TW201902973A - Photosensitive resin composition, dry film, and printed wiring board - Google Patents

Abstract

The present invention addresses the problem of providing a photosensitive resin composition which has high resolution and which is capable of forming a cured product having high copper-plating adhesiveness. This photosensitive resin composition is photocurable. The photosensitive resin composition contains: a carboxyl group-containing resin (A) that has an aromatic ring; an organic filler (B) that has an average primary particle size of 1 [mu]m or less and has a carboxyl group; a coupling agent (C) that has at least one type of atom selected from the group consisting of a silicon atom, an aluminum atom, a titanium atom, and a zirconium atom, and that has two or more functional groups including at least one selected from the group consisting of alkoxy groups, acyloxy groups, and alkoxides; and a silica filler (D) that has an average primary particle size within the range of 1-150 nm.

Description

Photosensitive resin composition, dry film, and printed wiring board

The present invention relates to a photosensitive resin composition, a dry film, and a printed wiring board.

Conventionally, in order to manufacture printed wiring boards, various electrically insulating resin compositions are used to produce electrically insulating layers such as a solder resist layer, a plating resist layer, a resist layer, and an interlayer insulating layer.

In recent years, in accordance with the requirements for high performance, miniaturization, and thinness of electronic devices such as communication devices and personal computers, it is necessary to form fine through holes and fine through holes in an electrically insulating layer formed of such a resin composition. The opening pattern etc. use a photosensitive resin composition as a resin composition for forming an electrically insulating layer.

For example, Patent Document 1 discloses a photosensitive resin composition for an insulating film, which contains: (A) a carboxyl group-containing resin obtained by reacting a diol compound with a polycarboxylic acid, and having a weight average molecular weight of 2,000 to 40,000, The acid value is 50-200 mgKOH / g; (B) an unsaturated compound containing at least one ethylenically unsaturated bond capable of photopolymerization in one molecule; (C) an epoxy compound; and (D) Photopolymerization initiator. Furthermore, it is described that the addition of a rubber component to the photosensitive resin composition for an insulating film can improve the adhesion with a metal plating.

However, although the photosensitive resin composition for an insulating film described in Patent Document 1 can improve the adhesion to metal plating to some extent, it is not possible to reduce the amount of curing of the photosensitive resin composition for an insulating film. The surface roughness of the hardened product after desmear treatment does not provide good high-frequency characteristics. In addition, since a rubber component is added, when developing processing is performed with an aqueous solution containing at least one of an alkali metal salt and an alkali metal hydroxide, the resolution is lowered, and fine through holes and opening patterns cannot be formed. Fear. It is not easy to obtain a photosensitive resin composition which can form a hardened product having high copper plating adhesion and low roughness after removing slag, and has excellent resolvability. [Prior Art Literature] (Patent Literature)

Patent Document 1: Japanese Patent No. 4508929

An object of the present invention is to provide a photosensitive resin composition capable of forming a hardened product having high copper plating adhesion and low roughness after removing slag, and having excellent resolvability; and a dry film containing the photosensitive material. A printed wiring board including an interlayer insulating layer including a cured product of the photosensitive resin composition; and a printed wiring board including a solder resist layer including the solder resist layer A cured product of a photosensitive resin composition.

A photosensitive resin composition according to an embodiment of the present invention has photocurability. The photosensitive resin composition includes: a carboxyl group-containing resin (A) having an aromatic ring; and an organic filler (B). The average primary particle diameter is 1 μm or less and having a carboxyl group; the coupling agent (C) 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 two or more functional groups, and the aforementioned The functional group includes at least one group selected from the group consisting of an alkoxy group, a fluorenyloxy group, and an alkoxide group; and a silicon oxide filler (D) having an average primary particle diameter in a range of 1 to 150 nm .

A dry film according to an embodiment of the present invention includes the photosensitive resin composition.

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

The present invention relates to a photosensitive resin composition, a dry film, and a printed wiring board. More specifically, the present invention relates to a photosensitive resin composition, which is suitable for forming a solder resist layer and plating resistance on a printed wiring board. An electrically insulating layer such as an etching layer, a resist layer, and an interlayer insulating layer; a dry film containing the photosensitive resin composition; and a printed wiring board having an interlayer insulating layer including the photosensitive layer A hardened product of a resin composition; and a printed wiring board including a solder resist layer containing the hardened product of the photosensitive resin composition.

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

The photosensitive resin composition of this embodiment is photocurable. The photosensitive resin composition of this embodiment contains: a carboxyl group-containing resin (A) having an aromatic ring; an organic filler (B) having an average primary particle diameter of 1 μm or less and having a carboxyl group; and a coupling agent (C) having At least one atom selected from the group consisting of silicon atom, aluminum atom, titanium atom, and zirconium atom, and two or more functional groups; and silicon oxide filler (D), which has an average primary particle diameter of 1 to 150 In the range of nm. The functional group includes at least one functional group selected from the group consisting of an alkoxy group, a fluorenyloxy group, and an alkoxide group.

Since the photosensitive resin composition contains an organic filler (B), the hardened | cured material of the photosensitive resin composition has high copper-plating adhesiveness. In addition, since the photosensitive resin composition contains a carboxyl group-containing resin (A) having an aromatic ring, an organic filler (B), a coupling agent (C), and a silica filler (D), the photosensitive resin composition contains an organic filler ( B), still has high transparency. Therefore, the resolution is improved. Usually, when a filler is mix | blended with a photosensitive resin composition, the photosensitive resin composition will become cloudy, and transparency will fall. When the transparency of the photosensitive resin composition is low, light is easily scattered when the photosensitive resin composition is exposed, and good resolution cannot be obtained. However, since the photosensitive resin composition of this embodiment contains a carboxyl group-containing resin (A) having an aromatic ring, an organic filler (B), a coupling agent (C), and a silica filler (D), it can have high transparency. Therefore, it is possible to improve the resolution of the photosensitive resin composition, and it is possible to form fine through holes, opening patterns, and the like in a layer composed of a cured product of the photosensitive resin composition. In addition, it is possible to reduce the surface roughness of the cured product obtained by subjecting the cured product of the photosensitive resin composition to a desmearing treatment. In other words, the photosensitive resin composition can form a cured product with low roughness after removing the dross. The reduced roughness of the cured product after deslagging is reduced, whereby a printed wiring board having a layer composed of the cured product can have excellent high-frequency characteristics. In addition, since the photosensitive resin composition contains a silicon oxide filler (D), the glass transition point of the cured product of the photosensitive resin composition can be increased, and the thermal expansion coefficient can be reduced. Therefore, even if a layer made of a cured product of a photosensitive resin composition is subjected to stress caused by heat, it is not easily warped and has excellent resistance to thermal and thermal cycle cracking. Therefore, it can be used for thin printing. circuit board. In addition, the photosensitive resin composition contains a silicon oxide filler (D), that is, the dielectric loss tangent of the cured product of the photosensitive resin composition can be reduced. Therefore, the printed wiring board includes a layer composed of a cured product of a photosensitive resin composition, and can improve high-frequency transmission performance. In addition, it is considered that in this embodiment, since the photosensitive resin composition contains a carboxyl group-containing resin (A), an organic filler (B), a coupling agent (C), and a silica filler (D), the silica filler (D) The coupling agent (C) interacts or bonds with the carboxyl group of the carboxyl group-containing resin (A) and the carboxyl group of the organic filler (B) to form a compound or a mixture. Therefore, the glass transition point of the cured product of the photosensitive resin composition is further increased, and the thermal expansion coefficient and the dielectric loss tangent are further reduced.

The photosensitive resin composition is photocurable. Since the photosensitive resin composition has photocurability, the photosensitive resin composition can be cured by irradiating the photosensitive resin composition with light. The photocurability of the photosensitive resin composition can be imparted, for example, as follows: the carboxyl group-containing resin (A) has a photopolymerizable unsaturated group. In addition, the photocurability of the photosensitive resin composition can be imparted, for example, as follows: the photosensitive resin composition contains an unsaturated compound (E) as described later.

The carboxyl group-containing resin (A) has an aromatic ring. Since the carboxyl group-containing resin (A) has an aromatic ring, the photosensitive resin composition can have good transparency. The carboxyl group-containing resin (A) is not particularly limited as long as it is a resin having an aromatic ring and a carboxyl group.

The carboxyl group-containing resin (A) preferably has a hydroxyl group. The carboxyl group-containing resin (A) has a hydroxyl group, whereby the reactivity with the coupling agent (C) is particularly improved, and the transparency of the photosensitive resin composition can be further improved.

The carboxyl group-containing resin (A) preferably contains a resin obtained by reacting a polyol resin with at least one compound selected from the group consisting of a polycarboxylic acid and an acid anhydride thereof. At this time, the polyol resin preferably has an aromatic ring, and it is also preferable that at least one compound selected from the group consisting of a polycarboxylic acid and an anhydride thereof has an aromatic ring. The carboxyl group-containing resin (A) more preferably contains a copolymer obtained by reacting a polyol resin and an acid dianhydride. In this case, the polyol resin preferably has an aromatic ring, and more preferably the acid dianhydride has an aromatic ring. When the carboxyl group-containing resin (A) contains a copolymer obtained by reacting a polyol resin and an acid dianhydride, it is possible to impart high alkali developability to a photosensitive resin composition and to impart a cured product of the photosensitive resin composition. High heat resistance and insulation.

The carboxyl group-containing resin (A) preferably contains a carboxyl group-containing resin having an ethylenically unsaturated group. The carboxyl-containing resin (A) contains a carboxyl-containing resin having an ethylenically unsaturated group, whereby the carboxyl-containing resin (A) is photoreactive. Therefore, it is possible to impart photocurability to a photosensitive resin composition containing a carboxyl group-containing resin (A).

The carboxyl group-containing resin having an ethylenically unsaturated group contains, for example, an intermediate and a reactant with at least one compound (g3) selected from the group consisting of a polycarboxylic acid and its anhydride, which is also a resin (referred to as the first Resin (g)), the intermediate is a reaction product of an epoxy compound (g1) having two or more epoxy groups in one molecule and an ethylenically unsaturated compound (g2). The first resin (g) has an aromatic ring derived from at least one of an epoxy compound (g1), an ethylenically unsaturated compound (g2), and a compound (g3). The first resin (g) is obtained, for example, by reacting an epoxy group in an epoxy compound (g1) with a carboxyl group in an ethylenically unsaturated compound (g2) to obtain an intermediate having a hydroxyl group, Compound (g3) is added to this intermediate. The epoxy compound (g1) can contain appropriate epoxy resins, such as a cresol novolak-type epoxy resin and a phenol novolak-type epoxy resin. The epoxy compound (g1) preferably contains an epoxy compound having an aromatic ring. The epoxy compound (g1) may contain a polymer of an ethylenically unsaturated compound (h). The ethylenically unsaturated compound (h) includes, for example, a compound (h1) having an epoxy group such as glycidyl (meth) acrylate, or 2- (meth) acryloxyethyl phthalate, etc. Compound (h2) having no epoxy group. The ethylenically unsaturated compound (g2) preferably contains at least one of acrylic acid and methacrylic acid. The compound (g3) contains, for example, one or more compounds selected from the group consisting of polycarboxylic acids and anhydrides of polycarboxylic acids, and the polycarboxylic acids are phthalic acid, tetrahydrophthalic acid, Methyltetrahydrophthalic acid and the like. The compound (g3) preferably contains an acid dianhydride. In addition, it is preferable that the acid dianhydride contains an acid dianhydride having an aromatic ring. At this time, the transparency of the photosensitive resin composition is further improved, and the resolution is accompanied by further improvement.

The carboxyl group-containing resin having an ethylenically unsaturated group may contain a resin (referred to as a second resin (i)), which is a reaction of a polymer of an ethylenically unsaturated monomer and an ethylenically unsaturated compound having an epoxy group. This ethylenically unsaturated monomer contains an ethylenically unsaturated compound having a carboxyl group. The ethylenically unsaturated monomer may further contain an ethylenically unsaturated compound having no carboxyl group. The second resin (i) is obtained by reacting an ethylenically unsaturated compound having an epoxy group with a part of a carboxyl group in a polymer. The second resin (i) has an aromatic ring which is at least one of a polymer derived from an ethylenically unsaturated monomer and an ethylenically unsaturated compound having an epoxy group. An ethylenically unsaturated compound having a carboxyl group, containing, for example, acrylic acid, methacrylic acid, ω-carboxyl-polycaprolactone (n ≒ 2) monoacrylate, and 2- (meth) acrylic acid ethoxylate Compounds such as esters, and compounds such as 2- (meth) acryloxyethyl 2-hydroxyethyl phthalate. The ethylenically unsaturated compound having no carboxyl group includes, for example, a linear or branched aliphatic or cycloaliphatic compound (wherein the ring may have an unsaturated bond in a part thereof), and other compounds. The ethylenically unsaturated compound having an epoxy group preferably contains glycidyl (meth) acrylate.

The carboxyl group-containing resin (A) preferably has a benzene ring. In other words, the aromatic ring which the carboxyl group-containing resin (A) has is preferably a benzene ring. The carboxyl group-containing resin (A) has a benzene ring, whereby the transparency of the photosensitive resin composition is further improved, and therefore the photosensitive resin composition has excellent resolution. The carboxyl group-containing resin (A) more preferably contains a carboxyl group-containing resin having at least one polycyclic aromatic ring selected from the group consisting of a biphenyl skeleton, a naphthalene skeleton, a fluorene skeleton, and an anthracene skeleton. At this time, since the transparency of the photosensitive resin composition containing a carboxyl group-containing resin (A) is further improved, the photosensitive resin composition has more excellent resolution. The carboxyl group-containing resin (A) further preferably contains a carboxyl group-containing resin having at least one of a biphenyl skeleton and a bisphenol fluorene skeleton, and particularly preferably includes a carboxyl group-containing resin having a bisphenol fluorene skeleton. In this case, it is possible to further reduce the dielectric loss tangent of the cured product of the photosensitive resin composition containing the carboxyl group-containing resin (A).

The carboxyl-containing resin (A) preferably contains a carboxyl-containing resin (hereinafter referred to as a carboxyl-containing resin (A1)), which is a reaction product of an intermediate and an acid anhydride (a3), and the intermediate is A reaction product of an epoxy compound (a1) of a bisphenol fluorene skeleton represented by) and a carboxylic acid (a2) containing an unsaturated carboxylic acid (a2-1), and in the formula (1), R ₁ to R ₈ are respectively It is independently hydrogen, an alkyl group having 1 to 5 carbon atoms, or halogen. When the photosensitive resin composition contains a carboxyl group-containing resin (A1), the transparency of the photosensitive resin composition is further improved.

The carboxyl group-containing resin (A1) has an aromatic ring derived from an epoxy compound (a1) having a bisphenol fluorene skeleton. The carboxyl group-containing resin (A1) has an ethylenically unsaturated group and is derived from a carboxylic acid (a2) containing an unsaturated group-containing carboxylic acid (a2-1). The carboxyl group-containing resin (A1) is synthesized by combining an epoxy compound (a1) having a bisphenol fluorene skeleton represented by the following formula (1) and a carboxylic acid containing an unsaturated group-containing carboxylic acid (a2-1) (a2) After reacting to obtain an intermediate, the intermediate is reacted with an acid anhydride (a3).

In the formula (1), R ₁ to R ₈ are each independently hydrogen, an alkyl group having 1 to 5 carbon atoms, or a halogen. In other words, in Formula (1), R ₁ to R ₈ may each be hydrogen, or may be an alkyl group or a halogen group having 1 to 5 carbon atoms. The reason is that even if the hydrogen in the aromatic ring is replaced with a low-molecular-weight alkyl group or halogen, the physical properties of the carboxyl-containing resin (A1) will not be affected. On the contrary, the carboxyl-containing resin may be improved by substitution. (A) The heat resistance or flame retardance of the hardened | cured material of the photosensitive resin composition.

The carboxyl group-containing resin (A1) has a bisphenol fluorene skeleton represented by the formula (1) derived from the epoxy compound (a1), and can impart high heat resistance and insulation to the cured product of the photosensitive resin composition. The carboxyl group-containing resin (A1) has a carboxyl group derived from the acid anhydride (a3), that is, it can impart excellent developability to the photosensitive resin composition.

The carboxyl group-containing resin (A1) will be described more specifically. In order to synthesize a carboxyl group-containing resin (A1), an intermediate is first synthesized in such a manner that at least a part of the epoxy group in the epoxy compound (a1) having a bisphenol fluorene skeleton represented by the following formula (1) and The carboxylic acid (a2) of the unsaturated carboxylic acid (a2-1) is reacted. The synthesis of the intermediate was defined as the first reaction. The intermediate has a secondary hydroxyl group, which is generated by a ring-opening addition reaction of an epoxy group with a carboxylic acid (a2) containing an unsaturated group-containing carboxylic acid (a2-1). 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 a second reaction. The acid anhydride (a3) can include an acid monoanhydride and an acid dianhydride. The acid anhydride refers to a compound having an acid anhydride group formed by dehydration condensation of two carboxyl groups in one molecule. The so-called acid dianhydride refers to a compound having an acid anhydride group formed by dehydration condensation of two carboxyl groups in two molecules.

The carboxyl group-containing resin (A1) may contain unreacted components in the intermediate. In addition, when the acid anhydride (a3) contains an acid monoanhydride and an acid dianhydride, the carboxyl group-containing resin (A1) contains, in addition to a reactant of a component in the intermediate and a component in the acid monoanhydride and a component in the acid dianhydride. Either or both of a reactant of a component in an intermediate and a component in an acid monoanhydride, and a reactant of a component in an intermediate and a component in an acid dianhydride may be contained. In other words, the carboxyl group-containing resin (A1) may be a mixture containing a plurality of compounds having different structures like these.

The carboxyl group-containing resin (A1) has an ethylenically unsaturated group derived from an unsaturated group-containing carboxylic acid (a2-1), and is photoreactive. Therefore, the carboxyl group-containing resin (A1) can impart photosensitivity to the photosensitive resin composition, specifically, ultraviolet curability. In addition, the carboxyl group-containing resin (A1) has a carboxyl group derived from the acid anhydride (a3), whereby the photosensitive resin composition can be provided with developability by an alkaline aqueous solution containing an alkali metal salt and an alkali metal. At least one of hydroxides.

The weight average molecular weight of the carboxyl group-containing resin (A1) is preferably in the range of 700 to 10,000. When the weight average molecular weight is 700 or more, the insulation of the cured product of the photosensitive resin composition can be improved, and the dielectric loss tangent can be reduced. In addition, when the weight average molecular weight is 10,000 or less, the developability of the photosensitive resin composition with an alkaline aqueous solution is particularly improved. The weight average molecular weight is more preferably in the range of 900 to 8000, and particularly preferably in the range of 1,000 to 5,000.

The polydispersity of the carboxyl group-containing resin (A1) is preferably in the range of 1.0 to 4.8. In this case, it is possible to impart excellent developability to the photosensitive resin composition while ensuring good insulation of the cured product formed from the photosensitive resin composition. The polydispersity of the carboxyl group-containing resin (A1) is preferably 1.1 to 4.0, and more preferably 1.2 to 2.8.

The number average molecular weight and molecular weight distribution of the carboxyl-containing resin (A1) as described above can be achieved by using the carboxyl-containing resin (A1) as a mixture, and the mixture suitably contains: unreacted components in the intermediate and components in the intermediate Reactants with components in acid monoanhydride and components in acid dianhydride, reactants with components in intermediate and component in acid monoanhydride, reactants with components in intermediate and component in acid dianhydride Ingredients. More specifically, it can be achieved, for example, by controlling parameters such as the average molecular weight of the epoxy compound (a1), the amount of the acid monoanhydride relative to the epoxy compound (a1), and the acid dianhydride relative to the epoxy compound (a1).

The polydispersity is the value (Mw / Mn) of the ratio of the weight average molecular weight (Mw) of the carboxyl group-containing resin (A1) to the number average molecular weight (Mn).

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

The molecular weight of the carboxyl group-containing resin (A1) can be adjusted by crosslinking an acid dianhydride. In this case, a carboxyl group-containing resin (A1) having an adjusted acid value and molecular weight can be obtained. By controlling the amount of the acid dianhydride contained in the acid anhydride (a3), it is possible to easily adjust the molecular weight and acid value of the carboxyl group-containing resin (A1). The molecular weight of the carboxyl group-containing resin (A1) was calculated from the results of measurement by gel permeation chromatography under the following conditions. GPC device: SHODEX SYSTEM 11 made by Showa Denko Corporation; column: four branches of SHODEX KF-800P, KF-005, KF-003, KF-001 in series; mobile phase: tetrahydrofuran (THF); flow rate: 1 mL / min; Column temperature: 45 ° C; Detector: Refractive Index (RI); Conversion: Polystyrene.

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

The epoxy compound (a1) has a structure represented by the following formula (2), for example. In Formula (2), n is an integer in the range of 0-20, for example. In order to appropriately control the molecular weight of the carboxyl group-containing resin (A1), the average of n is particularly preferably in the range of 0 to 1. When the average of n is in the range of 0 to 1, it is easy to control an excessive increase in molecular weight even if the acid anhydride (a3) contains an acid dianhydride.

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. More specifically, the unsaturated group-containing carboxylic acid (a2-1) can contain, for example, one or more compounds selected from the group consisting of acrylic acid, methacrylic acid, and ω-carboxyl-polycaprolactone. Esters (n ≒ 2) monoacrylates, crotonic acid, cinnamic acid, 2-propenyloxyethylsuccinic acid, 2-methacryloxyethyl succinic acid, 2-propenyloxyethyl o-benzene Dicarboxylic acid, 2-methacryloxyethyl phthalic acid, 2-acryloxypropyl phthalate, 2-methacryloxypropyl phthalic acid, 2-acrylic acid Oxyethylmaleic acid, 2-methacrylic acid, oxyethylmaleic acid, β-carboxyethyl acrylate, 2-propenemethyloxyethyltetrahydrophthalic acid, 2-methacrylic acid Oxyethyl tetrahydrophthalic acid, 2-propenyloxyethylhexahydrophthalic acid, 2-methacryloxyethylhexahydrophthalic acid. Preferably, the unsaturated group-containing carboxylic acid (a2-1) contains acrylic acid.

The carboxylic acid (a2) may include a polyacid (a2-2). The polybasic acid (a2-2) is an acid capable of replacing two or more hydrogen atoms in one molecule with 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) cross-links two epoxy groups in the molecule of the epoxy compound (a1), that is, an increase in molecular weight can be obtained. Thereby, the insulation of the hardened | cured material of the photosensitive resin composition can be improved, and the dielectric loss tangent can be reduced.

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

When reacting an epoxy compound (a1) with a carboxylic acid (a2), a conventional method can be used. 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 needed to obtain a reactive solution. By reacting this reactive solution at a temperature of more preferably 60 to 150 ° C, particularly preferably 80 to 120 ° C by a conventional method, an intermediate can be obtained. The solvent can contain, for example, at least one component selected from the group consisting of ketones such as methyl ethyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene and xylene; ethyl acetate and butyl acetate Cellulose acetate, butylcellulose acetate, carbitol acetate, butylcarbitol acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether Acetates such as acetate; and dioxane 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 component selected from the group consisting of tertiary amines such as benzyldimethylamine and triethylamine; trimethylbenzyl ammonium chloride, and chloride Quaternary ammonium salts such as methyltriethylammonium; triphenylphosphine; and triphenylantimony.

Preferably, the catalyst contains triphenylphosphine in particular. In other words, it is preferred that the epoxy compound (a1) and the carboxylic acid (a2) are reacted in the presence of triphenylphosphine. In this case, the ring-opening addition reaction between the epoxy group in the epoxy compound (a1) and the carboxylic acid (a2) can be particularly promoted, and a reaction rate (conversion of 95% or more, or 97% or more, or almost 100) can be achieved. rate). In addition, ion migration can be suppressed in the layer containing the cured product of the photosensitive resin composition, and the insulation of the layer containing the cured product can be improved.

When the epoxy compound (a1) and the carboxylic acid (a2) are reacted, the amount of the carboxylic acid (a2) is preferably in the range of 0.5 to 1.2 mol relative to 1 mol of the epoxy group of the epoxy compound (a1). . In this case, excellent photosensitivity and stability of the photosensitive resin composition can be obtained. From the same viewpoint, the amount of the unsaturated group-containing carboxylic acid (a2-1) is preferably in the range of 0.5 to 1.2 mol relative to 1 mol of the epoxy group of the epoxy compound (a1). Alternatively, when the carboxylic acid (a2) contains a carboxylic acid other than the unsaturated group-containing carboxylic acid (a2-1), the unsaturated group-containing carboxylic acid (a2- The amount of 1) may be in the range of 0.5 to 0.95 mol. In addition, when the carboxylic acid (a2) contains a polyacid (a2-2), the amount of the polyacid (a2-2) is preferably 0.025 to 0.25 mol relative to 1 mol of the epoxy group of the epoxy compound (a1). In the range. In this case, excellent photosensitivity and stability of the photosensitive resin composition can be obtained.

It is also preferable that the epoxy compound (a1) and the carboxylic acid (a2) are reacted under air bubbling. In this case, the addition polymerization reaction of the unsaturated group can be suppressed, and the increase in the molecular weight of the intermediate and the gelation of the solution of the intermediate can be suppressed. In addition, the carboxyl group-containing resin (A1), which is the final product, can be prevented from being excessively colored.

The intermediate obtained in the above-mentioned manner has a hydroxyl group produced in such a manner that an epoxy group in the epoxy compound (a1) and a carboxyl group in the carboxylic acid (a2) react.

The acid anhydride (a3) preferably contains an acid monoanhydride. An acid monoanhydride is a compound having one acid anhydride group.

The acid monoanhydride can contain an anhydride of a dicarboxylic acid. The acid monoanhydride can contain, for example, one or more compounds selected from the group consisting of 1,2,3,6-tetrahydrophthalic anhydride, phthalic anhydride, succinic anhydride, methyl Succinic anhydride, maleic anhydride, citraconic anhydride, glutaric anhydride, itaconic anhydride, methyltetrahydrophthalic anhydride, methylnadic anhydride, hexahydrophthalic anhydride, cyclohexane-1,2 , 4-tricarboxylic acid-1,2-anhydride, and methylhexahydrophthalic anhydride. Particularly preferred is that the acid monoanhydride contains 1,2,3,6-tetrahydrophthalic anhydride. In this case, it is possible to improve the insulation of the cured product of the photosensitive resin composition while ensuring good developability of the photosensitive resin composition. Relative to the entire acid monoanhydride, 1,2,3,6-tetrahydrophthalic anhydride is preferably in the range of 20 to 100 mol%, more preferably in the range of 40 to 100 mol%, but not Limited to this.

The acid anhydride (a3) preferably contains an acid dianhydride. An acid dianhydride is a compound having two acid anhydride groups. The acid dianhydride can contain an anhydride of a tetracarboxylic acid. The acid dianhydride can contain, for example, at least one compound selected from the group consisting of 1,2,4,5-benzenetetracarboxylic dianhydride, benzophenonetetracarboxylic dianhydride, methylcyclohexene Tetracarboxylic dianhydride, tetracarboxylic dianhydride, naphthalene-1,4,5,8-tetracarboxylic dianhydride, ethylene tetracarboxylic dianhydride, 9,9'-bis (3,4-dicarboxyphenyl) fluorene dianhydride , Glycerol bis (trimellitic anhydride) monoacetate, ethylene glycol bis (trimellitic anhydride), 3,3 ', 4,4'-diphenylphosphonium tetracarboxylic dianhydride, 1, 3,3a, 4,5,9b-hexahydro-5- (tetrahydro-2,5-diketo-3-furanyl) naphtho [1,2-c] furan-1,3-dione, 1,2,3,4-butanetetracarboxylic dianhydride and 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride. The acid dianhydride preferably contains an acid dianhydride having an aromatic ring. Particularly preferred is that the acid dianhydride contains 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride. In this case, it is possible to improve the insulation of the cured product of the photosensitive resin composition while ensuring good developability of the photosensitive resin composition. In addition, the transparency of the photosensitive resin composition is improved, and the resolution is improved. Relative to the entire acid dianhydride, 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride is preferably in the range of 20 to 100 mol%, more preferably in the range of 40 to 100 mol%, but Not limited to this.

When the intermediate is reacted 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. By reacting this reactive solution at a temperature of more preferably 60 to 150 ° C, particularly preferably 80 to 120 ° C by a conventional method, a carboxyl group-containing resin (A1) can be obtained. Suitable solvents, catalysts, and polymerization inhibitors can be used, and solvents, catalysts, and polymerization inhibitors used in the synthesis of intermediates can also be used directly.

Preferably, the catalyst contains triphenylphosphine in particular. In other words, it is preferred that the intermediate is reacted 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) can be particularly promoted, and a reaction rate (conversion rate) of 90% or more, 95% or more, 97% or more, or almost 100 can be achieved. In addition, it is possible to suppress ion migration in the layer containing the cured product of the photosensitive resin composition, and to further improve the insulation of the layer containing the cured product.

It is also preferable that the intermediate is reacted with the acid anhydride (a3) under air bubbling. In this case, excessive increase in the molecular weight of the carboxyl group-containing resin (A1) is suppressed, and the developability of the photosensitive resin composition with an alkaline aqueous solution is particularly improved.

The carboxyl group-containing resin (A1) may include a carboxyl group-containing resin having an aromatic ring and not having photopolymerization. A carboxyl group-containing resin having an aromatic ring and having no photopolymerizability, for example, a polymer containing an ethylenically unsaturated monomer including an ethylenically unsaturated compound having a carboxyl group. The ethylenically unsaturated compound having a carboxyl group may contain, for example, acrylic acid, methacrylic acid, ω-carboxyl-polycaprolactone (n ≒ 2) monoacrylate, 2- (meth) acrylic acid phthalate Ethyl ester, 2- (meth) acryloxyethyl 2-hydroxyethyl phthalate and other compounds. The ethylenically unsaturated compound having a carboxyl group may also contain a reactant of pentaerythritol triacrylate, pentaerythritol trimethacrylate, and the like with a dibasic acid anhydride. The ethylenically unsaturated monomer may further contain, for example, a linear or branched aliphatic or cycloaliphatic (wherein a ring may have an unsaturated bond in part) (meth) acrylate, etc., which does not have a carboxyl group. Saturated compounds.

The carboxyl-containing resin (A) may include only the carboxyl-containing resin (A1), or may include a carboxyl-containing resin (A1) and a carboxyl-containing resin other than the carboxyl-containing resin (A1), or may include only the carboxyl-containing resin (A1). Carboxyl resin. From the viewpoint of obtaining high transparency of the photosensitive resin composition and reducing the dielectric loss tangent of the cured product of the photosensitive resin composition, the carboxyl-containing resin (A) preferably contains the carboxyl-containing resin (A1). 30 mass% or more, more preferably 60 mass% or more of the carboxyl group-containing resin (A1), and still more preferably 100 mass% of the carboxyl group-containing resin (A1).

The content of the carboxyl group-containing resin (A) is preferably in a range of 5 to 85% by mass, more preferably in a range of 10 to 75% by mass, and more preferably still more in terms of the solid content of the photosensitive resin composition. Within the range of 26 to 60% by mass, particularly preferred is within the range of 30 to 45% by mass. In addition, when the photosensitive resin composition contains a carboxyl group-containing resin (A1), the content of the carboxyl group-containing resin (A1) is preferably within a range of 5 to 85% by mass based on the solid content of the photosensitive resin composition. It is more preferably in the range of 10 to 75% by mass, even more preferably in the range of 26 to 60% by mass, and particularly preferably in the range of 30 to 45% by mass. The term “solid content” refers to the total amount of all components remaining after removing volatile components such as solvents from the photosensitive resin composition.

The acid value of the solid content of the carboxyl group-containing resin (A) is preferably in the range of 40 to 160 mgKOH / g. In this case, the stability of the photosensitive resin composition is particularly improved. It is more preferable if the acid value is in the range of 60 to 140 mgKOH / g. It is even more preferable if the acid value is in the range of 80 to 135 mgKOH / g, and it is particularly preferable if the acid value is in the range of 90 to 130 mgKOH / g.

The organic filler (B) has a carboxyl group. The carboxyl group of the organic filler (B) can be obtained, for example, by polymerizing or crosslinking a carboxylic acid monomer having a polymerizable unsaturated double bond, and the carboxylic acid monomer is acrylic acid, methacrylic acid, crotonic acid, Maleic acid, fumaric acid, itaconic acid, etc. The organic filler (B) can impart high copper-plating adhesion to the cured product of the photosensitive resin composition. In addition, the organic filler (B) can improve the thixotropy of the photosensitive resin composition and improve stability (especially storage stability). Moreover, since the organic filler (B) has a carboxyl group, the developability of the cured product of the photosensitive resin composition can be improved, and when the photosensitive resin composition contains a crystalline epoxy compound, the phase of the crystalline epoxy compound can be improved. Soluble to prevent crystallization. The carboxyl group content of the organic filler (B) is not particularly limited, and the acid value of the organic filler (B) is preferably 1 to 60 mgKOH / g based on the acid value obtained by acid-base titration. When the acid value is less than 1 mgKOH / g, the stability of the photosensitive resin composition and the developability of the cured product may be reduced. If the acid value is more than 60 mgKOH / g, the humidity resistance reliability of the cured product may be reduced. The acid value of the organic filler (B) is more preferably 3 to 40 mgKOH / g.

The organic filler (B) also preferably has a hydroxyl group. The organic filler (B) has a hydroxyl group, that is, the dispersibility of the organic filler (B) in the photosensitive resin composition can be improved.

The average primary particle diameter of the organic filler (B) is 1 μm or less. When the average primary particle diameter of the organic filler (B) is 1 μm or less, the thixotropy of the photosensitive resin composition can be efficiently improved. Therefore, the stability of the photosensitive resin composition is further improved. The lower limit of the average primary particle diameter of the organic filler (B) is not particularly limited, but is preferably 0.001 μm or more. The average primary particle diameter of the organic filler (B) was measured as D ₅₀ using a laser diffraction particle size distribution measuring device. The average primary particle diameter of the organic filler (B) is preferably 0.1 μm or less. In this case, the stability of the photosensitive resin composition is further improved, and the scattering during exposure can be suppressed, so that the resolution is further improved.

The organic filler (B) is preferably contained in the photosensitive resin composition in a state where the particle diameter is 10 μm or less. The organic filler (B) may aggregate in the photosensitive resin composition and may contain secondary particles. In this case, the particle diameter of the organic filler (B) in the photosensitive resin composition means the particle diameter of particles including secondary particles. In the photosensitive resin composition, the particle diameter of the organic filler (B) can be measured using a laser diffraction scattering particle size distribution measuring device or an optical microscope. When the organic filler (B) is contained in the photosensitive resin composition in a state where the particle diameter is 10 μm or less, the stability of the photosensitive resin composition is further improved, and scattering during exposure can be suppressed, so that The resolution will be improved. The organic filler (B) is more preferably contained in the photosensitive resin composition in a state where the particle diameter is 5 μm or less, and even more preferably is contained in the photosensitive resin composition in a state where the particle diameter is 1 μm or less. Among them, it is particularly preferable that the particles are contained in the photosensitive resin composition in a state where the particle diameter is 0.5 μm or less. In this case, the stability of the photosensitive resin composition is further improved, and the scattering during exposure can be suppressed, so that the resolution is further improved. The lower limit of the particle size of the organic filler (B) in the photosensitive resin composition is not particularly limited, and may be, for example, 0.01 μm or more.

The organic filler (B) preferably contains a rubber component. The rubber component can impart flexibility to the cured product of the photosensitive resin composition. Even if the photosensitive resin composition of this embodiment contains a rubber component, it can have high resolution. The rubber component can be composed of a resin. The rubber component preferably includes 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 photosensitive resin composition can have high transparency and can improve resolution. In addition, the rubber component can effectively impart flexibility to the cured product of the photosensitive resin composition. 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 (B) include, for example, model XER-91-MEK manufactured by JSR Corporation. This organic filler is a crosslinked rubber (NBR) with a carboxyl group having an average primary particle diameter of 0.07 μm, and is provided as a 15% by weight methyl ethyl ketone dispersion containing a crosslinked rubber. The acid value is 10.0 mgKOH / g. As described above, the organic filler (B) can be prepared as a dispersion liquid. The rubber component can be prepared as a dispersion. In addition, as specific examples of the organic filler (B), in addition to the above, for example, models XER-32 and XER-92 manufactured by JSR Corporation can be mentioned. In addition, examples of the dispersion liquid of a crosslinked rubber (SBR) having a carboxyl group and a hydroxyl group include a model XSK-500 manufactured by JSR Corporation.

The organic filler (B) may contain particle components other than a rubber component. At this time, the organic filler (B) may 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 can 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 diameter: 0.5 μm) manufactured by Nipponpaint Industrial Coatings Co., Ltd. Specific examples of the crosslinked styrene-acrylic resin fine particles include, for example, model MG-351 (average primary particle diameter 1.0 μm) and model BGK-001 (average primary particle diameter 1.0 μm) manufactured by Nipponpaint Industrial Coatings Co., Ltd. ). Moreover, the organic filler (B) may contain a particle component other than a particle component selected from the rubber component, the acrylic resin fine particles, and the cellulose fine particles. In this case, the organic filler (B) can contain a particle component having a carboxyl group. In other words, the particle component having a carboxyl group may be different from a particle component selected from rubber components, acrylic resin fine particles, and cellulose fine particles.

The photosensitive resin composition may further contain an organic filler other than the organic filler (B). Organic fillers other than the organic filler (B) may not have a carboxyl group, and the average primary particle diameter may be larger than 1 μm. When the photosensitive resin composition contains an organic filler (B) and an organic filler other than the organic filler (B), the organic filler (B) is based on the total content of the organic filler (B) and the organic fillers other than the organic filler (B). The content of) is preferably 30% by mass or more, and more preferably 50% by mass or more.

The content of the organic filler (B) is preferably in the range of 1 to 50 parts by mass based on 100 parts by mass of the content of the carboxyl group-containing resin (A). The content of the organic filler (B) is 1 part by mass or more with respect to 100 parts by mass of the content of the carboxyl group-containing resin (A), that is, good copper-plating adhesion of the cured product of the photosensitive resin composition can be obtained. In addition, when the content of the organic filler (B) is 50 parts by mass or less, excellent resolution of the photosensitive resin composition can be obtained. In addition, when the content of the organic filler (B) is within the above range, the thixotropy of the photosensitive resin composition is improved, and thus the stability is improved. The content of the organic filler (B) is more preferably within a range of 5 to 30 parts by mass, and still more preferably within a range of 10 to 20 parts by mass with respect to 100 parts by mass of the content of the carboxyl group-containing resin (A).

The coupling agent (C) has 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 (C) further has two or more functional groups, and the functional group includes at least one type selected from the group consisting of an alkoxy group, a fluorenyloxy group, and an alkoxide group. The coupling agent (C) may have two or more alkoxy groups, may have two or more alkoxy groups, or may have two or more alkoxide groups. In addition, the coupling agent (C) 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 coupling agent (C) can improve the dispersibility of the organic filler (B) and the silica filler (D) in the photosensitive resin composition, and therefore can improve the transparency and thixotropy of the photosensitive resin composition. The resin composition has excellent resolvability and stability (especially storage stability). Two or more functional groups containing at least one group selected from the group consisting of alkoxy, fluorenyloxy and alkoxide groups, preferably: and two or more functional groups selected from silicon atoms, aluminum atoms, titanium atoms and zirconium At least one atom selected from the group of atoms is directly bonded together.

When the coupling agent (C) has a silicon atom, examples of the coupling agent (C) include: tetraethoxysilane, tetramethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinylformate Didiethoxysilane, vinylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidyloxypropylmethyldimethoxy Silane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidyloxy Propylmethyldimethoxysilane, p-styryltrimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- ( Aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropylmethyldimethoxysilane, 3-aminopropylmethyldiethoxysilane, 3-aminopropyl Trimethoxysilane, 3-aminopropyltriethoxysilane, 3- (2-aminoethylamino) propyltriethoxysilane, N, N-dimethyl-3- (trimethyl Oxysilyl) propylamine, 3-triethoxysilyl-N- (1,3-dimethylbutylene) propyl Methylamine, N-phenyl-3-aminopropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxy Silane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethyl Oxysilane, 3-methacryloxypropyltriethoxysilane, allyltriethoxysilane, allyltrimethoxysilane, allylchlorodimethylsilane, 3-chloropropane Trimethoxysilane, 3-chloropropyltriethoxysilane, 3-chloropropyldimethoxymethylsilane, chloromethyltriethoxysilane, chloromethyltrimethoxysilane, 3-chloro Propylmethyldiethoxysilane, 3-isocyanatopropyltriethoxysilane, 3-propenyloxypropyltrimethoxysilane, bis (triethoxysilanepropyl) tetrasulfide , Cyclohexyltrimethoxysilane, methyltriethoxysilane, methyltrimethoxysilane, ethyltriethoxysilane, ethyltrimethoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane Cetyltri Oxysilane, octadecyltriethoxysilane, octadecyltrimethoxysilane, n-octyltriethoxysilane, n-octyltrimethoxysilane, dodecyltriethoxysilane, Dodecyltrimethoxysilane, propyltrimethoxysilane, propyltriethoxysilane, benzyltriethoxysilane, methylphenyldimethoxysilane, methylphenyldiethoxy Silane, phenyltriethoxysilane, phenyltrimethoxysilane, p-tolyltrimethoxysilane, 4-vinylphenyltrimethoxysilane, 1-naphthyltrimethoxysilane, 3,3, 3-trifluoropropyltrimethoxysilane, 11-pentafluorophenoxyundecyltrimethoxysilane, pentafluorophenyltrimethoxysilane, 11-azidoundecyltrimethoxysilane, 2-cyanoethyltriethoxysilane and vinyltriethoxysilane.

When the coupling agent (C) has an aluminum atom, examples of the coupling agent (C) include: acetamido aluminum diisopropoxide, aluminum monoethyl acetate diisopropoxide, and ginseng (acetamidine Ethyl acetate) aluminum.

When the coupling agent (C) has a titanium atom, examples of the coupling agent (C) include: isopropyloxytristearyl titanium, isopropoxy titanium (dioctyl pyrophosphate) titanium, and tetraoctyloxybis (Bis (tridecyl phosphate)) titanium, tetra (2,2-diallyloxymethyl-1-butoxy) bis (bis (tridecyl) phosphate) titanium, bis (dipyrophosphate) Octyl) titanium oxyacetate, and bis (dioctyl pyrophosphate) titanium ethoxylate.

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

The coupling agent (C) can contain at least one component selected from the group consisting of the above-mentioned components.

The coupling agent (C) preferably has a silicon atom. In other words, the coupling agent (C) is preferably a silane coupling agent. The coupling agent (C) has silicon atoms, that is, the reactivity with the silicon oxide filler (D) can be particularly improved, and the dispersibility of the silicon oxide filler (D) in the photosensitive resin composition can be improved more efficiently. Therefore, the transparency and stability of the photosensitive resin composition can be further improved. In addition, the coupling agent (C) has silicon atoms, that is, the glass transition point of the cured product of the photosensitive resin composition can be further increased, and the thermal expansion coefficient can be further reduced.

The coupling agent (C) preferably has at least one group selected from the group consisting of a methoxy group, an ethoxy group, and an ethoxy group. Methoxy and ethoxy are classified as alkoxy. In addition, ethoxy is classified as ethoxy. The coupling agent (C) may have only a methoxy group, only an ethoxy group, or only an ethoxy group. In addition, the coupling agent (C) may have two or more different functional groups selected from the group consisting of a methoxy group, an ethoxy group, and an ethoxy group. The coupling agent (C) has at least one group selected from the group consisting of a methoxy group, an ethoxy group, and an ethoxy group, that is, a carboxyl group-containing resin (A) having an aromatic ring and an organic filler (B ) And the reactivity between the silica filler (D) and the coupling agent (C), and the organic filler (B) and the silica filler (D) in the photosensitive resin composition are less likely to agglutinate. Therefore, the transparency and stability of the photosensitive resin composition can be further improved.

The coupling agent (C) preferably has two to four functional groups selected from the group consisting of an alkoxy group, a fluorenyloxy group, and an alkoxide group. The coupling agent (C) may have two to four alkoxy groups, may have two to four alkoxy groups, or may have two to four alkoxide groups. For example, the coupling agent (C) may have two to four methoxy groups, two to four ethoxy groups, or two to four ethoxy groups. In addition, the coupling agent (C) may have two to four different functional groups selected from the group consisting of an alkoxy group, a fluorenyloxy group, and an alkoxide group. The coupling agent (C) has two to four functional groups selected from the group consisting of alkoxy, fluorenyloxy and alkoxide groups, that is, it can inhibit the organic filler (B) and the coupling agent (C) Reaction, or excess crosslinking reaction caused by the reaction of the coupling agent (C) and the silica filler (D), which can improve the organic filler (B) and the silica filler (D) in the photosensitive resin composition. Dispersibility while inhibiting gelation.

The coupling agent (C) preferably has at least one group selected from the group consisting of an amine group, an epoxy group, a vinyl group, a methacryl group, a mercapto group, an isocyanate group, and a thioether group. . In this case, it is possible to react with the carboxyl group contained in the carboxyl group-containing resin (A) and the carboxyl group contained in the organic filler (B), and it is possible to more efficiently improve the organic filler (B) in the photosensitive resin composition. Dispersibility. Therefore, the transparency and stability of the photosensitive resin composition can be further improved.

The coupling agent (C) may have an alkylamine group and an amine group. The coupling agent (C) may have a glycidyloxy group and an epoxy group. When the coupling agent (C) contains a vinyl group, the vinyl group is, for example, directly bonded to a silicon atom. The coupling agent (C) has an amine group, an epoxy group, or a vinyl group, that is, it can improve the reactivity with the carboxyl group contained in the carboxyl group-containing resin (A) and the carboxyl group contained in the organic filler (B), and can The dispersibility of the organic filler (B) in the photosensitive resin composition is improved more efficiently. Preferably, the coupling agent (C) has an epoxy group or a vinyl group. In this case, the insulation of the photosensitive resin composition is improved, and the stability is further improved.

The photosensitive resin composition may further contain a coupling agent other than the coupling agent (C). The coupling agent other than the coupling agent (C) may not have 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 (C) may not have two or more functional groups, and the functional group includes at least one type selected from the group consisting of an alkoxy group, a fluorenyloxy group, and an alkoxide group. Among these, the photosensitive resin composition may not contain the organic resin (B) and the silicon oxide filler (D) from the viewpoint of efficiently obtaining the dispersibility and improving the transparency and stability of the photosensitive resin composition. Coupling agents other than couplant (C). When the photosensitive resin composition contains a coupling agent (C) and a coupling agent other than the coupling agent (C), the coupling agent (C) is added to the total content of the coupling agent (C) and the coupling agent other than the coupling agent (C). The content of) is preferably 30% by mass or more, and more preferably 50% by mass or more. In this case, good dispersibility of the organic filler (B) and the silica filler (D) of the photosensitive resin composition can be obtained.

The content of the coupling agent (C) is preferably in the range of 0.01 to 10 parts by mass with respect to 100 parts by mass of the total content of the organic filler (B) and the content of the silica filler (D). When the content of the coupling agent (C) is within this range, the organic filler (B) and the silica filler (D) in the photosensitive resin composition can be prevented from agglomerating and the dispersibility can be improved. The content of the coupling agent (C) is more preferably within a range of 0.05 to 5 parts by mass with respect to 100 parts by mass of the total content of the organic filler (B) and the content of the silica filler (D).

The average primary particle diameter of the silica filler (D) is in the range of 1 to 150 nm. When the average primary particle diameter of the silica filler (D) is within this range, the transparency of the photosensitive resin composition containing the organic filler (B) can be effectively improved. Therefore, the resolution of the photosensitive resin composition can be further improved. The average primary particle diameter of the silica filler (D) was measured using a dynamic light scattering method. The silicon oxide filler (D) is more preferably an average primary particle diameter in a range of 1 to 60 nm, and even more preferably an average primary particle diameter in a range of 1 to 30 nm. In this case, the transparency and resolution of the photosensitive resin composition can be further improved.

The silica filler (D) preferably contains silica particles derived from a silica sol. In this case, the transparency of the photosensitive resin composition containing the organic filler (B) can be further improved, and the resolution of the photosensitive resin composition can be further improved. Examples of the silica sol include spherical silica sol and chain silica sol. Specific examples of the silica filler (D) include, for example, organic silica sols manufactured by Nissan Chemical Industries, Ltd .: Models MA-ST-M, MA-ST-L, IPA-ST, and IPA-ST-ZL , IPA-ST-UP, EG-ST, NPC-ST-30, PGM-ST, DMAC-ST, MEK-ST-40, MIBK-ST, MIBK-ST-L, CHO-ST-M, EAC-ST , TOL-ST, MEK-AC-4130Y, MEK-AC-5140Z, PGM-AC-2140Y, PGM-AC-4130Y, MIBK-AC-2140Z, MIKB-SD-L, MEK-EC-6150P, MEK-EC -7150P, EP-F2130Y, EP-F6140P, EP-F7150P, PMA-ST, MEK-EC-2130Y, MEK-AC-2140Z, MEK-ST-L, MEK-ST-ZL, MEK-ST-UP; Hanse -NANOCRYL manufactured by Chemie: Models XP0396, XP0596, XP0733, XP0746, XP0765, XP0768, XP0953, XP0954, XP1045; NANOPRY manufactured by Hanse-Chemie: Models XP0516, XP0525, XP0314, etc.

The photosensitive resin composition may further contain an inorganic filler other than the silica filler (D). The inorganic filler other than the silicon oxide filler (D) may include a silicon oxide filler having an average primary particle diameter not in the range of 1 to 150 nm, and may also include an inorganic filler other than the silicon oxide filler. Examples of the inorganic filler other than the silica filler (D) include barium sulfate, crystalline silica, nano silica, carbon nanotubes, talc, bentonite, aluminum hydroxide, magnesium hydroxide, and titanium oxide. For example, when the photosensitive resin composition contains a white material such as titanium oxide and zinc oxide, the photosensitive resin composition and the cured product thereof can be whitened. Among these, from the viewpoint of obtaining good transparency and resolution of the photosensitive resin composition, the photosensitive resin composition may not contain inorganic fillers other than the silicon oxide filler (D). When the photosensitive resin composition contains an inorganic filler other than the silica filler (D) and the silica filler (D), the silica is larger than the total of the silica filler (D) and the inorganic filler other than the silica filler (D). The content of the filler (D) is preferably 30% by mass or more, and more preferably 50% by mass or more. In this case, good transparency and resolution of the photosensitive resin composition can be obtained.

The content of the silica filler (D) is preferably in the range of 5 to 200 parts by mass based on 100 parts by mass of the content of the carboxyl group-containing resin (A). The content of the silica filler (D) is 5 parts by mass or more, that is, the transparency of the photosensitive resin composition can be further improved. In addition, when the content of the silicon oxide filler (D) is 200 parts by mass or less, it is possible to have more excellent resolvability. In addition, when the content of the silicon oxide filler (D) is within this range, the glass transition point of the cured product of the photosensitive resin composition can be further increased, and the coefficient of thermal expansion and the dielectric loss tangent can be further reduced. In addition, it is possible to reduce the surface roughness of the cured product obtained by subjecting the cured product of the photosensitive resin composition to a desmearing treatment. The content of the silica filler (D) is more preferably in the range of 20 to 150 parts by mass, and particularly preferably in the range of 40 to 100 parts by mass, with respect to 100 parts by mass of the content of the carboxyl group-containing resin (A).

The photosensitive resin composition preferably further contains an unsaturated compound (E), which has at least one ethylenically unsaturated bond in one molecule. The unsaturated compound (E) can impart photocurability to the photosensitive resin composition. The unsaturated compound (E) includes, for example, at least one compound selected from the group consisting of: monofunctional (meth) acrylates such as 2-hydroxyethyl (meth) acrylate; and diethylene glycol Di (meth) acrylate, trimethylolpropane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate Polyfunctional esters, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, ε-caprolactone modified pentaerythritol hexaacrylate, tricyclodecane dimethanol di (meth) acrylate, etc. (Meth) acrylate.

The unsaturated compound (E) preferably contains at least one compound selected from the group consisting of trimethylolpropane tri (meth) acrylate and tricyclodecanedimethanol bis (methyl) )Acrylate. At this time, since the unsaturated compound (E) has high solubility in the photosensitive resin composition, the photosensitive resin composition can have excellent transparency and stability. The unsaturated compound (E) is more preferably tricyclodecanedimethanol di (meth) acrylate. In this case, the dielectric loss tangent of the cured product of the photosensitive resin composition can be further reduced.

The unsaturated compound (E) is also preferably a trifunctional compound, that is, a compound having three unsaturated bonds in one molecule. In this case, the resolution of the photosensitive resin composition can be further improved, and the developability of the photosensitive resin resin composition with an alkaline aqueous solution can be particularly improved. Trifunctional compounds, including, for example, at least one compound selected from the group consisting of: trimethylolpropane tri (meth) acrylate, ethylene oxide (EO) modified trimethylolpropane tri (Meth) acrylate, pentaerythritol tri (meth) acrylate, ethoxylated isocyanurate tri (meth) acrylate, and ε-caprolactone modification parameters (2-propenyloxyethyl) Isocyanurate and ethoxylated glycerol tri (meth) acrylate.

The unsaturated compound (E) also preferably contains a phosphorus-containing compound (phosphorus-containing unsaturated compound). In this case, the flame retardance of the hardened | cured material of the photosensitive resin composition can be improved. The phosphorus-containing unsaturated compound can contain, for example, one or more compounds selected from the group consisting of 2-methacryloxyethyl phosphate (a specific example is manufactured by Kyoeisha Chemical Co., Ltd. Models LIGHT ESTER P-1M and LIGHT ESTER P-2M), 2-propenyloxyethyl phosphate (specific examples are model LIGHT ACRYLATE P-1A manufactured by Kyoeisha Chemical Co., Ltd.), and diphenyl phosphate 2 -Methacryloxyethoxyethyl ester (specific example is model MR-260 manufactured by Daiba Industrial Co., Ltd.) and HFA series (specific example: dipentaerythritol hexaacrylate and hydroxy Addition reactants of citric acid (HCA) are model HFA-6003 and HFA-6007; addition reactions of caprolactone modified dipentaerythritol hexaacrylate and HCA are model HFA-3003 and HFA-6127, etc.) .

The unsaturated compound (E) may contain a prepolymer. The prepolymer can contain, for example, at least one compound selected from the group consisting of a prepolymer obtained by polymerizing a monomer having an ethylenically unsaturated bond and adding an ethylenically unsaturated group, and Oligomeric (meth) acrylate prepolymers. The oligo (meth) acrylate prepolymers can contain, for example, at least one component selected from the group consisting of epoxy (meth) acrylate, polyester (meth) acrylate, Urethane (meth) acrylate, alkyd resin (meth) acrylate, silicone resin (meth) acrylate, and spirane resin (meth) acrylate.

When the photosensitive resin composition contains an unsaturated compound (E), the content of the unsaturated compound (E) is preferably in the range of 1 to 50% by mass, and more preferably, relative to the content of the carboxyl group-containing resin (A). In the range of 10 to 45 mass%, it is more preferably in the range of 21 to 40 mass%.

The photosensitive resin composition preferably further contains a photopolymerization initiator (F). The photopolymerization initiator (F) includes, for example, a fluorenylphosphine oxide-based photopolymerization initiator. In other words, the photosensitive resin composition contains, for example, a fluorenylphosphine oxide-based photopolymerization initiator. In this case, when the photosensitive resin composition is exposed, high sensitivity can be imparted to the photosensitive resin composition. In addition, it is possible to suppress ion migration in the layer containing the cured product of the photosensitive resin composition, and to further improve the insulation of the layer containing the cured product.

The fluorenylphosphine oxide-based photopolymerization initiator includes, for example, one or more components selected from the group consisting of: 2,4,6-trimethylbenzylfluorenyldiphenylphosphine oxide, ethyl Mono-fluorenylphosphine oxide-based photopolymerization initiators such as methyl-2,4,6-trimethylbenzylidenephenylphosphinate; and bis (2,6-dichlorobenzylidene) benzene Phosphine oxide, bis (2,6-dichlorobenzyl) -2,5-dimethylphenylphosphine oxide, bis (2,6-dichlorobenzyl) -4-propylphenyl 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 oxidation Phosphine, bis (2,4,6-trimethylbenzyl) phenylphosphine oxide, bis (2,5,6-trimethylbenzyl) -2,4,4-trimethylpentane Difluorenylphosphine oxide-based photopolymerization initiators such as phosphonium oxide. It is particularly preferred that the fluorenylphosphine oxide-based photopolymerization initiator includes 2,4,6-trimethylbenzylidenediphenylphosphine oxide, and the fluorenylphosphine oxide-based photopolymerization initiator may include only 2, 4,6-trimethylbenzylidene diphenylphosphine oxide.

The photopolymerization initiator (F) preferably contains a hydroxyketone-based photopolymerization initiator in addition to the fluorenylphosphine oxide-based photopolymerization initiator. In other words, the photosensitive resin composition preferably contains a hydroxyketone-based photopolymerization initiator. Compared with a case where a hydroxyketone-based photopolymerization initiator is not contained, it is possible to impart higher sensitivity to the photosensitive resin composition. Accordingly, when the photosensitive resin composition is cured by exposure, the coating film formed from the photosensitive resin composition can be sufficiently cured from the surface to the deep portion. Examples of the hydroxyketone-based photopolymerization initiator include: 1-hydroxycyclohexylphenyl ketone, methyl phenylglyoxylate, 1- [4- (2-hydroxyethoxy) phenyl] -2-hydroxy-2 -Methyl-1-propan-1-one, 2-hydroxy-1- {4- [4- (2-hydroxy-2-methylpropanyl) benzyl] phenyl} -2-methylpropane 1-one and 2-hydroxy-2-methyl-1-phenylpropan-1-one.

When the photosensitive resin composition contains a fluorenyl phosphine oxide-based photopolymerization initiator and a hydroxyketone photopolymerization initiator, the mass ratio of the fluorenylphosphine oxide-based photopolymerization initiator to the hydroxyketone photopolymerization initiator , Preferably in the range of 1: 0.01 to 1:10. In this case, the hardenability in the vicinity of the surface of the coating film formed of the photosensitive resin composition and the hardenability in the deep portion can be improved in a well-balanced manner.

It is also preferable that the photopolymerization initiator (F) contains bis (diethylamino) benzophenone. In other words, it is also preferable that the photosensitive resin composition contains a fluorenyl phosphine oxide-based photopolymerization initiator and bis (diethylamino) benzophenone, or a hydroxyketone-based photopolymerization initiator and bis ( Diethylamino) benzophenone. At this time, when a part of the coating film formed from the photosensitive resin composition is exposed and developed, the unexposed portion is suppressed from being hardened, and the resolution is particularly improved. 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 small diameter hole is formed in the interlayer insulating layer by a photolithography method (see FIG. 1), A small-diameter hole can be formed precisely and easily.

When the photosensitive resin composition contains a bis (diethylamino) benzophenone and a fluorenylphosphine oxide-based photopolymerization initiator, the bis (diethylamine) The content of benzophenone is preferably in the range of 0.5 to 20% by mass. When the content of bis (diethylamino) benzophenone is 0.5% by mass or more, the resolution can be particularly improved. In addition, when the content of bis (diethylamino) benzophenone is 20% by mass or less, bis (diethylamino) benzophenone does not easily hinder the electrical insulation of the cured product of the photosensitive resin composition.

The content of the photopolymerization initiator (F) with respect to the content of the carboxyl group-containing resin (A) is preferably in the range of 1 to 30% by mass, and more preferably in the range of 1 to 25% by mass.

The photosensitive resin composition preferably further contains an epoxy compound (G). The epoxy compound (G) can impart thermosetting properties to the photosensitive resin composition. The epoxy compound (G) preferably contains a crystalline epoxy resin. The crystalline epoxy resin is an epoxy resin having a melting point. The crystalline epoxy resin can impart thermosetting properties to the photosensitive resin composition. In addition, the crystalline epoxy resin improves the heat resistance and developability of the cured product.

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

The crystalline epoxy resin may have two epoxy groups in one molecule. In this case, it is possible to make the cured product less prone to cracking during repeated temperature changes.

The crystalline epoxy resin preferably has an epoxy equivalent of 150 to 300 g / eq. This epoxy equivalent is the g weight of the crystalline epoxy resin containing 1 g equivalent of an epoxy group.

Examples of the melting point of the crystalline epoxy resin include 70 to 180 ° C. In particular, it is preferable that the crystalline epoxy resin contains a crystalline epoxy resin having a melting point of 110 ° C or lower. In this case, the developability of the photosensitive resin composition with an alkaline aqueous solution is particularly improved. A crystalline epoxy resin having a melting point of 110 ° C. or lower includes, for example, at least one component selected from the group consisting of a biphenyl epoxy resin (a specific example is a model YX4000 manufactured by Mitsubishi Chemical Corporation) , Biphenyl ether type epoxy resin (specific example is model NSLV-80DE made by Nippon Steel & Sumitomo Chemical Co., Ltd.), and bisphenol type epoxy resin (specific example is model made by Nippon Steel & Sumitomo Chemical Co., Ltd.) YSLV-80XY), bisphenol fluorene type crystalline epoxy resin (a specific example is an epoxy resin having a structure represented by formula (2)).

The epoxy compound (G) may contain epoxy compounds other than a crystalline epoxy resin. The epoxy compound other than the crystalline epoxy resin includes an amorphous epoxy resin. The amorphous epoxy resin is an epoxy resin having no melting point. The amorphous epoxy resin can impart thermosetting properties to the photosensitive resin composition. The amorphous epoxy resin preferably has at least two epoxy groups in one molecule.

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

The epoxy compound (G) may contain a phosphorus-containing epoxy resin. In this case, the flame retardance of the hardened | cured material of the photosensitive resin composition improves. Examples of the phosphorus-containing epoxy resin include phosphoric acid modified bisphenol F-type epoxy resin (specific examples are models EPICLON EXA-9726 and EPICLON EXA-9710 manufactured by DIC Corporation), and Nippon Steel & Sumitomo Chemical Co., Ltd. Co., Ltd. model Epotohto FX-305 and so on.

The epoxy compound (G) preferably contains only a crystalline epoxy resin, or contains a crystalline epoxy resin and an amorphous epoxy resin. The epoxy compound (G) preferably contains 10% by mass or more of the crystalline epoxy resin, more preferably 30% by mass or more of the crystalline epoxy resin, and even more preferably 50% by mass or more of the crystalline epoxy resin. In this case, the developability of the photosensitive resin composition with an alkaline aqueous solution can be improved, and the heat resistance and insulation properties of the cured product of the photosensitive resin composition can be particularly improved.

The content of the epoxy compound (G) is preferably 0.7 to 2.5 based on 1 equivalent of the carboxyl group contained in the carboxyl group-containing resin (A). The range is more preferably in the range of 0.7 to 2.3, and even more preferably in the range of 0.7 to 2.0. When the epoxy compound (G) contains a crystalline epoxy resin, it is preferably a total of the equivalent of the epoxy group contained in the crystalline epoxy resin with respect to 1 equivalent of the carboxyl group contained in the carboxyl group-containing resin (A). The range is 0.7 to 2.5, more preferably 0.7 to 2.3, and still more preferably 0.7 to 2.0.

The photosensitive resin composition may contain melamine. At this time, the adhesiveness between the cured product of the photosensitive resin composition and a metal such as copper is improved. Therefore, the photosensitive resin composition is particularly suitable as an insulating material for a printed wiring board. In addition, the hardened product of the photosensitive resin composition has improved plating resistance, that is, whitening resistance when subjected to electroless nickel plating / gold plating treatment.

When the photosensitive resin composition contains melamine, the melamine is preferably in a range of 0.1 to 10% by mass, and more preferably in a range of 0.5 to 5% by mass, relative to the content of the carboxyl group-containing resin (A).

The photosensitive resin composition may contain an organic solvent. The organic solvent is used for purposes such as liquefaction or varnishing of the photosensitive resin composition, adjustment of viscosity, adjustment of coating property, adjustment of film forming property, and the like.

Organic solvents include, for example, one or more compounds selected from the group consisting of linear, branched, secondary, or polyhydric alcohols such as ethanol, propanol, isopropanol, hexanol, and ethylene glycol. Ketones such as methyl ethyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene and xylene; petroleum-based aromatic mixed solvents such as SWASOL series (manufactured by Maruzan Petrochemical), Solvesso (manufactured by ExxonMobil Chemical) ; Cellulose such as Cellulose and Butyl Cellulose; Carbitols such as Carbitol and Butylcarbitol; Propylene glycol alkyl ethers such as propylene glycol methyl ether; Polypropylene glycol alkyls such as dipropylene glycol methyl ether Ethers; acetates such as ethyl acetate, butyl acetate, cellulose acetate, and carbitol acetate; and dialkyl glycol ethers.

When the photosensitive resin composition contains an organic solvent, the amount of the organic solvent is preferably adjusted in such a manner that the organic solvent is rapidly volatilized when the coating film formed from the photosensitive resin composition is dried, even if the organic solvent is not affected. Residual in dry film. In particular, the organic solvent is preferably in a range of 0 to 99.5% by mass, and more preferably in a range of 15 to 60% by mass, with respect to the entire photosensitive resin composition. Moreover, since the preferable ratio of an organic solvent differs according to a coating method etc., it is preferable to adjust a ratio suitably according to a coating method.

The photosensitive resin composition may further contain components other than the above components without departing from the gist of the present invention.

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 component selected from the group consisting of benzoin and its alkyl ethers; acetophenones such as acetophenone and acetophenone dimethyl ketal. ; Anthraquinones such as 2-methylanthraquinone; 2,4-dimethylthioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diisopropylthioxanthone Thioxanthone such as tonone; benzophenones such as benzophenone, 4-benzylidene-4'-methyldiphenyl sulfide; 2,4-diisopropylxanthene Xanthones such as ketones; and α-hydroxyketones such as 2-hydroxy-2-methyl-1-phenylpropan-one; 2-methyl-1- [4- (methylthio) A nitrogen atom-containing compound such as phenyl] -2- (N-morpholinyl) -1-acetone. The photosensitive resin composition may contain: a photopolymerization initiator (F); and ethyl p-dimethylbenzoate, isoamyl p-dimethylaminobenzoate, and ethyl-2-dimethylaminobenzoate. Conventional photopolymerization accelerators and sensitizers such as tertiary amines such as acid 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 (F); and a sensitizer for laser exposure, that is, coumarin derivatives such as 7-diethylamino-4-methylcoumarin , Carbocyanine pigments, xanthene pigments, etc.

The photosensitive resin composition may contain one or more resins selected from the group consisting of: toluene diisocyanate-based capped with caprolactam, oxime, malonate, etc. Blocked isocyanates such as phthaloline diisocyanate, isophorone diisocyanate, and hexamethylene diisocyanate; melamine resin, n-butylated melamine resin, isobutylated melamine resin, butylated urea resin, butylated Amine resins such as melamine urea co-condensation resins and benzoguanamine co-condensation resins; various thermosetting resins other than the foregoing; UV-curable epoxy (meth) propyl esters; addition of (meth) acrylic acid Resins obtained from epoxy resins such as bisphenol A type, phenol novolac type, cresol novolac type, and alicyclic type; and diallyl phthalate resin, phenoxy resin, amine ester resin, Polymer compounds such as fluororesin.

When the photosensitive resin composition contains an epoxy compound (G), the photosensitive resin composition may contain a hardener for hardening the epoxy compound (G). The hardener contains, for example, one or more components selected from the group consisting of imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenyl Imidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, 1- (2-cyanoethyl) -2-ethyl-4-methylimidazole and other imidazole derivatives; dicyandiamide, benzene Methyldimethylamine, 4- (dimethylamino) -N, N-dimethylbenzylamine, 4-methoxy-N, N-dimethylbenzylamine, 4-methyl -N, N-dimethylbenzylamine and other amine compounds; hydrazine compounds such as hexamethylene hydrazine and sebacide; phosphorus compounds such as triphenylphosphine; acid anhydrides; phenols; thiols; Lewis acid amine complexes ; And, onium salts. Examples of commercially available products of these ingredients include, for example: 2MZ-A, 2MZ-OK, 2PHZ, 2P4BHZ, 2P4MHZ (all are trade names of imidazole compounds) manufactured by Shikoku Chemical Co., Ltd .; San-Apro Limited U-CAT3503N, U-CAT3502T (both are trade names of dimethylamine-blocked diisocyanate compounds); DBU, DBN, U-CATSA102, U-CAT5002 (all are amidine compounds and amidine compounds) Its salt).

The photosensitive resin composition may contain an adhesion-imparting agent other than melamine. Examples of the adhesion-imparting agent include meguanamine, benzoguanamine, and 2,4-diamino-6-methacryloxyethyl-s-triazine, 2-vinyl-4,6 -Diamino-s-triazine, 2-vinyl-4,6-diamino-s-triazine / isocyanuric acid adduct, 2,4-diamino-6-methacrylium S-triazine derivatives such as oxyethyl-s-triazine and isocyanuric acid adducts.

The photosensitive resin composition may contain one or more components selected from the group consisting of: a hardening accelerator; a colorant; a copolymer such as silicon oxide and acrylate; a leveling agent; and adhesion Additives; thixotropic agents; polymerization inhibitors; anti-halation agents; flame retardants; defoamers; antioxidants; surfactants; and polymer dispersants.

The content of the amine compound in the photosensitive resin composition is preferably as small as possible. In this case, it is not easy to impair the electrical insulation of the layer composed of the cured product of the photosensitive resin composition. In particular, the content of the amine compound is preferably 8% by mass or less with respect to the content of the carboxyl group-containing resin (A), and more preferably 5% by mass or less.

The photosensitive resin composition can be prepared by blending the raw materials of the photosensitive resin composition as described above and by a conventional kneading method using, for example, a three-roll mill, a ball mill, a sand mill, or the like. Knead. When the raw material of the photosensitive resin composition contains a liquid component, a component with a low viscosity, etc., the photosensitive resin composition can be prepared in the following manner: First, the liquid material and the component with a low viscosity are excluded from the raw material. After kneading a portion, a liquid component and a low viscosity component are added to the obtained mixture and mixed. In addition, the photosensitive resin composition can be prepared without kneading, by stirring, mixing, dissolving, or the like of the raw materials.

In consideration of storage stability and the like, a part of the components of the photosensitive resin composition may be mixed to prepare a first agent, and then the remainder of the components may be mixed to prepare a second agent. In other words, the photosensitive resin composition may include a first agent and a second agent. In this case, for example, a part of the components of the photosensitive resin composition may be mixed in advance and dispersed to prepare a first agent, and the remainder of the components of the photosensitive resin composition may be mixed and dispersed to prepare a first agent. Two doses. At this time, a required amount of the first agent and the second agent can be mixed at an appropriate time to prepare a mixed liquid, and the mixed liquid can be hardened to obtain a cured product.

The photosensitive resin composition of this embodiment is suitable as an electrically insulating material for printed wiring boards. In particular, the photosensitive resin composition is suitable for forming electrically insulating layers such as a solder resist layer, a resist plating layer, a resist layer, and an interlayer insulating layer.

Hereinafter, an example of a method for manufacturing a printed wiring board including an interlayer insulating layer formed of the photosensitive resin composition of 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, a core material 1 is prepared as shown in FIG. 1A. 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 film 4 is formed of a photosensitive resin composition on the surface of the core material 1 on which the first conductor line 3 is provided. Examples of the method for forming the film 4 include 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 is a conventional method, for example, it is selected from the group consisting of a dipping method, a spray method, a spin coating method, a roll coating method, a curtain coating method, and Screen printing. 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 such as polyester and then dried, and a dry film containing the photosensitive resin composition is formed on the support. Thereby, 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 dry film with the support 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, and the dry film is transferred from the support to On the core material 1. As a result, a coating film 4 made of a dry film is provided on the core material 1.

The film 4 is exposed, and partially light-cured as shown in FIG. 1C. To perform exposure, for example, a negative mask is closely adhered to the film 4, and then the film 4 is irradiated with ultraviolet rays through the negative mask. The negative mask includes an exposure portion that transmits ultraviolet rays, and a non-exposure portion that blocks ultraviolet rays. The non-exposure portion is provided at a position corresponding to the position of the through hole 10. The negative mask is, for example, a phototool such as a mask film or a dry plate. The ultraviolet light source is selected from the group consisting of, for example, a chemical lamp, a low-pressure mercury lamp, a medium-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a xenon lamp, a metal halide lamp, a light-emitting diode (LED), A combination of two or more of g-rays (436 nm), h-rays (405 nm), i-rays (365 nm), and g-rays, h-rays, and i-rays.

In addition, as the exposure method, a method other than a method using a negative mask can be used. For example, the film 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 film 4. The light source used in the direct drawing method is, for example, selected from the group consisting of a chemical lamp, a low-pressure mercury lamp, a medium-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a xenon lamp, a metal halide lamp, and a light-emitting diode. (LED), g-ray (436 nm), h-ray (405 nm), i-ray (365 nm), and a combination of two or more of g-ray, h-ray, and i-ray.

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

Then, the film 4 is subjected to a development process, and the unexposed portion 5 of the film 4 shown in FIG. 1C is removed, whereby a hole 6 is provided at a position where the through hole 10 is to be formed as shown in FIG. The developing process can use an appropriate developing solution in accordance with 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 component selected from the group consisting of sodium carbonate, potassium carbonate, ammonium carbonate, sodium bicarbonate, potassium bicarbonate, ammonium bicarbonate, sodium hydroxide, Potassium hydroxide, ammonium hydroxide, tetramethylammonium hydroxide, and lithium hydroxide. The solvent in the alkaline aqueous solution may be only water or a mixture of water and a hydrophilic organic solvent such as a lower alcohol. The organic amine contains, for example, at least one component 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 heated and thermally cured. 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 150 minutes. When the film 4 is heat-cured in the manner described above, the strength, hardness, and chemical resistance of the interlayer insulating layer 7 can be improved.

If necessary, 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 10 to 50 μm.

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

An example of a method for manufacturing a printed wiring board including a solder resist layer formed of the photosensitive resin composition of 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 on the surface of the core material on which the first conductor line is provided from the photosensitive resin composition. 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 above-mentioned interlayer insulating layer can be adopted. The film is exposed and partially light-cured. 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 treatment, and the unexposed portion of the film is removed, whereby the exposed portion of the film remains on the core material. Then, the film on the core material is heated to perform thermosetting. The development method and the heating method can be the same as those in the case where 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 in a range of 10 to 50 nm.

As described above, a solder resist layer made of a cured product of a photosensitive resin composition is provided on the core material. Thereby, there is obtained a printed wiring board including a core material including an insulating layer and a conductor line thereon, and a solder resist layer covering a part of a surface of the core material on which the conductor line is provided. [Example]

(1) Synthesis of carboxyl group-containing resin having aromatic ring: [Synthesis Example A-1] The carboxyl group-containing resin having an aromatic ring in Synthesis Example A-1 was prepared in the following manner. In a four-necked flask equipped with a reflux cooler, a thermometer, an air blowing tube, and a stirrer, a bisphenol fluorene epoxy resin represented by formula (2) and R ₁ to R ₇ in formula (2) are all hydrogen is added. (Epoxy equivalent 250 g / eq) 250 parts by mass, propylene glycol monomethyl ether acetate 60 parts by mass, diethylene glycol monoethyl ether acetate 140 parts by mass, methyl hydroquinone 0.2 parts by mass, acrylic acid 72 Part by mass and 1.5 parts by mass of triphenylphosphine to prepare a mixture. This mixture was stirred in a flask under air bubbling while heating at a temperature of 115 ° C. for 12 hours. Thereby, a solution of the intermediate was prepared.

Then, into the solution of the intermediate in the flask, 58.8 parts by mass of 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride, 60.8 parts by mass of tetrahydrophthalic anhydride, and propylene glycol monomethyl ether were charged. 38.7 parts by mass of acetate was heated at 115 ° C. for 6 hours while stirring under air bubbling, and further heated at 80 ° C. for 1 hour. Thereby, a 65% by mass solution of the carboxyl group-containing resin A-1 was obtained. The weight average molecular weight of the carboxyl group-containing resin A-1 was 3,096, and the acid value was 105 mgKOH / g.

[Synthesis Example A-2] The carboxyl group-containing resin having an aromatic ring in Synthesis Example A-2 was prepared in the following manner. In a four-necked flask equipped with a reflux cooler, a thermometer, an air blowing tube, and a stirrer, add biphenol novolac epoxy resin (manufactured by Nippon Kayaku Co., Ltd., model NC-3000-H, epoxy equivalent 288 g / eq) 288 parts by mass, 155 parts by mass of diethylene glycol monoethyl ether acetate, 0.2 parts by mass of methylhydroquinone, 72 parts by mass of acrylic acid, and 3 parts by mass of triphenylphosphine to prepare a mixture. This mixture was stirred in a flask under air bubbling while heating at a temperature of 115 ° C. for 12 hours. Thereby, a solution of the intermediate was prepared.

Then, into the solution of the intermediate in the flask, 91.2 parts by mass of tetrahydrophthalic anhydride and 90 parts by mass of diethylene glycol monoethyl ether acetate were added, while stirring under the bubbling of air, Heated at 90 ° C for 4 hours. Thereby, a 65% by mass solution of the carboxyl group-containing resin A-2 was obtained. The weight average molecular weight of the carboxyl-containing resin A-2 was 8,120, and the acid value was 76 mgKOH / g.

(2) Synthesis of carboxyl group-containing resin without aromatic ring: [Synthesis Example B-1] The carboxyl group-containing resin without aromatic ring of Synthesis Example B-1 was prepared in the following manner. In a four-necked flask equipped with a reflux cooler, a thermometer, an air blowing tube, and a stirrer, 77 parts by mass of methacrylic acid, 123 parts by mass of methyl methacrylate, 370 parts by mass of dipropylene glycol monomethyl ether, and azo were added. 5 parts by mass of bisisobutyronitrile was used to prepare a mixture. This mixture was heated in a flask under a stream of nitrogen at a temperature of 80 ° C. for 5 hours to perform a polymerization reaction. Thereby, a copolymer solution having a concentration of 35% was obtained.

Then, into the copolymer solution in the flask, 0.1 parts by mass of hydroquinone, 50 parts by mass of 3,4-epoxycyclohexyl methyl acrylate, 47 parts by mass of dipropylene glycol monomethyl ether, and dimethylbenzyl were charged. 0.8 part by mass of amine was heated at 110 ° C. for 6 hours to perform an addition reaction. Thereby, a 38% by mass solution of the carboxyl group-containing resin B-1 was obtained. The weight average molecular weight of the carboxyl-containing resin B-1 was 61,324, and the acid value was 132 mgKOH / g.

(3) Synthesis of carboxyl group-free resin having aromatic ring: [Synthesis Example B-2] The carboxyl group-containing resin having an aromatic ring of Synthesis Example B-2 was prepared in the following manner. In a four-necked flask equipped with a reflux cooler, a thermometer, an air blowing tube, and a stirrer, a bisphenol fluorene epoxy resin represented by formula (2) and R ₁ to R ₇ in formula (2) are all hydrogen is added. (Epoxy equivalent 250 g / eq) 250 parts by mass, 173 parts by mass of propylene glycol monomethyl ether acetate, 0.2 parts by mass of methylhydroquinone, 72 parts by mass of acrylic acid, and 1.5 parts by mass of triphenylphosphine were prepared. This mixture was stirred in a flask under air bubbling while heating at a temperature of 115 ° C. for 12 hours. Thus, a 65% by mass solution of the carboxyl resin B-2 was not obtained.

(4) Preparation of photosensitive resin composition: (1) The photosensitive resin compositions of Examples 1 to 18 and Comparative Examples 1 to 5 were prepared as follows. The components shown in the following table were prepared in a flask, and stirred and mixed at a temperature of 35 ° C. for 2 hours to obtain a photosensitive resin composition (see Tables 1 to 3). The photosensitive resin composition was filtered with a 300-sieve filter, and then filtered with a filter having a pore size of 10 μm.

In addition, the compounding quantity in a table | surface is a mass part which shows the solid content of a marking component. Although not shown in the table, methyl ethyl ketone was blended as a diluent in the photosensitive resin composition.

The details of the components shown in the table are as follows.・ Dispersion liquid of organic filler A: Crosslinked rubber (NBR) with a carboxyl group having an average primary particle diameter of 0.07 μm, manufactured by JSR Corporation, model XER-91-MEK, containing 15% by weight of methyl groups in the crosslinked rubber Ethyl ketone dispersion, acid value 10.0 mgKOH / g.・ Dispersion of organic filler B: Crosslinked rubber (SBR) with carboxyl and hydroxyl groups with an average primary particle diameter of 0.07 μm, manufactured by JSR Co., Ltd., model XSK-500, containing 15% by weight of methyl groups in crosslinked rubber Ethyl ketone dispersion.・ Coupling agent A: Tetraethoxysilane.・ Coupling agent B: methyltrimethoxysilane.・ Coupling agent C: 3-glycidyloxypropyltrimethoxysilane. -Coupling agent D: N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane.・ Coupling agent E: vinyltrimethoxysilane.・ Silicon oxide filler A: made by Nissan Chemical Industry Co., Ltd., model PMA-ST, propylene glycol monomethyl ether acetate dispersed silica sol, solid content concentration of 30% by mass, and average primary particle diameter of 10 to 15 nm.・ Silicon oxide filler B: made by Nissan Chemical Industry Co., Ltd., model MEK-EC-2130Y, methyl ethyl ketone dispersed silica sol, grade with improved compatibility with epoxy resin, solid content concentration 30 mass %, Average primary particle diameter is 10-15 nm.・ Silicon oxide filler C: Made by Nissan Chemical Industry Co., Ltd., model MEK-AC-2140Z, methyl ethyl ketone dispersed silica sol, grade with improved compatibility with acrylic resin, solid content concentration of 40 mass %, Average primary particle diameter is 10-15 nm.・ Silicon oxide filler D: manufactured by Nissan Chemical Industries, Ltd., model MEK-ST-L, methyl ethyl ketone dispersed silica sol, solid content concentration of 30% by mass, and average primary particle diameter of 40 to 50 nm.・ Silicon oxide filler E: manufactured by Nissan Chemical Industry Co., Ltd., model MEK-ST-ZL, methyl ethyl ketone dispersed silica sol, solid content concentration of 30% by mass, and average primary particle diameter of 70 to 100 nm.・ Silicon oxide filler F: made by Nissan Chemical Industry Co., Ltd., model MEK-ST-UP, methyl ethyl ketone dispersed chain-shaped silica sol, with a solid content concentration of 20% by mass, and an average primary particle diameter of 40 to 100 nm.・ Silicon oxide filler G: manufactured by Longsen Co., Ltd., model IMSIL A8, crystalline silicon oxide, with an average primary particle diameter of 2 μm.・ Unsaturated compound A: tricyclodecane dimethanol diacrylate.・ Unsaturated compound B: trimethylolpropane triacrylate.・ Unsaturated compound C: A mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate, manufactured by Nippon Kayaku Co., Ltd., model KAYARAD DPHA.・ Photopolymerization initiator A: 2,4,6-trimethylbenzylidene diphenylphosphine oxide, manufactured by BASF Corporation, model Irgacure TPO.・ Photopolymerization initiator B: 1-hydroxycyclohexylphenyl ketone, manufactured by BASF Corporation, model Irgacure 184. -Photopolymerization initiator C: 4,4'-bis (diethylamino) benzophenone.・ Epoxy compound: Bisphenol-type crystalline epoxy resin, manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd., model YSLV-80XY, melting point 75-85 ° C, epoxy equivalent 192 g / eq.・ Antioxidant: Hindered phenolic antioxidant, manufactured by BASF, model IRGANOX 1010.・ Surface modifier: MEGAFACE F-477, manufactured by DIC Corporation.

(5) Preparation of test piece Using the photosensitive resin composition of each Example and Comparative Example, a test piece was produced in the following manner.

The photosensitive resin composition was applied to a film made of polyethylene terephthalate by using an applicator, and then dried at 95 ° C for 25 minutes to form a thickness on the film. 30 μm dry film.

A glass epoxy copper clad laminate (FR-4 type) with a copper foil thickness of 17.5 μm was prepared. A core electrode was obtained by using a subtractive process to form a comb electrode having a line width / space width of 50 μm / 50 μm on the glass epoxy copper clad laminate as a conductor line. The surface of the conductor line of this core material having a thickness of about 1 μm is dissolved and removed with an etchant (organic acid-based micro etchant manufactured by MEC Co., Ltd., model CZ-8101) to roughen the conductor line. . A vacuum laminator is used to heat and laminate the dry film on the entire surface of the core material. The conditions for heating the laminate were 0.5 MPa, 80 ° C, and 1 minute. Thereby, a film having a thickness of 30 μm made of a dry film was formed on the core material. From a film made of polyethylene terephthalate, the film was irradiated with ultraviolet rays under a condition of 250 mJ / cm ² through a negative mask in a state where the negative mask was directly attached to the film. The negative mask has a non-exposed portion including a circular pattern having a diameter of 30 μm, 40 μm, and 50 μm. The polyethylene terephthalate film was peeled from the dry film (film) after exposure and before development. The exposed film is subjected to a development treatment. During the development process, 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, the film was sprayed with pure water at a spray pressure of 0.2 MPa for 90 seconds to wash it. Thereby, the unexposed part in the film is removed, and a hole is formed. Then, the film was heated at 180 ° C. for 60 minutes, and then the film was irradiated with ultraviolet rays under the conditions of 1000 mJ / cm ² . Thereby, a layer composed of a cured product of a photosensitive resin composition (also referred to as a cured product of a dry film) is formed on the core material. Thereby, a test piece was obtained.

(6) Evaluation test (6-1) Particle size distribution For each of the examples and comparative examples, the particle size distribution of the photosensitive resin composition filtered through a 300 sieve filter was measured using MT3300EX11 manufactured by MicrotracBEL Co., Ltd. . In Examples 1 to 18 and Comparative Examples 3 and 5, the particle diameter measured by D _{50 of the} photosensitive resin composition obtained by a laser diffraction scattering particle size distribution measurement device was 1 μm or less, and the maximum particle diameter was 10 μm or less. In Comparative Examples 1, 2, 4 and 6, the particle size measured by D _{50 of the} photosensitive resin composition obtained by a laser diffraction scattering particle size distribution measurement device was larger than 1 μm, and the maximum particle diameter was larger than 10 μm.

(6-2) Transparency For each of the examples and comparative examples, the photosensitive resin composition was observed with the naked eye, and the results were evaluated in the following manner. A: No turbidity was observed, and transparency was high. B: Although a little turbidity was observed, it was transparent. C: Although turbidity was observed, it was slightly transparent. D: Cloudiness was observed without transparency.

(6-3) Stability For each Example and Comparative Example, after the photosensitive resin composition was stored at 25 ° C, the photosensitive resin composition was observed, and the results were evaluated in the following manner. A: After storage at 25 ° C for 4 weeks, no component separation occurred. B: Although component separation did not occur after storage at 25 ° C for 3 weeks, component separation occurred after storage at 25 ° C for 4 weeks. C: Although component separation did not occur after storage at 25 ° C for 2 weeks, component separation occurred after storage at 25 ° C for 3 weeks. D: After storage at 25 ° C for 2 weeks, component separation occurred.

(6-4) Developability For each of the examples and comparative examples, the non-exposed portion of the film after the development treatment was observed during the production of the test piece, and the results were evaluated in the following manner. A: The film has been completely removed. B: A part of the film remains on the core material. C: Development cannot be performed.

Comparative Example 5 whose evaluation of the developability was C was not evaluated in the following (6-5) to (6-11). In addition, in Example 17 and Comparative Example 6 in which the developability was evaluated as B, the film remaining on the non-exposed portion on the core material could be completely removed in the evaluation test of the roughness after removing the slag (6-6) below. .

With respect to Examples 1 to 18 and Comparative Examples 1 to 4 and 6, the openings of the layer made of a cured material formed in the test piece were observed, and the results were evaluated in the following manner. A: An opening having a diameter of 30 μm is formed. B: Although an opening having a diameter of 35 μm was formed, an opening having a diameter of 30 μm was not formed. C: Although an opening portion having a diameter of 40 μm was formed, an opening portion having a diameter of 35 μm was not formed. D: Although an opening portion having a diameter of 50 μm was formed, an opening portion having a diameter of 40 μm was not formed. E: No opening with a diameter of 50 μm was formed.

(6-6) Roughness after slag removal For Examples 1 to 18 and Comparative Examples 1 to 4, 6, according to the conventional slag removal treatment method, the test piece made of hardened material was formed in the following manner. The layer is subjected to a desmearing treatment. A commercially available expansion fluid (Swelling Dip Securiganth P, manufactured by ATOTECH Japan Co., Ltd.) was used as the expansion fluid for deslagging, and the surface of the layer composed of the cured product was subjected to an expansion treatment at 70 ° C. for 15 minutes to harden the The surface of the layer formed by the object swells. The surface of the expanded layer made of the cured product 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 slag solution, and the surface of the layer composed of the cured product was roughened at 70 ° C for 10 minutes. While roughening the surface of the layer made of hardened material. The surface of the roughened layer made of the hardened material was washed with hot water. Then, using a neutralizing solution (Reduction Solution Securiganth P, manufactured by ATOTECH Japan Co., Ltd.), the residue of the degumming solution on the surface of the layer made of the cured product was removed at 40 ° C. for 5 minutes. Then, the surface of the layer composed of the cured product was washed with water. A laser microscope was used to measure the surface roughness Ra of the surface of the layer composed of the hardened material that was roughened by the desmearing treatment, and the roughness after the desmearing was evaluated in the following manner. A: Ra is less than 0.2 μm. B: Ra is 0.2 μm or more and less than 0.25 μm. C: Ra is 0.25 μm or more and less than 0.3 μm. D: Ra is 0.3 μm or more.

(6-7) Copper plating adhesion For the examples 1 to 18 and comparative examples 1 to 4, 6, the commercially available chemical agent was used to perform the test after the slag removal treatment in the evaluation test of (6-6) above. The layer of the sheet made of hardened material is subjected to electroless copper plating to form an initial circuit. The test piece in which the initial line was formed was heated at 150 ° C. for 1 hour. Then, a commercially available chemical agent was used to perform electrolytic copper plating treatment at a current density of 2 A / dm ² , so that copper having a thickness of 33 μm was directly deposited in the initial wiring. The copper-plated layer was formed by heating the test piece which precipitated copper at 180 degreeC for 30 minutes. The adhesion between the copper-plated layer and the layer made of a cured material on the test piece was evaluated in the following manner. In addition, for the test piece whose air bubbles could not be confirmed in the test piece when both the electroless copper plating and the electrolytic copper plating were heated, the copper plating layer and the layer composed of the hardened material were measured in accordance with JIS-C6481. Peel strength. A: The peel strength of the copper-plated layer is 0.4 kN / m or more. B: The peel strength of the copper-plated layer is 0.3 kN / m or more and less than 0.4 kN / m. C: The peel strength of the copper-plated layer did not reach 0.3 kN / m. D: Bubbles are generated during heating after electroless copper plating or heating after electrolytic copper plating.

(6-8) Insulating property A bias voltage of 30 V DC was applied to the conductor lines (comb electrodes) of the test pieces of Examples 1 to 18 and Comparative Examples 1 to 4, 6 while the test pieces were at 130 ° C and 85%. Exposure to RH test environment for 100 hours. The resistance value between the comb-type electrodes of a layer made of a hardened material in this test environment is often measured, and the results are evaluated in the following manner. A: During the period from the start of the test until 100 hours have passed, the resistance value is often maintained at 10 ⁶ Ω or more. B: From the start of the test until 85 hours have passed, the resistance value often remains at 10 ⁶ Ω or more, but the resistance value does not reach 10 ⁶ Ω before 100 hours have passed from the start of the test. C: From the start of the test until 70 hours have passed, the resistance value often remains at 10 ⁶ Ω or more, but the resistance value does not reach 10 ⁶ Ω before 85 hours from the start of the test. D: The resistance value did not reach 10 ⁶ Ω before 70 hours passed from the start of the test.

(6-9) Thermal expansion coefficient The thermal expansion coefficient evaluation test uses the photosensitive resin compositions of Examples 1 to 18 and Comparative Examples 1 to 4, and 6 to produce test pieces in the following manner.

The photosensitive resin composition was coated on a polyethylene terephthalate film using an applicator, and then dried at 95 ° C for 25 minutes to form a 30 μm-thick film on the film. Dry film. This dry film was heated and laminated on the entire surface of a film made of Teflon (registered trademark) using a vacuum laminator. The conditions for heating the laminate were 0.5 MPa, 80 ° C, and 1 minute. Thereby, a film having a thickness of 30 μm made of a dry film was formed on a thin film made of Teflon (registered trademark). The polyethylene terephthalate film was irradiated with ultraviolet rays under a condition of 250 mJ / cm ² through a mask in a state where the mask was directly in close contact with the film. It has a rectangular-shaped exposure part of 3 mm x 15 mm. The polyethylene terephthalate film was peeled from the dry film (film) after exposure and before development. The exposed film is subjected to a development treatment. During the development process, 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, the film was sprayed with pure water at a spray pressure of 0.2 MPa for 90 seconds to wash it. Then, the film was heated at 180 ° C. for 60 minutes, and then the film was irradiated with ultraviolet rays under the conditions of 1000 mJ / cm ² . Thereby, a cured product of a photosensitive resin composition is formed on a thin film made of Teflon (registered trademark). This hardened | cured material was peeled from the film made from Teflon (registered trademark), and the test piece was obtained.

A thermomechanical analysis (TMA) test device (Thermoplus EVOII TMA8310, manufactured by Rigaku Co., Ltd.) was used to measure the second cycle under the conditions of a temperature range of 25 to 250 ° C, a heating and cooling rate of 10 ° C / min, and a load of 5 g. Coefficient of thermal expansion (CTE) of the test piece at 30 to 150 ° C. The results were evaluated in the following manner. A: The CTE does not reach 60 ppm / ° C. B: The CTE is 60 ppm / ° C or more and less than 65 ppm / ° C. C: CTE is 65 ppm / ° C or more and less than 70 ppm / ° C. D: CTE is 70 ppm / ° C or more.

(6-10) Glass transition point The evaluation test for glass transition point was made using the photosensitive resin composition of Examples 1 to 18 and Comparative Examples 1 to 4, 6 in the same manner as in (6-9) above. And obtain test pieces.

A TMA test device (Thermoplus EVOII TMA8310, manufactured by Rigaku Co., Ltd.) was used to perform the measurement under the conditions of a temperature range of 25 to 250 ° C, a heating and cooling rate of 10 ° C / min, and a load of 5 g. From the measurement results of the second cycle The glass transition point (Tg) of the test piece was determined. The results were evaluated in the following manner. A: Tg is 160 ° C or higher. B: Tg is 145 ° C or higher and less than 160 ° C. C: Tg is 130 ° C or higher and less than 145 ° C. D: Tg is less than 130 ° C.

(6-11) Dielectric loss tangent The dielectric loss tangent evaluation test uses the photosensitive resin compositions of Examples 1 to 18 and Comparative Examples 1 to 4 and 6 to produce test pieces in the following manner.

The photosensitive resin composition was coated on a polyethylene terephthalate film using an applicator, and then dried by heating at 95 ° C for 25 minutes to form a 50 μm-thick film on the film. Dry film. This dry film was heated and laminated on the entire surface of a film made of Teflon (registered trademark) using a vacuum laminator. The conditions for heating the laminate were 0.5 MPa, 80 ° C, and 1 minute. Thereby, a film having a thickness of 50 μm made of a dry film was formed on a thin film made of Teflon (registered trademark). The polyethylene terephthalate film was irradiated with ultraviolet rays under a condition of 250 mJ / cm ² through a mask in a state where the mask was directly in close contact with the film. It has a rectangular-shaped exposure section of 3 mm x 85 mm. The polyethylene terephthalate film was peeled from the dry film (film) after exposure and before development. The exposed film is subjected to a development treatment. During the development process, 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, the film was sprayed with pure water at a spray pressure of 0.2 MPa for 90 seconds to wash it. Then, the film was heated at 180 ° C. for 60 minutes, and then the film was irradiated with ultraviolet rays under the conditions of 1000 mJ / cm ² . Thereby, a cured product of a photosensitive resin composition is formed on a thin film made of Teflon (registered trademark). This hardened | cured material was peeled from the film made from Teflon (registered trademark), and the test piece was obtained.

The dielectric loss tangent of the test piece was measured using a dielectric constant measuring device (manufactured by AET Co., Ltd., ADMS01O) by a cavity resonator method at a frequency of 1 GHz. The results were evaluated in the following manner. A: tan δ is less than 0.020. B: tan δ is 0.020 or more and less than 0.025. C: tan δ is 0.025 or more and less than 0.030. D: tan δ is 0.030 or more.

[Table 1]

[Table 2]

[table 3]

As is apparent from the above embodiment, the photosensitive resin composition according to the first aspect of the present invention has photocurability, and the photosensitive resin composition contains: a carboxyl group-containing resin (A) having an aromatic ring; Its average primary particle diameter is 1 μm or less and it has a carboxyl group; the coupling agent (C) has at least one atom selected from the group consisting of silicon atoms, aluminum atoms, titanium atoms, and zirconium atoms, and two or more Functional group, and the aforementioned functional group includes at least one group selected from the group consisting of alkoxy, fluorenyloxy, and alkoxide groups; and a silicon oxide filler (D) having an average primary particle diameter of 1 In the range of ~ 150 nm.

According to the first aspect, it is possible to obtain a photosensitive resin composition which can form a hardened product having high copper plating adhesion and low roughness after removing slag, and has excellent resolvability.

In a second aspect of the photosensitive resin composition of the present invention, in the first aspect, the coupling agent (C) has a silicon atom.

According to the second aspect, the dispersibility of the organic filler (B) in the photosensitive resin composition can be efficiently improved, and the transparency and stability of the photosensitive resin composition can be improved. The glass transition point of the hardened | cured material of the photosensitive resin composition can be raised, and a thermal expansion coefficient can be reduced.

In a third aspect of the present invention, in the photosensitive resin composition, in the first or second aspect, the silica filler (D) contains silica particles derived from silica sol.

According to the third aspect, the transparency of the photosensitive resin composition can be improved, and the resolution of the photosensitive resin composition can be improved.

In a fourth aspect of the present invention, the photosensitive resin composition is any one of the first to third aspects, wherein the average primary particle diameter of the silica filler (D) is in the range of 1 to 60 nm. .

According to the fourth aspect, the transparency and resolution of the photosensitive resin composition can be improved.

In a fifth aspect of the present invention, the photosensitive resin composition is any one of the first to fourth aspects, wherein the organic filler (B The content of) is in a range of 1 to 50 parts by mass.

According to the 5th aspect, the hardened | cured material of the photosensitive resin composition can obtain favorable copper-plating adhesiveness. In addition, excellent resolution of the photosensitive resin composition can be obtained. In addition, the thixotropy and stability of the photosensitive resin composition are improved.

In the sixth aspect of the present invention, the photosensitive resin composition is any one of the first to fifth aspects, and the silica filler (100 parts by mass with respect to the content of the carboxyl group-containing resin (A)) The content of D) is in the range of 5 to 200 parts by mass.

According to the sixth aspect, the transparency of the photosensitive resin composition can be further improved, and the photosensitive resin composition can have excellent resolution. Moreover, the glass transition point of the hardened | cured material of the photosensitive resin composition can be raised, and a thermal expansion coefficient and a dielectric loss tangent can be reduced. In addition, it is possible to further reduce the surface roughness of the cured product obtained by subjecting the cured product of the photosensitive resin composition to a desmearing treatment.

In a seventh aspect of the present invention, the photosensitive resin composition is any one of the first to sixth aspects, wherein the carboxyl group-containing resin (A) includes a carboxyl group-containing resin having an ethylenically unsaturated group.

According to the seventh aspect, it is possible to impart photocurability to the photosensitive resin composition.

In the eighth aspect of the present invention, the photosensitive resin composition is any one of the first to seventh aspects with respect to the content of the organic filler (B) and the content of the silicon oxide filler (D). 100 mass parts in total, and the content of the coupling agent (C) is in a range of 0.01 to 10 mass parts.

According to the eighth aspect, the organic filler (B) and the silica filler (D) in the photosensitive resin composition can be prevented from agglomerating, and the dispersibility can be improved.

In the ninth aspect of the present invention, the photosensitive resin composition is any one of the first to eighth aspects, and the organic filler (B) is contained in the state in a state where the particle diameter is 10 μm or less. In the photosensitive resin composition.

According to the ninth aspect, the stability of the photosensitive resin composition is improved, and the scattering during exposure can be suppressed, so that the resolution is improved.

In a tenth aspect of the present invention, the photosensitive resin composition is any one of the first to ninth aspects, wherein the organic filler (B) contains a rubber component.

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

In a tenth aspect of the photosensitive resin composition of the present invention, in the tenth aspect, the rubber component includes a group consisting of crosslinked acrylic rubber, crosslinked NBR, crosslinked MBS, and crosslinked SBR. Selected at least one polymer.

According to the eleventh aspect, the photosensitive resin composition can have high transparency and can improve the resolution of the photosensitive resin composition.

In a twelfth aspect of the present invention, the photosensitive resin composition is any one of the first to eleventh aspects, wherein the carboxyl group-containing resin (A) includes a carboxyl group-containing resin having a benzene ring.

According to the twelfth aspect, the transparency of the photosensitive resin composition can be improved, and the photosensitive resin composition can have excellent resolution.

In the thirteenth aspect of the present invention, the photosensitive resin composition is any one of the first to twelfth aspects, wherein the carboxyl group-containing resin (A) includes a reaction of a polyol resin and an acid dianhydride. The copolymer obtained.

According to the thirteenth aspect, high alkali developability can be imparted to the photosensitive resin composition, and high heat resistance and insulation can be imparted to the cured product of the photosensitive resin composition.

In a fourteenth aspect of the present invention, the photosensitive resin composition is the thirteenth aspect, wherein the acid dianhydride contains an acid dianhydride having an aromatic ring.

According to the fourteenth aspect, high alkali developability can be imparted to the photosensitive resin composition, and high heat resistance and insulation can be imparted to the cured product of the photosensitive resin composition.

In a fifteenth aspect of the present invention, the photosensitive resin composition is any one of the first to fourteenth aspects, wherein the carboxyl group-containing resin (A) includes a biphenyl skeleton and a bisphenol fluorene skeleton. At least one skeleton of a carboxyl-containing resin.

According to the fifteenth aspect, the dielectric loss tangent of the cured product of the photosensitive resin composition can be further reduced.

The photosensitive resin composition of a sixteenth aspect of the present invention is, in any one of the first to fifteenth aspects, further comprising: an unsaturated compound (E), which has at least one ethylenic compound in one molecule. A saturated bond; and, a photopolymerization initiator (F).

According to the sixteenth aspect, it is possible to impart high sensitivity to the photosensitive resin composition. In addition, ion migration can be suppressed in the layer containing the cured product of the photosensitive resin composition, and the insulation of the layer containing the cured product can be improved.

In a seventeenth aspect of the present invention, the photosensitive resin composition is the sixteenth aspect, wherein the unsaturated compound (E) includes trimethylolpropane tri (meth) acrylate and tricyclodecanedi At least one compound selected from the group consisting of methanol di (meth) acrylate.

According to the seventeenth aspect, the photosensitive resin composition can have excellent transparency and stability.

In the eighteenth aspect of the present invention, the photosensitive resin composition further includes an epoxy compound (G) in any one of the first to seventeenth aspects.

According to the eighteenth aspect, thermosetting properties can be imparted to the photosensitive resin composition.

A dry film according to a nineteenth aspect of the present invention includes the photosensitive resin composition according to any one of the first to eighteenth aspects.

According to the 19th aspect, it is possible to obtain a dry film which can form a hardened product having high copper plating adhesion and low roughness after removing slag, and has excellent resolvability.

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

According to the twentieth aspect, it is possible to obtain a printed wiring board including an interlayer insulating layer having high copper plating adhesion and low roughness after removing slag.

A printed wiring board according to a twenty-first aspect of the present invention 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 twenty-first aspect, it is possible to obtain a printed wiring board including a solder resist layer having high copper plating adhesion and low roughness after removing slag.

1‧‧‧ core material

2‧‧‧ Insulation

3‧‧‧ the first conductor line

4‧‧‧ capsule

5‧‧‧ unexposed part

6‧‧‧hole

7‧‧‧ interlayer insulation film

8‧‧‧Second Conductor Line

9‧‧‧ hole plating

10‧‧‧through hole

11‧‧‧printed circuit board

FIG. 1A is a cross-sectional view showing one of the steps of manufacturing a multilayer printed wiring board. FIG. 1B is a cross-sectional view showing one of the steps of manufacturing a multilayer printed wiring board. FIG. 1C is a cross-sectional view showing one of the steps of manufacturing a multilayer printed wiring board. FIG. 1D is a cross-sectional view showing one of the steps of manufacturing a multilayer printed wiring board. FIG. 1E is a cross-sectional view showing one of the steps of manufacturing a multilayer printed wiring board.

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Information on foreign deposits (please note in order of deposit country, institution, date, and number) None

Claims (21)

A photosensitive resin composition having photo-hardening property, the photosensitive resin composition contains: 羧基 a carboxyl group-containing resin (A) having an aromatic ring; an organic filler (B) having an average primary particle diameter of 1 μm or less and having a carboxyl group Coupling agent (C), which 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 two or more functional groups, and the functional group includes At least one group selected from the group consisting of oxy, fluorenyloxy and alkoxide groups; and fluorene silica filler (D), the average primary particle diameter of which is in the range of 1 to 150 nm. The photosensitive resin composition according to claim 1, wherein the coupling agent (C) has a silicon atom. The photosensitive resin composition according to claim 1 or 2, wherein the silica filler (D) contains silica particles derived from a silica sol. The photosensitive resin composition according to claim 1 or 2, wherein the average primary particle diameter of the silicon oxide filler (D) is in a range of 1 to 60 nm. The photosensitive resin composition according to claim 1 or 2, wherein the content of the organic filler (B) is within a range of 1 to 50 parts by mass based on 100 parts by mass of the content of the carboxyl group-containing resin (A). The photosensitive resin composition according to claim 1 or 2, wherein the content of the silica filler (D) is within a range of 5 to 200 parts by mass based on 100 parts by mass of the content of the carboxyl group-containing resin (A). . The photosensitive resin composition according to claim 1 or 2, wherein the carboxyl group-containing resin (A) includes a carboxyl group-containing resin having an ethylenically unsaturated group. The photosensitive resin composition according to claim 1 or 2, wherein the content of the coupling agent (C) is 100 parts by mass based on a total of 100 parts by mass of the content of the organic filler (B) and the content of the silica filler (D). The content is in the range of 0.01 to 10 parts by mass. The photosensitive resin composition according to claim 1 or 2, wherein the organic filler (B) is contained in the photosensitive resin composition in a state where a particle diameter is 10 μm or less. The photosensitive resin composition according to claim 1 or 2, wherein the organic filler (B) contains a rubber component. The photosensitive resin composition according to claim 10, wherein the rubber component includes at least one polymer selected from the group consisting of crosslinked acrylic rubber, crosslinked NBR, crosslinked MBS, and crosslinked SBR. . The photosensitive resin composition according to claim 1 or 2, wherein the carboxyl group-containing resin (A) includes a carboxyl group-containing resin having a benzene ring. The photosensitive resin composition according to claim 1 or 2, wherein the carboxyl group-containing resin (A) includes a copolymer obtained by reacting a polyol resin and an acid dianhydride. The photosensitive resin composition according to claim 13, wherein the acid dianhydride contains an acid dianhydride having an aromatic ring. The photosensitive resin composition according to claim 1 or 2, wherein the carboxyl group-containing resin (A) includes a carboxyl group-containing resin having at least one of a biphenyl skeleton and a bisphenol fluorene skeleton. The photosensitive resin composition according to claim 1 or 2, further comprising: a fluorene unsaturated compound (E) having at least one ethylenically unsaturated bond in one molecule thereof; and a fluorene photopolymerization initiator (F) . The photosensitive resin composition according to claim 16, wherein the unsaturated compound (E) includes trimethylolpropane tri (meth) acrylate and tricyclodecanedimethanol di (meth) acrylic acid. At least one compound selected from the group consisting of esters. The photosensitive resin composition according to claim 1 or 2, further comprising an epoxy compound (G). A dry film containing the photosensitive resin composition according to any one of claims 1 to 18. 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 18. A printed wiring board comprising a solder resist layer containing a cured product of the photosensitive resin composition according to any one of claims 1 to 18.