧ core material

2‧‧‧Insulation

3‧‧‧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, an 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); And, epoxy compound (D).

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.

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 removing most of the structure (S2) and the structure (S6) 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, two secondary hydroxyl groups present in the intermediate of one molecule may be cross-linked with each other by the acid dianhydride (a3). In the case, the two secondary hydroxyl groups respectively present in the intermediate of two molecules are crosslinked by the acid dianhydride (a3). 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 is imparted with developability by 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 from 1,000 to 5,000. When the weight average molecular weight is 1000 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. In addition, when the weight average molecular weight is 5,000 or less, the developability of the photosensitive resin composition by the alkaline aqueous solution can be particularly improved.

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 molecular weight measurement by Gel Permeation Chromatography (GPC). Calculation. 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 increase in molecular weight 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 intermediate solution can be obtained by a conventional method, preferably by reacting the reactive solution at a temperature of from 60 to 150 ° C, particularly preferably from 80 to 120 ° C. 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, it is possible to suppress the occurrence of ion migration in the layer of the cured product containing the photosensitive resin composition, and it is possible to further improve the insulation reliability of the layer.

When the epoxy compound (a1) is reacted with the unsaturated group-containing carboxylic acid (a2), it is 1 mol of the epoxy group of the epoxy compound (a1). The amount of the unsaturated carboxylic acid (a2) is preferably in the range of 0.8 to 1.2 mol. 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) while air bubbling. 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(trimellitic anhydride) monoacetate, ethylene glycol bis(trimellitic anhydride), 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 preferred that the acid 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 3,3',4,4'-biphenyltetracarboxylic dianhydride. Residues. 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 is preferably in the range of 20 to 100 mol%, more preferably 40 to 100 mol, based on the total of the acid monoanhydride (a4). Within the range of % of ears, but 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 carboxyl group-containing resin (A1) can be obtained by a conventional method, preferably by reacting the reactive solution at a temperature of from 60 to 150 ° C, particularly preferably from 80 to 120 ° C. 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, it is possible to suppress the occurrence of ion migration in the layer of the cured product containing the photosensitive resin composition, and it is possible to further improve the insulation reliability of the layer.

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 in the range of 0.3 to 0.7 mol with respect to 1 mol of the epoxy group of the epoxy compound (a1). 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, This intermediate is a reaction product of an epoxy compound (g1) having two or more epoxy groups in one molecule and an ethylenically unsaturated compound (g2). The first resin (g), for example, may be such that the epoxy group in the epoxy compound (g1) is not ethylenic. The carboxyl group in the saturated compound (g2) is reacted to obtain an intermediate, and then the compound (g3) is added to an intermediate to obtain it. The epoxy compound (g1) may contain an appropriate epoxy resin: a cresol novolac type epoxy resin, a phenol novolak type epoxy resin, or the like. 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.

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, which contains, for example, the following compounds: acrylic acid, methacrylic acid, ω-carboxy-polycaprolactone (n≒2) monoacrylate, pentaerythritol triacrylate, pentaerythritol trimethyl Acrylate and the like. 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. Moreover, the viscosity of the film formed from the photosensitive resin composition can be sufficiently reduced. Further, the developability of the photosensitive resin composition by the alkaline aqueous solution can be ensured.

Next, components other than the carboxyl group-containing resin (A) contained in the photosensitive resin composition of the present embodiment will be described.

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). And epoxy compound (D).

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 monofunctional (meth) acrylates such as 2-hydroxyethyl (meth)acrylate; and, diethyl 2 Alcohol (methyl) Acrylate, trimethylolpropane di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol Polyfunctional (meth)acrylic acid such as (meth) acrylate, dipentaerythritol hexa(meth) acrylate, ε-caprolactone modified pentaerythritol hexaacrylate, tricyclodecane dimethanol di(meth) acrylate ester.

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 by 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, ethylene oxide (EO) modified trimethylolpropane III (Meth) acrylate, pentaerythritol tri(meth) acrylate, ethoxylated isocyanuric acid tri(meth) acrylate, ε-caprolactone modified ginseng (2-propenyl methoxyethyl) Isocyanurate, 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 For the specific example, the product model LIGHT ACRYLATE P-1A) manufactured by Kyoeisha Chemical Co., Ltd., and diphenyl-2-methylpropenyl methoxyethyl phosphate (as a specific example, manufactured by Daiba Industry Co., Ltd. Product model MR-260), and HFA series manufactured by Showa Polymer Co., Ltd. (as a specific example, dipentaerythritol hexaacrylate and HCA (9,10-dihydro-9-oxa-10-phosphaphenanthrene- The addition reactants of 10-oxide) are also the commercial models HFA-6003 and HFA-6007, caprolactone modified dipentaerythritol hexaacrylate and HCA (9,10-dihydro-9-oxa-10-phosphine) The addition reactant of phenanthrene-10-oxide is also the product models 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 thereto. Prepolymer; and, oligomeric (meth) acrylate 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 Ethyl (meth) acrylate, alkyd (meth) acrylate, oxirane (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). At this time, although the photosensitive resin composition contains the carboxyl group-containing resin (A1), it is still possible to apply the photosensitive resin group. The product imparts high sensitivity to ultraviolet light. Further, it is possible to suppress the occurrence of ion migration 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- Monothiol phosphine-based photopolymerization initiators 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-dichlorobenzhydryl)-1-naphthylphosphine oxide, bis-(2,6-dimethoxybenzylidene)phenyl oxide Phosphine, bis-(2,6-dimethoxybenzylidene)-2,4,4-trimethylpentylphosphine oxide, bis-(2,6-dimethoxybenzylidene)- 2,5-Dimethylphenylphosphine oxide, bis-(2,4,6-trimethylbenzylidene)phenylphosphine oxide, (2,5,6-trimethylbenzylidene)- A bis-indenylphosphine oxide-based photopolymerization initiator such as 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-based photopolymerization initiator (C1) to the hydroxyketone-based photopolymerization initiator (C2) is preferably in the range of 1:0.01 to 1:10. 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, the first pair of photosensitivity trees When the coating film formed of the lipid composition is partially exposed and then developed, since the hardening of the portion which is not exposed is suppressed, 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), precision can be performed. And it is easy to form a hole with a small diameter.

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. In addition, when the amount of bis(diethylamino)diphenyl ketone (C3) is 20% by mass or less based on the fluorenyl phosphine oxide-based photopolymerization initiator (C1), bis(diethylamino group) Diphenyl ketone (C3) does not easily impede the electrical insulation 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; , 4-diisopropyl xanthone and the like xanthone; and, Α-hydroxyketones such as 2-hydroxy-2-methyl-1-phenyl-propan-1-one; 2-methyl-1-[4-(methylthio)phenyl]-2-(N- A compound containing a nitrogen atom such as morpholinyl)-1-propanone. The photosensitive resin composition may contain, in addition to the photopolymerization initiator (C), ethyl p-dimethylbenzoate, p-amyl dimethylaminobenzoate, 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. As described above, the epoxy compound (D) contains a crystalline epoxy resin and 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.), a biphenyl type crystalline epoxy resin (a specific example, a trade name YX-4000 manufactured by Mitsubishi Chemical Corporation) and a diphenyl ether type crystalline epoxy resin (for specific examples, A product type YSLV-80DE manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd., a bisphenol-type crystalline epoxy resin (as a specific example, trade name YSLV-80XY manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd.), 肆 (hydroxyl a phenyl) ethane type crystalline epoxy resin (a specific example, a product model GTR-1800 manufactured by Nippon Kayaku Co., Ltd.) or a bisphenol fluorene type crystalline epoxy resin (having a specific example (S7) Epoxy resin).

The crystalline epoxy resin preferably has two epoxy groups in one molecule. At this time, it is more possible to make the cured product less likely to crack during the temperature change.

The crystalline epoxy resin preferably has an epoxy equivalent of from 150 to 300 g/eq. The epoxy equivalent is the gram weight of the crystalline epoxy resin containing 1 gram equivalent of the epoxy 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 of the photosensitive resin composition by an alkaline aqueous solution is particularly enhanced. 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. Product model manufactured by Chemical Co., Ltd. YSLV-80XY), a bisphenol quinone type crystalline epoxy resin (as a specific 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, biphenyl aldehyde varnish type epoxy resin (as a specific example) , product type NC-3000 manufactured by Nippon Kayaku Co., Ltd., 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, product type EPICLON HP-4032, EPICLON HP-4700, EPICLON HP-4770 manufactured by DIC Corporation), and tertiary catechol type epoxy resin (as a specific example) , product type EPICLON HP-820 manufactured by DIC Co., Ltd., and dicyclopentadiene type epoxy resin (as a specific example, the product model EPICLON manufactured by DIC Corporation) HP-7200), adamantane type epoxy resin (as a specific example, product type ADAMANTATE XE-201 manufactured by Idemitsu Kosan Co., Ltd.), special difunctional epoxy resin (as a specific example, manufactured by Mitsubishi Chemical Corporation) Models YL7175-500, and YL7175-1000; DIC Corporation's product models 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; product type YSLV-120TE manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd.), rubbery core-shell polymer modified bisphenol A type epoxy resin (as a specific example, Product model MX-156) manufactured by Kaneka Co., Ltd., rubber-like core-shell polymer modified bisphenol F-type epoxy resin (as a specific example, product model MX-136 manufactured by Kaneka Co., Ltd.), and rubber-containing particles Bisphenol F-type epoxy resin (commodity model MX-130 manufactured by Kaneka Co., Ltd. as a specific example).

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 phosphorus-containing epoxy resin may be contained in the crystalline epoxy resin, or the phosphorus-containing epoxy resin may be contained in the amorphous 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 EPOTOHTO FX-305 and so on.

The amorphous epoxy resin preferably contains an epoxy resin (da) having a bisphenol type structural unit (d1) and a structural unit (d2). When the amorphous epoxy resin contains an epoxy resin (da), the thermal shock resistance of the cured product of the photosensitive resin composition can be improved.

The structural unit (d1) may, for example, be a structural unit derived from bisphenol A, bisphenol F or bisphenol S. Specific examples of the structural unit (d1) include a unit obtained by removing OH groups at the terminal of these compounds, and a unit represented by the following formula (8). A part of the phenyl group and the phenyl group in the unit represented by the formula (8) may be hydrogenated. Further, the phenyl group and the phenyl group in the unit represented by the formula (8) may have a substituent such as a hydrocarbon group, an alkoxy group, an aryl group, an aryloxy group or a hydroxyl group.

The structural unit (d2) is composed of at least one selected from the group consisting of a linear hydrocarbon structural unit (d21) having 4 or more and 20 or less carbon atoms, and an ether oxygen atom number of 3 or more. A polyalkylene ether structural unit (d22) of 20 or less.

The linear hydrocarbon structural unit (d21) is a structural unit in which y of -(CH ₂ )y- is 4 or more and 20 or less. y is preferably 4 to 10. Further, in the structural unit in which y of -(CH ₂ )y- is 4 or more and 20 or less, a substituent such as a hydroxyl group may be substituted for the hydrogen atom. Further, at least one hydrogen atom of the structural unit in which y of -(CH ₂ )y- is 4 or more and 20 or less may be substituted with a hydrocarbon group, an alkoxy group, an aryl group, an aryloxy group or the like. The hydrocarbon group and the alkoxy group as the substituent are preferably 4 or less carbon atoms. The aryl group in the aryl group and the aryloxy group is preferably a phenyl group. The linear hydrocarbon structural unit (d21) may have such substituents within a range that does not impair the flexibility of the structural unit (d2).

The polyalkylene ether structural unit (d22) has an ether oxygen atom number of 3 or more and 20 or less, preferably 3 to 10. The polyalkylene ether structural unit (d22) may, for example, be a structural unit derived from a polymer selected from one or a plurality of alkylene oxides selected from the group consisting of ethylene oxide, propylene oxide, and epoxy. Butane, epoxy isobutane, pentylene oxide, tetrahydrofuran, and the like. Further, one or more hydrogen atoms of the alkylene oxide may be substituted with, for example, a hydroxyl group, an alkoxy group, an aryl group, an aryloxy group, a hydrocarbon group or the like. The hydrocarbon group and the alkoxy group as the substituent are preferably 4 or less carbon atoms. The aryl group in the aryl group and the aryloxy group is preferably a phenyl group. The polyalkylene ether structural unit (d22) may have such substituents within a range that does not impair the flexibility of the structural unit (d2).

The molar ratio of the structural unit (d1) to the structural unit (d2) is preferably 10:1 to 1:5, more preferably 5:1 to 1:3. When the molar ratio of the structural unit (d1) is higher than the above range, the amorphous epoxy resin does not have sufficient flexibility, and the cured product of the photosensitive resin composition is liable to be cracked. In addition, when the molar ratio of the structural unit (d1) is less than the above range, the Tg of the amorphous epoxy resin is too low, and the heat resistance of the cured product of the photosensitive resin composition is lowered.

Specifically, the epoxy resin (da) preferably has a structure of any one or more of the following structural formulae (9-i) to (9-iv). Further, a plurality of hydroxyl groups of the structural formula shown below may be subjected to a crosslinking reaction to bond an oxygen atom of a hydroxyl group to form an undefined structure.

In the structural formulae (9-i) to (9-iv), Ar ₁ and Ar ₂ are a structural unit (d1) which may be hydrogenated and may have a substituent. Ar ₁ and Ar ₂ may be the same or different. X is at least one selected from the group consisting of a linear hydrocarbon group having 4 or more and 20 or less carbon atoms, and a polyalkylene ether structure having an ether oxygen number of 1 or more and 18 or less. When X is a linear hydrocarbon group having 4 or more and 20 or less carbon atoms, X constitutes a structural unit (d2). When X is a polyalkylene ether structure having an ether oxygen atom number of 1 or more and 18 or less, -O-XO- constitutes a structural unit (d2). Further, n is an average value of the repeating unit and is 1 to 30.

The method of obtaining such an epoxy compound (da) is, for example, a method of curing a predetermined epoxy resin using a curing agent.

As such a predetermined epoxy resin, for example, a method of using an epoxy compound having structural units (d1) and (d2) as described above; using an epoxy compound having a structural unit (d1) in combination with a structural unit ( A method of the epoxy compound of d2); a method of using an epoxy compound having a structural unit (d1) in combination with a chain extender capable of imparting a structural unit (d2) to the epoxy compound by a reaction, or the like.

Specific examples of the epoxy compound (da) include, for example, product models EPICLON EXA4816 and EPICLON EXA4822 manufactured by DIC Corporation; and product models YL7175-500 and YL7175-1000 manufactured by Mitsubishi Chemical Corporation.

The epoxy equivalent of the epoxy compound having the structural unit (d1) and the structural unit (d1) is preferably 200 to 800 g/eq, more preferably 350 to 650 g/eq.

The amorphous epoxy resin preferably contains an epoxy resin (db) having a novolac structure and a biphenyl skeleton. A photosensitive resin composition containing an epoxy resin (db) has improved electrical insulating properties of the cured product. Therefore, the photosensitive resin composition is particularly suitable as an insulating material for a printed wiring board, and the insulating material of the printed wiring board requires high reliability such as inter-line insulation and interlayer migration resistance. Epoxy resin (db) containing amorphous biphenyl aldehyde varnish type epoxy resin (specific example is day) The product model NC-3000, model NC-3000-L, model NC-3000-H, model NC-3000-FH-75M, CER-3000-L) manufactured by the Chemical Co., Ltd.

The photosensitive resin composition of the present embodiment may contain melamine (E). At this time, the adhesion between the cured product of the photosensitive resin composition and a metal such as copper is improved. Therefore, the photosensitive resin composition is particularly suitable as an insulating material for a printed wiring board. Moreover, the plating resistance of the cured product of the photosensitive resin composition, that is, the whitening resistance at the time of electroless nickel plating/gold treatment is improved.

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; celecoxib, butyl acesulfame, etc.; carbitol, carbitol, propylene glycol methyl ether and other propylene glycol alkyl ether; a polypropylene glycol alkyl ether such as propylene glycol methyl ether; an acetate such as ethyl acetate, butyl acetate, celecoxib acetate or carbitol acetate; and a dialkyl glycol ether.

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.

The total amount of equivalents of the epoxy groups contained in the crystalline epoxy resin and the amorphous epoxy resin is 2.5 or less with respect to 1 equivalent of the carboxyl group contained in the carboxyl group-containing resin (A), and the developability can be improved. a crystalline epoxy resin and a non-valent carboxyl group contained in the carboxyl group-containing resin (A) The total amount of the epoxy groups contained in the crystalline epoxy resin is preferably 0.7 to 2.3, more preferably 0.7 to 2.0.

The equivalent of the epoxy group of the crystalline epoxy resin is preferably in the range of 0.2 to 1.9 with respect to 1 equivalent of the carboxyl group contained in the carboxyl group-containing resin (A). In this case, the developability of the photosensitive resin composition can be particularly improved. The equivalent of the epoxy group of the crystalline epoxy resin is preferably in the range of 0.3 to 1.7 with respect to 1 equivalent of the carboxyl group contained in the carboxyl group-containing resin (A).

The equivalent of the epoxy group of the amorphous epoxy resin is preferably in the range of 0.05 to 1.5 with respect to 1 equivalent of the carboxyl group contained in the carboxyl group-containing resin (A). In this case, the developability of the photosensitive resin composition can be particularly improved, and the crack resistance of the cured product in the repeated progress of the temperature change can be improved. The equivalent of the epoxy group of the amorphous epoxy resin is preferably in the range of 0.1 to 1.2 with respect to 1 equivalent of the carboxyl group contained in the carboxyl group-containing resin (A).

When the photosensitive resin composition contains melamine (E), the amount of melamine (E) is preferably in the range of 0.1 to 10% by mass, and 0.5 to 5% by mass based on the carboxyl group-containing resin (A). Further within the range is further preferred.

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 in the range of 15 to 60% by mass, based on the entire photosensitive resin composition. It is further preferred. 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.

For example, the photosensitive resin composition may contain an inorganic filler. At this time, the hardening shrinkage of the film formed of the photosensitive resin composition is lowered. The inorganic filler may contain, for example, one or more materials selected from the group consisting of barium sulfate, crystalline cerium oxide, nano cerium oxide, carbon nanotubes, talc, and bentonite. , aluminum hydroxide, magnesium hydroxide, and titanium dioxide. When the inorganic filler contains a white material such as titanium oxide or zinc oxide, the photosensitive resin composition and the cured product thereof can be whitened. The amount of the inorganic filler in the photosensitive resin composition can be appropriately set. However, the amount of the inorganic filler is preferably in the range of 1 to 300% by mass based on the carboxyl group-containing resin (A).

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 cocondensation resin , an amide-based resin such as a benzoguanamine-based co-condensation resin; various thermosetting resins other than the above; an ultraviolet curable ring Oxy (meth) acrylate; a resin obtained by adding (meth)acrylic acid to an epoxy resin such as a bisphenol A type, a phenol novolac type, a cresol novolak type, or an alicyclic type; and, adjacent A polymer compound such as diallyl phthalate resin, phenoxy resin, amine ester resin or fluororesin.

The photosensitive resin composition may contain a hardener for hardening 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. Commercial products of these components include, for example, 2MZ-A, 2MZ-OK, 2PHZ, 2P4BHZ, and 2P4MHZ manufactured by Shikoku Chemicals Co., Ltd. (all trade names of imidazole compounds); manufactured by San-Apro Co., Ltd. U-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 an adhesiveness imparting agent other than melamine (E). The adhesion imparting agent is, for example, guanamine, acetamide, benzoguanamine, and 2,4-diamino-6-methylpropenyloxyethyl-S-three. Isophthalic acid, 2-vinyl-4,6-diamino-S-triazine, 2-vinyl-4,6-diamino-S-triazine, isomeric cyanuric acid adduct, 2,4 An S-triazine derivative such as an isomeric cyanuric acid addition product of diamino-6-methacryloxyethyl-S-triazine.

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 first adding a component having a low viscosity in addition to a liquid component in the raw material. The other portions are kneaded, 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 previously mixing 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 by 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 as 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 form 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 40 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 could be developed by the aqueous sodium carbonate solution.

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 make sense The organic solvent in the photo-resin composition is volatilized, and the wet film is dried, for example, 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 ultraviolet light source may be selected from the group consisting of a chemical lamp, a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, an ultra high pressure mercury lamp, a xenon lamp, and a 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 film. 4 of the desired part of the exposure. The light source suitable for the direct drawing method may be selected 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), and 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 developer is, for example, an alkaline aqueous solution containing at least one of an alkali metal salt and an alkali metal hydroxide; or an organic amine. 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. 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, preferably an alkaline aqueous solution containing at least one of an alkali metal salt and an alkali metal hydroxide, particularly preferably sodium carbonate water-soluble liquid. 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, the printed wiring board 11 can be obtained, as shown in FIG. 1E, comprising: a first conductor line 3; a second conductor line 8; and an interlayer insulating layer 7 interposed between the first conductor lines 3 and the second conductor line 8; and the through hole 10 electrically connects the first conductor line 3 and the second conductor line 8. Further, in FIG. 1E, the perforated plating 9 has a tubular shape in which the inner surface of the hole 6 is covered, but the perforated plating 9 may be entirely filled inside the hole 6.

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 the film, a coating method and a dry film method are exemplified. 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 at one of the time points before and after the heating, or before and after the 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.

[Synthesis Example A-1 to Synthesis Examples A-10 and B-2]

(1) Synthesis Example A-1 to Synthesis Examples A-10 and B-2

In the four-necked flask equipped with a reflux condenser, a thermometer, an air blowing tube, and a stirrer, add the column shown in the "First Reaction" column in Tables 1 and 2. The raw material components are stirred and the raw material components are stirred in a state where air foaming is performed, thereby blending the mixture. The mixture was stirred while being air-bubble in a four-necked flask, and heated under the reaction temperature and reaction time shown in the column of "reaction conditions". Thereby, a solution of the intermediate is formulated.

Then, the raw material components shown in the "second reaction" column of Tables 1 to 2 were placed in the solution of the intermediate in the four-necked flask, and the inside of the four-necked flask was stirred while air bubbling was performed. The solution was heated while reacting at the reaction temperature and reaction time shown in the column of "Reaction conditions (1)". Then, in addition to the synthesis example B-2, the solution in the four-necked flask was stirred while air bubbling was performed, and the reaction temperature and reaction time shown in the column of "reaction condition (2)" were used. Heat up. 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 1-2. The molar ratio between the components is also shown in Tables 1-2.

In addition, the details of the components shown in the column (a1) in Tables 1-2 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.

(2) Synthesis Example B-1

48 parts by mass of methacrylic acid and 50 parts by mass of ω-carboxy-polycaprolactone (n≒2) monoacrylic acid were added to a four-necked flask equipped with a reflux condenser, a thermometer, a glass tube for nitrogen substitution, and a stirrer. Ester (ARONIX M-5300, manufactured by Toagosei Co., Ltd.), 92 parts by mass of methyl methacrylate, 10 parts by mass of styrene, 430 parts by mass of dipropylene glycol monomethyl ether, and 3.5 parts by mass of azo Double isobutyronitrile. 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.

Then, 0.1 parts by mass of hydroquinone, 64 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. Thereby an addition reaction is carried out. Thereby, a 38 mass% solution of the carboxyl group-containing resin (B-1) was obtained. The acid value of the carboxyl group-containing resin (B-1) was 67 mgKOH/g.

[Examples X1 to X22, Examples Y1 to Y19, Examples Z1 to Z21, Comparative Examples X1 to X11, Comparative Examples Y1 to Y5, and Comparative Examples Z1 to Z7]

After the components shown in the "composition" column of Tables 3 to 13 described later were blended in a three-roll mill, the components were stirred and mixed in a flask to obtain a photosensitive resin composition. Furthermore, the details of the components are as follows. The following crystalline epoxy resin was separately pulverized in advance using a jet mill or a mortar to have an average particle diameter of 20 μm or less.

‧ Unsaturated Compound A: Trimethylolpropane triacrylate.

‧ Unsaturated compound B: ε-caprolactone modified dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd., product model DPCA-60).

‧ Unsaturated compound C: tricyclodecane dimethanol diacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., product model A-DCP).

‧ Unsaturated compound D: ε-caprolactone modified dipentaerythritol hexaacrylate, manufactured by Nippon Kayaku Co., Ltd., product model KAYARAD DPCA-20.

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

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

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

‧Crystalline epoxy resin A: 1,3,5-gin(2,3-epoxypropyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione (High melting point type, melting point 150~158 ° C, epoxy equivalent 99 g/eq).

‧ Crystalline Epoxy Resin B: Hydroquinone-type crystalline epoxy resin (trade name: YDC-1312, manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd., melting point: 138 to 145 ° C, epoxy equivalent: 176 g/eq).

‧ Crystalline Epoxy Resin C: 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 D: Diphenyl ether type crystalline epoxy resin (trade name: YSLV-80DE, manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd., melting point: 80 to 90 ° C, epoxy equivalent: 163 g/eq).

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

‧A solution of amorphous epoxy resin A: Amorphous biphenyl aldehyde varnish type epoxy resin (manufactured by Nippon Kayaku Co., Ltd., product model NC-3000, softened in a solid content of 80%) a solution of 53-63 ° C, an epoxy equivalent of 280 g / eq, an epoxy resin having a novolac structure and a biphenyl skeleton, dissolved in diethylene glycol monoethyl ether acetate (80% solid content) The converted epoxy equivalent is 350 g/eq).

‧A solution of amorphous epoxy resin B: a bisphenol A type epoxy resin containing a long-chain carbon chain (manufactured by DIC Corporation, product type EPICLON EXA-4816, liquid) Resin, An epoxy equivalent of 410 g/eq, a structural unit (d1) comprising a bisphenol A skeleton, and a structural unit (d2) comprising a linear hydrocarbon having 6 carbon atoms) dissolved in diethylene glycol monoethyl ether acetate The solution (the epoxy equivalent in terms of 90% of the solid content was 455.56 g/eq).

‧Solid epoxy resin C solution: rubbery core-shell polymer liquid bisphenol F-type epoxy resin (manufactured by Kaneka Co., Ltd., product type MX-136, liquid resin, epoxy equivalent 220g/eq) .

‧ A solution of amorphous epoxy resin D: a cresol novolac type epoxy resin (manufactured by DIC Co., Ltd., product type EPICLON N-695, softening point 90 to 100 ° C, in a solid content of 75%) The epoxy equivalent (214 g/eq) was dissolved in diethylene glycol monoethyl ether acetate (the epoxy equivalent in terms of solid content of 75% was 285 g/eq).

‧Solid epoxy resin E solution: A bisphenol A type epoxy resin containing a long-chain carbon chain (manufactured by DIC Co., Ltd., product model EPICLON EXA-4822, a solid content of 85%) Resin, epoxy equivalent 389g / eq, structural unit (d1) contains bisphenol A skeleton, structural unit (d2) contains polyethylene glycol and ether oxygen atom number is 4) soluble in diethylene glycol monoethyl ether The solution obtained from the acid ester (the epoxy equivalent in terms of 85% of the solid content was 457.65 g/eq).

‧ A solution of amorphous epoxy resin F: an amorphous biphenyl aldehyde varnish type epoxy resin (epoxy resin having a novolac structure and a biphenyl skeleton) in a solid content of 80% (Japan) Manufactured by Chemical Pharmaceutical Co., Ltd., product type NC-3000H, softening point 65~75°C, epoxy equivalent 290 g/eq) A solution obtained by dissolving diethylene glycol monoethyl ether acetate (the epoxy equivalent in terms of 80% solid content was 362.5 g/eq).

‧ Melamine: Made by Nissan Chemical Industry Co., Ltd., melamine micropowder.

‧Antioxidant: A hindered phenolic antioxidant (manufactured by BASF, product model IRGANOX 1010).

‧ Blue pigment: Phthalocyanine blue.

‧ yellow pigment: 1,1'-[(6-phenyl-1,3,5-triazine-2,4-diyl)bis(imino)]bis(9,10-nonanedione)

‧ Barium sulfate: manufactured by 堺Chemical Industries Co., Ltd., product model BARIACE B31.

‧ Talc: Made by Talc, Japan, product model SG-2000.

‧ Bentonite: manufactured by REOX, the product model Bentone SD-2.

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

‧Interactive surfactant: DIC Co., Ltd., product model MEGAFACE F-477.

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

‧ Solvent A: Diethylene glycol monoethyl ether acetate.

‧ Solvent B: methyl ethyl ketone.

[Production of test pieces using Examples X1 to X22 and Comparative Examples X1 to X11]

With respect to Examples X1 to X16, Examples X18 to X22, and Comparative Examples X1 to X11, test pieces were produced in the following manner.

A glass epoxy copper clad laminate (FR-4 type) having a thickness of 35 μm copper foil 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 core material having a line width/space of 50 μm /50 μm . A photosensitive resin composition is applied onto the entire surface of one side of the core material by a screen printing method to form a wet coating film. The wet coating film was heated at 80 ° C for 40 minutes to carry out preliminary drying to form a film having a film thickness of 25 μm . The film was irradiated 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. Then, the film was irradiated with ultraviolet rays under the conditions of 1000 mJ/cm ² , and then heated at 160 ° C for 60 minutes. Thereby, a layer composed of a cured product of the photosensitive resin composition is formed on the core material. Thereby, a test piece was obtained.

With respect to Example X17, a test piece was produced in the following manner.

The photosensitive resin composition was applied onto a film made of polyethylene terephthalate by an applicator, and then dried by heating at 95 ° C for 25 minutes. A dry film having a thickness of 25 μm was formed on the film. Further, the dry film was heated and laminated on the entire surface of one of the core materials of the same manner as in the examples X1 to X16, the examples X18 to X22, and the comparative examples X1 to X11 by a vacuum laminator. The heating lamination was carried out under the conditions of 0.5 MPa, 80 ° C, and 1 minute. Thereby, a film having a thickness of 25 μm composed of a dry film was formed on the core material. The film was subjected to exposure, development, and ultraviolet irradiation treatment under the same conditions as above. Further, after the exposure, the film of polyethylene terephthalate was peeled off from the dry film (film) before development. Thereby, a layer composed of a cured product of a photosensitive resin composition (also referred to as a cured product of a dry film) is formed on the core material. Thereby, a test piece was obtained.

[Preparation of test pieces using Examples Y1 to Y19 and Comparative Examples Y1 to Y5, and Examples Z1 to Z21 and Comparative Examples Z1 to Z7]

With respect to Examples Y1 to Y18 and Comparative Examples Y1 to Y5, and Examples Z1 to Z20 and Comparative Examples Z1 to Z7, test pieces were produced in the following manner.

The core materials were obtained in the same manner as in the examples X1 to X22 and the comparative examples X1 to X11. The conductor layer C5-8100 manufactured by MEC Co., Ltd. was used to dissolve and remove the surface layer portion of the conductor wiring of the printed wiring board having a thickness of about 1 μm , thereby roughening the conductor wiring. Then, in the same manner as in the examples X1 to X22 and the comparative examples X1 to X11, a layer composed of a cured product of a photosensitive resin composition was formed on the core material. Thereby, a test piece was obtained.

When the photosensitive resin compositions of Example Y19 and Example Z21 were used, test pieces were produced in the following manner. A dry film was formed in the same manner as in Example X17. Further, the dry film was heated and laminated on one side of the same core material as in the examples Y1 to Y18 and the comparative examples Y1 to Y5, and the examples Z1 to Z20 and the comparative examples Z1 to Z7 by a vacuum laminator. The entire face. The heating lamination was carried out under the same conditions as in Example X17. Then, the same treatment as in Example X17 was carried out to obtain a test piece.

[evaluation test]

(1) Viscosity

With respect to the examples and comparative examples other than Example X17, Example Y19, and Example Z21, when the test piece was produced, the degree of viscosity of the film when the negative mask was removed from the film after exposure of the film was as follows. Ways to evaluate.

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, regarding Comparative Example X5, Comparative Example X9, and Comparative Example X11 in which the viscosity evaluation was C, the evaluation of (2) to (8) was not performed. Further, regarding Comparative Example Y4, Comparative Example Y5, and Comparative Example Z6 in which the viscosity evaluation was C, the evaluations of (3) to (8) were not performed. Further, regarding the embodiment X17, the embodiment Y19 and Example Z21 were films formed from a dry film, and therefore no evaluation of stickiness was performed.

(2) developability

With respect to the examples and comparative examples other than Example X17, Example Y19, and Example Z21, the photosensitive resin composition was applied by screen printing on the entire surface of one side of the printed wiring board, thereby forming a photosensitive resin composition. Wet the film. The wet coating film was heated at 80 ° C for 40 minutes and 60 minutes to form a film having a film thickness of 25 μm . The film is subjected to development treatment without exposure. 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, and then pure water was sprayed onto the film at an ejection pressure of 0.2 MPa for 90 seconds. The treated printed wiring board was observed and the results were evaluated in the following manner.

A: When the wet coating film was heated for any time of 40 minutes and 60 minutes, the film was completely removed.

B: When the wet coating film was heated for 40 minutes, the film was completely removed, but when the wet film was heated for 60 minutes, a part of the film remained on the printed wiring board.

C: When the wet coating film is heated for 40 minutes or 60 minutes, a part of the film remains on the printed wiring board.

Further, with respect to Comparative Example X4, Comparative Example X7, Comparative Example Y4, and Comparative Example Y5 in which developability was evaluated as C, evaluation of (3) to (8) was not performed. Further, in Example X17, Example Y19, and Example Z21, since the film was formed from the dry film, evaluation of developability was not performed. About implementation Example X17, Example Y19, and Example Z21, in the development step after exposure, can be developed without causing problems.

(3) Resolution

The pores formed on the layer composed of the cured product in the test pieces of the examples and the 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.

(4) Plating resistance

First, a nickel plating layer was formed using a commercially available electroless nickel plating bath on a portion where the conductor lines of the test pieces of the examples and the comparative examples were exposed to the outside, and a gold plating 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. The layer composed of the cured material and the metal layer were visually observed. Further, a cellophane adhesive tape peeling test was carried out on the layer composed of the cured product. 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 layer composed of the cured product was not peeled off due to the cellophane adhesive tape peeling test.

B: Discoloration was confirmed in the layer composed of the cured product, but the layer formed of the cured product was not peeled off due to the cellophane adhesive tape peeling test.

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

(5) Insulation between wires

A conductor line (comb electrode) in the test pieces of the examples X1 to X22, the comparative examples X1 to X11, the examples Y1 to Y19, the comparative examples Y1 to Y5, the examples Z1 to Z21, and the comparative examples Z1 to Z7. A direct current (DC) bias voltage of 30 V was applied, and the printed wiring board was exposed to a test environment of 121 ° C and 97% relative humidity (RH) for 150 hours (Examples Z1 to Z21, Comparative Example). The test piece of Z1~Z7 is 200 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 was maintained at 10 ⁶ Ω or more from the start of the test until 150 hours (the test pieces of Examples Z1 to Z21 and Comparative Examples Z1 to Z7 were 200 hours).

B: The resistance value was maintained at 10 ⁶ Ω or more from the start of the test to the lapse of 100 hours (the test pieces of Examples Z1 to Z21 and Comparative Examples Z1 to Z7 were 180 hours), but from the start of the test to the passage of the test The resistance value was less than 10 ⁶ Ω before 150 hours (the test pieces of Examples Z1 to Z21 and Comparative Examples Z1 to Z7 were 200 hours).

C: The resistance value was less than 10 ⁶ Ω from the start of the test to 100 hours (the test pieces of Examples Z1 to Z21 and Comparative Examples Z1 to Z7 were 180 hours).

(6) interlayer insulation

On the layers composed of the cured materials in the test pieces of Examples X1 to X22, Comparative Examples X1 to X11, Examples Y1 to Y19, Comparative Examples Y1 to Y5, Examples Z1 to Z21, and Comparative Examples Z1 to Z7, Adhesive conductive adhesive band. 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% RH for 60 hours (the test pieces of Examples Z1 to Z21 and Comparative Examples Z1 to Z7 were 80 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 to the lapse of 60 hours (the test pieces of Examples Z1 to Z21 and Comparative Examples Z1 to Z7 were 80 hours).

B: The resistance value was maintained at 10 ⁶ Ω or more from the start of the test to the lapse of 50 hours (the test pieces of Examples Z1 to Z21 and Comparative Examples Z1 to Z7 were 70 hours), but from the start of the test to the passage of the test The resistance value was less than 10 ⁶ Ω before 60 hours (the test pieces of Examples Z1 to Z21 and Comparative Examples Z1 to Z7 were 80 hours).

C: The resistance value was less than 10 ⁶ Ω from the start of the test to 50 hours (the test pieces of Examples Z1 to Z21 and Comparative Examples Z1 to Z7 were 70 hours).

(7) Pressure cooker test (PCT)

The test pieces of Examples X1 to X22, Comparative Examples X1 to X11, Examples Y1 to Y19, Comparative Examples Y1 to Y5, Examples Z1 to Z21, and Comparative Examples Z1 to Z7 were placed in an environment of 121 ° C and 100% RH. 100 hours (the test pieces of Examples Z1 to Z21 and Comparative Examples Z1 to Z7 were 150 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.

(8) Thermal cycle

The test pieces of Examples X1 to X22, Comparative Examples X1 to X11, Examples Y1 to Y19, Comparative Examples Y1 to Y5, Examples Z1 to Z21, and Comparative Examples Z1 to Z7 were repeatedly cooled at -65 ° C for 10 minutes. The treatment was carried out by heating at 150 ° C for 10 minutes for 1000 times. The appearance of the layer composed of the cured product in the test piece was evaluated based on the following evaluation criteria at the time of performing 500 treatments and at the time of performing 1000 treatments.

A: No cracking occurred in 500 treatments and 1000 treatments.

B: No crack occurred at the time of 500 treatments, but cracking occurred at 1000 treatments.

C: Cracking occurred in 500 treatments and 1000 treatments.

As is apparent from the above-described embodiment, the photosensitive resin composition of the first aspect contains: a carboxyl group-containing resin (A); and an unsaturated compound (B) having at least one ethylenically unsaturated bond in one molecule; a polymerization initiator (C); and an epoxy compound (D); and the carboxyl group-containing resin (A) contains a carboxyl group-containing resin (A1) which is a reaction product of an intermediate and an acid anhydride. 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 represented by the above formula (1), and has the following formula In (1), R ₁ to R ₈ are each independently hydrogen, an alkyl group having 1 to 5 carbon atoms, or a halogen; and the epoxy compound (D) contains a crystalline epoxy resin and an amorphous epoxy resin, and The total amount of equivalents of the epoxy groups contained in the crystalline epoxy resin and the amorphous epoxy resin is in the range of 0.7 to 2.5 with respect to 1 equivalent of the carboxyl group of the carboxyl group-containing resin (A).

In the photosensitive resin composition, the carboxy group-containing resin (A1) has a bisphenol fluorene skeleton represented by the formula (1) derived from the epoxy compound (a1), and is capable of sensitizing the carboxyl group-containing resin (A1). The cured product of the resin composition imparts high heat resistance and insulation reliability. When the epoxy compound (D) contains a crystalline epoxy resin, the developability of the photosensitive resin composition can be improved. When the epoxy compound (D) contains only a crystalline epoxy resin, the cured product of the photosensitive resin composition contains a temperature rise and a temperature decrease. The temperature change is repeated and cracking is likely to occur. However, in the present embodiment, the epoxy resin (D) contains the crystalline epoxy resin and the amorphous epoxy resin in the predetermined ratio, and the cured product of the photosensitive resin composition can be prevented from being repeatedly changed in temperature. It is prone to cracking. The total amount of equivalents of the epoxy groups contained in the crystalline epoxy resin and the amorphous epoxy resin is 0.7 or more with respect to 1 equivalent of the carboxyl group contained in the carboxyl group-containing resin (A), and the photosensitive property can be improved. The insulation reliability of the layer of the cured product of the resin composition can improve the crack resistance of the cured product in the repeated progress of the temperature change. The total amount of equivalents of the epoxy groups contained in the crystalline epoxy resin and the amorphous epoxy resin is 2.5 or less with respect to 1 equivalent of the carboxyl group contained in the carboxyl group-containing resin (A), and the developability can be improved. Therefore, even if the photosensitive resin composition of the present embodiment contains a carboxyl group-containing resin having a bisphenol fluorene skeleton, excellent developability can be obtained, and the cured product of the photosensitive resin composition can be prevented from being easily changed in temperature. Cracking occurred.

The photosensitive resin composition of the second aspect is preferably one equivalent of a carboxyl group with respect to the carboxyl group-containing resin (A), and the epoxy group of the crystalline epoxy resin has an equivalent weight of 0.2 to 1.9.

The photosensitive resin composition can improve the developability as compared with the photosensitive resin composition in which the equivalent of the epoxy group of the crystalline epoxy resin is in the range of 0.2 to 1.9.

The photosensitive resin composition of the third aspect is preferably a crystalline epoxy resin having two epoxy groups in one molecule.

In the photosensitive resin composition, the cured product of the photosensitive resin composition can be prevented from being cracked easily during the temperature change.

In the photosensitive resin composition of the fourth aspect, preferably, the amorphous epoxy resin contains an epoxy resin (da) having a bisphenol structural unit (d1) and a structural unit (d2) The structural unit (d2) is at least one of a linear hydrocarbon structural unit having 4 or more and 20 or less carbon atoms and a polyalkylene ether structural unit having an ether oxygen number of 3 or more and 20 or less.

This photosensitive resin composition can improve the thermal shock resistance of the cured product as compared with the case where the epoxy resin (da) is not contained.

In the photosensitive resin composition of the fifth aspect, it is preferable that the amorphous epoxy resin contains an epoxy resin (db) having a novolac structure and a biphenyl skeleton.

This photosensitive resin composition has improved electrical insulating properties of the cured product. Therefore, the photosensitive resin composition is particularly suitable as an insulating material for a printed wiring board, and the insulating material of the printed wiring board requires high reliability such as inter-line insulation and interlayer migration resistance.

In the photosensitive resin composition of the sixth aspect, it is preferred that the acid anhydride contains acid dianhydride.

At this time, the carboxyl group-containing resin (A1) is crosslinked by the acid dianhydride (a3) to adjust the molecular weight. Therefore, a carboxyl group-containing resin (A1) having a moderately adjusted acid value and molecular weight can be obtained. Further, by controlling the amount of the acid dianhydride (a3), the molecular weight and the acid value of the carboxyl group-containing resin (A1) can be easily adjusted.

In the photosensitive resin composition of the seventh aspect, it is preferred that the acid dianhydride contains 3,3',4,4'-biphenyltetracarboxylic dianhydride.

The photosensitive resin composition can easily obtain a film having a suppressed viscosity while ensuring good developability, and a cured product having improved insulation reliability and plating resistance can be easily obtained.

In the photosensitive resin composition of the eighth aspect, it is preferred that the weight average molecular weight of the carboxyl group-containing resin (A1) is in the range of 1,000 to 5,000.

In this case, it is easy to suppress the viscosity of the film formed of the photosensitive resin composition, and it is easy to improve the insulation reliability and the plating resistance of the cured product formed of the photosensitive resin composition, and it is easy to improve the composition of the photosensitive resin. The developability of the substance by an aqueous alkaline solution.

In the photosensitive resin composition of the ninth aspect, the acid value of the solid content of the carboxyl group-containing resin (A1) is preferably in the range of 60 to 140 mgKOH/g.

At this time, the developability of the photosensitive resin composition is easily improved.

In the photosensitive resin composition of the tenth aspect, it is preferred that the acid anhydride contains 1,2,3,6-tetrahydrophthalic anhydride.

At this time, it is easy to suppress the viscosity of the film formed of the photosensitive resin composition, and it is easy to improve the insulation reliability and the plating resistance of the cured product formed of the photosensitive resin composition.

A dry film according to the eleventh aspect, which is characterized in that it is a dried product of the above-mentioned photosensitive resin composition.

In this case, even if the dry film contains a carboxyl group-containing resin having a bisphenol fluorene skeleton, excellent developability can be obtained, and the cured product can be prevented from being cracked easily during the temperature change.

A printed wiring board according to a twelfth aspect, comprising: a solder resist layer comprising a cured product of the photosensitive resin composition.

At this time, the solder resist layer is less prone to cracking during the temperature change.

A printed wiring board according to a thirteenth aspect, comprising: an interlayer insulating layer comprising a cured product of the photosensitive resin composition.

At this time, the interlayer insulating layer is less prone to cracking during the temperature change.

A method for producing a photosensitive resin composition according to a fourteenth aspect, comprising the steps of: reacting an epoxy compound (a1) with an unsaturated group-containing carboxylic acid (a2), thereby obtaining an intermediate; The intermediate is reacted with an acid anhydride to synthesize a carboxyl group-containing resin (A1), and the carboxyl group-containing resin (A) containing the carboxyl group-containing resin (A1) and an unsaturated compound having at least one ethylenically unsaturated bond in one molecule. (B) a step of mixing the photopolymerization initiator (C) and the epoxy compound (D); and the epoxy compound (a1) has a bisphenol fluorene skeleton represented by the above formula (1), and In (1), R ₁ to R ₈ are each independently hydrogen, an alkyl group having 1 to 5 carbon atoms, or a halogen; and the epoxy compound (D) contains a crystalline epoxy resin and an amorphous epoxy resin, and The total amount of equivalents of the epoxy groups contained in the crystalline epoxy resin and the amorphous epoxy resin is in the range of 0.7 to 2.5 with respect to 1 equivalent of the carboxyl group of the carboxyl group-containing resin (A).

In the photosensitive resin composition obtained by the production method, the carboxyl group-containing resin (A1) has a bisphenol fluorene skeleton represented by the formula (1) derived from the epoxy compound (a1), and can contain a carboxyl group-containing resin. The cured product of the photosensitive resin composition of (A1) imparts high heat resistance and insulation reliability. When the epoxy compound (D) contains a crystalline epoxy resin, the developability of the photosensitive resin composition can be improved. When the epoxy compound (D) contains only the crystalline epoxy resin, the cured product of the photosensitive resin composition is likely to be cracked when the temperature change including temperature rise and temperature decrease is repeated. However, in the present embodiment, the epoxy resin (D) contains the crystalline epoxy resin and the amorphous epoxy resin in the predetermined ratio, and the cured product of the photosensitive resin composition can be prevented from being repeatedly changed in temperature. It is prone to cracking. The total amount of equivalents of the epoxy groups contained in the crystalline epoxy resin and the amorphous epoxy resin is 0.7 or more with respect to 1 equivalent of the carboxyl group contained in the carboxyl group-containing resin (A), and the photosensitive property can be improved. The insulation reliability of the layer of the cured product of the resin composition can improve the crack resistance of the cured product in the repeated progress of the temperature change. The total amount of equivalents of the epoxy groups contained in the crystalline epoxy resin and the amorphous epoxy resin is 2.5 or less with respect to 1 equivalent of the carboxyl group contained in the carboxyl group-containing resin (A), and the developability can be improved. Therefore, even if the photosensitive resin composition of the present embodiment contains a carboxyl group-containing resin having a bisphenol fluorene skeleton, excellent developability can be obtained, and the cured product of the photosensitive resin composition can be prevented from being easily changed in temperature. Cracking occurred.

1‧‧‧ core material

2‧‧‧Insulation

3‧‧‧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 (13)

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); The oxygen-containing compound (D); and the carboxyl group-containing resin (A) contains a carboxyl group-containing resin (A1) which is a reactant of an intermediate and an acid anhydride, and the intermediate is an epoxy compound (a1) and The reactant containing the unsaturated carboxylic acid (a2); the epoxy compound (a1) has a bisphenol fluorene skeleton represented by the following formula (1), and in the following formula (1), each of R ₁ to R ₈ It is independently hydrogen, an alkyl group having 1 to 5 carbon atoms, or a halogen; and the epoxy compound (D) contains a crystalline epoxy resin and an amorphous epoxy resin, and is further based on the carboxyl group-containing resin (A). 1 equivalent of a carboxyl group, and the total equivalent of the epoxy group of the crystalline epoxy resin and the amorphous epoxy resin is in the range of 0.7 to 2.5. The photosensitive resin composition according to claim 1, wherein the equivalent epoxy group of the crystalline epoxy resin is in the range of 0.2 to 1.9 with respect to 1 equivalent of the carboxyl group of the carboxyl group-containing resin (A). The photosensitive resin composition according to claim 1 or 2, wherein the crystalline epoxy resin has two epoxy groups in one molecule. The photosensitive resin composition according to claim 1 or claim 2, wherein the amorphous epoxy resin contains an epoxy resin (da) having a bisphenol structural unit (d1) And the structural unit (d2), wherein the structural unit (d2) is at least 4 or more and 20 or less linear hydrocarbon structural units and at least 3 or more and 20 or less polyalkylene ether structural units having an ether oxygen atom number; One. The photosensitive resin composition according to claim 1 or 2, wherein the amorphous epoxy resin contains an epoxy resin (db) having a novolac structure and a biphenyl skeleton. The photosensitive resin composition according to claim 1 or 2, wherein the acid anhydride contains an acid dianhydride. The photosensitive resin composition according to claim 6, wherein the acid dianhydride contains 3,3',4,4'-biphenyltetracarboxylic dianhydride. The photosensitive resin composition according to claim 1 or 2, wherein the weight average molecular weight of the carboxyl group-containing resin (A1) is in the range of 1,000 to 5,000. The photosensitive resin composition according to claim 1 or 2, wherein the solid content of the carboxyl group-containing resin (A1) is in the range of 60 to 140 mgKOH/g. The photosensitive resin composition according to claim 1 or 2, wherein the acid anhydride contains 1,2,3,6-tetrahydrophthalic anhydride. A dry film which is a dried product of the photosensitive resin composition according to any one of claims 1 to 10. 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 10. A printed wiring board comprising an interlayer insulating layer, which comprises a cured product of the photosensitive resin composition according to any one of claims 1 to 10.