TW201937288A - Photosensitive resin composition, dry film and printed wiring board capable of suppressing excessive decrease in the thickness of cured product caused by oxidizing agent - Google Patents

Abstract

An object of the invention is to provide a photosensitive resin composition capable of being formed as a cured product by curing, wherein, when the surface of the cured product is roughened by treating with an oxidizing agent, an excessive decrease in the thickness of the cured product caused by the oxidizing agent can be suppressed, and non-uniform surface after the treatment can be suppressed. The photosensitive resin composition of the invention comprises: a carboxyl-containing resin (A), an unsaturated compound (B) having at least one ethylenically unsaturated bond in one molecule, a photopolymerization initiator (C), an epoxy compound (D), an organic filler (E) containing an organic filler with a carboxyl group (E1), and a triazine resin (F). The triazine resin (F) satisfies at least one of the following conditions: the triazine resin (F) is in a liquid state at 25 DEG C; and the photosensitive resin composition contains a solvent (H) and the triazine resin (F) dissolves in the solvent (H) at 25 DEG C.

Description

Photosensitive resin composition, dry film and printed wiring board

The present invention relates to: a photosensitive resin composition; a dry film containing the photosensitive resin composition; a printed wiring board having an interlayer insulating layer, the interlayer insulating layer containing a cured product of the photosensitive resin composition; And, a printed wiring board including a solder resist layer including a cured product of the photosensitive resin composition.

Conventionally, in order to form an electrically insulating layer of a printed wiring board, various curable resin compositions have been used. The electrically insulating layer is a solder resist layer, a plating resist layer, a resist layer, and interlayer insulation. Layers etc. Such a resin composition is, for example, a photosensitive resin composition.

In order to impart high heat resistance to a layer formed of a photosensitive resin composition, a method of containing an epoxy compound in the photosensitive resin composition is performed, and the photosensitive resin composition contains a carboxyl group-containing resin. When a plating layer is formed on a layer (hereinafter, also referred to as a cured material layer) composed of a cured material of the photosensitive resin composition, the cured material layer may be formed in a pretreatment step of the plating process. The surface is roughened using, for example, an oxidant containing potassium permanganate. At this time, the surface of the hardened layer may be excessively corroded by the oxidizing agent, and the thickness of the hardened layer may be reduced.

Patent Document 1 (International Publication No. 2017/125966) proposes a method of blending organic fillers and melamine in a photosensitive resin composition, thereby suppressing excessive surface roughening of the surface of the cured resin layer. Corrosion.

However, in the photosensitive resin composition of Patent Document 1, when the hardened material layer is roughened by an oxidizing agent, large pits may be partially formed on the surface of the hardened material layer. The surface may sometimes be uneven.

An object of the present invention is to provide a photosensitive resin composition which is hardened to become a hardened material, and when the surface of the hardened material is roughened with an oxidizing agent, the hardening of the hardened material due to the oxidizing agent is suppressed. The thickness is excessively reduced, and the unevenness of the treated surface can be suppressed; a dry film is a dried product of the photosensitive resin composition; a printed wiring board includes an interlayer insulating layer, and the interlayer insulating layer A hardened product containing a photosensitive resin composition; and a printed wiring board including a solder resist layer containing a hardened product of a photosensitive resin composition.

The photosensitive resin composition in one aspect of the present invention 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 ); An epoxy compound (D); an organic filler (E) containing an organic filler (E1) having a carboxyl group; and a triazabenzene resin (F). In addition, the triazine resin (F) satisfies at least one of the following conditions: it is in a liquid state at 25 ° C; and the photosensitive resin composition contains a solvent (H), and at 25 ° C Will dissolve in the aforementioned solvent (H).

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

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

Hereinafter, the aspect for implementing this invention is demonstrated. In the following description, the "(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".

When a printed wiring board is manufactured, the printed wiring board includes a layer containing a cured material of a photosensitive resin composition (hereinafter, also referred to as a "cured material layer"). The inventors paid attention to the following characteristics: When the surface of the hardened layer is roughened by the oxidizing agent, the stability of the thickness of the hardened layer, the uniformity of the surface of the hardened layer, and the adhesion between the hardened layer and the plating layer during the plating treatment after roughening.

When a plating layer is formed on a hardened layer of a photosensitive resin composition containing a carboxyl-containing resin, an oxidizing agent containing potassium permanganate (hereinafter, it is only called as long as it is not particularly limited) before the plating treatment. (Oxidizing agent) roughens the surface of the hardened material layer. At this time, the surface of the hardened material layer is excessively corroded by the action of the oxidizing agent, which causes problems such as the thickness of the hardened material layer (thickness of the hardened material layer) becoming thin, or cracks occurring on the surface of the hardened material layer.

On the other hand, by blending a melamine compound in a photosensitive resin composition containing a carboxyl-containing resin, improvement in roughening resistance can be expected. For example, when roughening the surface of a hardened layer, it can be expected that The slag-treated oxidant has corrosion resistance and the like, and the melamine compound includes melamine and a melamine derivative. In addition, in the pre-treatment step of the plating treatment, if the surface of the cured product layer of the photosensitive resin composition is roughened by the oxidizing agent, it is possible to suppress a decrease in the film thickness thereof. However, it is known that when the photosensitive resin composition contains a melamine or a melamine derivative, roughening the hardened material layer may cause large pits on the surface. For this reason, it is known that the surface of the roughened hardened | cured material layer becomes uneven easily, and the peeling strength after a plating process is reduced. Therefore, it is known that the adhesiveness of a plating layer and a hardened | cured material layer is reduced.

In view of the above-mentioned problems, as a result of intensive research by the inventors, a combination of photosensitive resin compositions was found, and the present invention was completed. The combination of the photosensitive resin compositions can suppress the cured product of the photosensitive resin composition. The thickness of the layer due to the roughening treatment is excessively reduced, and even if the surface of the roughened hardened layer is subjected to a plating treatment, the adhesion with the plating layer can be achieved.

The photosensitive resin composition in this embodiment 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) An epoxy compound (D); an organic filler (E) containing an organic filler (E1) having a carboxyl group; and a triazabenzene resin (F). In addition, the triazabenzene resin (F) satisfies at least one of the following conditions: it is in a liquid state at 25 ° C; and the photosensitive resin composition contains a solvent (H) and is soluble in 25 ° C In the solvent (H) in the photosensitive resin composition. Here, the triazabenzene resin (F) in this embodiment is a condensation product of an aminotriazabenzene and formaldehyde having one or more amino groups on a triazabenzene skeleton, or the condensation product A thermosetting resin obtained by polymerization; the triazabenzene resin (F) has at least one triazabenzene skeleton and has an amine group bonded to the triazabenzene skeleton. The specific structure, physical properties, and types of the triazabenzene resin (F) will be described in the description of each component described later.

The reason why the photosensitive resin composition of the present invention has the aforementioned characteristics is still unclear, but it is thought that the organic filler (E1) and the triazabenzene resin (F) have the following effects in the photosensitive resin composition.

First, if the photosensitive resin composition contains an organic filler (E1) having a carboxyl group, the carboxyl group in the organic filler (E1) can be combined with an epoxy compound (for example, an epoxy compound ( D)) Perform the reaction. This makes it possible to contain a uniformly dispersed organic filler (E1) inside the hardened material layer. Therefore, even when the surface of the hardened layer is roughened with an oxidizing agent, the unreacted carboxyl group in the organic filler (E1) can be modified. That is, among the organic fillers (E1) contained in the hardened material layer, the organic fillers (E1) located near the surface of the hardened material layer can be easily changed at the stage of roughening the surface of the hardened material layer. quality. The organic filler (E1) modified in this way is easily removed from the hardened material layer. Thereby, a rough surface can be provided on the surface of a hardened | cured material layer. In addition, if the photosensitive resin composition further contains a triazabenzene resin (F), even when the hardened material layer is roughened with an oxidizing agent, the hardened material layer can be made less likely to be corroded. Therefore, when the photosensitive resin composition contains a triazabenzene resin (F), when the surface of the cured product of the photosensitive resin composition is roughened before the plating treatment, it is possible to suppress an excessive reduction in the thickness of the cured product layer. . In addition, since the roughened surface of the hardened material layer is difficult to generate partial and large pits, the unevenness of the roughened surface can be suppressed. This is considered to be because the triazabenzene resin (F) satisfies at least one of the following conditions, and therefore has high dispersibility in the photosensitive resin composition. The condition is that the triazabenzene resin (F) is The liquid state is at 25 ° C; and the photosensitive resin composition contains a solvent (H), and the triazabenzene resin (F) is dissolved in the solvent (H) in the photosensitive resin composition at 25 ° C. Thereby, it can contribute to the improvement of the adhesiveness of a hardened | cured material layer and the plating layer which consists of copper, gold, etc.

As described above, in the present embodiment, when the surface of the hardened material layer is roughened by using an oxidizing agent, the thickness of the hardened material due to the oxidizing agent can be prevented from being excessively reduced, and the treated surface can be prevented from becoming uneven. . Therefore, when the plating layer is formed on the hardened layer having a roughened surface, the adhesion between the hardened layer and the plated layer can be improved.

Each component which comprises the photosensitive resin composition in this embodiment is demonstrated in detail.

The carboxyl group-containing resin (A) is preferably a carboxyl group-containing resin having an ethylenically unsaturated group and a carboxyl group. When the carboxyl group-containing resin (A) has an ethylenically unsaturated group, the photosensitive resin composition containing the carboxyl group-containing resin (A) has photoreactivity. Therefore, the carboxyl group-containing resin (A) can impart photosensitivity to the photosensitive resin composition, and specifically can impart ultraviolet curability.

The carboxyl group-containing resin (A) preferably contains a carboxyl group-containing resin having an aromatic ring. When the carboxyl group-containing resin (A) contains an aromatic ring, the cured product of the photosensitive resin composition containing the carboxyl group-containing resin (A) can be provided with high heat resistance and high insulation reliability. The carboxyl group-containing resin (A) is more preferably a carboxyl group-containing resin having a polycyclic aromatic ring, and the polycyclic aromatic ring is any one of a biphenyl skeleton, a naphthalene skeleton, a fluorene skeleton, and an anthracene skeleton. When the carboxyl group-containing resin (A) contains a polycyclic aromatic ring of any of a biphenyl skeleton, a naphthalene skeleton, a fluorene skeleton, and an anthracene skeleton, a cured product of a photosensitive resin composition containing a carboxyl group resin (A) can be used. Provides higher heat resistance and insulation reliability. The carboxyl group-containing resin (A) is more preferably a carboxyl group-containing resin having a bisphenol fluorene skeleton. When the carboxyl group-containing resin (A) contains a bisphenol fluorene skeleton, it is possible to impart further higher heat resistance and insulation reliability to the cured product of the photosensitive resin composition containing the carboxyl group-containing resin (A).

The carboxyl group-containing resin (A) is preferably a carboxyl group-containing resin (A1) having a bisphenol fluorene skeleton as described below. The carboxyl group-containing resin (A1) is, for example, a reactant of the following intermediate and an acid anhydride (a3), the intermediate is a reactant of an epoxy compound (a1) and a carboxylic acid (a2), and the epoxy compound (a1) has The bisphenol fluorene skeleton represented by the following formula (1), and the carboxylic acid (a2) contains an unsaturated group-containing carboxylic acid (a2-1). In Formula (1), R ₁ to R ₈ are each independently hydrogen, an alkyl group having 1 to 5 carbon atoms, or a halogen. The carboxyl group-containing resin (A1) is synthesized by combining an epoxy compound (a1) having a bisphenol fluorene skeleton (S1) represented by the following formula (1) and an unsaturated group-containing carboxylic acid The carboxylic acid (a2) of (a2-1) is reacted, and the intermediate obtained by this is reacted with an acid anhydride (a3).

In Formula (1), R ₁ to R ₈ are each independently hydrogen, an alkyl group having 1 to 5 carbon atoms, or a halogen. That is, each of R ₁ to R ₈ in formula (1) may be hydrogen, or may be an alkyl group or a halogen group having 1 to 5 carbon atoms. This is due to the fact that even if the hydrogen in the aromatic ring is replaced by a low-molecular-weight alkyl or halogen, the physical properties of the carboxyl-containing resin (A1) will not be adversely affected. In the case of a cured product of a photosensitive resin composition of a carboxyl resin (A1), heat resistance or flame retardancy may be obtained.

When the carboxyl group-containing resin (A1) has a bisphenol fluorene skeleton derived from the epoxy compound (a1) and represented by the formula (1), it is possible to impart high heat resistance and high insulation reliability to the cured product of the photosensitive resin composition. Further, since the carboxyl group-containing resin (A1) has a carboxyl group derived from the acid anhydride (a3), it is possible to impart excellent developability to the photosensitive resin composition. Furthermore, when the photosensitive resin composition contains an epoxy resin, it is possible to impart thermosetting properties to the photosensitive resin composition.

The carboxyl group-containing resin (A1) can be synthesized by, for example, the operations described below. In order to synthesize a carboxyl group-containing resin (A1), first, at least a part of the epoxy group (see formula (2)) of the epoxy compound (a1) and a carboxyl group containing an unsaturated group-containing carboxylic acid (a2-1) The acid (a2) is reacted to synthesize an intermediate. The synthesis of an intermediate is defined as the first reaction. The intermediate has a structure (S3) represented by the following formula (3), and the structure (S3) is produced by a ring-opening addition reaction of an epoxy group and a carboxylic acid (a2). That is, the intermediate has a secondary hydroxyl group in the structure (S3), and the secondary hydroxyl group is produced by a ring-opening addition reaction of an epoxy group with a carboxylic acid (a2). In formula (3), A is a carboxylic acid residue. The A contains an unsaturated carboxylic acid residue.

Then, the secondary hydroxyl group in the intermediate is reacted with the acid anhydride (a3). Thereby, a carboxyl group-containing resin (A1) can be synthesized. The reaction between the intermediate and the acid anhydride (a3) is defined as the second reaction. The acid anhydride (a3) may include an acid monoanhydride or an acid dianhydride. The so-called acid monoanhydride is a compound having one acid anhydride group, which is formed by dehydration condensation of two carboxyl groups in one molecule. The so-called acid dianhydride is a compound having two acid anhydride groups, which is formed by dehydration condensation of 4 carboxyl groups in one molecule.

The acid anhydride (a3) may contain at least one of an acid dianhydride (a3-2) and an acid monoanhydride (a3-1). When the acid anhydride (a3) contains the acid monoanhydride (a3-1), the carboxyl group-containing resin (A1) has a bisphenol fluorene skeleton (S1) represented by the formula (1) and a structure represented by the following formula (4) ( S4).

The structure (S4) is generated by reacting a secondary hydroxyl group in the structure (S3) of the intermediate with an acid anhydride group in the acid monoanhydride (a3-1). In formula (4), A is a carboxylic acid residue and B is an acid-anhydride residue. The A contains an unsaturated carboxylic acid residue.

When the acid anhydride (a3) contains an acid dianhydride (a3-2), the carboxyl group-containing resin (A1) has a bisphenol fluorene skeleton (S1) represented by the formula (1) and a structure represented by the formula (5) S5).

The structure (S5) is generated by reacting two acid anhydride groups in the acid dianhydride (a3-2) with two secondary hydroxyl groups in the intermediate. That is, the structure (S5) is generated by cross-linking the hydroxyl groups of two secondary hydroxyl groups with each other by an acid dianhydride (a3-2). Furthermore, it may be the case that two secondary hydroxyl groups are cross-linked to each other in one molecule of the intermediate; and two secondary carboxyl groups that are respectively present in two molecules of the intermediate are cross-linked to each other.

If two secondary hydroxyl groups in two molecules respectively present in the intermediate are cross-linked to each other, the molecular weight increases. In formula (5), A is a carboxylic acid residue and D is an acid dianhydride residue. The A contains an unsaturated carboxylic acid residue.

By reacting the secondary hydroxyl group in the intermediate with the acid anhydride (a3), a carboxyl group-containing resin (A1) can be obtained. When the acid anhydride (a3) contains an acid dianhydride (a3-2) and an acid monoanhydride (a3-1), a part of the secondary hydroxyl groups in the intermediate can be reacted with the acid dianhydride (a3-2), and The other secondary hydroxyl group in the intermediate is reacted with the acid monoanhydride (a3-1). Thereby, a 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 generated by reacting only one of the two acid anhydride groups in the acid dianhydride (a3-2) with a secondary hydroxyl group in the intermediate. In Formula (6), A is a carboxylic acid residue and D is an acid dianhydride residue. The A contains an unsaturated carboxylic acid residue.

When synthesizing an intermediate, when a part of the epoxy group in the epoxy compound (a1) remains without reaction, the carboxyl group-containing resin (A1) may have a structure (S2) represented by the formula (2), that is, Epoxy. When a part of the structure (S3) in the intermediate is left unreacted, the carboxyl group-containing resin (A1) may have the structure (S3).

When the acid anhydride (a3) contains an acid dianhydride (a3-2), by optimizing the reaction conditions when synthesizing the carboxyl-containing resin (A1), the structure (S2) and the carboxyl-containing resin (A1) can be reduced. The number of the structures (S6) or the structures (S2) and (S6) can be substantially eliminated from the carboxyl-containing resin (A1).

As described above, the carboxyl group-containing resin (A1) has a bisphenol fluorene skeleton (S1), and can be a case where the acid anhydride has an acid monoanhydride (a3-1) and has a structure (S4); when the acid anhydride contains an acid dianhydride ( a3-2) has a structure (S5). Furthermore, when the acid anhydride (a3) contains an acid monoanhydride (a3-1), the carboxyl group-containing resin (A1) may have at least one of a structure (S2) and a structure (S3). When the acid anhydride (a3) contains the acid dianhydride (a3-2), the carboxyl group-containing resin (A1) may have at least one of a structure (S2) and a structure (S6). Furthermore, when the acid anhydride (a3) contains an acid monoanhydride (a3-1) and an acid dianhydride (a3-2), the carboxyl group-containing resin (A1) may have a structure (S2), a structure (S3), and At least one of the structures (S6).

When the epoxy compound (a1) itself has a secondary hydroxyl group, that is, when n = 1 or more in the formula (7) described later, for example, the carboxyl group-containing resin (A1) may have an epoxy compound. Structure in which a secondary hydroxyl group in (a1) reacts with an acid anhydride (a3).

Furthermore, the structure of the carboxyl-containing resin (A1) can be reasonably analogized based on technical common sense, and in reality, the structure of the carboxyl-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 in Formula (7) described below is 1 or more), the number of secondary hydroxyl groups in the epoxy compound (a1) may cause a carboxyl group. The structure of the resin (A1) has changed drastically. In addition, when the intermediate is reacted with the acid dianhydride (a3-2), as described above, the following may occur: two secondary hydroxyl groups present in one molecule of the intermediate are mutually acid dianhydride (a3-2). ) Performing cross-linking; and, two secondary carboxyl groups respectively present in two molecules of the intermediate are cross-linked with each other with an acid dianhydride (a3-2). Therefore, the carboxyl-containing resin (A1) finally obtained includes a plurality of molecules having different structures from each other, so that even if the carboxyl-containing resin (A1) is analyzed, its structure cannot be specified.

Since the carboxyl group-containing resin (A1) has an ethylenically unsaturated group derived from an unsaturated group-containing carboxylic acid (a2-1), it has photoreactivity. Therefore, the carboxyl group-containing resin (A1) can impart photosensitivity (specifically, ultraviolet curability) to the photosensitive resin composition. Further, since the carboxyl group-containing resin (A1) has a carboxyl group derived from the acid anhydride (a3), it can impart developability to a photosensitive resin composition by an alkaline aqueous solution containing an alkali metal salt and an alkali metal hydrogenation. At least one of these. Further, when the acid anhydride (a3) contains the acid dianhydride (a3-2), the molecular weight of the carboxyl group-containing resin (A1) is positively related to the number of crosslinks generated by the acid dianhydride (a3-2). Therefore, a carboxyl group-containing resin (A1) whose acid value and molecular weight are moderately adjusted can be obtained. When the acid anhydride (a3) contains the acid dianhydride (a3-2) and the acid monoanhydride (a3-1), the amount of the acid dianhydride (a3-2) and the acid monoanhydride (a3-1) and the acid The amount of the monoanhydride (a3-1) relative to the acid dianhydride (a3-2) 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 700 or more and 10,000 or less. When the weight average molecular weight is 700, the viscosity of the coating film formed from the photosensitive resin composition can be further suppressed, and the insulation reliability and plating resistance of the cured product can be further improved. In addition, if the weight average molecular weight is 10,000 or less, the developability of the photosensitive resin composition with an alkaline aqueous solution can be improved. The weight average molecular weight is more preferably 900 or more and 8,000 or less, and particularly preferably 1,000 or more and 5,000 or less.

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

The polydispersity of the carboxyl group-containing resin (A1) is preferably 1.0 or more and 4.8 or less. At this time, the photosensitivity can be imparted while ensuring good insulation reliability and plating resistance (for example, whitening resistance during electroless nickel / gold plating treatment) of the cured product formed from the photosensitive resin composition. The resin composition has excellent developability. The polydispersity of the carboxyl group-containing resin (A1) is more preferably 1.1 or more and 4.0 or less, and even more preferably 1.2 or more and 2.8 or less. The polydispersity is the ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) of the carboxyl group-containing resin (A1).

The weight average molecular weight (Mw) of the carboxyl group-containing resin (A1) can be calculated from the molecular weight measurement results by gel permeation chromatography (GPC). The molecular weight measurement by gel permeation chromatography can be performed under the following conditions, for example.
GPC device: SHODEX SYSTEM 11 manufactured by Showa Denko Corporation;
Tubing: SHODEX KF-800P, KF-005, KF-003, KF-001 four in series;
Mobile phase: tetrahydrofuran (THF);
Flow: 1 mL / min;
Column temperature: 45 ° C;
Detector: refractive index (RI);
Conversion: polystyrene.

The raw materials of the carboxyl-containing resin (A1) and the reaction conditions when synthesizing the carboxyl-containing resin (A1) will be described in detail.

The epoxy compound (a1) has, for example, a structure (S7) represented by the following formula (7). N in formula (7) is a number of 0 or more and 20 or less, for example. In order to appropriately control the molecular weight of the carboxyl group-containing resin (A1), the average of n is particularly preferably 0 or more and 1 or less. If the average of n is in the range of 0 or more and 1 or less, even when the acid dianhydride (a3-2) is contained in the acid anhydride (a3), the addition of the acid dianhydride (a3-2) can be easily controlled Excessive increase in molecular weight.

The carboxylic acid (a2) includes an unsaturated group-containing carboxylic acid (a2-1). The carboxylic acid (a2) may include only the unsaturated group-containing carboxylic acid (a2-1). Alternatively, the carboxylic acid (a2) may include an unsaturated group-containing carboxylic acid (a2-1) and a carboxylic acid other than the unsaturated group-containing carboxylic acid (a2-1).

The unsaturated group-containing carboxylic acid (a2-1) can contain, for example, a compound having only one ethylenically unsaturated group in one molecule. More specifically, the unsaturated group-containing carboxylic acid (a2-1) can contain, for example, at least one selected from the group consisting of acrylic acid, methacrylic acid, and ω-carboxy-polycaprolactone ( n ≒ 2) Monoacrylate, crotonic acid, cinnamic acid, 2-propenyloxyethyl succinate, 2-methacrylic acid ethoxyethyl succinate, 2-propenyloxyethyl phthalate , 2-methacrylic acid ethoxyethyl phthalate, 2-propenemethyl oxypropyl phthalate, 2-methacrylic acid oxypropyl phthalate, 2-propylene maleate Ethyl ethoxylate, 2-methacryl ethoxylate maleate, β-carboxyethyl acrylate, 2-acryl ethoxylate tetrahydrophthalate, 2-tetrahydrophthalate 2- Methacryloxyethyl, hexahydrophthalic acid 2-propenyloxyethyl, and 2-methacryloxyethyl hexahydrophthalate. The unsaturated group-containing carboxylic acid (a2-1) preferably contains acrylic acid.

The carboxylic acid (a2) may include a polyacid (a2-2). The polybasic acid (a2-2) is an acid in which two or more hydrogen atoms in one molecule can be replaced by metal atoms. The polybasic acid (a2-2) preferably has two or more carboxyl groups. At this time, the epoxy compound (a1) reacts with both the unsaturated group-containing carboxylic acid (a2-1) and the polybasic acid (a2-2). The polybasic acid (a2-2) obtains an increase in molecular weight by crosslinking two epoxy groups present in the molecule of the epoxy compound (a1). Thereby, it is possible to further control the viscosity of the coating film formed of the photosensitive resin composition, and to further improve the insulation reliability and plating resistance of the cured product.

The polybasic acid (a2-2) preferably contains a dicarboxylic acid. The polybasic acid (a2-2) can contain, for example, one or more members selected from the group consisting of 4-cyclohexene-1,2-dicarboxylic acid, oxalic acid, malonic acid, succinic acid, and glutaric acid. , Adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, maleic acid, fumaric acid, phthalic acid, isophthalic acid, terephthalic acid. Preferably, the polybasic acid (a2-2) contains 4-cyclohexene-1,2-dicarboxylic acid.

When the epoxy compound (a1) and the carboxylic acid (a2) are reacted, a conventional method can be adopted. For example, a 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 and mixed as required to obtain a reactive solution. By reacting this reactive solution at a temperature of preferably 60 ° C. or higher and 150 ° C. or lower, particularly preferably 80 ° C. or higher and 120 ° C. or lower by a conventional method, an intermediate can be obtained. The solvent at this time can contain, for example, at least one selected from the group consisting of ketones such as methyl ethyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene and xylene; ethyl acetate Acetate, butyl acetate, cellulose acetate, butylcellulose acetate, carbitol acetate, butylcarbitol acetate, propylene glycol monomethyl ether acetate, etc. And dioxane glycol ethers. The thermal polymerization inhibitor contains, for example, at least one of hydroquinone and hydroquinone monomethyl ether. The catalyst can contain, for example, at least one selected from the group consisting of tertiary amines such as benzyldimethylamine, triethylamine, and the like; trimethylbenzyl chloride, and methyl chloride Quaternary ammonium salts such as triethylammonium; triphenylphosphine; and triphenylphosphonium.

The catalyst is particularly preferably one containing triphenylphosphine. That is, it is preferred that the epoxy compound (a1) and the carboxylic acid (a2) are reacted in the presence of triphenylphosphine. In this case, in particular, the ring-opening addition reaction of the epoxy group in the epoxy compound (a1) and the carboxylic acid (a2) can be promoted, and a reaction rate of 95% or more, or 97% or more, or almost 100% can be achieved ( Conversion rate). Therefore, an intermediate having the structure (S3) can be obtained in a high yield. In addition, it is possible to suppress the occurrence of ion migration in the layer containing the cured product of the photosensitive resin composition, and to further improve the insulation reliability including the layer.

When the epoxy compound (a1) and the carboxylic acid (a2) are reacted, the amount of the carboxylic acid (a2) is preferably 0.5 mol or more and 1.2 relative to 1 mol of epoxy group of the epoxy compound (a1). Moore below. In this case, a photosensitive resin composition having excellent sensitivity and stability can be obtained. From the same viewpoint, the amount of unsaturated carboxylic acid (a2-1) is preferably 0.5 mol or more and 1.2 mol or less with respect to 1 mol epoxy group of the epoxy compound (a1). It is more preferably 0.8 mol or more and 1.2 mol or less. Alternatively, when the carboxylic acid (a2) contains a carboxylic acid other than the unsaturated carboxylic acid (a2-1), the unsaturated carboxylic acid (e.g., 1 mole) of the epoxy compound (a1) contains an unsaturated carboxylic acid ( The amount of a2-1) may be 0.5 mol or more and 0.95 mol or less. When the carboxylic acid (a2) contains a polyacid (a2-2), the amount of the polyacid (a2-2) is preferably 0.025 mol relative to 1 mol of epoxy group of the epoxy compound (a1). Above and below 0.25 mol. In this case, a photosensitive resin composition having excellent sensitivity and stability can be obtained.

The intermediate thus obtained is provided with a hydroxyl group produced by a reaction between an epoxy group of the epoxy compound (a1) and a carboxyl group of the carboxylic acid (a2).

The acid monoanhydride (a3-1) is a compound having one acid anhydride group. The acid monoanhydride (a3-1) can contain an acid anhydride of a dicarboxylic acid. The acid monoanhydride (a3-1) can contain, for example, at least one selected from the group consisting of phthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, methyl Tetrahydrophthalic anhydride, methylnadic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, succinic anhydride, methylsuccinic anhydride, maleic anhydride, citraconic anhydride, glutaric acid Acid anhydride, cyclohexane 1,2,4-tricarboxylic acid-1,2-anhydride, and itaconic anhydride. In particular, the acid monoanhydride (a3-1) preferably contains 1,2,3,6-tetrahydrophthalic anhydride. That is, the carboxyl group-containing resin (A1) preferably has a structure (S4), and B in the formula (4) contains a 1,2,3,6-tetrahydrophthalic acid residue. In this case, while ensuring good developability of the photosensitive resin composition, it is possible to further suppress the viscosity of the film formed from the photosensitive resin composition, and further improve the insulation reliability and plating resistance of the cured product. The amount of 1,2,3,6-tetrahydrophthalic anhydride is preferably 20 mol% or more and 100 mol% or less, more preferably 40 mol, relative to the entire acid monoanhydride (a3-1). The ears are not less than 100% and not more than 100%.

The acid dianhydride (a3-2) is a compound having two acid anhydride groups. The acid dianhydride (a3-2) can contain an acid anhydride of a tetracarboxylic acid. The acid dianhydride (a3-2) can contain, for example, at least one selected from the group consisting of 1,2,4,5-benzenetetracarboxylic dianhydride, diphenylketone tetracarboxylic acid di Anhydride, methylcyclohexanetetracarboxylic dianhydride, tetracarboxylic dianhydride, naphthalene-1,4,5,8-tetracarboxylic dianhydride, ethylene tetracarboxylic dianhydride, 9,9'-bis (3,4-Dicarboxybenzene) dianhydride, glycerine bisanhydrotrimellitate monoacetate, ethylene glycol bistrimellitic anhydride, 3,3 ', 4,4'-diphenylarsinetetracarboxylic acid di Anhydride, 1,3,3a, 4,5,9b-Hexahydro-5 (tetrahydro-2,5-diox-3-anyl) naphtho- [1,2-c] furan-1,3- Dione, 1,2,3,4-butanetetracarboxylic dianhydride and 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride. In particular, the acid dianhydride (a3-2) preferably contains 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride. That is, it is preferable that D in the formulae (5) and (6) contains a 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride residue. In this case, while ensuring good developability of the photosensitive resin composition, it is possible to further suppress the viscosity of the film formed from the photosensitive resin composition, and further improve the insulation reliability and plating resistance of the cured product. The amount of 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride is preferably 20 mol% or more and 100 mol% or less with respect to the entire acid dianhydride (a3-2), more preferably 40 Molar% or more and 100 Molar% or less are not limited to this range.

In order to make the intermediate react with the acid anhydride (a3), a conventional method can be used. For example, an acid anhydride (a3) is added to a solvent solution of the intermediate, and a thermal polymerization inhibitor and a catalyst are further added and mixed as needed to obtain a reactive solution. The carboxyl group-containing resin (A1) can be obtained by reacting the reactive solution at a temperature of more preferably 60 ° C. to 150 ° C., particularly preferably 80 ° C. to 120 ° C., according to a general method. As a solvent, a catalyst, and a polymerization inhibitor, an appropriate component can be used, and the solvent, a catalyst, and a polymerization inhibitor used at the time of synthesis of an intermediate can be used directly.

The catalyst is particularly preferably one containing triphenylphosphine. That is, it is preferred to react the intermediate with the acid anhydride (a3) in the presence of triphenylphosphine. In this case, the reaction between the secondary hydroxyl group in the intermediate and the acid anhydride (a3) is particularly promoted, and a reaction rate (conversion rate) of 90% or more, 95% or more, 97% or more, or approximately 100% can be achieved. Therefore, the carboxyl group-containing resin (A1) having at least one of the structure (S4) and the structure (S5) can be obtained in high yield. In addition, ion migration can be suppressed in a layer containing a cured product of a photosensitive resin composition, and the insulation reliability of the layer can be further improved.

When the acid anhydride (a3) contains the acid dianhydride (a3-2) and the acid monoanhydride (a3-1), the acid dianhydride (a3-2) is relative to 1 mole of epoxy group of the epoxy compound (a1). The amount is preferably 0.05 mol or more and 0.24 mol or less. The amount of the acid monoanhydride (a3-1) is preferably 0.3 mol or more and 0.7 mol or less with respect to 1 mol of epoxy group of the epoxy compound (a1). In this case, a carboxyl group-containing resin (A1) whose acid value and molecular weight are appropriately adjusted can be easily obtained.

The intermediate is preferably reacted with the acid anhydride (a3) under air bubbling. In this case, it is possible to suppress the molecular weight of the carboxyl group-containing resin (A1) generated from becoming excessively large, thereby improving the developability of the photosensitive resin composition by an alkaline aqueous solution.

The carboxyl-containing resin (A) may contain only the carboxyl-containing resin (A1) or only a carboxyl-containing resin other than the carboxyl-containing resin (A1), or may contain a carboxyl-containing resin (A1) and a carboxyl-containing resin other than the Carboxy resin. The carboxyl group resin other than the carboxyl group resin (A1) includes a carboxyl group resin (hereinafter, also referred to as a carboxyl group resin (A2)) having no bisphenol fluorene skeleton.

The carboxyl group-containing resin (A2) can contain, for example, a compound (hereinafter, also referred to as (A2-1) component) having a carboxyl group but having no photopolymerizable property. (A2-1) A component is, for example, a polymer containing an ethylenically unsaturated monomer containing an ethylenically unsaturated compound having a carboxyl group. The ethylenically unsaturated compound having a carboxyl group can contain compounds such as acrylic acid, methacrylic acid, ω-carboxyl-polycaprolactone (n ≒ 2) monoacrylate, and the like. The ethylenically unsaturated compound having a carboxyl group can also contain a reactant of pentaerythritol triacrylate, pentaerythritol trimethacrylate, and the like with a dibasic acid anhydride. The ethylenically unsaturated monomer may further include an ethylenically unsaturated monomer having no carboxyl group. The ethylenically unsaturated monomer having no carboxyl group is 2- (meth) acryloxyethyl phthalate, 2- (meth) acryloxyethyl-2-hydroxyethyl phthalate, linear or branched aliphatic or cycloaliphatic (wherein the ring may have partially unsaturated bonds) ( (Meth) acrylates and the like.

The carboxyl group-containing resin (A2) may contain a compound having a carboxyl group and an ethylenically unsaturated group (hereinafter, also referred to as (A2-2) component). The carboxyl group-containing resin (A2) may contain only the (A2-2) component. The component (A2-2) contains, for example, a resin (referred to as a first resin (x)), which is a reactant of an epoxy compound (x1) and an ethylenically unsaturated compound (x2), that is, an intermediate, and A reactant of at least one compound (x3) in the group of free polycarboxylic acids and their anhydrides, and the epoxy compound (x1) contains two or more epoxy groups in one molecule. The first resin (x) can be obtained, for example, by adding compound (x3) to an intermediate which is an epoxy group in epoxy compound (x1) and a carboxyl group in ethylenically unsaturated compound (x2). Obtained by carrying out the reaction. The epoxy compound (x1) can contain appropriate epoxy resins, such as a cresol novolak-type epoxy resin, a phenol novolak-type epoxy resin, and a biphenol novolak-type epoxy resin. In particular, the epoxy compound (x1) preferably contains at least one compound selected from the group consisting of a biphenol novolac epoxy compound and a cresol novolac epoxy compound. The epoxy compound (x1) may contain only a biphenol novolak-type compound, or may contain only a cresol novolak-type epoxy compound. At this time, since the main chain of the epoxy compound (x1) contains an aromatic ring, the cured product of the photosensitive resin composition can reduce, for example, a significant degree of corrosion caused by an oxidant such as potassium permanganate. . The epoxy compound (x1) may contain a polymer of an ethylenically unsaturated compound (z). The ethylenically unsaturated compound (z) contains, for example, a compound having an epoxy group (z1) such as glycidyl (meth) acrylate, or further contains 2- (meth) acryloxyethyl phthalate, and the like Compound (z2) having no epoxy group. The ethylenically unsaturated compound (x2) preferably contains at least one of acrylic acid and methacrylic acid. The compound (x3) contains, for example, one or more compounds selected from the group consisting of polycarboxylic acids and anhydrides of the polycarboxylic acids, and the polycarboxylic acids are phthalic acid, tetrahydrophthalic acid, and formic acid. Tetrahydrophthalic acid and the like. In particular, the compound (x3) preferably contains at least one polycarboxylic acid selected from the group consisting of phthalic acid, tetrahydrophthalic acid, and methyltetrahydrophthalic acid.

The component (A2-2) may also contain a resin (referred to as a second resin (y)), which is a reaction product of a polymer of an ethylenically unsaturated monomer and an ethylenically unsaturated compound having an epoxy group. The unsaturated 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 (y) is obtained by reacting an ethylenically unsaturated compound having an epoxy group on a part of a carboxyl group in a polymer. The ethylenically unsaturated monomer may further contain an ethylenically unsaturated compound having no carboxyl group. The ethylenically unsaturated compound having a carboxyl group includes compounds such as acrylic acid, methacrylic acid, ω-carboxyl-polycaprolactone (n ≒ 2) monoacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, and the like. An ethylenically unsaturated compound having no carboxyl group, and contains, for example, 2- (meth) acryloxyethyl phthalate, 2- (meth) acryloxyethyl-2-hydroxyethyl phthalate Compounds such as esters, linear or branched aliphatic or alicyclic (wherein the ring may have unsaturated bonds in part), and the like. The ethylenically unsaturated compound having an epoxy group preferably contains glycidyl (meth) acrylate.

The carboxyl-containing resin (A) may contain only the carboxyl-containing resin (A1), may contain only the carboxyl-containing resin (A2), or may contain the carboxyl-containing resin (A1) and the carboxyl-containing resin (A2). The carboxyl-containing resin (A) preferably contains 30% by mass or more of the carboxyl-containing resin (A1), more preferably contains 50% by mass or more, still more preferably contains 60% by mass or more, and still more preferably contains 100% by mass . In this case, in particular, the heat resistance and insulation reliability of the cured product of the photosensitive resin composition can be improved. In addition, it is possible to sufficiently reduce the viscosity of a film formed of a photosensitive resin composition. Furthermore, the developability of the photosensitive resin composition with an alkaline aqueous solution can be secured.

The unsaturated compound (B) can impart photocurability to the photosensitive resin composition. The unsaturated compound (B) can contain, for example, at least one compound selected from the group consisting of a monofunctional (meth) acrylate and a polyfunctional (meth) acrylate, and the monofunctional (meth) acrylate is ( 2-hydroxyethyl meth) acrylate and the like, and the multifunctional (meth) acrylates are diethylene glycol di (meth) acrylate, trimethylolpropane di (meth) acrylate, and trimethylol Propane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, ε-hexane Lactone modified dipentaerythritol hexaacrylate, tricyclodecane dimethanol di (meth) acrylate, etc.

In particular, the unsaturated compound (B) is preferably a trifunctional compound, that is, a compound having three unsaturated bonds in one molecule. In this case, it is possible to improve the resolution when the film formed of the photosensitive resin composition is exposed and developed, and in particular, the developability of the photosensitive resin composition by an alkaline aqueous solution can be improved. The trifunctional compound can contain, for example, at least one selected from the group consisting of trimethylolpropane tri (meth) acrylate, EO modified trimethylolpropane tri (meth) acrylate , Pentaerythritol tri (meth) acrylate, ethoxylated isotricyanate tri (meth) acrylate, and ε-caprolactone modification parameters- (2-propenyloxyethyl) trimeric isocyanate and tris (methyl Based) ethoxylated glycidyl acrylate.

The unsaturated compound (B) preferably contains a phosphorus-containing compound (phosphorus-containing unsaturated compound). In this case, the flame retardancy of the hardened | cured material of the photosensitive resin composition can be improved. The phosphorus-containing unsaturated compound can contain, for example, at least one selected from the group consisting of 2-methacrylic acid oxyethyl phosphate (a specific example is a model manufactured by Kyoeisha Chemical Co., Ltd. LIGHT ESTER P-1M and LIGHT ESTER P-2M), 2-acrylic acid oxyethyl phosphate (specific examples are LIGHT ACRYLATE P-1A manufactured by Kyoeisha Chemical Co., Ltd.), diphenyl phosphate 2-Methacryl-2-methoxyethyl ester (specific example is model MR-260 manufactured by Daiba Industrial Co., Ltd.), and HFA series manufactured by Showa Polymer Co., Ltd. (specific example is dipentaerythritol six Addition reactants of acrylate with HCA (9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide), namely models HFA-6003 and HFA-6007; caprolactone modified two Addition reactants of pentaerythritol hexaacrylate with HCA (9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide) are types HFA-3003 and HFA-6127, etc.).

The unsaturated compound (B) may contain a prepolymer. The prepolymer can contain, for example, a prepolymer obtained by polymerizing a monomer having an ethylenically unsaturated bond and then adding an ethylenically unsaturated group; and prepolymerizing with an oligo (meth) acrylate At least one compound in a group of species. The oligo (meth) acrylate prepolymers can contain, for example, at least one selected from the group consisting of epoxy (meth) acrylate, polyester (meth) acrylate, and amine. Urethane (meth) acrylate, alkyd resin (meth) acrylate, silicone resin (meth) acrylate, and spirane resin (meth) acrylate.

The photopolymerization initiator (C) contains, for example, a fluorenylphosphine oxide-based photopolymerization initiator (C1). That is, the photosensitive resin composition contains, for example, a fluorenylphosphine oxide-based photopolymerization initiator (C1). In this case, when the photosensitive resin composition is exposed by ultraviolet rays, high sensitivity can be imparted to the photosensitive resin composition. In addition, it is possible to suppress the occurrence of ion migration in the layer containing the cured product of the photosensitive resin composition, and to further improve the insulation reliability of the layer.

The fluorenylphosphine oxide-based photopolymerization initiator (C1) does not easily interfere with the electrical insulation of the cured product. Therefore, by exposing and curing the photosensitive resin composition, a cured product having excellent electrical insulation properties can be obtained. The cured product is suitable for use as, for example, a solder resist layer, a plating resist, a resist layer, and an interlayer insulating layer. .

The fluorenylphosphine oxide-based photopolymerization initiator (C1) can contain, for example, at least one selected from the group consisting of 2,4,6-trimethylbenzylfluorenyldiphenylphosphine oxide Monofluorenylphosphine oxide-based photopolymerization initiators such as 2,4,6-trimethylbenzylideneethylphenylphosphinate, and bis (2,6-dichlorobenzylidene) Phenylphosphine oxide, bis (2,6-dichlorobenzyl) -2,5-dimethylphenylphosphine oxide, bis (2,6-dichlorobenzyl) -4-propylbenzene Phosphine oxide, bis (2,6-dichlorobenzylidene) -1-naphthylphosphine oxide, bis (2,6-dimethoxybenzylidene) phenylphosphine oxide, bis (2,6 -Dimethoxybenzyl) -2,4,4-trimethylpentylphosphine oxide, bis (2,6-dimethoxybenzyl) -2,5-dimethylphenyl Phosphine oxide, bis (2,4,6-trimethylbenzyl) phenylphosphine oxide, (2,5,6-trimethylbenzyl) -2,4,4-trimethylpentane Difluorinyl phosphine oxide-based photopolymerization initiators such as phosphine oxide. In particular, the fluorenylphosphine oxide-based photopolymerization initiator (C1) preferably contains 2,4,6-trimethylbenzylfluorenyldiphenylphosphine oxide, and the fluorenylphosphine oxide-based photopolymerization initiator ( C1) It is also preferred that it contains only 2,4,6-trimethylbenzylidene diphenylphosphine 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 higher sensitivity to the photosensitive resin composition than in the case where the hydroxyketone-based photopolymerization initiator (C2) is not contained. Accordingly, 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 part. Examples of the hydroxyketone-based photopolymerization initiator (C2) include 1-hydroxycyclohexylphenyl ketone, methyl phenylglyoxylate, and 1- [4- (2-hydroxyethoxy) phenyl]- 2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1- {4- [4- (4- (2-hydroxy-2-methylpropanyl) benzyl] phenyl}- 2-methylpropan-1-one and 2-hydroxy-2-methyl-1-phenylpropan-1-one.

The mass ratio of the fluorenyl phosphine 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 and the hardenability in the deep portion of the coating film formed of the photosensitive resin composition can be improved in a well-balanced manner. Here, since the photosensitive resin composition contains an organic filler (E), the organic filler (E) may cause light scattering in the photosensitive resin composition during exposure. In this case, there may be a problem that good developability cannot be obtained with the photosensitive resin composition. From such a viewpoint, in order to obtain a photosensitive resin composition that improves the resolution and has good developability, the fluorenyl phosphine oxide-based photopolymerization initiator (C1) and the hydroxyketone-based photopolymerization initiator (C2) The quality ratio is particularly preferably in the range of 1: 0.01 to 1: 1.

The photopolymerization initiator (C) preferably contains a photopolymerization initiator (C3) having a diphenylketone skeleton. That is, the photosensitive resin composition preferably contains a fluorenylphosphine oxide-based photopolymerization initiator (C1) and a photopolymerization initiator (C3) having a diphenylketone skeleton, or contains a fluorenylphosphine oxide-based system. A photopolymerization initiator (C1), a hydroxyketone-based photopolymerization initiator (C2), and a photopolymerization initiator (C3) having a diphenylketone skeleton. At this time, when a part of the coating film formed of the photosensitive resin composition is exposed and then developed, since the hardening of the unexposed part can be suppressed, the resolution becomes particularly high. Therefore, a very fine pattern can be formed on the cured product of the photosensitive resin composition. In particular, when an interlayer insulating layer of a multilayer printed wiring board is produced from a photosensitive resin composition, and a photolithography method is used to provide a small-diameter hole for the through-hole in the interlayer insulating layer (see FIG. 1), Precisely and easily form a small diameter hole. Examples of the photopolymerization initiator (C3) having a diphenylketone skeleton include bis (diethylamino) diphenylketone.

The amount of the photopolymerization initiator (C3) having a diphenylketone skeleton relative to the fluorenylphosphine oxide-based photopolymerization initiator (C1) is preferably 0.5 mass or more and 20 mass% or less. When the amount of the photopolymerization initiator (C3) having a diphenylketone skeleton is 0.5% by mass or more with respect to the fluorenylphosphine oxide-based photopolymerization initiator (C1), the developability is particularly high. When the amount of the photopolymerization initiator (C3) having a diphenylketone skeleton is 20% by mass or less with respect to the fluorenylphosphine oxide-based photopolymerization initiator (C1), the light having a diphenylketone skeleton The polymerization initiator (C3) does not easily interfere with the electrical insulation of the cured product of the photosensitive resin composition. From the same viewpoint, the amount of bis (diethylamino) diphenyl ketone is preferably 0.5% by mass or more and 20% by mass or less based on the fluorenylphosphine oxide-based photopolymerization initiator (C1). Here, since the photosensitive resin composition contains an organic filler (E), the organic filler (E) may cause light scattering in the photosensitive resin composition during exposure. In this case, there may be a problem that good developability cannot be obtained with the photosensitive resin composition. From such a viewpoint, in order to obtain a photosensitive resin composition having good resolution, the photopolymerization initiator (C3) having a diphenylketone skeleton is used in comparison with the fluorenylphosphine oxide-based photopolymerization initiator (C1). The amount is particularly preferably 1 mass% or more and 18 mass% or less. From the same viewpoint, the amount of bis (diethylamino) diphenyl ketone is particularly preferably 1% by mass or more and 18% by mass or less based on the fluorenylphosphine oxide-based photopolymerization initiator (C1).

The photosensitive resin composition may further contain a conventional photopolymerization accelerator, a sensitizer, and the like. For example, the photosensitive resin composition can contain at least one selected from the group consisting of 1,2-octanedione 1- [4- (phenylthio) -2- (O-benzidine oxime) )], Ethyl ketone 1 [9-ethyl-6- (2-methylbenzyl) -9H-carbazol-3-yl] -1- (O-acetimoxime) and other oxime esters; Benzoin and its alkyl ethers; acetophenones such as acetophenone, diacetophenone dimethyl ketal; anthraquinones such as 2-methylanthraquinone; 2,4-dimethylthioxanthone Ketones, 2,4-diethylthioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diisopropylthioxanthone, and other thioxanthone Class; diphenyl ketones, such as diphenyl ketone, 4-benzyl-4'-methyldiphenyl sulfide; xanthone such as 2,4-diisopropyl xanthone ); And α-hydroxy ketones such as 2-hydroxy-2-methyl-1-phenylpropan-1-one; 2-methyl-1- [4- (methylthio) phenyl]- A nitrogen atom-containing compound such as 2-morpholinyl-1-acetone. The photosensitive resin composition may contain: a photopolymerization initiator (C); and ethyl p-dimethylbenzoate, iso-amyl p-dimethylaminobenzoate, and 2-dimethylaminoethylbenzoic acid. Conventional photopolymerization accelerators and sensitizers such as tertiary amines such as esters. The photosensitive resin composition may contain at least one of a photopolymerization initiator for visible light exposure and a photopolymerization initiator for near-infrared light exposure as needed. The photosensitive resin composition may contain: a photopolymerization initiator (C); and a coumarin derivative such as 7-diethylamino-4-methylcoumarin, which is a sensitizer for a laser exposure method. , Carbocyanine pigments, xanthene pigments, etc.

The epoxy compound (D) can impart thermosetting properties to the photosensitive resin composition. The epoxy compound (D) preferably contains a crystalline epoxy resin (D1). In this case, the developability of the photosensitive resin composition can be improved. Furthermore, since the organic filler (E1) has a carboxyl group, the compatibility of the crystalline epoxy resin (D1) can be improved by using the organic filler (E1), and the crystalline epoxy resin (D1) in the photosensitive resin composition can be prevented. ). The epoxy compound (D) may further contain an amorphous epoxy resin (D2). 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 (D1) preferably contains one or more selected from the group consisting of, for example: 1,3,5-ginseng (2,3-epoxypropyl) -1 , 3,5-triazabenzene-2,4,6 (1H, 3H, 5H) -trione, hydroquinone type crystalline epoxy resin (a specific example is a product made by Nippon Steel & Sumitomo Chemical Co., Ltd. Name YDC-1312), biphenyl type crystalline epoxy resin (as a specific example, a trade name of YX-4000 manufactured by Mitsubishi Chemical Corporation), diphenyl ether type crystalline epoxy resin (as a specific example, Shinichi Model YSLV-80DE manufactured by Tetsusumi Jin Chemical Co., Ltd.), bisphenol type crystalline epoxy resin (as a specific example, the product name is YSLV-80XY manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd.), and phenol ethane type A specific example is a model GTR-1800 manufactured by Nippon Kayaku Co., Ltd., and a bisphenol fluorene type crystalline epoxy resin (as a specific example, an epoxy resin having a structure (S7)).

The crystalline epoxy resin (D1) preferably has two epoxy groups in one molecule. In this case, it is possible to make the hardened material less prone to cracks during repeated temperature changes.

The crystalline epoxy resin (D1) preferably has an epoxy equivalent of 150 to 300 g / eq. This epoxy equivalent is the g weight of the crystalline epoxy resin (D1) containing an epoxy group of 1 g equivalent (gram equivalent). The crystalline epoxy resin (D1) has a melting point. Examples of the melting point of the crystalline epoxy resin (D1) include 70 ° C to 180 ° C.

In particular, the epoxy compound (D) preferably contains a crystalline epoxy resin (D1-1) having a melting point of 110 ° C or lower. In this case, in particular, the developability of the photosensitive resin composition with an alkaline aqueous solution can be improved. The crystalline epoxy resin (D1-1) having a melting point of 110 ° C. or lower may contain, for example, at least one selected from the group consisting of a biphenyl epoxy resin (a specific example is Mitsubishi Chemical Corporation) Model YX-4000 manufactured), biphenyl ether type epoxy resin (model NSLV-80DE manufactured by Nippon Steel & Sumikin Chemical Co., Ltd. as a specific example), and bisphenol type epoxy resin (Sinichi as a specific example) Model No. YSLV-80XY manufactured by Tetsusui Jin Chemical Co., Ltd.), bisphenol fluorene type crystalline epoxy resin (specifically, an epoxy resin having a structure (S7)).

The amorphous epoxy resin (D2) preferably contains, for example, at least one selected from the group consisting of a phenol novolac epoxy resin (a specific example is the model EPICLON manufactured by DIC Corporation) N-775), cresol novolac epoxy resin (as a specific example, model EPICLON N-695 manufactured by DIC Corporation), bisphenol A novolac epoxy resin (as a specific example, manufactured by DIC Corporation) Model EPICLON N-865), bisphenol A type epoxy resin (as a specific example, model jER1001 manufactured by Mitsubishi Chemical Corporation), bisphenol F type epoxy resin (as a specific example, manufactured by Mitsubishi Chemical Corporation) Model jER4004P), bisphenol S-type epoxy resin (model EPICLON EXA-1514 manufactured by DIC Corporation as a specific example), bisphenol AD-type epoxy resin, biphenol novolac-type epoxy resin (specific examples are Model NC-3000 manufactured by Nippon Kayaku Co., Ltd.), hydrogenated bisphenol A type epoxy resin (as a specific example, model ST-4000D manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.), naphthalene type epoxy resin (as Specific examples Models EPICLON HP-4032, EPICLON HP-4700, EPICLON HP-4770 manufactured by DIC Co., Ltd., and tertiary butyl catechol type epoxy resin (specific examples are model EPICLON HP-820 manufactured by DIC Co., Ltd. ), Dicyclopentadiene type epoxy resin (as a specific example, the model EPICLON HP-7200 manufactured by DIC Corporation), adamantane type epoxy resin (as a specific example, a model ADAMANTATE XE manufactured by Idemitsu Kosan Co., Ltd. -201), special bifunctional epoxy resin (as specific examples are models YL7175-500 and YL7175-1000 manufactured by Mitsubishi Chemical Corporation; models EPICLON TSR-960, EPICLON TER-601, EPICLON manufactured by DIC Corporation) TSR-250-80BX, EPICLON 1650-75MPX, EPICLON EXA-4850, EPICLON EXA-4816, EPICLON EXA-4822, and EPICLON EXA-9726; Nippon Steel & Sumikin Chemical Co., Ltd. model YSLV-120TE), rubber-like Core-shell polymer modified bisphenol A type epoxy resin (model MX-156 manufactured by KANEKA Co., Ltd. as a specific example), rubber-like core-shell polymer modified bisphenol F type epoxy resin (a specific example is KANEKA shares Model MX-136 manufactured by Limited) and a bisphenol F type epoxy resin containing rubber particles of (Specific examples are manufactured by KANEKA Co. Model MX-130).

The epoxy compound (D) may contain a phosphorus-containing epoxy resin. In this case, the flame retardancy of the cured product of the photosensitive resin composition is improved. The phosphorus-containing epoxy resin may be contained in the crystalline epoxy resin (D1) or the amorphous epoxy resin (D2). Examples of the phosphorus-containing epoxy resin include: phosphoric acid modified bisphenol F-type epoxy resin (specific examples are EPICLON EXA-9726 and EPICLON EXA-9710 manufactured by DIC Corporation), and Nippon Steel & Sumitomo Chemical Co., Ltd. Epotohto FX-305 made by the company.

The organic filler (E) can impart rheology to the photosensitive resin composition. The organic filler (E) includes an organic filler (E1). The organic filler (E1) has a carboxyl group. Among the carboxyl groups, a part of the carboxyl groups may be exposed on the surface of the organic filler (E1).

The organic filler (E1) has high compatibility in the photosensitive resin composition, and can impart stronger rheology to the photosensitive resin composition. The photosensitive resin composition can improve the developability of the photosensitive resin composition by containing the organic filler (E1) having a carboxyl group.

In addition, by containing the organic filler (E1) in the photosensitive resin composition, it is possible to further reduce unevenness of the cured product layer due to the fluidity of the photosensitive resin composition. Thereby, the thickness of a hardened | cured material layer can be made uniform easily. In this case, the photosensitive resin composition may not contain a rheology control agent.

The carboxyl group of the organic filler (E1) can be formed as a side chain in a product by polymerizing or crosslinking a carboxylic acid monomer. The carboxylic acid monomer is, for example, acrylic acid, methacrylic acid, crotonic acid, or horse Acid, fumaric acid, itaconic acid, etc. The carboxylic acid monomer has a carboxyl group and a polymerizable unsaturated double bond. Since the organic filler (E1) can improve the rheology of the photosensitive resin composition, the stability (especially storage stability) of the photosensitive resin composition can be improved. Furthermore, since the organic filler (E1) has a carboxyl group, it can improve the developability of the cured product containing the photosensitive resin composition, and can improve the compatibility of the crystalline epoxy compound and prevent the resin from being contained in the photosensitive resin composition. Crystallize. The carboxyl group content of the organic filler (E1) is preferably, for example, an acid value of the organic filler (E1), which is 1 mg KOH / g or more and 60 mg KOH / g or less based on the acid value obtained by acid-base titration. When the acid value is less than 1 mg KOH / g, there is a concern that the stability of the photosensitive resin composition and the developability of the cured product may decrease. If the acid value is more than 60 mg KOH / g, there is a concern that the moisture resistance reliability of the hardened product will decrease. The acid value of the organic filler (E1) is more preferably 3 mg KOH / g or more and 40 mg KOH / g or less.

The organic filler (E1) preferably has a hydroxyl group. Among the hydroxyl groups, a part of the hydroxyl groups may be exposed on the surface of the organic filler (E1). As described above, when the organic filler (E1) has a hydroxyl group, the dispersibility of the organic filler (E1) in the photosensitive resin composition can be further improved.

The average primary particle diameter of the organic filler (E1) is preferably 1 μm or less. When the average primary particle diameter of the organic filler (E1) is 1 μm or less, the rheology of the photosensitive resin composition can be efficiently improved. Therefore, the stability of the photosensitive resin composition is further improved. In addition, when the average primary particle diameter of the organic filler (E1) is 1 μm or less, the roughness of the rough surface formed on the hardened product can be made fine. Thereby, the anchoring effect becomes large with the increase of the surface area of the hardened | cured material, and the adhesiveness of a rough surface and the said plating layer can be improved. The lower limit of the average primary particle diameter of the organic filler (E1) is not particularly limited, but is preferably 0.001 μm or more. The average primary particle diameter was measured as a D ₅₀ using a laser diffraction particle size distribution measuring device. The average primary particle diameter of the organic filler (E1) is more preferably 0.4 μm or less, and still more preferably 0.1 μm or less. In this case, the roughness of the rough surface formed on the hardened material can be made particularly fine. In addition, it is possible to suppress scattering at the time of exposure in the photosensitive resin composition, whereby the resolution of the photosensitive resin composition can be further improved.

The organic filler (E1) is preferably dispersed in the photosensitive resin composition such that the maximum particle diameter is less than 1.0 μm, and more preferably dispersed in a manner smaller than 0.5 μm. The maximum particle diameter is measured by a laser diffraction type particle size distribution measuring device. Alternatively, the maximum particle diameter can be measured by observing the hardened material with a transmission electron microscope (TEM). The organic filler (E1) may be aggregated in the photosensitive resin composition (for example, secondary particles may be formed). In this case, the maximum particle size means the particle size after aggregation. When the maximum particle diameter of the organic filler (E1) in the dispersed state is within the aforementioned range, the roughness of the rough surface formed on the hardened material can be made finer. In addition, it is possible to suppress scattering during exposure in the photosensitive resin composition, thereby improving the resolution of the photosensitive resin composition. In addition, the stability of the photosensitive resin composition is improved. It is particularly preferable that the average primary particle diameter of the organic filler (E1) is 0.1 μm or less, and the organic filler (E1) is dispersed so as to have a particle diameter of 0.5 μm or less. Furthermore, when agglomeration of particles occurs, the maximum particle diameter is usually larger than the average primary particle diameter.

The organic filler (E1) preferably contains a rubber component. The organic filler (E1) preferably contains only a rubber component. The rubber component can impart flexibility to the cured product of the photosensitive resin composition. The rubber component can be composed of a resin. The rubber component preferably contains at least one polymer selected from the group consisting of a crosslinked acrylic rubber, a crosslinked NBR, a crosslinked MBS, and a crosslinked SBR. In this case, the rubber component can impart excellent flexibility to the cured product of the photosensitive resin composition. Furthermore, the surface of the hardened | cured material layer can be provided with a more appropriate rough surface. Here, the rubber component includes a crosslinked structure formed when the monomers constituting the above-mentioned polymer are copolymerized. NBR is generally a copolymer of butadiene and acrylonitrile, and is classified as a nitrile rubber. MBS is generally a copolymer composed of three components: methyl methacrylate, butadiene, and styrene, and is classified as a butadiene rubber. SBR is generally a copolymer of styrene and butadiene, and is classified as a styrene rubber. Specific examples of the organic filler (E1) include, for example, model XER-91-MEK manufactured by JSR Corporation, model XER-32-MEK manufactured by JSR Corporation, and model XSK-500 manufactured by JSR Corporation Wait. Among these organic fillers (E1), XER-91-MEK is a crosslinked rubber (NBR) having an average primary particle diameter of 0.07 μm and having a carboxyl group, and is a methyl ethyl ester containing 15% by weight of the crosslinked rubber The ketone was provided as a dispersion with an acid value of 10.0 mg KOH / g. XER-32-MEK is a dispersion obtained by dispersing a polymer (linear particles) of a carboxyl-modified hydrogenated nitrile rubber in methyl ethyl ketone so that the total content of the dispersion is 17% by weight. XSK-500 is a crosslinked rubber (SBR) having an average primary particle diameter of 0.07 μm and having a carboxyl group and a hydroxyl group, and is in the form of a methyl ethyl ketone dispersion containing 15% by weight of the crosslinked rubber. provide. In this way, the organic filler (E1) can be prepared as a dispersion liquid in the photosensitive resin composition. That is, a rubber component can be mix | blended with a photosensitive resin composition as a dispersion liquid. As a specific example of the organic filler (E1), in addition to the above, for example, model XER-92 manufactured by JSR Co., Ltd. and the like can be mentioned.

The organic filler (E1) may contain particle components other than a rubber component. At this time, the organic filler (E1) can contain at least one particle component selected from the group consisting of acrylic resin fine particles having a carboxyl group and cellulose fine particles having a carboxyl group. The acrylic resin fine particles having a carboxyl group may contain at least one particle component selected from the group consisting of non-crosslinked styrene-acrylic resin fine particles and crosslinked styrene-acrylic resin fine particles. Specific examples of the non-crosslinked styrene-acrylic resin fine particles include, for example, model FS-201 (average primary particle size: 0.5 μm) manufactured by Nippon paint Industrial Coatings Co., Ltd. Specific examples of the crosslinked styrene-acrylic resin fine particles include, for example, model MG-351 (average primary particle diameter of 1.0 μm) and model BGK-001 (average primary particle diameter) manufactured by Nippon paint Industrial Coatings Co., Ltd. 1.0 μm). The organic filler (E1) may contain a particle component other than the particle components selected from the rubber component acrylic resin fine particles and cellulose fine particles. In this case, the organic filler (E1) can contain a particle component having a carboxyl group. That is, the particle component having a carboxyl group may be different from a particle component selected from a rubber component, acrylic resin fine particles, and cellulose fine particles.

The organic filler (E) may further include an organic filler other than the organic filler (E1). Organic fillers other than the organic filler (E1) may not have a carboxyl group. Organic fillers other than the organic filler (E1) may have an average primary particle diameter larger than 1 μm. Among them, the photosensitive resin composition preferably does not contain an organic filler from the viewpoint of efficiently obtaining rheology, the viewpoint of providing a roughened surface to the cured product, and the viewpoint of improving the resolution of the photosensitive resin composition ( E1) other organic fillers.

The organic filler (E) may contain only the organic filler (E1), or may contain organic fillers other than the organic filler (E1) and the organic filler (E1). The organic filler (E) preferably contains 30% by mass or more of the organic filler (E1), more preferably contains 50% by mass or more, and even more preferably 100% by mass. At this time, the stability of the photosensitive resin composition is further improved. In this case, it is easier to provide a roughened surface to the cured product of the photosensitive resin composition. Thereby, the adhesiveness of a hardened | cured material and a plating layer can be improved more.

The triazabenzene resin (F), as described above, satisfies at least one of the following conditions: a liquid state at 25 ° C; and a photosensitive resin composition containing a solvent (H), and at 25 ° C The azabenzene resin (F) is dissolved in the solvent (H). In other words, the triazine resin (F) can satisfy only the liquid state at 25 ° C, or only the photosensitive resin composition containing the solvent (H), and the triazine resin at 25 ° C ( F) Will dissolve in the solvent (H). Alternatively, the triazabenzene resin (F) satisfies two conditions: it is in a liquid state at 25 ° C; and the photosensitive resin composition contains a solvent (H), and the triazabenzene resin (F) at 25 ° C Will dissolve in solvent (H). The triazabenzene resin (F) satisfies any of the above conditions. When the photosensitive resin composition is adjusted, the triazabenzene resin (F) can be adjusted in a liquid state or a solution state. The resin (F) can have high dispersibility in the photosensitive resin composition. In particular, as long as the triazabenzene resin (F) is in a liquid state at 25 ° C, the triazabenzene resin (F) has a particularly high dispersibility in the photosensitive resin composition. In this case, since the dispersibility of the photosensitive resin composition is excellent and the coatability becomes good, it is possible to reduce occurrence of unevenness in the cured product of the photosensitive resin composition. Therefore, even if a rough surface is provided on the surface of the cured resin layer of the photosensitive resin composition after roughening, the surface uniformity can be maintained. Thereby, the adhesiveness of the hardened | cured material layer and the plating layer which consists of copper, gold, etc. can be improved. Furthermore, since the photosensitive resin composition contains a triazabenzene resin (F), even when the hardened layer of the photosensitive resin composition is roughened with an oxidizing agent, the degree of corrosion of the hardened layer can be reduced. Therefore, when the surface of a hardened | cured material layer is roughened before a plating process, the thickness of a hardened | cured material layer can hardly become thin.

In this embodiment, the photosensitive resin composition may contain a solvent (H), and when the triazabenzene resin (F) is in a liquid state at 25 ° C, the photosensitive resin composition may not contain the solvent (H). Among these, from the viewpoints of liquefaction or varnishing of the photosensitive resin composition, adjustment of viscosity, adjustment of coatability, adjustment of film-forming property, etc., even when the triazabenzene resin (F) is at 25 ° C When it is in a liquid state, it is preferable to contain a solvent (H). When the solvent (H) is contained, even when the triazabenzene resin (F) is in a liquid state at 25 ° C, it can be dissolved in the solvent (H) at 25 ° C.

The solvent (H) contains, for example, at least one selected from the group consisting of: water; linear, branched, secondary, or polyhydric alcohols, which are ethanol, isobutanol, 1-butanol , Isopropanol, hexanol, ethylene glycol, 3-methyl-3-methoxybutanol, etc .; ketones such as methyl ethyl ketone, cyclohexanone; aromatic hydrocarbons such as toluene and xylene ; Petroleum-based aromatic mixed solvents such as SWASOL series (manufactured by Maruzen Petrochemical Co., Ltd.), Solvesso series (manufactured by ExxonMobil Chemical Co., Ltd.); celluloids such as celluloid, butylcellulose, etc .; carbitol, butyl Carbitols such as carbitol; alkyl glycol alkyl ethers such as ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, and propylene glycol methyl ether; polypropylene glycols such as dipropylene glycol methyl ether Alkyl ethers; acetates such as ethyl acetate, butyl acetate, cellulose acetate, and carbitol acetate; and dioxane glycol ethers.

When the photosensitive resin composition contains a solvent (H) and triazabenzene (F) at 25 ° C, it is preferably soluble in at least one selected from the group consisting of the following solvents: isobutanol , 1-butanol, isopropanol, ethylene glycol monoisopropyl ether, 3-methyl-3-methoxybutanol, ethylene glycol monobutyl ether, xylene, and water. In other words, the solvent (H) preferably contains a solvent selected from the group consisting of isobutanol, 1-butanol, isopropanol, ethylene glycol monoisopropyl ether, 3-methyl-3-methoxybutanol, ethyl At least one of the group consisting of glycol monobutyl ether, xylene, and water. At this time, the solvent in the photosensitive resin composition can be selected so that the triazabenzene resin (F) has solubility in the solvent (H). The solubility of the triazabenzene resin (F) in a solvent, for example, with respect to 100 parts by mass of isobutanol or 1-butanol, if it is confirmed that the triazabenzene resin (F) can dissolve 70 parts by mass at 80 ° C. Above, and the solution state can be maintained at 25 ° C. The triazabenzene resin (F) is soluble in the solvent (H) at 25 ° C, and it can be confirmed, for example, that when these are formulated in a photosensitive resin composition, they are compatible with the photosensitive resin. The solvent (H) and the triazabenzene resin (F) are mixed with the same mass ratio in the composition.

The triazabenzene resin (F) is a condensation product of an aminotriazabenzene and formaldehyde having at least one amine group bonded to a triazabenzene skeleton, or a thermosetting resin obtained by polymerizing the condensation product . Therefore, the triazabenzene resin (F) has at least one triazabenzene skeleton and has at least one amine group bonded to the triazabenzene skeleton. The amine group may be any of a primary amine group, a secondary amine group, and a tertiary amine group. In particular, the amine group is preferably a secondary amine group or a tertiary amine group, and is preferably not a primary amine group. That is, the triazabenzene resin (F) preferably does not have a primary amine group. In a triazabenzene skeleton, one or more amine groups can be bonded, but the amine group bonded to the triazabenzene skeleton may include only secondary amine groups, or only three The secondary amine group, or may include both secondary and tertiary amine groups. At this time, even if the surface of the hardened material layer is roughened with an oxidizing agent, the surface uniformity can be maintained, and the adhesion between the hardened material layer and the plating layer can be improved.

The triazine resin (F) is, for example, that the three amine groups bonded to the triazine skeleton are all primary amine groups, that is, melamine (1,3,5-triazabenzene-2,4,6 -A condensate of triamine) and formaldehyde, or a thermosetting resin obtained by polymerizing the condensate. At this time, the triazine resin (F) includes, for example, a methylol compound in which at least one hydrogen atom in each primary amine group of melamine is methylated, or a hydroxyl group in the methylol compound. A compound which is further alkoxylated.

The triazabenzene resin (F) preferably has a group selected from the group consisting of N-hydroxymethyl (-N (CH ₂ OH) H group) and N-alkoxyalkyl (-N (R ₉ OR ₁₀ ) H group At least one of the groups consisting of) is used as a secondary amine group. At this time, even if the surface of the hardened layer is roughened by using an oxidizing agent, the surface uniformity can be maintained, and the adhesion between the hardened layer and the plating layer can be improved. The aforementioned R _{9 is} , for example, a linear or branched hydrocarbon. Specifically, R _{9 is,} for example, a methylenyl group, an ethylidene group, a propylidene group, or a butylene group. R _{10 is,} for example, an alkyl group having 1 to 4 carbon atoms. Specifically, R _{10 is,} for example, methyl, ethyl, propyl, or butyl. Propyl is 1-propyl or 2-propyl (isopropyl), and butyl is n-butyl, secondary butyl, isobutyl or tertiary butyl. The secondary amine group is more preferably at least one amine group selected from the group consisting of N-hydroxymethyl and N-alkoxymethyl.

The triazabenzene resin (F) preferably has a material selected from the group consisting of N, N-dimethylol (-N (CH ₂ OH) ₂ group) and N-hydroxymethyl-N-alkoxyalkyl group. (-N (CH ₂ OH) (R ₁₁ OR ₁₂ ) group), N, N-bis (alkoxyalkyl) group (-N (R ₁₁ OR ₁₂ ) ₂ group, -N (R ₁₁ OR ₁₂ ) ( At least one of the group consisting of R ₁₃ OR ₁₄ ) group and -N (R ₁₃ OR ₁₄ ) ₂ group) is used as a tertiary amine group. At this time, even if the surface of the hardened layer is roughened by using an oxidizing agent, the surface uniformity can be maintained, and the adhesion between the hardened layer and the plating layer can be improved. The above-mentioned R ₁₁ and R ₁₃ are each independently a linear or branched hydrocarbon, and specifically, R ₁₁ and R _{13 are,} for example, a alkenyl group, an ethylene group, a propyl group, or a butylene group. R ₁₂ and R ₁₄ are each independently an alkyl group having 1 to 4 carbon atoms, and specifically, R ₁₂ and R ₁₄ are each independently a methyl group, an ethyl group, a propyl group, or a butyl group. Propyl is 1-propyl or 2-propyl (isopropyl), and butyl is n-butyl, secondary butyl, isobutyl or tertiary butyl.

The tertiary amino group is more preferably selected from the group consisting of N, N-dimethylol, N-hydroxymethyl-N-alkoxymethyl, and N, N-bis (alkoxymethyl) At least one group. Examples of N, N-bis (alkoxymethyl) include: -N (CH ₂ OCH ₃ ) ₂ , -N (CH ₂ OBu) ₂ , and -N (CH ₂ OCH ₃ ) (CH ₂ OBu) (Bu means butyl).

The tertiary amine group bonded to the triazabenzene skeleton is more preferably N, N-bis (alkoxymethyl) or N-hydroxymethyl-N-alkoxymethyl. Here, N, N-bis (alkoxymethyl) is -N (CH ₂ OR ₁₂ ) ₂ group, -N (CH ₂ OR ₁₂ ) (CH ₂ OR ₁₄ ) group, or -N (CH ₂ OR ₁₄ ) ₂ groups, and N-hydroxymethyl-N-alkoxymethyl is a (-N (CH ₂ OH) (CH ₂ OR ₁₂ ) group. Also, as described above, R ₁₂ and R _{14 are} preferably each Independently, it is an alkyl group having 1 to 4 carbon atoms. Specifically, R ₁₂ and R ₁₄ are each preferably independently methyl, ethyl, propyl, or butyl. For example, propyl is 1-propyl. Or 2-propyl (isopropyl), and butyl is n-butyl, secondary butyl, isobutyl, or tertiary butyl. In this case, even if the roughened surface of the hardened layer is given a rough surface, It can maintain higher uniformity of the surface, and can further improve the adhesion between the hardened layer and the plating layer.

Specific examples of the triazine resin (F) include, for example, product names CYMEL 300, CYMEL 301, CYMEL 303, CYMEL 350, CYMEL 370, and CYMEL manufactured by Cytec Industries Japan Co., Ltd. 771, CYMEL 325, CYMEL 327, CYMEL 703, CYMEL 712, CYMEL 715, CYMEL 701, CYMEL 267, CYMEL 285, CYMEL 232, CYMEL 235, CYMEL 236, CYMEL 238, CYMEL 211, CYMEL254, CYMEL 204, MYMCOAT 212 202, CYMEL 207, MYCOAT 506, MYCOAT 508, CYMEL1123, MYCOAT 102, MYCOAT 105, MYCOAT 106, CYMEL 1128; product names AMIDIR J-820-60, AMIDIR L-109-65, AMIDIR L- 117-60, AMIDIR L-127-60, AMIDIR 13-548, AMIDIR G-821-60, AMIDIR L-110-60, AMIDIR L-125-60, AMIDIR L-166-60B, AMIDIR L-105-60 , AMIDIR S-695, AMIDIR S-683-IM, AMIDIR TD-126 and AMIDIR 15-594; and, the product names MW-30MLF, MW-30M, MW-30LF, MW-30 manufactured by Sanwa Chemical Co., Ltd. , MW-22, MS-11, MW-12LF, MS-001, MZ-351, MX-730, MX-750, MX-706, MX-035, MX-45, MX-410, BL-60 BX-4000 and the like.

The number average molecular weight of the triazabenzene resin (F) is preferably 170 or more and 10,000 or less, more preferably 180 or more and 5,000 or less, and still more preferably 200 or more and 3,000 or less.

When the photosensitive resin composition contains a triazabenzene resin (F), for example, when a hardened material layer is formed on a conductor line provided on a plating layer or a core material, the photosensitive resin composition is dispersed in the photosensitive resin composition. The triazabenzene resin (F) in can form a coordination bond in a metal element in a contact surface with the hardened layer. Therefore, the adhesiveness of the hardened | cured material layer of a photosensitive resin composition and a plating layer can be improved more. Examples of the metal element include gold, silver, copper, and nickel.

In this embodiment, the photosensitive resin composition may not contain a triazabenzene resin other than the triazabenzene resin (F), but it can still contain other than the triazabenzene resin (F) within a range that achieves the effects of the present invention. Triazabenzene resin. Examples of the triazine resin other than the triazine resin (F) include a melamine derivative and a guanamine derivative, and the melamine derivative does not satisfy the following two conditions: a triazine resin (F) a liquid state at 25 ° C; and the photosensitive resin composition contains a solvent (H), and the triazabenzene resin (F) at 25 ° C to the solvent (H) in the photosensitive resin composition Soluble.

The photosensitive resin composition preferably further contains a coupling agent (G). The coupling agent (G) includes a coupling agent (G1), and the coupling agent (G1) contains at least one atom selected from the group consisting of a silicon atom, an aluminum atom, a titanium atom, and a zirconium atom. The coupling agent (G1) further has two or more functional groups selected from the group consisting of an alkoxy group, a fluorenyloxy group, and an alkoxide group. That is, the photosensitive resin composition preferably further contains a coupling agent (G), the coupling agent (G) contains a coupling agent (G1), and the coupling agent (G1) contains a member selected from the group consisting of silicon atoms, aluminum atoms, titanium atoms and zirconium atoms At least one atom in the group formed, and has two or more functional groups selected from the group consisting of alkoxy, fluorenyloxy, and alkoxide groups. The coupling agent (G1) can improve the dispersibility of the organic filler (E1) in the photosensitive resin composition by reacting or interacting with the carboxyl group-containing resin (A) and the carboxyl group contained in the organic filler (E1). Improve the rheology and stability (especially storage stability) of the photosensitive resin composition. The coupling agent (G1) may have two or more alkoxy groups, may have two or more alkoxy groups, or may have two or more alkoxide groups. The coupling agent (G1) may have two or more different functional groups selected from the group consisting of an alkoxy group, a fluorenyloxy group, and an alkoxide group. The functional group selected from the group consisting of an alkoxy group, a fluorenyloxy group, and an alkoxide group is preferably directly bonded to at least one atom selected from a silicon atom, an aluminum atom, a titanium atom, and a zirconium atom.

The coupling agent (G1) is particularly preferably one containing silicon atoms. When the coupling agent (G1) contains a silicon atom, examples of the coupling agent (G1) include tetraethoxysilane, tetramethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyl Methyldiethoxysilane, vinylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidyloxypropylmethyldimethoxy Silane, 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropylmethyldiethoxysilane, 3-glycidyloxypropyltriethoxysilane, 3-glycidyl Oxypropylmethyldimethoxysilane, p-styryltrimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (amine (Ethyl) -3-aminopropyltrimethoxysilane, 3-aminopropylmethyldimethoxysilane, 3-aminopropylmethyldiethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3- (2-aminoethylamino) propyltriethoxysilane, N, N-dimethyl-3- (trimethoxysilyl) propylamine, 3 -Triethoxysilyl-N- (1,3-dimethylbutylene) propylamine, N-phenyl-3-amine Trimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-methacryloxypropyl Methyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyl Triethoxysilane, allyltriethoxysilane, allyltrimethoxysilane, allylchlorodimethylsilane, 3-chloropropyltrimethoxysilane, 3-chloropropyltriethyl Oxysilane, 3-chloropropyldimethoxymethylsilane, chloromethyltriethoxysilane, chloromethyltrimethoxysilane, 3-chloropropylmethyldiethoxysilane, 3-isocyanate Propyltriethoxysilane, 3-propenyloxypropyltrimethoxysilane, bis (triethoxysilanepropyl) tetrasulfide, cyclohexyltrimethoxysilane, methyltriethoxysilane, Methyltrimethoxysilane, ethyltriethoxysilane, ethyltrimethoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, cetyltrimethoxysilane, octadecane Triethoxysilane, octadecyltrimethoxysilane, n-octyltriethoxysilane, n-octyltrimethoxysilane, dodecyltriethoxysilane, dodecyltrimethoxysilane , Propyltrimethoxysilane, propyltriethoxysilane, benzyltriethoxysilane, tolyldimethoxysilane, tolyldiethoxysilane, phenyltriethoxysilane, benzene Trimethoxysilane, p-tolyltrimethoxysilane, 4-vinylphenyltrimethoxysilane, 1-naphthyltrimethoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, 11 -Pentafluorophenoxyundecyltrimethoxysilane, pentafluorophenyltrimethoxysilane, 11-azidoundecyltrimethoxysilane, 2-cyanoethyltriethoxysilane, and Vinyl triethoxysilane and the like.

When the coupling agent (G1) contains an aluminum atom, examples of the coupling agent (G1) include ethyl acetoxy aluminum diisopropoxide, aluminum monoethyl acetate diisopropoxide, and ginseng (ethyl醯 ethyl acetate) aluminum and the like.

When the coupling agent (G1) contains a titanium atom, examples of the coupling agent (G1) include: isopropyltristearate titanium, isopropyl ginseng (dioctyl pyrophosphate) titanium, and tetraoctylbis (phosphoric acid) Di (tridecyl ester)) titanium, bis (di (tridecyl) phosphate) (2,2-diallyloxymethyl-1-butyl) phosphate, bis (dioctyl pyrophosphate) Titanium oxyacetate, and bis (dioctyl pyrophosphate) ethylene titanate.

When the coupling agent (G1) contains a zirconium atom, examples of the coupling agent (G1) include zirconium tetra-n-propoxide and zirconium tetra-n-butoxide.

The coupling agent (G1) preferably contains a silicon atom. The coupling agent (G1) can effectively improve the dispersibility of the organic filler (E1) in the photosensitive resin composition by containing a silicon atom. Therefore, the rheology and stability of the photosensitive resin composition are further improved. The coupling agent (G1) may be a silane coupling agent.

The coupling agent (G1) preferably contains a functional group selected from the group consisting of a methoxy group, an ethoxy group, and an ethoxy group. Methoxy and ethoxy are classified as alkoxy. The ethoxy group is classified as a methoxy group. The coupling agent (G1) may contain only a methoxy group, only an ethoxy group, or only a fluorenyl group. The coupling agent (G1) may contain different functional groups selected from the group consisting of methoxy, ethoxy, and ethoxy. The coupling agent (G1) contains a functional group selected from the group consisting of a methoxy group, an ethoxy group, and a fluorenyl group, thereby improving the reactivity of the organic filler (E1) and the coupling agent (G1), thereby making the photosensitive resin composition The organic filler (E1) becomes less prone to agglutination. Therefore, the rheology and stability of the photosensitive resin composition are further improved. In addition, the photosensitive resin composition can obtain good resolution.

The coupling agent (G1) preferably contains 2 to 4 functional groups selected from the group consisting of an alkoxy group, a fluorenyloxy group, and an alkoxide group. The coupling agent (G1) may contain 2 to 4 alkoxy groups, may contain 2 to 4 alkoxy groups, and may contain 2 to 4 alkoxide groups. For example, the coupling agent (G1) may contain 2 to 4 methoxy groups, may contain 2 to 4 ethoxy groups, and may contain 2 to 4 ethoxy groups. The coupling agent (G1) may contain 2 to 4 different functional groups selected from alkoxy, fluorenyl, and alkoxide groups. The coupling agent (G1) can contain an excess of 2 to 4 functional groups selected from the group consisting of alkoxy, fluorenyloxy, and alkoxide groups, which can be caused by the reaction between the organic filler (E1) and the coupling agent (G1). The cross-linking reaction can improve the dispersibility of the organic filler (E1) in the photosensitive resin composition and suppress gelation at the same time.

The coupling agent (G1) preferably has at least one functional group selected from the group consisting of an amine group, an epoxy group, a vinyl group, a (meth) acrylic group, a mercapto group, an isocyanate group, and a thioether group. The coupling agent (G1) can interact with the organic filler (E1) by containing at least one functional group selected from the group consisting of an amine group, an epoxy group, a vinyl group, a (meth) acrylic group, a mercapto group, an isocyanate group, and a thioether group. The carboxyl group contained in the reaction proceeds to further improve the dispersibility of the organic filler (E1) in the photosensitive resin composition with good efficiency. Therefore, the rheology, stability (especially storage stability) and resolution of the photosensitive resin composition are further improved.

When the coupling agent (G1) contains an amine group, for example, an amine group can be introduced into the amine group. When the coupling agent (G1) contains an epoxy group, for example, an epoxy group can be introduced into a glycidyloxy group. When the coupling agent (G1) contains a vinyl group, the vinyl group can be directly bonded to a silicon atom, for example. The coupling agent (G1) can improve the reactivity with the organic filler (E1) by having an amine group, an epoxy group or a vinyl group, and further improve the dispersion of the organic filler (E1) in the photosensitive resin composition efficiently. Sex. The coupling agent (G1) preferably has an epoxy group or a vinyl group. When the coupling agent (G1) has an epoxy group or a vinyl group, the insulation between the wires of the photosensitive resin composition is improved, and the stability is further improved.

The coupling agent (G) may further include a coupling agent other than the coupling agent (G1). The coupling agent other than the coupling agent (G1) may not contain at least one atom selected from the group consisting of a silicon atom, an aluminum atom, a titanium atom, and a zirconium atom. The coupling agent other than the coupling agent (G1) may not have two or more functional groups selected from the group consisting of an alkoxy group, a fluorenyloxy group, and an alkoxide group. Among them, the photosensitive resin composition may not contain other than the coupling agent (G1) from the viewpoint of efficiently obtaining the dispersibility of the organic filler (E1) and from the viewpoint of improving the rheology and stability of the photosensitive resin composition. Couplant.

The couplant (G) may include only the couplant (G1), or may include a couplant (G1) and a couplant other than the couplant (G1). The coupling agent (G) preferably contains 30% by mass or more of the coupling agent (G1), more preferably contains 50% by mass or more, and even more preferably 100% by mass. In this case, the dispersibility of the organic filler (E) in the photosensitive resin composition can be particularly improved.

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

The amount of the carboxyl group-containing resin (A) is preferably 5 mass% or more and 85 mass% or less, more preferably 10 mass% or more and 75 mass% or less with respect to the solid content of the photosensitive resin composition, and more preferably 30 mass% or more and 60 mass% or less. In addition, the amount of the carboxyl group-containing resin (A1) is preferably 5 mass% or more and 85 mass% or less, more preferably 10 mass% or more and 75 mass% or less with respect to the solid content of the photosensitive resin composition. It is preferably 30% by mass or more and 60% by mass or less.

The amount of the unsaturated compound (B) relative to the carboxyl group-containing resin (A) is preferably 1% by mass or more and 50% by mass or less, more preferably 10% by mass or more and 45% by mass or less, and still more preferably 21% by mass. % To 40% by mass.

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

The amount of the epoxy compound (D) is preferably 0.7 or more and 2.5 or less, based on 1 equivalent of the carboxyl group contained in the carboxyl group-containing resin (A). It is more preferably 0.7 or more and 2.3 or less, and still more preferably 0.7 or more and 2.0 or less. The total equivalent weight of the epoxy group contained in the crystalline epoxy resin (D1) is preferably 0.1 or more and 2.0 or less, and more preferably 0.2 or more and 1 equivalent of the carboxyl group contained in the carboxyl group-containing resin (A). 1.9 or less, more preferably 0.3 or more and 1.5 or less. Alternatively, the total equivalent weight of the epoxy group contained in the crystalline epoxy resin (D1) may be 0.7 or more and 2.5 or less with respect to 1 equivalent of the carboxyl group contained in the carboxyl group-containing resin (A).

When the content of the carboxyl group-containing resin (A) is 100 parts by mass, the content of the organic filler (E) is preferably 1 part by mass or more and 40 parts by mass or less. When the content of the organic filler (E) is set within this range, the rheology of the photosensitive resin composition is improved, and the stability is improved. Moreover, the surface of the hardened | cured material of the photosensitive resin composition can be moderately roughened, and the adhesiveness of the rough surface of a hardened | cured material and a plating layer can be improved by this. When the content of the carboxyl group-containing resin (A) is 100 parts by mass, the content of the organic filler (E) is more preferably 5 parts by mass or more and 20 parts by mass or less, and still more preferably 10 parts by mass or more and 17 parts by mass or less. . The content of the organic filler (E1) is preferably 1% by mass or more and 25% by mass or less based on the solid content of the photosensitive resin composition. Within this range, it is possible to impart resolution to a hardened material formed of a photosensitive resin composition, and further, to perform plating treatment on a hardened material layer having a roughened surface provided in the hardened material to form a plating. When it is laminated, the adhesion between the hardened material layer and the plating layer can be further improved. The content of the organic filler (E1) is more preferably 2% by mass or more and 20% by mass or less, and still more preferably 3% by mass or less and 18% by mass or less. Particularly preferred is 4% by mass or more and 16% by mass or less. When the content of the carboxyl group-containing resin (A) is 100 parts by mass, the content of the rubber component is preferably within a range of 1 to 40 parts by mass, more preferably within a range of 5 to 20 parts by mass, and further preferably It is 10 to 17 parts by mass.

The content of the triazabenzene resin (F) relative to the carboxyl group-containing resin (A) is preferably 0.5% by mass or more and 20% by mass or less. Within this range, when a roughened surface is provided on the hardened body of the photosensitive resin composition, the thickness of the hardened body layer at this time can be further suppressed, and the surface after the roughening treatment can be further suppressed. Uneven situation. Moreover, if it is this range, the resolution of the hardened | cured material which consists of a photosensitive resin composition can be maintained. Furthermore, when the hardened | cured material layer which has been provided with the rough surface in this hardened | cured material is plated, and a plating layer is formed, the adhesiveness of a hardened | cured material layer and a plating layer can be improved more. The content of the triazabenzene resin (F) is more preferably 1% by mass or more and 18% by mass or less, further preferably 1.5% by mass or more and 15% by mass or less, and particularly preferably 2% by mass or more and 12% by mass or less.

When the photosensitive resin composition contains a coupling agent (G), when the content of the carboxyl group-containing resin (A) is 100 parts by mass, the content of the coupling agent (G) is preferably 0.01 parts by mass or more and 7 parts by mass or less . When the content of the coupling agent (G) is set within this range, aggregation of the organic filler (E) in the photosensitive resin composition can be prevented, and dispersibility can be improved. When the content of the organic filler (E) is 100 parts by mass, the content of the coupling agent (G) is more preferably 0.05 parts by mass or more and 5 parts by mass or less. When the content of the carboxyl group-containing resin (A) is 100 parts by mass, the content of the coupling agent (G1) is preferably 0.01 parts by mass or more and 7 parts by mass or less. When the content of the coupling agent (G1) is set within this range, aggregation of the organic filler (E) in the photosensitive resin composition can be effectively prevented, and dispersibility can be effectively improved. When the content of the organic filler (E1) is 100 parts by mass, the content of the coupling agent (G1) is more preferably 0.05 parts by mass or more and 5 parts by mass or less.

When the photosensitive resin composition contains a solvent (H), the amount of the solvent (H) can be appropriately adjusted depending on the characteristics of the triazabenzene resin (F). For example, it can adjust so that the solvent (H) may be rapidly evaporated when a coating film formed from a photosensitive resin composition is dried, and even if a solvent does not remain in a dry film. The amount of the solvent (H) is preferably in the range of more than 0% by mass and 99.5% by mass or less, and more preferably in the range of 15% by mass or more and 60% by mass or less with respect to the entire photosensitive resin composition. The appropriate ratio of the organic solvent varies depending on the method of adjusting the photosensitive resin composition, the method of coating, and the like. Therefore, it is preferable to appropriately adjust the ratio to the appropriate ratio according to the method of adjusting, the method of coating, and the like.

The term “solid content” refers to the total amount of the total components after removing volatile components such as solvents from the photosensitive resin composition.

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

The photosensitive resin composition may contain an inorganic filler. In this case, the curing shrinkage of the film formed of the photosensitive resin composition is reduced. The inorganic filler can contain, for example, one or more members selected from the group consisting of barium sulfate, crystalline silica, nano silica, nano carbon tubes, talc, bentonite, hydrotalcite, and aluminum hydroxide , Magnesium hydroxide, and titanium oxide. When the inorganic filler contains a white material such as titanium oxide and zinc oxide, the photosensitive resin composition and the cured product thereof can be whitened by the white material. The proportion of the inorganic filler in the photosensitive resin composition can be appropriately set, but it is preferably within a range of 0 to 300% by mass based on the carboxyl group-containing resin (A).

The photosensitive resin composition may contain at least one selected from the group consisting of toluene diisocyanate-based capped with caprolactam, oxime, malonate, etc., and morpholine diisocyanate. Blocked isocyanates such as isocyanate, isophorone diisocyanate, and hexamethylene diisocyanate; butylated urea resins; various thermosetting resins other than the above; UV-curable epoxy (methyl) Acrylates; resins obtained by adding (meth) acrylic acid to epoxy resins such as bisphenol A type, phenol novolac type, cresol novolac type, and alicyclic type; and phthalic dienes Polymer compounds such as propyl resin, phenoxy resin, amine ester resin, and fluororesin.

The photosensitive resin composition may contain a hardener for hardening an epoxy compound (D). The hardener can contain, for example, at least one selected from the group consisting of imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole , 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, 1- (2-cyanoethyl) -2-ethyl-4-methylimidazole, and other imidazole derivatives; dicyandiamine, Benzyldimethylamine, 4- (dimethylamino) -N, N-dimethylbenzylamine, 4-methoxy-N, N-dimethylbenzylamine, 4-methyl-N , Amine compounds such as N-dimethylbenzylamine; hydrazine compounds such as hexamethylene hydrazine and sebacic acid; phosphorus compounds such as triphenylphosphine; acid anhydrides; phenols; thiols; ; And, onium salts. Examples of commercially available products of these ingredients include: 2MZ-A, 2MZ-OK, 2PHZ, 2P4BHZ, 2P4MHZ (all are trade names of imidazole compounds) manufactured by Shikoku Chemical Co., Ltd .; manufactured by San-Apro Co., Ltd. U-CAT3503N, U-CAT3502T (both are the trade names of blocked isocyanate compounds of dimethylamine); DBU, DBN, U-CATSA102, U-CAT5002 (all are amidine compounds and their salts) .

The photosensitive resin composition may contain an adhesion-imparting agent other than the triazabenzene resin (F). Examples of the adhesiveness-imparting agent include acetoguanamine (2,4-diamino-6-methyl-1,3,5-triazabenzene) and benzoguanamine (2,4) -Diamino-6-phenyl-1,3,5-triazabenzene) and other guanazine derivatives; and 2,4-diamino-6-methacryloxyethyl-s -Triazabenzene, 2-vinyl-4,6-diamino-s-triazabenzene, 2-vinyl-4,6-diamin-s-triazabenzene, isocyanuric acid S-triazabenzene derivatives such as adducts, 2,4-diamino-6-methacryloxyethyl-s-triazabenzene, isocyanuric acid adducts, and the like.

The photosensitive resin composition may contain melamine within a range that does not inhibit the effect of the present invention, but it is preferable that it does not contain melamine. When melamine is contained, when the content of the carboxyl group-containing resin (A) is 100 parts by mass, the content of melamine is preferably 0.1% by mass or more and 6% by mass or less.

The photosensitive resin composition may contain a rheology control agent. With the rheology control agent, the viscosity of the photosensitive resin composition becomes appropriate. Examples of the rheology controlling agent include polar polyamidonium (models BYK-430 and BYK-431 manufactured by Bigchemi Japan Co., Ltd.) and polyhydroxycarboxamide (manufactured by Bigchemi Japan Co., Ltd.) in urea modification. Model BYK-405), modified urea (models BYK-410, BYK-411, BYK-420 manufactured by Bigchemi Japan Co., Ltd.), polymer urea derivatives (model BYK-415 manufactured by Bigchemi Japan Co., Ltd.), Urea modified amine ester (model BYK-425 manufactured by Bigchemi Japan Co., Ltd.), polyurethane (model BYK-428 manufactured by Bigchemi Japan Co., Ltd.) castor oil wax, polyethylene wax, polyamide wax, bentonite, two Silica, silica gel, kaolin, clay. Among these, the photosensitive resin composition can obtain more suitable viscosity by using the organic filler (E1). Therefore, the photosensitive resin composition may not contain a rheology control agent.

The photosensitive resin composition may contain at least one selected from the group consisting of: a hardening accelerator; a colorant; a copolymer of silicone, acrylate, and the like; a leveling agent; a thixotropic agent; Polymerization inhibitors; anti-halation agents; flame retardants; defoamers; antioxidants; surfactants; pigments; and polymer dispersants.

In order to prepare the photosensitive resin composition of the present embodiment, for example, the raw materials of the photosensitive resin composition are mixed and kneaded by a conventional kneading method using, for example, a three-roll mill, a ball mill, or a sand mill. A photosensitive resin composition is prepared. When the raw material contains a liquid component, a low viscosity component, etc., the photosensitive resin composition can be prepared in the following manner: First, knead a portion of the raw material other than the liquid component and the low viscosity component. After being prepared into a mixture, a liquid component and a component having a low viscosity are added to the obtained mixture and mixed. When the photosensitive resin composition contains a solvent (H), a part or all of the solvent (H) may be mixed with the triazabenzene resin (F) and then mixed with the remaining raw materials.

In consideration of storage stability and the like, the first agent can be prepared by mixing the 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 include a first agent and a second agent. At this time, for example, among the components of the photosensitive resin composition, the first agent can be prepared by mixing and dispersing the unsaturated compound (B), a part of the solvent (H), and the thermosetting component in advance, and by light-sensitive The rest of the components of the resin composition are mixed and dispersed to prepare a second agent. At this time, a required amount of the first agent and the second agent are mixed in a timely manner to prepare a mixed liquid, and the hardened body can be obtained by hardening the mixed liquid.

The photosensitive resin composition in this embodiment is suitable for an electrically insulating material for a printed wiring board. The photosensitive resin composition is particularly suitable for a material of an electrically insulating layer, which is a solder resist layer, a resist plating layer, a resist layer, an interlayer insulating layer, and the like.

The photosensitive resin composition in this embodiment preferably has a property that it can be developed with a sodium carbonate aqueous solution even if it is a film having a thickness of 25 μm. At this time, since a sufficiently thick electrically insulating layer can be produced from a photosensitive resin composition by a photolithography method, it can be widely used for producing an interlayer insulating layer, a solder resist layer, and the like in a printed wiring board. As a matter of course, an electrically insulating layer having a thickness of less than 25 μm can also be produced from the photosensitive resin composition.

Whether a film having a thickness of 25 μm can be developed with an aqueous sodium carbonate solution can be confirmed by the following method. A wet coating film was formed by coating a photosensitive resin composition on an appropriate substrate, and the wet coating film was heated at 80 ° C. for 40 minutes to form a coating film having a thickness of 25 μm. The negative mask is directly attached to the film, and the film is irradiated with ultraviolet rays under the condition of 500 mJ / cm ² to perform exposure. The negative mask has an ultraviolet-transmissive exposure portion and can block ultraviolet rays. Non-exposed section. After the exposure, the film was sprayed with a 1% Na ₂ CO ₃ aqueous solution at 30 ° C. for 90 seconds at a spray pressure of 0.2 MPa, and then sprayed with pure water for 90 seconds at a spray pressure of 0.2 MPa. As a result of observing the coating film after this treatment, when it was confirmed that the portion corresponding to the non-exposed portion in the coating film was removed and no residue could be recognized, it was determined that the coating film having a thickness of 25 μm could be developed with an aqueous sodium carbonate solution. In addition, it is possible to similarly confirm whether or not development can be performed with a sodium carbonate aqueous solution for a film having another thickness (for example, 30 μm).

Hereinafter, an example of a method for manufacturing a printed wiring board including an interlayer insulating layer formed of a photosensitive resin composition according to the present embodiment will be described with reference to FIGS. 1A to 1E. In this method, a photolithography method is used to form a through hole in the interlayer insulating layer.

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

The coating method is, for example, applying a photosensitive resin composition to the core material 1 to form a wet coating film. The coating method of the photosensitive resin composition may be selected from a group consisting of a conventionally known method, such as a dipping method, a spray method, a spin coating method, a roll coating method, a curtain coating method, and a screen printing method. law. Then, in order to volatilize the organic solvent in the photosensitive resin composition, the wet coating film can be dried at a temperature in a range of, for example, 60 to 120 ° C. to obtain the coating film 4.

In the dry film method, a photosensitive resin composition is first coated on an appropriate support made of polyester or the like and then dried, thereby forming a dried film of the photosensitive resin composition on the support, that is, a dry film. Thereby, a laminated body (a dry film with a support) is provided, which includes: a dry film; and a support, which is used to support the dry film. After the dry film in the laminated body is superposed on the core material 1, pressure is applied to the dry film and the core material 1, and then the support is peeled from the dry film, thereby transferring the dry film from the support to the core material 1. . Thereby, a cover film 4 made of a dry film is provided on the core material 1.

By exposing the coating film 4, the coating film 4 is partially cured as shown in FIG. 1C. Therefore, for example, after the negative mask is closely adhered to the coating film 4, the coating film 4 is irradiated with ultraviolet rays. The negative mask includes an exposure portion that allows ultraviolet rays to pass through, and a non-exposure portion that shields ultraviolet rays, and the non-exposure portions are provided at positions corresponding to the positions of the through holes 10. The negative mask is, for example, a photo tool such as a mask film or a dry plate. The ultraviolet light source is selected from, for example, chemical lamps, low-pressure mercury lamps, medium-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, xenon lamps, metal halide lamps, light-emitting diodes (LEDs), yttrium aluminum garnet lasers (YAG) , G-ray (436 nm), h-ray (405 nm), i-ray (365 nm); and, a combination of two or more of the group consisting of g-ray, h-ray, and i-ray. The ultraviolet light source is not limited to these examples, and any light source may be used as long as it can irradiate ultraviolet rays that can cure the photosensitive resin composition.

The exposure method may be a method other than a method using a negative mask. For example, the cover film 4 is exposed by a direct drawing method in which only the portion to be exposed is irradiated with ultraviolet rays emitted from a light source on the cover film 4. The light source used in the direct drawing method is, for example, selected from: chemical lamps, low-pressure mercury lamps, medium-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, xenon lamps, metal halide lamps, LEDs, YAG, g-rays (436 nm), h-rays (405 nm), i-rays (365 nm); and combinations of two or more of the groups consisting of g-rays, h-rays, and i-rays. The ultraviolet light source is not limited to these examples, and any light source may be used as long as it can irradiate ultraviolet rays that can cure the photosensitive resin composition.

In the dry film method, after the dry film in the laminate is superimposed on the core material 1, the support film 4 made of the dry film can be irradiated with ultraviolet rays through the support without peeling off the support. The cover film 4 is exposed, and then the support is peeled from the cover film 4 before the development process is performed.

Then, the developing process is performed on the coating film 4 to remove the unexposed portion 5 of the coating film 4 shown in FIG. 1C, thereby, as shown in FIG. Position setting hole 6. The development process can use an appropriate developing solution depending on the composition of the photosensitive resin composition. The developing solution is, for example, an alkaline aqueous solution containing at least one of an alkali metal salt and an alkali metal hydroxide, or an organic amine. The alkaline aqueous solution more specifically contains, for example, at least one selected from the group consisting of sodium carbonate, potassium carbonate, ammonium carbonate, sodium bicarbonate, potassium bicarbonate, ammonium bicarbonate, sodium hydroxide, hydrogen Potassium oxide, 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 contains, for example, at least one selected from the group consisting of monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, and triisopropanolamine.

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

Then, the coating film 4 is hardened by heating it. The heating conditions are, for example, a heating temperature in a range of 120 to 200 ° C and a heating time in a range of 30 to 120 minutes. If the cover film 4 is hardened in this way, the strength, hardness, chemical resistance, and other properties of the interlayer insulating layer 7 can be improved.

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

The thickness of the interlayer insulating film 7 is not particularly limited, and may be within a range of 5 to 50 μm.

As described above, the interlayer insulating layer 7 made of the cured product of the photosensitive resin composition is provided on the core material 1. A second conductive line 8 and a hole plating 9 can be provided on the interlayer insulating layer 7 by a known method such as an additive process. Thereby, the printed wiring board 11 is obtained as shown in FIG. 1E, and the printed wiring board 11 is provided with: a first conductor line 3; a second conductor line 8; and an interlayer insulating layer 7 interposed between the first conductor line 3 and Between the second conductor lines 8; and a through hole 10 for electrically connecting the first conductor lines 3 and the second conductor lines 8. In FIG. 1E, the hole plating 9 has a cylindrical shape that covers the inner surface of the hole 6. However, the hole plating 9 may be filled in the entire inner side of the hole 6.

In addition, before the hole plating 9 as shown in FIG. 1E is provided, the entire inner surface of the hole 6 and the outer surface of the part of the interlayer insulating layer 7 can be roughened. In this way, by roughening the outer surface of the part of the interlayer insulating layer 7 and the surface inside the hole 6, the adhesion between the core material 1 and the hole plating 9 can be improved.

In order to roughen the outer surface of the part of the interlayer insulating layer 7 and the surface inside the hole 6, the same procedure as that of a general slag removal treatment using an oxidizing agent can be performed. For example, an oxidizing agent is brought into contact with the outer surface of the interlayer insulating layer 7 to provide a rough surface to the interlayer insulating layer 7. However, the method is not limited to this method, and a method of applying a rough surface to a hardened material such as plasma treatment, UV treatment, or ozone treatment can also be adopted as appropriate.

The oxidant may be an oxidant that can be purchased for use as a desmear liquid. For example, the oxidizing agent can be constituted by a commercially available sizing liquid and a sizing liquid. Such an oxidant can contain, for example, at least one permanganate selected from the group consisting of sodium permanganate and potassium permanganate.

In order to provide the hole plating 9, the outer surface of the roughened portion and the surface inside the hole 6 may be subjected to an electroless metal plating treatment to form an initial line. After that, the metal in the electrolytic plating solution is precipitated on the initial line by electrolytic metal plating treatment, and thereby the hole plating 9 can be formed.

A method for manufacturing a printed wiring board including a solder resist layer formed of a photosensitive resin composition according to this embodiment will be described.

First, prepare a core material. The core material includes, for example, at least one insulating layer and at least one conductor line. A film is formed of a photosensitive resin composition on the surface of the core material on which the conductor lines are provided. Examples of the method for forming the film include a coating method and a dry film method. As the coating method and the dry film method, the same method as in the case of forming the interlayer insulating layer described above can be adopted. The film can be partially hardened by exposing it. The exposure method can be the same as that in the case of forming the interlayer insulating layer. Then, the film is subjected to a development process to remove the unexposed portion of the film, thereby leaving the exposed portion of the film on the core material.

Then, the film on the core material is heated to perform thermal curing. The developing method and the heating method can be the same as those described above when the interlayer insulating layer is formed. As required, the film may be further irradiated with ultraviolet rays before or after heating. In this case, the photocuring of the film can be further advanced.

The thickness of the solder resist layer is not particularly limited, and may be within a range of 5 to 50 μm.

With the above operations, a solder resist layer composed of a cured product of a photosensitive resin composition can be provided on the core material. Thereby, it is possible to obtain a printed wiring board including: a core material including an insulating layer and a conductor circuit on the insulating layer; and a solder resist layer partially covering a surface of the core material on which the conductor circuit is provided. . The solder resist layer may be provided with a rough surface similarly to the interlayer insulating layer. Thereby, the adhesiveness of a solder resist layer and the metal material which comprises a conductor line, a solder ball, etc. can be improved.

In this embodiment, an electrically insulating layer such as a solder resist layer and an interlayer insulating layer can be formed particularly favorably from a dried material of the photosensitive resin composition, that is, a dry film or a coating film of the photosensitive resin composition. By providing a rough surface to the electrically insulating layer, the adhesion between the electrically insulating layer and the metal material can be improved.
[Example]

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

(1) Synthesis of carboxyl-containing resin
(1-1) Synthesis Example A-1 to Synthesis Example A-4 and Synthesis Example B-1 to Synthesis Example B-3
In a four-necked flask equipped with a reflux cooler, a thermometer, an air blowing tube, and a stirrer, the components shown in the "First Reaction" column in Table 1 were added, and the components were prepared by stirring the components with air bubbles . This mixture was stirred in the flask under the bubbling of air while heating the mixture under the conditions of the reaction temperature and reaction time shown in the "Reaction Conditions" column. Thereby, a solution of the intermediate was prepared.
Next, the components shown in the "Second Reaction" column of Table 1 were poured into the solution of the intermediate in the flask, and the reaction temperature shown in the "Reaction Conditions (1)" column was stirred while being bubbled with air. And reaction conditions. Next, in addition to Synthesis Example B-1 to Synthesis Example B-3, the mixture was heated under conditions of reaction temperature and reaction time shown in the column of "Reaction Conditions (2)" while being stirred under the bubbling of air. Thus, a 65% by mass solution of a carboxyl group-containing resin was obtained. The polydispersity of the carboxyl group-containing resin (excluding the carboxyl group-containing resins of Synthesis Examples B-1 to B-3), the weight average molecular weight, and the acid value are as shown in Table 1. The mole ratios between the components are also shown in Table 1.
The details of the components shown in the column (a1) in Table (1) are as follows.
‧Epoxy compound 1: A bisphenol fluorene type epoxy compound, which is represented by formula (7), and R ₁ to R ₈ in formula (7) are all hydroxyl groups, and the epoxy equivalent is 250 g / eq.
‧Epoxy compound 2: A bisphenol fluorene type epoxy compound, which is represented by formula (7), and R ₁ and R ₅ in formula (7) are both methyl groups, R ₂ to R ₄ and R ₆ to R _{8 is} all hydrogen and epoxy equivalent is 279 g / eq.
The details of the components shown in the column (g1) in Table 1 are as follows.
‧Epoxy compound 3: Biphenol novolac epoxy resin (product name NC-3000-H manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent 288 g / eq).
‧Epoxy compound 4: formaldehyde novolac epoxy resin (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., model YDC-700-5, epoxy equivalent 203 g / eq).
‧Epoxy Compound 5: Bisphenol A epoxy resin (manufactured by Mitsubishi Chemical Corporation, model jER1001, epoxy equivalent 472 g / eq).
The details of the components shown in the column (a2) or (g2) in Table 1 are as follows.
‧Ω-carboxy-polycaprolactone (n ≒ 2) monoacrylate: manufactured by Toa Synthesis Co., Ltd. under the trade name Aronix M-5300 (number average molecular weight 290).

[Table 1]

[Examples 1 to 23, Comparative Examples 1 to 5]
A part of the components shown in Tables 2 to 5 described below was kneaded with a three-roll mill, and then all the components shown in Tables 2 to 5 described below were stirred and mixed in a flask to obtain a photosensitive resin composition. When a photosensitive resin composition is produced, when melamine is used, it is dispersed uniformly in the photosensitive resin composition. The details of the components shown in Tables 2 to 5 are as follows.
‧Unsaturated compound A: Trimethylolpropane triacrylate.
‧Unsaturated compound B: tricyclodecane dimethanol diacrylate.
‧Unsaturated compound C: ε-caprolactone modified dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd., model KAYARAD DPCA-20)
‧Photopolymerization initiator A: 2,4,6-trimethylbenzylidene diphenylphosphine oxide (manufactured by BASF, model Irgacure TPO).
‧Photopolymerization initiator B: 1-hydroxycyclohexylphenyl ketone (manufactured by BASF, model Irgacure 184)
‧Photopolymerization initiator C: 4,4'-bis (diethylamine) diphenyl ketone.
‧Crystalline epoxy resin A: Biphenyl type crystalline epoxy resin (product name YX-4000 manufactured by Mitsubishi Chemical Corporation, melting point 105 ° C, epoxy equivalent 187 g / eq).
‧Crystalline epoxy resin B: Bisphenol-type crystalline epoxy resin (product name: YSLV-80XY manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., melting point: 75-85 ° C, 192 g / eq).
‧Amorphous solution of amorphous epoxy resin C: Long chain carbon chain bisphenol A type epoxy resin (manufactured by DIC Corporation, model EPICLON EXA-4816, liquid resin, epoxy equivalent 410g / eq) is used as a solid The component was 90% dissolved in diethylene glycol monoethyl ether acetate as a reference solution (the epoxy equivalent was 455.56 g / eq in terms of 90% solid content conversion).
‧Amorphous epoxy resin solution D: Biphenol novolac epoxy resin (product name: NC-3000 manufactured by Nippon Kayaku Co., Ltd., softening point: 53-63 ° C, epoxy equivalent: 280 g / eq): solid The component was based on a solution in which 80% was dissolved in diethylene glycol monoethyl ether acetate (the epoxy equivalent was 350 g / eq based on 80% conversion of solid content).
‧ Dispersion liquid of organic filler A having a carboxyl group: a crosslinked rubber (NBR) having an average primary particle diameter of 0.07 μm is dispersed in methyl ethyl ketone so that the content of the total dispersion liquid is 15% by weight. The resulting dispersion (manufactured by JSR Corporation, model XER-91-MEK, acid value 10.0 mg KOH / g).
‧ Dispersion liquid of organic filler B containing carboxyl group: The polymer (linear particles) of carboxyl modified hydrogenated nitrile rubber is dispersed in methyl ethyl ketone so that the content of the carboxyl group-containing filler is 17% by weight. The resulting dispersion (manufactured by JSR Corporation, model XER-32-MEK).
‧ Dispersion of organic filler C with carboxyl and hydroxyl groups: The crosslinked rubber (SBR) having an average primary particle diameter of 0.07 μm is dispersed in methyl ethyl ketone so that the content relative to the total amount of the dispersion is 15% by weight. Dispersion liquid (made by JSR Corporation, model XSK-500).
‧Epoxy-based organic filler: powdery, glycidyl modified acrylonitrile butadiene rubber with average primary particle diameter of 0.3 μm.
‧ Maleic acid modified polybutadiene: Model Ricon 130 MA 8 manufactured by Sartomer.
‧Triazabenzene resin A: Methylbutylated melamine formaldehyde resin having N- (CH ₂ OR) (CH ₂ OR ') groups (R and R' are each independently methyl or n-butyl) (Japan (Product name: CYMEL 235, number average molecular weight: 630, polymerization degree: 1.4, liquid state at 25 ° C).
‧Triazabenzene resin B: Isobutanol solution of N- (CH ₂ OCH ₃ ) -based imino-type melamine formaldehyde resin (non-volatile content 80%, manufactured by Japan Hydro Industry Co., Ltd., product name CYMEL325 , The number average molecular weight is 1000, the degree of polymerization is 2.3, the liquid state is at 25 ° C, and the solvent is isobutanol).
‧Triazabenzene resin C: 3-methyl-3methoxybutanol solution of N- (CH ₂ OCH ₃ ) H group imino-type benzoguanamine formaldehyde resin (non-volatile content 80%, Manufactured by Japan Hydro Industrial Co., Ltd. under the product name MYCOAT 105, with a polymerization degree of 1.32, in a solution state at 25 ° C, and the solvent is 3-methyl-3methoxybutanol).
‧Melamine: manufactured by Nissan Chemical Industry Co., Ltd., a fine powder of melamine, dispersed in a photosensitive resin composition with an average particle size of 8 μm.
‧ Silane coupling agent (GP-TMS): 3-Glycidoxypropyltrimethoxysilane.
‧Coupling agent (TEOS): Tetraethoxysilane.
‧Coupling agent (MTMS): methyltrimethoxysilane.
‧Coupling agent (AEAP-MDMS): N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane.
‧Coupling agent (VL-TMS): vinyltrimethoxysilane.
‧Antioxidant: Hindered phenolic antioxidant (manufactured by BASF, model IRGANOX 1010).
‧Surfactant: Made by DIC Corporation, model MEGAFAC F-477.
‧Rheology control agent: manufactured by Bigchemi Japan Co., Ltd., model BYK-430.
‧Solvent A: Diethylene glycol monoethyl ether acetate.
‧Solvent B: methyl ethyl ketone.

(1-2) Preparation of test piece The photosensitive resin composition of each Example and Comparative Example was coated on a film made of polyethylene terephthalate with a coater, and then heated at 95 ° C for 25 minutes. It was dried in minutes to form a dry film having a thickness of 30 μm on the film.
A glass epoxy-based copper-clad laminate (FR-4 type) including a copper foil with a thickness of 17.5 μm was prepared. Using a subtractive method, a comb-shaped electrode having a line width / spacing of 30 μm / 30 μm was formed on the glass epoxy-copper-clad laminate as a conductor line, thereby obtaining a printed wiring board (core material). The surface of the conductor wiring of this printed wiring board having a thickness of about 1 μm is dissolved and removed with an etchant (model CZ-8101 manufactured by MEC Co., Ltd.), thereby roughening the conductor wiring. The dry film was heated and laminated on a surface of one side of the printed wiring board using a vacuum laminator. The conditions for heating the laminate were set to 0.5 MPa, 80 ° C, and 1 minute. Thereby, a coating film composed of the dry film is formed on a printed wiring board. The film is irradiated with ultraviolet rays at a condition of 250 mJ / cm ² in a state where the film is directly in close contact with a negative mask. The negative mask has a pattern including a circular shape with a diameter of 100 μm or 40 μm and is non-exposed. unit. The exposed film is subjected to a development process.
When the development process was performed, the coating was sprayed with a 1% Na ₂ CO ₃ aqueous solution at 30 ° C. for 90 seconds at a spray pressure of 0.2 MPa. Then, pure water was sprayed on the film at a spray pressure of 0.2 MPa for 90 seconds. Thereby, the unexposed part of the film is removed, and holes are formed in the film.
The polyethylene terephthalate film was peeled from the dry film (film) after exposure and before development.
Then, the film was heated at 180 ° C for 120 minutes. Thereby, a layer composed of a cured product of the photosensitive resin composition (also referred to as a cured product of a dry film) is formed on the printed wiring board (core material). Thereby, a test piece was obtained.

[Evaluation test]
The test pieces of Examples 1 to 23 and Comparative Examples 1 to 5 were evaluated according to the following procedures. The results are shown in Tables 2 to 5 below. The following (1) to (8) are evaluated by performing a specific treatment on a test piece or each test piece having a film formed of a dry film having a thickness of 30 μm.

(1) Developability With respect to the test pieces of each of the examples and comparative examples, the non-exposed portions of the printed wiring board after the above development treatment and after the desmear removal treatment were observed, and the results were evaluated in the following manner. It should be noted that the desmearing treatment is carried out in accordance with a method of an evaluation test of "(6) roughening resistance" described later.
A: All unexposed films are removed.
B: In the opening portion having a diameter of 100 μm, although residues were still found after development, no residues were found after the desmearing treatment.
C: A part of the unexposed film remains on the printed wiring board.

(2) Resolvability For the test pieces of each of the examples and comparative examples, the holes having a diameter of 40 μm in the openings formed in the layer made of the cured product were observed, and the results were evaluated in the following manner.
A: The diameter of the bottom of the hole is 30 μm or more.
B: The diameter of the bottom of the hole is 20 μm or more and less than 30 μm.
C: The diameter of the bottom of the hole is less than 20 μm, or no clear hole is formed.

(3) Plating resistance After the nickel plating layer was formed on the exposed portions of the conductor lines of the test pieces of each of the examples and comparative examples by using a commercially available electroless nickel plating bath, a commercially available one was used. Electroless gold plating bath to form a gold plating layer. The layers made of hardened material and metal layers were visually observed. A celluloid adhesive tape peeling test was performed on the layer composed of the cured product. The results were evaluated in the following manner.
A: No abnormality was observed in the appearance of the layer made of the hardened material and the metal layer, and the layer made of the hardened material did not peel off due to the celluloid adhesive tape peeling test.
B: Discoloration of the layer composed of the cured product was confirmed, but the layer composed of the cured product did not peel off due to the celluloid adhesive tape peeling test.
C: It was confirmed that protrusions occurred in the layer composed of the cured product, and peeling caused by the celluloid adhesive tape peeling test occurred in the layer composed of the cured product.

(4) Inter-wire insulation layer Exposed the printed wiring board to 121 ° C and 97% RH (relative humidity) while applying a bias voltage of 30 V DC to the conductor lines (comb electrodes) in the test pieces of each of the examples and comparative examples 100 hours under the test environment. In this test environment, the resistance value between the comb-shaped electrodes of the layer composed of the hardened material in this environment was measured over time, and the results were evaluated based on the following evaluation criteria.
A: The resistance value was maintained at 10 ⁶ Ω or more from the time when the test was started until 100 hours passed.
B: The resistance value was maintained at 10 ⁶ Ω or more from the start of the test to the elapse of 80 hours, but the resistance value became less than 10 ⁶ Ω from the start of the test to 100 hours elapsed.
C: During the period from the start of the test to the elapse of 80 hours, the resistance value became less than 10 ⁶ Ω.

PCT (Pressure Cooker Test)
After the test pieces of each example and comparative example were left in an environment of 121 ° C. and 100 R.H. for 100 hours, the appearance of a layer composed of a cured product was evaluated according to the following evaluation criteria.
A: No abnormality was found on the layer made of hardened material.
B: Discoloration was found on the layer made of hardened material.
C: A wide range of discoloration was observed on the layer composed of the hardened material, and a part thereof was swelled.

(6) Roughness resistance For the test pieces of each of the examples and comparative examples, in the previous step of the plating process, the outer surface of the layer composed of the hardened material was subjected to a step of removing the slag in accordance with the general process Roughening. A commercially available swelling treatment solution (Swelling Dip Securiganth P, manufactured by ATOTECH Japan Co., Ltd.) was used as a swelling solution for deslagging, and the outer surface of the layer composed of the cured product was swelling at 60 ° C. for 5 minutes, so that The hardened surface swells. Then, the swollen surface was washed with hot water. Then, a commercially available oxidant (Concentrate Compact CP, manufactured by ATOTECH Japan Co., Ltd.) containing potassium permanganate was used as a desmearing solution, and the surface of the layer composed of the cured product was roughened at 80 ° C for 10 minutes. , And roughen the surface washed with hot water. The surface of the hardened product thus roughened was washed with hot water, and a neutralization solution (Reduction Solution Securiganth P, manufactured by ATOTECH Japan Co., Ltd.) was further used to treat the residue on the surface of the hardened product for 5 minutes at 40 ° C. Remove residue. And the surface of the hardened | cured material after neutralization was washed with water. In this way, the thickness of the layer made of the cured product of the photosensitive resin composition provided with the rough surface was measured, and the roughened resistance of the cured product to the degumming solution was evaluated according to the following evaluation criteria.
A: The reduction in thickness due to roughening is less than 3 μm.
B: The reduction in thickness due to roughening is 3 μm or more and less than 6 μm.
C: The reduction in thickness due to roughening is 6 μm or more.

(7) Roughening stability With respect to the test pieces of each of the examples and comparative examples, the surface of the hardened layer of the photosensitive resin composition provided with a rough surface was observed by the method of (6) above, and based on the following Evaluation criteria to evaluate.
A: It becomes a uniform rough surface.
B: Although slight cracks were found on the surface, it became a uniform roughened surface in other parts.
C: It becomes an uneven roughened surface, or a wide range of cracks occur on the surface.

(8) Adhesion of copper plating layer For the test pieces of each of the examples and comparative examples, a rough surface was provided on the layer made of hardened material according to the method of (6) above, and then a commercially available liquid agent was used. An electroless copper plating process was used to form an initial circuit on the rough surface of the test piece. The test piece provided with the initial circuit was heated at 150 ° C for 1 hour.
Then, by electrolytic copper plating treatment, copper having a thickness of 33 μm was directly precipitated from a commercially available liquid agent at a current density of ² A / dm ² , and then a test piece having the copper precipitated was heated at 180 ° C. for 30 minutes to form Copper plating. The adhesion between the copper plating layer formed in this way and the cured product in the test piece was evaluated according to the following evaluation criteria.
Here, when no blistering was observed in the test piece during heating of both the electroless copper plating treatment and the electrolytic copper plating treatment, the adhesion between the copper plating layer and the cured product was evaluated according to the following procedure.合 Strength. The adhesion strength is measured in accordance with Japanese Industrial Standard JIS C6481. In addition, in order to confirm the adhesion stability of the copper plating layer, four tests were performed.
A: After the electroless copper plating process, no foaming was confirmed during heating, and after the electrolytic copper plating process, no foaming was also confirmed during heating. In addition, in four tests, the adhesion strength of copper was 0.6 kN / m or more. The difference between the maximum value and the minimum value of the peel strength is less than 0.2 kN / m.
B: After the electroless copper plating treatment, no foaming was confirmed during heating, and after the electrolytic copper plating treatment, no foaming was confirmed during heating. However, in four tests, the adhesion strength of copper may be less than 0.6 kN / m. The difference between the maximum value and the minimum value of the peel strength is less than 0.2 kN / m.
C: Foaming was confirmed after the electroless copper plating treatment and heating, or after the electrolytic copper plating treatment and heating. In addition, although no blistering was observed during the electroless copper plating process and during heating, or after the electrolytic copper plating process and during heating, the difference between the maximum and minimum peel strengths was 0.2 kN / m or more. .

[Table 2]

[table 3]

[Table 4]

[table 5]

(to sum up)
As shown by the above results, the photosensitive resin composition in the first aspect of the present invention contains: a carboxyl group-containing resin (A); an unsaturated compound (B) having at least one ethylenically unsaturated bond in one molecule; light A polymerization initiator (C); an epoxy compound (D); an organic filler (E) containing an organic filler (E1) having a carboxyl group; and a triazabenzene resin (F). The triazabenzene resin (F) satisfies at least one of the following conditions: the liquid state is at 25 ° C; and the photosensitive resin composition contains a solvent (H), and the triazabenzene is at 25 ° C. The resin (F) is dissolved in the solvent (H).

The photosensitive resin composition of the first aspect becomes a hardened material by hardening. When the surface of the hardened material is roughened with an oxidizing agent, it can suppress an excessive reduction in the thickness of the hardened material due to the oxidizing agent. In addition, it is possible to suppress the unevenness of the surface after the treatment.

The second aspect of the photosensitive resin composition is directed to the first aspect, wherein the triazabenzene resin (F) has at least one triazabenzene skeleton and has at least one bond to the triazabenzene skeleton. On the amine group. The amine group is a secondary amine group or a tertiary amine group.

According to the second aspect, even if the surface of the hardened layer is roughened with an oxidizing agent, the surface uniformity can be maintained, and the adhesion between the hardened layer and the plating layer can be improved.

The third aspect of the photosensitive resin composition is directed to the second aspect, wherein the secondary amine group is N-hydroxymethyl or N-alkoxyalkyl, and the tertiary amine group is N, N-dihydroxy. Methyl, N-hydroxymethyl-N-alkoxyalkyl or N, N-bis (alkoxyalkyl).

According to the third aspect, even if the surface of the hardened layer is roughened with an oxidizing agent, the surface uniformity can be maintained, and the adhesion between the hardened layer and the plating layer can be improved.

The fourth aspect of the photosensitive resin composition is directed to the second aspect or the third aspect, wherein the tertiary amine group is selected from the group consisting of -N (CH ₂ OR ₁₂ ) ₂ and -N (CH ₂ OR ₁₂ ) (CH ₂ OR ₁₄ ) group, -N (CH ₂ OR ₁₄ ) ₂ group, and -N (CH ₂ OH) (CH ₂ OR ₁₂ ) group. R ₁₂ and R ₁₄ are each independently an alkyl group having 1 to 4 carbon atoms.

According to the fourth aspect, even if the surface of the hardened layer is roughened with an oxidizing agent, the surface uniformity can be maintained, and the adhesion between the hardened layer and the plating layer can be improved.

The fifth aspect of the photosensitive resin composition is directed to any one of the first aspect to the fourth aspect, wherein the organic filler (E1) with respect to the total solid content of the photosensitive resin composition. The amount is 1 mass% or more and 25 mass% or less.

According to the fifth aspect, it is possible to impart resolution to a hardened material composed of a photosensitive resin composition, and further to form a plating layer by subjecting the hardened material layer having a roughened surface to the hardened material to form a plating layer. , The adhesion between the hardened layer and the plating layer at this time can be further improved.

The sixth aspect of the photosensitive resin composition is directed to any of the first aspect to the fifth aspect, wherein the triazabenzene resin (F) is relative to the amount of the carboxyl group-containing resin (A). The amount is 0.5% by mass to 20% by mass.

According to the sixth aspect, when a roughened surface is provided to the cured product of the photosensitive resin composition, the reduction in thickness of the hardened layer at this time can be further suppressed, and the unevenness of the surface after the roughened surface treatment can be further suppressed. Happening. Moreover, if it is this range, the resolution of the hardened | cured material which consists of a photosensitive resin composition can be maintained. Further, at this time, when a plating layer is formed on the hardened material layer obtained by providing the hardened surface with a rough surface to form a plating layer, the adhesion between the hardened material layer and the plated layer at this time can be further improved. .

The seventh aspect of the photosensitive resin composition is directed to any one of the first aspect to the sixth aspect, wherein the average primary particle diameter of the organic filler (E1) is 1 μm or less.

According to the seventh aspect, the rheology of the photosensitive resin composition can be efficiently improved. Therefore, the stability of the photosensitive resin composition is further improved. At this time, the roughness of the rough surface formed on the hardened material can be made fine. Thereby, the anchoring effect becomes large as the surface area of the hardened material increases, and the adhesion with the plating layer can be improved.

An eighth aspect of the photosensitive resin composition is any one of the first aspect to the seventh aspect, wherein the organic filler (E1) contains a rubber component.

According to the eighth aspect, flexibility can be imparted to the cured product of the photosensitive resin composition.

The ninth aspect of the photosensitive resin composition is directed to the eighth aspect, wherein the rubber component contains at least one selected from the group consisting of crosslinked acrylic rubber, crosslinked NBR, crosslinked MBS, and crosslinked SBR. A polymer.

According to the ninth aspect, the rubber component can impart excellent flexibility to the cured product of the photosensitive resin composition. Furthermore, the surface of the hardened | cured material layer can be provided with a more appropriate rough surface.

The tenth aspect of the photosensitive resin composition is any one of the first aspect to the ninth aspect, wherein the carboxyl group-containing resin (A) includes a carboxyl group-containing resin having a bisphenol fluorene skeleton.

According to the tenth aspect, the cured product of the photosensitive resin composition can have higher heat resistance and insulation reliability.

The eleventh aspect of the photosensitive resin composition is any one of the first aspect to the tenth aspect, and further includes a coupling agent (G). The coupling agent (G) has at least one atom selected from the group consisting of a silicon atom, an aluminum atom, a titanium atom, and a zirconium atom, and further includes a coupling agent (G1), which has two or more options Free functional groups in the group consisting of alkoxy, fluorenyl and alkoxide groups.

According to the eleventh aspect, the coupling agent (G1) can improve the organic filler (E1) in the photosensitive resin composition by reaction or interaction with the carboxyl group-containing resin (A) and the carboxyl group contained in the organic filler (E1). ), The rheology and stability (especially storage stability) of the photosensitive resin composition can be improved.

The twelfth aspect of the photosensitive resin composition is the eleventh aspect, wherein the coupling agent (G1) has a silicon atom.

According to the twelfth aspect, the dispersibility of the organic filler (E1) in the photosensitive resin composition is effectively improved. Therefore, the rheology and stability of the photosensitive resin composition are further improved.

The thirteenth aspect of the photosensitive resin composition is directed to the eleventh or twelfth aspect, wherein the coupling agent (G1) further has a group selected from the group consisting of an amine group, an epoxy group, a vinyl group, and a (meth) acrylic group. At least one functional group in the group consisting of sulfhydryl group, isocyanate group and thioether group.

According to the thirteenth aspect, it is possible to react with the carboxyl group contained in the organic filler (E1), and to further improve the dispersibility of the organic filler (E1) in the photosensitive resin composition more efficiently. Therefore, the rheology, stability (especially storage stability) and resolution of the photosensitive resin composition are further improved.

A fourteenth aspect of the dry film includes the photosensitive resin composition according to any one of the first to thirteenth aspects.

In the fourteenth aspect of the dry film, a hardened material is formed by hardening. When the surface is roughened with an oxidizing agent, the thickness of the hardened material due to the oxidizing agent at this time can be suppressed from being excessively reduced, and it can be suppressed. The treated surface becomes uneven. In addition, an electrically insulating layer such as a solder resist layer and an interlayer insulating layer can be formed particularly favorably from this dry film.

A fifteenth aspect of the printed wiring board includes an interlayer insulating layer including a cured product of the photosensitive resin composition according to any one of the first to thirteenth aspects.

According to the fifteenth aspect, the interlayer insulating layer can be provided with a rough surface to improve the adhesion between the interlayer insulating layer and the metal material.

A sixteenth aspect of the printed wiring board includes a solder resist layer including a cured product of the photosensitive resin composition according to any one of the first to thirteenth aspects.

According to the sixteenth aspect, the roughening of the solder resist layer can improve the adhesion between the interlayer insulating layer and the metal material.

1‧‧‧ core material

2‧‧‧ Insulation

3‧‧‧ the first conductor line

4‧‧‧ film

5‧‧‧ unexposed part of the film

6‧‧‧hole

7‧‧‧ interlayer insulation film

8‧‧‧Second Conductor Line

9‧‧‧hole plating

10‧‧‧through hole

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

Domestic storage information (please note in order of storage organization, date, and number)
no

Information on foreign deposits (please note according to the order of the country, institution, date, and number)
no

Claims (17)

A photosensitive resin composition containing: Carboxyl-containing resin (A); Unsaturated compound (B), which has at least one ethylenically unsaturated bond in one molecule; Photopolymerization initiator (C); Epoxy compound (D); An organic filler (E) comprising an organic filler (E1) having a carboxyl group; and, Triazabenzene resin (F); The triazabenzene resin (F) satisfies at least one of the following conditions: the liquid state is at 25 ° C; and the photosensitive resin composition contains a solvent (H) at 25 ° C At this time, the aforementioned triazabenzene resin (F) is dissolved in the solvent (H). The photosensitive resin composition according to claim 1, wherein the triazabenzene resin (F) has at least one triazabenzene skeleton and at least one amine bonded to the triazabenzene skeleton. base, The aforementioned amine group is a secondary amine group or a tertiary amine group. The photosensitive resin composition according to claim 2, wherein the secondary amine group is N-methylol or N-alkoxyalkyl, The tertiary amine group is N, N-dimethylol, N-hydroxymethyl-N-alkoxyalkyl, or N, N-bis (alkoxyalkyl). The photosensitive resin composition according to claim 2 or 3, wherein the tertiary amine group is selected from the group consisting of -N (CH ₂ OR ₁₂ ) ₂ and -N (CH ₂ OR ₁₂ ) (CH ₂ OR ₁₄ ) At least one group in the group consisting of -N (CH ₂ OR ₁₄ ) ₂ group and -N (CH ₂ OH) (CH ₂ OR ₁₂ ) group, each of the aforementioned R ₁₂ and R _{14 is} independently carbon An alkyl group having a number of 1 or more and 4 or less. The photosensitive resin composition according to any one of claims 1 to 3, wherein the amount of the organic filler (E1) is 1% by mass or more and 25% with respect to the total solid content of the photosensitive resin composition. Mass% or less. The photosensitive resin composition according to any one of claims 1 to 3, wherein the amount of the triazabenzene resin (F) is 0.5% by mass and 20% with respect to the amount of the carboxyl group-containing resin (A). Mass% or less. The photosensitive resin composition as described in any one of Claims 1-3 whose average primary particle diameter of the said organic filler (E1) is 1 micrometer or less. The photosensitive resin composition according to any one of claims 1 to 3, wherein the organic filler (E1) contains a rubber component. The photosensitive resin composition according to claim 8, wherein the rubber component contains at least one polymer selected from the group consisting of a crosslinked acrylic rubber, a crosslinked NBR, a crosslinked MBS, and a crosslinked SBR. The photosensitive resin composition according to any one of claims 1 to 3, wherein the carboxyl group-containing resin (A) includes a carboxyl group-containing resin having a bisphenol fluorene skeleton. The photosensitive resin composition according to any one of claims 1 to 3, further comprising a coupling agent (G), The coupling agent (G) has at least one atom selected from the group consisting of a silicon atom, an aluminum atom, a titanium atom, and a zirconium atom, and further includes a coupling agent (G1), which has two or more A functional group selected from the group consisting of alkoxy, fluorenyloxy, and alkoxide groups. The photosensitive resin composition according to claim 11, wherein the coupling agent (G1) has a silicon atom. The photosensitive resin composition according to claim 11, wherein the coupling agent (G1) further has a member selected from the group consisting of an amine group, an epoxy group, a vinyl group, a (meth) acrylic group, a mercapto group, an isocyanate group, and a thioether group. At least one functional group in the formed group. The photosensitive resin composition according to claim 12, wherein the coupling agent (G1) further has a member selected from the group consisting of an amine group, an epoxy group, a vinyl group, a (meth) acrylic group, a mercapto group, an isocyanate group, and a thioether group. At least one functional group in the formed group. A dry film containing the photosensitive resin composition according to any one of claims 1 to 14. A printed wiring board including an interlayer insulating layer including a cured product of the photosensitive resin composition according to any one of claims 1 to 14. A printed wiring board including a solder resist layer containing a cured product of the photosensitive resin composition according to any one of claims 1 to 14.