KR102208828B1 - Photosensitive resin composition, dry film, and printed wiring board - Google Patents

Abstract

An object of the present invention is to provide a photosensitive resin composition excellent in resolution while being able to form a cured product having high copper plating adhesion. The photosensitive resin composition according to the present invention has photocurability. The photosensitive resin composition includes 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, a carboxyl group, a silicon atom, an aluminum atom, a titanium atom, and a zirconium atom. A coupling agent (C) comprising at least one atom selected from the group consisting of, and having two or more functional groups, the functional group comprising at least one group selected from the group consisting of an alkoxy group, an acyloxy group and an alkoxide, and And a silica filler (D) having an average primary particle diameter in the range of 1 to 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 a printed wiring board, various electric insulating resin compositions have been used to form electric insulating layers such as a solder resist layer, a plating resist layer, an etching resist layer, and an interlayer insulating layer.

In recent years, in accordance with the demand for high performance, miniaturization, and thinness of electronic devices such as communication devices and personal computers, it is necessary to form a fine through hole or opening pattern in the electrical insulating layer formed of such a resin composition. As a resin composition for forming a layer, for example, a photosensitive resin composition can be used.

For example, in Patent Document 1, (A) a carboxyl group-containing resin obtained by reacting a diol compound with a polyvalent carboxylic acid, and having a weight average molecular weight of 2000 to 400,000 and an acid value of 50 to 200 mgKOH/g, ( B) An unsaturated compound containing at least one photopolymerizable ethylenically unsaturated bond per molecule, (C) an epoxy compound, and (D) a photosensitive resin composition for an insulating film containing a photopolymerization initiator is disclosed, and the photosensitive resin composition for the insulating film is disclosed. It describes that the adhesiveness with the plated metal can be improved by adding a rubber component to a resin composition.

However, in the photosensitive resin composition for an insulating film described in Patent Document 1, although the adhesion to the plated metal can be improved to some extent, the surface roughness of the cured product after the cured product of the photosensitive resin composition for an insulating film is desmeared. Can not be made small, and good high-frequency characteristics cannot be obtained. In addition, by adding a rubber component, in a developing treatment with an aqueous solution containing at least one of an alkali metal salt and an alkali metal hydroxide, the resolution is lowered, and there is a fear that a fine through hole or an opening pattern, etc. cannot be formed. It is difficult to obtain a photosensitive resin composition having high copper plating adhesion, and capable of forming a cured product having low roughness after desmearing, and having excellent resolution.

Japanese Patent No. 4508929

An object of the present invention is a photosensitive resin composition having high copper plating adhesion, and capable of forming a cured product having low roughness after desmearing, and excellent in resolution, a dry film containing the photosensitive resin composition, and the photosensitive resin A printed wiring board provided with an interlayer insulating layer containing a cured product of the composition, and a printed wiring board provided with a solder resist layer including a cured product of the photosensitive resin composition.

The photosensitive resin composition according to an embodiment of the present invention is a photosensitive resin composition having photocurability, comprising a carboxyl group-containing resin (A) having an aromatic ring, an average primary particle diameter of 1 μm or less, and an organic filler having a carboxyl group (B) 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 is composed of an alkoxy group, an acyloxy group, and an alkoxide. It contains a coupling agent (C) containing at least one group selected from the group, and a silica filler (D) having an average primary particle diameter in the range of 1 to 150 nm.

The dry film according to an embodiment of the present invention contains the photosensitive resin composition.

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

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

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

The present invention relates to a photosensitive resin composition, a dry film, and a printed wiring board, and more particularly, to form an electrically insulating layer such as a solder resist layer, a plating resist layer, an etching resist layer, and an interlayer insulating layer on the printed wiring board. A suitable photosensitive resin composition, a dry film containing the photosensitive resin composition, a printed wiring board having an interlayer insulating layer including a cured product of the photosensitive resin composition, and a solder resist layer including a cured product of the photosensitive resin composition It relates to a printed wiring board.

An embodiment for carrying out the present invention will be described. And in the following description, "(meth)acryl" means at least one of "acrylic" and "methacryl." For example, (meth)acrylate means at least one of acrylate and methacrylate.

The photosensitive resin composition according to the present embodiment has photocurability. The photosensitive resin composition according to the present embodiment has a carboxyl group-containing resin (A) having an aromatic ring, an average primary particle diameter of 1 μm or less, an organic filler (B) having a carboxyl group, a silicon atom, an aluminum atom, and titanium. It contains a coupling agent (C) having at least one atom selected from the group consisting of an atom and a zirconium atom, two or more functional groups, and a silica filler (D) having an average primary particle diameter in the range of 1 to 150 nm. . The functional group contains at least one functional group selected from the group consisting of an alkoxy group, an acyloxy group, and an alkoxide.

When the photosensitive resin composition contains the organic filler (B), the cured product of the photosensitive resin composition has high copper plating adhesion. 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 comprises an organic filler ( In spite of containing B), it has high transparency. For this reason, the resolution is improved. Usually, when a filler is blended into the photosensitive resin composition, turbidity occurs in the photosensitive resin composition, and transparency is lowered. When the transparency of the photosensitive resin composition is low, light is liable to scatter when the photosensitive resin composition is exposed, and good resolution cannot be obtained. However, since the photosensitive resin composition according to the present 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), high transparency is achieved. Can have. For this reason, the resolution of the photosensitive resin composition is improved, and a fine through hole, an opening pattern, etc. can be formed in a layer made of a cured product of the photosensitive resin composition. Further, the surface roughness of the cured product after desmearing the cured product of the photosensitive resin composition can be reduced. That is, the photosensitive resin composition can form a cured product having low roughness after desmearing. By reducing the roughness after desmearing of the cured product, a printed wiring board including a layer made of the cured product can have excellent high-frequency characteristics. Further, when the photosensitive resin composition contains the silica filler (D), the glass transition point of the cured product of the photosensitive resin composition can be increased and the coefficient of thermal expansion can be reduced. For this reason, the layer made of the cured product of the photosensitive resin composition is difficult to bend even when stress by heat is applied, and it is also excellent in resistance to cracking in cold and heat cycles, and thus can be used for a thin printed wiring board. Further, when the photosensitive resin composition contains the silica filler (D), the dielectric loss tangent of the cured product of the photosensitive resin composition can be reduced. For this reason, it is possible to improve the high frequency transmission performance of a printed wiring board including a layer made of a cured product of a photosensitive resin composition. In addition, 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), It is believed that through the coupling agent (C), the carboxyl group of the carboxyl group-containing resin (A) and the carboxyl group of the organic filler (B) interact or bond to form a composite or hybridize. For this reason, the glass transition point of the cured product of the photosensitive resin composition is further increased, and the coefficient of thermal expansion and the dielectric loss tangent are further reduced.

The photosensitive resin composition has photocurability. When the photosensitive resin composition has photocurability, light is irradiated to the photosensitive resin composition, and the photosensitive resin composition can be cured. The photocurability of the photosensitive resin composition is imparted, for example, when the carboxyl group-containing resin (A) has a photopolymerizable unsaturated group. In addition, the photocurability of the photosensitive resin composition is imparted even when the photosensitive resin composition contains an unsaturated compound (E) as described later.

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, and may be a resin having an aromatic ring and a carboxyl group.

It is preferable that the carboxyl group-containing resin (A) has a hydroxyl group. When the carboxyl group-containing resin (A) has a hydroxyl group, the reactivity with the coupling agent (C) becomes particularly high, and the transparency of the photosensitive resin composition is further improved.

It is preferable that the carboxyl group-containing resin (A) contains a resin obtained by reaction of a polyalcohol resin and at least one compound selected from the group consisting of a polyhydric carboxylic acid and an acid anhydride thereof. In this case, it is preferable that the polyalcohol resin has an aromatic ring, and it is also preferable that at least one compound selected from the group consisting of polyhydric carboxylic acids and anhydrides thereof has an aromatic ring. It is more preferable that the carboxyl group-containing resin (A) contains a copolymer obtained by reaction of a polyalcohol resin and an acid dianhydride. In this case, it is preferable that the polyalcohol resin has an aromatic ring, and it is also preferable that the acid dianhydride has an aromatic ring. When the carboxyl group-containing resin (A) contains a copolymer obtained by reaction of a polyalcohol resin and an acid dianhydride, it imparts high alkali developability to the photosensitive resin composition, and also provides high heat resistance and insulation properties to the cured product of the photosensitive resin composition. Can be given.

It is preferable that the carboxyl group-containing resin (A) contains a carboxyl group-containing resin having an ethylenically unsaturated group. Since the carboxyl group-containing resin (A) contains a carboxyl group-containing resin having an ethylenically unsaturated group, the carboxyl group-containing resin (A) has photoreactivity. For this reason, photocurability can be imparted to the photosensitive resin composition containing the carboxyl group-containing resin (A).

The carboxyl group-containing resin having an ethylenically unsaturated group is, for example, from the group of an intermediate, which is a reaction product of an epoxy compound (g1) having two or more epoxy groups in one molecule and an ethylenically unsaturated compound (g2), and a polyvalent carboxylic acid and anhydride thereof. It contains a resin (referred to as first resin (g)) that is a reaction product with at least one selected compound (g3). 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 adding the compound (g3) to an intermediate having a hydroxyl group obtained by reacting an epoxy group in an epoxy compound (g1) with a carboxyl group in an ethylenically unsaturated compound (g2). The epoxy compound (g1) may contain an appropriate epoxy resin such as a cresol novolak type epoxy resin and a phenol novolak type epoxy resin. It is preferable that the epoxy compound (g1) contains an epoxy compound having an aromatic ring. The epoxy compound (g1) may contain a polymer of the ethylenically unsaturated compound (h). The ethylenically unsaturated compound (h) contains, for example, a compound (h1) having an epoxy group such as glycidyl (meth)acrylate, or an epoxy group such as 2-(meth)acryloyloxyethylphthalate. It further contains the compound (h2) which does not have. It is preferable that the ethylenically unsaturated compound (g2) contains at least one of acrylic acid and methacrylic acid. Compound (g3) contains, for example, one or more compounds selected from the group consisting of polyhydric carboxylic acids such as phthalic acid, tetrahydrophthalic acid, and methyltetrahydrophthalic acid, and anhydrides of these polyhydric carboxylic acids. It is preferable that the compound (g3) contains an acid dianhydride. In addition, it is preferable that the acid dianhydride contains an acid dianhydride having an aromatic ring. In this case, the transparency of the photosensitive resin composition is further improved, and thus the resolution is further improved.

The carboxyl group-containing resin having an ethylenically unsaturated group contains a resin (referred to as the second resin (i)) that is a reaction product of a polymer of an ethylenically unsaturated monomer containing an ethylenically unsaturated compound having a carboxyl group and an ethylenically unsaturated compound having an epoxy group. You may. 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 the carboxyl groups in the polymer. The second resin (i) has an aromatic ring derived from at least one of a polymer of an ethylenically unsaturated monomer and an ethylenically unsaturated compound having an epoxy group. Ethylenically unsaturated compounds having a carboxyl group include, for example, acrylic acid, methacrylic acid, ω-carboxy-polycaprolactone (n≒) monoacrylate, 2-(meth)acryloyloxyethylphthalate, 2-(meth ) A compound such as acryloyloxyethyl-2-hydroxyethylphthalate is contained. The ethylenically unsaturated compound which does not have a carboxyl group contains, for example, a compound such as a linear or branched aliphatic or alicyclic (however, it may have some unsaturated bonds in the ring), such as a (meth)acrylic acid ester. It is preferable that the ethylenically unsaturated compound having an epoxy group contains glycidyl (meth)acrylate.

It is preferable that the carboxyl group-containing resin (A) has a benzene ring. That is, it is preferable that the aromatic ring which the carboxyl group-containing resin (A) has is a benzene ring. When the carboxyl group-containing resin (A) has a benzene ring, the transparency of the photosensitive resin composition is further increased, and the photosensitive resin composition has excellent resolution. It is more preferable that the carboxyl group-containing resin (A) 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. In this case, the transparency of the photosensitive resin composition containing the carboxyl group-containing resin (A) is further increased, and the photosensitive resin composition has more excellent resolution. The carboxyl group-containing resin (A) more preferably contains a carboxyl group-containing resin having at least one of a biphenyl skeleton and a bisphenol fluorene skeleton, and particularly preferably contains a carboxyl group-containing resin having a bisphenol fluorene skeleton. In this case, the dielectric loss tangent in the cured product of the photosensitive resin composition containing the carboxyl group-containing resin (A) can be further reduced.

The carboxyl group-containing resin (A) is represented by the following formula (1), and in formula (1), R ₁ to R ₈ are each independently hydrogen, an alkyl group having 1 to 5 carbon atoms, or an epoxy having a halogen bisphenol fluorene skeleton. A carboxyl group-containing resin (hereinafter referred to as a carboxyl group-containing resin (A1), which is a reaction product of a compound (a1) and a carboxylic acid (a2) containing an unsaturated group-containing carboxylic acid (a2-1), and an acid anhydride (a3). It is preferable to include). 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 derived from a carboxylic acid (a2) containing an unsaturated group-containing carboxylic acid (a2-1). The carboxyl group-containing resin (A1) reacts with an epoxy compound (a1) having a bisphenol fluorene skeleton represented by the following formula (1) and a carboxylic acid (a2) containing an unsaturated group-containing carboxylic acid (a2-1). It is synthesized by reacting the obtained intermediate with an acid anhydride (a3).

In formula (1), R ₁ to R ₈ are each independently hydrogen, an alkyl group having 1 to 5 carbon atoms, or a halogen. That is, each of R ₁ to R ₈ in formula (1) may be hydrogen, but may be an alkyl group having 1 to 5 carbon atoms or a halogen. Even if hydrogen in the aromatic ring is substituted with a low molecular weight alkyl group or halogen, it does not adversely affect the physical properties of the carboxyl group-containing resin (A1). Rather, by being substituted, the heat resistance of the cured product of the photosensitive resin composition containing the carboxyl group-containing resin (A1) or This is because the flame retardancy is sometimes improved.

The carboxyl group-containing resin (A1) can impart high heat resistance and insulation properties to the cured product of the photosensitive resin composition by having a bisphenol fluorene skeleton represented by formula (1) derived from the epoxy compound (a1). Further, by having a carboxyl group derived from an acid anhydride (a3) in the carboxyl group-containing resin (A1), excellent developability can be imparted to the photosensitive resin composition.

The carboxyl group-containing resin (A1) will be described more specifically. In order to synthesize the carboxyl group-containing resin (A1), first, at least some of the epoxy groups in the epoxy compound (a1) having a bisphenol fluorene skeleton represented by formula (1) and an unsaturated group-containing carboxylic acid (a2-1) are included. An intermediate is synthesized by reacting carboxylic acid (a2). The synthesis of the intermediate is defined as the first reaction. The intermediate has a secondary hydroxyl group generated by a ring-opening addition reaction of an epoxy group and a carboxylic acid (a2) containing an unsaturated group-containing carboxylic acid (a2-1). Next, the acid anhydride (a3) is reacted with the secondary hydroxyl group in the intermediate. Thereby, a carboxyl group-containing resin (A1) can be synthesized. The reaction between the intermediate and the acid anhydride (a3) is defined as the second reaction. The acid anhydride (a3) may include an acid anhydride and an acid dianhydride. An acid anhydride is a compound having one acid anhydride group in which two carboxyl groups in one molecule are dehydrated and condensed. An acid dianhydride is a compound having two acid anhydride groups in which four carboxyl groups in one molecule are dehydrated and condensed.

The carboxyl group-containing resin (A1) may contain an unreacted component in the intermediate. In addition, when the acid anhydride (a3) contains an acid anhydride and an acid dianhydride, the carboxyl group-containing resin (A1) is a component in the intermediate and a component in the intermediate as well as the reaction product of the component in the acid dianhydride and the component in the acid dianhydride. One or both of the reactants of the components in the intermediate and the reactants of the components in the intermediate and the acid dianhydride may be contained. That is, the carboxyl group-containing resin (A1) may be a mixture containing a plurality of compounds having different structures as described above.

The carboxyl group-containing resin (A1) has photoreactivity by having an ethylenically unsaturated group derived from an unsaturated group-containing carboxylic acid (a2-1). For this reason, the carboxyl group-containing resin (A1) can impart photosensitivity, specifically, ultraviolet curing property, to the photosensitive resin composition. In addition, since the carboxyl group-containing resin (A1) has a carboxyl group derived from an acid anhydride (a3), it is possible to impart developability to the photosensitive resin composition with an alkaline aqueous solution containing at least one of an alkali metal salt and an alkali metal hydroxide. have.

It is preferable that the weight average molecular weight of the carboxyl group-containing resin (A1) is in the range of 700 to 10000. When the weight average molecular weight is 700 or more, the insulating property 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 10000 or less, developability of the photosensitive resin composition by 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 1000 to 5000.

It is preferable that the polydispersity of the carboxyl group-containing resin (A1) is 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. It is more preferable that the polydispersity of the carboxyl group-containing resin (A1) is 1.1 to 4.0, and still more preferably 1.2 to 2.8.

The number average molecular weight and molecular weight distribution of the carboxyl group-containing resin (A1) as described above is that the carboxyl group-containing resin (A1) is an unreacted component in the intermediate, the component in the intermediate and the reactant of the component in the acid dianhydride and the component in the acid dianhydride, the intermediate This can be achieved by being a mixture appropriately containing various components, such as a reaction product of the component in the component and the component in the acid dianhydride, and the reaction product of the component in the intermediate and the component in the acid dianhydride. More specifically, it can be achieved by controlling parameters such as the average molecular weight of the epoxy compound (a1), the amount of the acid monohydride relative to the epoxy compound (a1), and the amount of the acid dianhydride relative to the epoxy compound (a1). have.

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

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

The molecular weight of the carboxyl group-containing resin (A1) can be adjusted by crosslinking the acid dianhydride. In this case, a carboxyl group-containing resin (A1) in which the acid value and molecular weight were adjusted is obtained. That is, by controlling the amount of the acid dianhydride contained in the acid anhydride (a3), the molecular weight and acid value of the carboxyl group-containing resin (A1) can be easily adjusted. In addition, the molecular weight of the carboxyl group-containing resin (A1) is calculated as the result of measurement under the following conditions by gel permeation chromatography.

GPC device: SHODEX SYSTEM 11 manufactured by Showa Electric Co., Ltd.,

Column: 4 series of SHODEX KF-800P, KF-005, KF-003, KF-001,

Mobile phase: THF,

Flow: 1 ml/min,

Column temperature: 45° C.,

Detector: RI,

Conversion: polystyrene.

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

The epoxy compound (a1) has, for example, a structure shown in the following formula (2). N in Formula (2) is an integer within the range of 0-20, for example. In order to properly 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, even when the acid anhydride (a3) contains an acid dianhydride, an excessive increase in molecular weight is easily suppressed.

Carboxylic acid (a2) contains an unsaturated group-containing carboxylic acid (a2-1). The carboxylic acid (a2) may contain only an unsaturated group-containing carboxylic acid (a2-1). Alternatively, the carboxylic acid (a2) may contain carboxylic acids other than the unsaturated group-containing carboxylic acid (a2-1) and the unsaturated group-containing carboxylic acid (a2-1).

The unsaturated group-containing carboxylic acid (a2-1) may contain, for example, a compound having only one ethylenically unsaturated group. More specifically, the unsaturated group-containing carboxylic acid (a2-1) is, for example, acrylic acid, methacrylic acid, ω-carboxy-polycaprolactone (n≒) monoacrylate, crotonic acid, cinnamic acid, and 2-acrylic. Royloxyethylsuccinic acid, 2-methacryloyloxyethylsuccinic acid, 2-acryloyloxyethylphthalic acid, 2-methacryloyloxyethylphthalic acid, 2-acryloyloxypropylphthalic acid, 2-methacryloyl Oxypropylphthalic acid, 2-acryloyloxyethylmaleic acid, 2-methacryloyloxyethylmaleic acid, β-carboxyethylacrylate, 2-acryloyloxyethyltetrahydrophthalic acid, 2-methacryloyloxyethyl It may contain at least one compound selected from the group consisting of tetrahydrophthalic acid, 2-acryloyloxyethylhexahydrophthalic acid, and 2-methacryloyloxyethylhexahydrophthalic acid. It is preferable that the unsaturated group-containing carboxylic acid (a2-1) contains acrylic acid.

The carboxylic acid (a2) may also contain a polybasic acid (a2-2). The polybasic acid (a2-2) is an acid in which two or more hydrogen atoms can be substituted with metal atoms in one molecule. It is preferable that the polybasic acid (a2-2) has two or more carboxyl groups. In this case, the epoxy compound (a1) reacts with both of the unsaturated group-containing carboxylic acid (a2-1) and the polybasic acid (a2-2). When the polybasic acid (a2-1) crosslinks the epoxy group present in the two molecules of the epoxy compound (a1), an increase in molecular weight is obtained. Thereby, the insulating property of the cured product of the photosensitive resin composition can be improved, and the dielectric loss tangent can be reduced.

It is preferable that the polybasic acid (a2-2) contains a dicarboxylic acid. For example, 4-cyclohexene-1,2-dicarboxylic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, maleic acid, fumaric acid, phthalic acid , Isophthalic acid, and terephthalic acid may contain one or more compounds selected from the group consisting of. Preferably, the polybasic acid (a2-2) contains 4-cyclohexene-1,2-dicarboxylic acid.

In making the epoxy compound (a1) and carboxylic acid (a2) react, a known method may be employed. For example, carboxylic acid (a2) is added to the solvent solution of the epoxy compound (a1), and if necessary, a thermal polymerization inhibitor and a catalyst are further added and mixed with stirring to obtain a reactive solution. By reacting this reactive solution at a temperature of preferably 60 to 150°C, particularly preferably 80 to 120°C by a conventional method, an intermediate can be obtained. The solvent is, for example, ketones such as methyl ethyl ketone and cyclohexanone, and aromatic hydrocarbons such as toluene and xylene, and ethyl acetate, butyl acetate, cellosolve acetate, butyl cellosolve acetate, carbitol acetate, It may contain at least one component selected from the group consisting of acetic acid esters such as butyl carbitol acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, and dialkyl glycol ethers. The thermal polymerization inhibitor contains, for example, at least one of hydroquinone and hydroquinone monomethyl ether. The catalyst is, for example, tertiary amines such as benzyldimethylamine and triethylamine, quaternary ammonium salts such as trimethylbenzyl ammonium chloride and methyltriethylammonium chloride, triphenylphosphine, and triphenylstyrene. It may contain at least one component selected from the group consisting of.

It is particularly preferred that the catalyst contains triphenylphosphine. That is, it is preferable to react the epoxy compound (a1) with the carboxylic acid (a2) in the presence of triphenylphosphine. In this case, the ring-opening addition reaction of the epoxy group and the carboxylic acid (a2) in the epoxy compound (a1) is particularly promoted, and a reaction rate (conversion rate) of 95% or more, or 97% or more, or approximately 100% can be achieved. Further, generation of ion migration in the layer containing the cured product of the photosensitive resin composition is suppressed, and the insulating property of the layer including the cured product is improved.

When reacting the epoxy compound (a1) with the carboxylic acid (a2), the amount of the carboxylic acid (a2) to 1 mole of the epoxy group of the epoxy compound (a1) is preferably in the range of 0.5 to 1.2 moles. In this case, good photosensitivity and stability of the photosensitive resin composition are obtained. From the same viewpoint, it is preferable that the amount of the unsaturated group-containing carboxylic acid (a2-1) per 1 mole of the epoxy group of the epoxy compound (a1) is in the range of 0.5 to 1.2 moles. Alternatively, when the carboxylic acid (a2) contains a carboxylic acid other than the unsaturated group-containing carboxylic acid (a2-1), the amount of the unsaturated group-containing carboxylic acid (a2-1) relative to 1 mole of the epoxy group of the epoxy compound (a1) is 0.5. It may be in the range of -0.95 mol. In addition, when the carboxylic acid (a2) contains a polybasic acid (a2-1), the amount of the polybasic acid (a2-1) relative to 1 mol of the epoxy group of the epoxy compound (a1) is preferably in the range of 0.025 to 0.25 mol. In this case, good photosensitivity and stability of the photosensitive resin composition are obtained.

It is also preferable to make the epoxy compound (a1) and carboxylic acid (a2) react under air bubbling. In this case, addition polymerization reaction of an unsaturated group can be suppressed, thereby increasing the molecular weight of the intermediate and suppressing gelation of the intermediate solution. In addition, excessive coloring of the carboxyl group-containing resin (A1) as the final product can be suppressed.

The intermediate body thus obtained has a hydroxyl group produced by reacting the epoxy group in the epoxy compound (a1) with the carboxyl group in the carboxylic acid (a2).

It is preferable that the acid anhydride (a3) contains an acid anhydride. An acid anhydride is a compound having one acid anhydride group.

The acid anhydride may contain an anhydride of a dicarboxylic acid. Acidyl anhydride is, for example, 1,2,3,6-tetrahydrophthalic anhydride, phthalic anhydride, succinic anhydride, methylsuccinic anhydride, maleic anhydride, citraconic anhydride, glutaric anhydride, itaconic anhydride, methyl One or more compounds selected from the group consisting of tetrahydrophthalic anhydride, methylnadic anhydride, hexahydrophthalic anhydride, cyclohexane-1,2,4-tricarboxylic acid-1,2-anhydride, and methylhexahydrophthalic anhydride It may contain. It is particularly preferable that the acid anhydride contains 1,2,3,6-tetrahydro phthalic anhydride. In this case, the insulating property of the cured product of the photosensitive resin composition can be improved while ensuring good developability of the photosensitive resin composition. With respect to the whole acid anhydride, 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 is not limited thereto.

It is preferable that the acid anhydride (a3) contains an acid dianhydride. An acid dianhydride is a compound having two acid anhydride groups. The acid dianhydride may contain an anhydride of tetracarboxylic acid. The dianhydride is, for example, 1,2,4,5-benzenetetracarboxylic dianhydride, benzophenone tetracarboxylic dianhydride, methylcyclohexene tetracarboxylic dianhydride, tetracarboxylic dianhydride, naphthalene-1,4,5, 8-tetracarboxylic dianhydride, ethylene tetracarboxylic dianhydride, 9,9'-bis(3,4-dicarboxyphenyl)fluorene dianhydride, glycerinbisanehydrotrimellitate monoacetate, ethylene glycolbisanhydrotrimelli Tate, 3,3',4,4'-diphenylsulfone tetracarboxylic dianhydride, 1,3,3a,4,5,9b-hexahydro-5 (tetrahydro-2,5-dioxo-3-fu Ranyl) naphtho[1,2-c]furan-1,3-dione, 1,2,3,4-butanetetracarboxylic dianhydride and 3,3',4,4'-biphenyltetracarboxylic acid anhydride It may contain at least one compound selected from the group. It is preferable that the acid dianhydride contains an acid dianhydride having an aromatic ring. In particular, it is preferable that the acid dianhydride contains 3,3',4,4'-biphenyltetracarboxylic dianhydride. In this case, the insulating property of the cured product of the photosensitive resin composition can be improved while ensuring good developability of the photosensitive resin composition. In addition, the transparency of the photosensitive resin composition is improved, and the resolution is thereby improved. With respect to the entire acid dianhydride, the 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 this Not limited.

For reacting the intermediate and the acid anhydride (a3), a known method can be employed. For example, an acid anhydride (a3) is added to the solvent solution of an intermediate, and if necessary, a thermal polymerization inhibitor and a catalyst are further added and mixed with stirring to obtain a reactive solution. By reacting this reactive solution at a temperature of preferably 60 to 150°C, particularly preferably 80 to 120°C by a conventional method, a carboxyl group-containing resin (A1) can be obtained. As the solvent, catalyst, and polymerization inhibitor, suitable ones can be used, and the solvent, catalyst and polymerization inhibitor used in the synthesis of the intermediate may be used as they are.

It is particularly preferred that the catalyst contains triphenylphosphine. That is, it is preferable to react the intermediate and the acid anhydride (a3) in the presence of triphenylphosphine. In this case, the reaction between the secondary hydroxyl group and the acid anhydride (a3) in the intermediate is particularly promoted, and a reaction rate (conversion rate) of 90% or more, 95% or more, 97% or more, or approximately 100% can be achieved. In addition, the occurrence of ion migration in the layer containing the cured product of the photosensitive resin composition is suppressed, and the insulating property of the layer containing the cured product is further improved.

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

The carboxyl group-containing resin (A) may contain a carboxyl group-containing resin that has an aromatic ring and does not have photopolymerization. The carboxyl group-containing resin which has an aromatic ring and does not have photopolymerization contains, for example, a polymer of an ethylenically unsaturated monomer containing an ethylenically unsaturated compound having a carboxyl group. Ethylenically unsaturated compounds having a carboxyl group include acrylic acid, methacrylic acid, ω-carboxy-polycaprolactone (n≒) monoacrylate, 2-(meth)acryloyloxyethylphthalate, and 2-(meth)acryloyl Compounds such as oxyethyl-2-hydroxyethylphthalate may be contained. The ethylenically unsaturated compound having a carboxyl group may also contain a reaction product of a dibasic acid anhydride, such as pentaerythritol triacrylate, pentaerythritol trimethacrylate, and the like. The ethylenically unsaturated monomer may further contain an ethylenically unsaturated compound having no carboxyl group, such as a (meth)acrylic acid ester of a linear or branched aliphatic or alicyclic (however, it may have some unsaturated bonds in the ring). .

The carboxyl group-containing resin (A) may contain only a carboxyl group-containing resin (A1), and may contain a carboxyl group-containing resin other than the carboxyl group-containing resin (A1) and the carboxyl group-containing resin (A1), and the carboxyl group-containing resin (A1) Only other carboxyl group-containing resins may be included. From the viewpoint of obtaining high transparency of the photosensitive resin composition, and from the viewpoint of reducing the dielectric loss tangent of the cured product of the photosensitive resin composition, the carboxyl group-containing resin (A) preferably contains 30% by mass or more of the carboxyl group-containing resin (A1), It is more preferable to contain 60 mass% or more, and it is still more preferable to contain 100 mass %.

The content of the carboxyl group-containing resin (A) is preferably in the range of 5 to 85 mass%, more preferably in the range of 10 to 75 mass%, and in the range of 26 to 60 mass% with respect to the solid content of the photosensitive resin composition. It is more preferable that it is inside, and it is especially preferable that it is in the range of 30-45 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 in the range of 5 to 85% by mass relative to the solid content of the photosensitive resin composition, and 10 to 75 It is more preferable to exist in the range of mass %, it is still more preferable to exist in the range of 26 to 60 mass %, It is especially preferable to exist in the range of 30 to 45 mass %. And the solid content is the total amount of all components excluding volatile elements such as a solvent from the photosensitive resin composition.

It is preferable that the solid content acid value of the carboxyl group-containing resin (A) is 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, even more preferably if the acid value is in the range of 80 to 135 mgKOH/g, and particularly preferably 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) is obtained by polymerizing or crosslinking a carboxylic acid monomer having a polymerizable unsaturated double bond such as acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid, and itaconic acid. 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) improves the thixotropic property of the photosensitive resin composition and improves stability (especially storage stability).

In addition, since the organic filler (B) has a carboxyl group, it improves the developability of the cured product of the photosensitive resin composition, and when the photosensitive resin composition contains a crystalline epoxy compound, the compatibility of the crystalline epoxy compound is溶性) can be improved to prevent crystallization. The content of the carboxyl group of the organic filler (B) is not particularly limited, but the acid value of the organic filler (B) is preferably 1 to 60 mgKOH/g in terms of an acid value obtained by acid-base titration. If the acid value is less than 1 mgKOH/g, there is a concern that the stability of the photosensitive resin composition and developability of the cured product may be deteriorated. If the acid value is greater than 60 mgKOH/g, there is a concern that the moisture resistance reliability of the cured product may decrease. It is more preferable that the acid value of the organic filler (B) is 3 to 40 mgKOH/g.

It is also preferable that the organic filler (B) has a hydroxyl group. When the organic filler (B) has a hydroxyl group, the dispersibility of the organic filler (B) in the photosensitive resin composition is 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 thixotropic property of the photosensitive resin composition is improved with good efficiency. For this reason, the stability of the photosensitive resin composition is further improved. The lower limit of the average primary particle diameter of the organic filler (E1) is not particularly limited, but, for example, it is preferably 0.001 µm or more. The average primary particle diameter of the organic filler (B) is measured as D ₅₀ by a laser diffraction particle size distribution measuring device. It is preferable that the average primary particle diameter of the organic filler (B) is 0.1 micrometers or less. In this case, the stability of the photosensitive resin composition is further improved, and scattering during exposure is suppressed, so that the resolution is further improved.

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

It is preferable that the organic filler (B) contains a rubber component. The rubber component can impart flexibility to the cured product of the photosensitive resin composition. The photosensitive resin composition according to the present embodiment can have high resolution even if it contains a rubber component. The rubber component may be composed of a resin. The rubber component preferably contains at least one polymer selected from the group consisting of crosslinked acrylic rubber, crosslinked NBR, crosslinked MBS, and crosslinked SBR. In this case, the photosensitive resin composition can have high transparency and can improve resolution. Further, the rubber component can more 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 nitrile rubber. MBS is generally a copolymer composed of three components of 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 styrene rubber. As a specific example of the organic filler (B), the article number XER-91-MEK manufactured by JSR Corporation is mentioned. This organic filler is a crosslinked rubber (NBR) having a carboxyl group having an average primary particle diameter of 0.07 µm, and is provided as a methyl ethyl ketone dispersion having a content ratio of 15% by weight of the crosslinked rubber, and the acid value is 10.0 mgKOH/g. Thus, the organic filler (B) may be blended in a dispersion. The rubber component can be formulated as a dispersion. Further, as a specific example of the organic filler (B), in addition to the above, product numbers XER-32, XER-92, etc. manufactured by JSR Corporation can be mentioned. Further, as a dispersion of a crosslinked rubber (SBR) having a carboxyl group and a hydroxyl group, the product number XSK-500 manufactured by JSR Corporation may be mentioned.

The organic filler (B) may contain particle components other than the rubber component. In this case, 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 may contain at least one particle component selected from the group consisting of non-crosslinked styrene acrylic resin fine particles and crosslinked styrene acrylic resin fine particles. As a specific example of the non-crosslinked styrene acrylic resin fine particles, product number FS-201 (average primary particle diameter 0.5 µm) manufactured by Nippon Paint Industrial Co., Ltd. is mentioned. As a specific example of crosslinked styrene/acrylic resin fine particles, product number MG-351 (average primary particle diameter 1.0 μm) manufactured by Nippon Paint Industrial Co., Ltd., and article number BGK-001 (average primary particle diameter 1.0 μm) ). In addition, the organic filler (B) may contain particle components other than the particle components selected from the above-described rubber components, acrylic resin fine particles, and cellulose fine particles. In this case, the organic filler (B) may contain a particle component having a carboxyl group. That is, the particle component having this 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 organic fillers 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 other than the organic filler (B) and the organic filler (B), with respect to the sum of the contents of the organic filler (B) and the organic filler other than the organic filler (B), the organic filler ( It is preferable that the content of B) is 30 mass% or more, and it is more preferable that it is 50 mass% or more.

The content of the organic filler (B) is preferably in the range of 1 to 50 parts by mass with respect to 100 parts by mass of the carboxyl group-containing resin (A). When the content of the organic filler (B) is 1 part by mass or more per 100 parts by mass of the carboxyl group-containing resin (A), good copper plating adhesion of the cured product of the photosensitive resin composition can be obtained. Moreover, 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. Further, when the content of the organic filler (B) falls within the above-described range, the thixotropic property of the photosensitive resin composition increases, and the stability is improved. The content of the organic filler (B) is more preferably in the range of 5 to 30 parts by mass, and still more preferably in the range of 10 to 20 parts by mass with respect to 100 parts by mass 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 contains at least one group selected from the group consisting of an alkoxy group, an acyloxy group, and an alkoxide. The coupling agent (C) may have two or more alkoxy groups, two or more acyloxy groups, and may have two or more alkoxides. Further, the coupling agent (C) may have two or more other functional groups selected from the group consisting of an alkoxy group, an acyloxy group, and an alkoxide. The coupling agent (C) can improve the transparency and thixotropy of the photosensitive resin composition in order to increase the dispersibility of the organic filler (B) and the silica filler (D) in the photosensitive resin composition, whereby the photosensitive resin composition It has excellent resolution and stability (especially storage stability). Two or more functional groups including at least one group selected from the group consisting of an alkoxy group, an acyloxy group and an alkoxide group are at least one atom selected from the group consisting of a silicon atom, an aluminum atom, a titanium atom, and a zirconium atom. It is preferred that they are directly bonded.

When the coupling agent (C) has a silicon atom, examples of the coupling agent (C) are tetraethoxysilane, tetramethoxysilane, vinyl trimethoxysilane, vinyl triethoxysilane, vinylmethyldiethoxysilane, vinyl Methyldimethoxysilane, 2-(3 4epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldie Toxoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, p-styryltrimethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxy Silane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropylmethyldimethoxysilane, 3-aminopropylmethyldiethoxysilane, 3-aminopropyltrimethoxysilane, 3-amino Propyltriethoxysilane, 3-(2-aminoethylamino)propyltriethoxysilane, N,N-dimethyl-3-(trimethoxysilyl)propylamine, 3-triethoxysilyl-N-(1, 3-dimethyl-butylideneden)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltri Ethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, allyltri Ethoxysilane, allyltrimethoxysilane, allylchlorodimethylsilane, 3-chloropropyltrimethoxysilane, 3-chloropropyltriethoxysilane, 3-chloropropyldimethoxymethylsilane, chloromethyltriethoxysilane, chloro Methyltrimethoxysilane, 3-chloropropylmethyldiethoxysilane, 3-isocyanatepropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, bis(triethoxysilylpropyl)tetrasulfide, cyclohexyltrime Toxoxysilane, methyltriethoxysilane, methyltrimethoxysilane, ethyltriethoxysilane, ethyltrimethoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, hexadecyltrimethoxysilane, octadecyltrie Toxoxysilane, octadecyltrimethoxysilane, n-octyltriethoxysilane, n-octyltrimethoxysilane, dodecyltriethoxysilane, dodecyltrimethoxysilane, propyl trimethoxysilane, propyltriethoxy Silane, Benzyltriethoxysilane, methylphenyldimethoxysilane, methylphenylethoxysilane, phenyltriethoxysilane, phenyltrimethoxysilane, p-tolyltrimethoxysilane, 4-vinylphenyltrimethoxysilane, 1-naphthyltrime Toxoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, 11-pentafluorophenoxyundecyltrimethoxysilane, pentafluorophenyltrimethoxysilane, 11-azidoundecyltrimethoxysilane Silane, 2-cyanoethyltriethoxysilane, and vinyltriacetoxysilane.

When the coupling agent (C) has an aluminum atom, examples of the coupling agent (C) include acetoalkoxyaluminum diisopropylate, aluminum diisopropoxymonoethylacetoacetate, and aluminum trisethylacetoacetate.

When the coupling agent (C) has a titanium atom, examples of the coupling agent (C) are isopropyltristearoyl titanate, isopropyltris(dioctylpyrrophosphate) titanate, tetraoctylbis(ditridecyl Phosphate titanate), tetra(2-2-diaryloxymethyl-1-butyl)bis(datridecyl)phosphate titanate, bis(dioctylpyrophosphate)oxyacetate titanate, and bis(dioctylpyro Phosphate) ethylene titanate.

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

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

It is preferable that the coupling agent (C) has a silicon atom. That is, it is preferable that the coupling agent (C) is a silane coupling agent. When the coupling agent (C) has a silicon atom, the reactivity with the silica filler (D) becomes particularly high, and the dispersibility of the silica filler (D) in the photosensitive resin composition is improved more efficiently. For this reason, the transparency and stability of the photosensitive resin composition are further improved. In addition, when the coupling agent (C) has a silicon atom, 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.

It is preferable that the coupling agent (C) has at least one group selected from the group consisting of a methoxy group, an ethoxy group and an acetoxy group. The methoxy group and the ethoxy group are classified as alkoxy groups. In addition, the acetoxy group is classified as an acyloxy group. The coupling agent (C) may have only a methoxy group, may have only an ethoxy group, or may have only an acetoxy group. Further, 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 acetoxy group. Since the coupling agent (C) has at least one group selected from the group consisting of a methoxy group, an ethoxy group and an acetoxy group, a carboxyl group-containing resin (A) having an aromatic ring, an organic filler (B), and a silica filler ( The reactivity of D) and the coupling agent (C) is improved, and aggregation of the organic filler (B) and the silica filler (D) in the photosensitive resin composition becomes more difficult to occur. For this reason, the transparency and stability of the photosensitive resin composition are further improved.

It is preferable that the coupling agent (C) has 2 to 4 functional groups selected from the group consisting of an alkoxy group, an acyloxy group and an alkoxide. The coupling agent (C) may have 2 to 4 alkoxy groups, 2 to 4 acyloxy groups, and may have 2 to 4 alkoxides. For example, the coupling agent (C) may have 2 to 4 methoxy groups, 2 to 4 ethoxy groups, and may have 2 to 4 acetoxy groups. Further, the coupling agent (C) may have 2 to 4 other functional groups selected from the group consisting of an alkoxy group, an acyloxy group, and an alkoxide. When the coupling agent (C) has 2 to 4 functional groups selected from the group consisting of an alkoxy group, an acyloxy group and an alkoxide, the reaction between the organic filler (B) and the coupling agent (C), or the coupling agent (C ) And the silica filler (D) can suppress excessive crosslinking reaction due to the reaction, improve the dispersibility of the organic filler (B) and the silica filler (D) in the photosensitive resin composition, and also suppress gelation. have.

It is preferable that the coupling agent (C) has at least one group selected from the group consisting of an amino group, an epoxy group, a vinyl group, a methacrylic group, a mercapto group, an isocyanate group, and a sulfide group. In this case, it can react with the carboxyl group contained in the carboxyl group-containing resin (A) and the carboxyl group contained in the organic filler (B), and the dispersibility of the organic filler (B) in the photosensitive resin composition becomes more efficient. For this reason, the transparency and stability of the photosensitive resin composition are further improved.

The coupling agent (C) may have an amino group by having an aminoalkyl group. In addition, the coupling agent (C) may have an epoxy group by having a glycidoxy group. When the coupling agent (C) contains a vinyl group, the vinyl group is directly bonded to, for example, a silicon atom. When the coupling agent (C) has an amino group, an epoxy group, or a vinyl group, the reactivity with the carboxyl group contained in the carboxyl group-containing resin (A) and the carboxyl group contained in the organic filler (B) increases, and the organic filler in the photosensitive resin composition The dispersibility of (B) increases more efficiently. It is preferable that the coupling agent (C) has an epoxy group or a vinyl group. In this case, the insulating property of the photosensitive resin composition becomes high, and stability is further improved.

The photosensitive resin composition may further contain a coupling agent other than the coupling agent (C). Coupling agents 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. Coupling agents other than the coupling agent (C) may not have two or more functional groups including at least one group selected from the group consisting of an alkoxy group, an acyloxy group, and an alkoxide. However, from the viewpoint of efficiently obtaining the dispersibility of the organic filler (B) and the silica filler (D), and from the viewpoint of improving the transparency and stability of the photosensitive resin composition, the photosensitive resin composition is a coupling agent other than the coupling agent (C). It may not include. When the photosensitive resin composition contains a coupling agent other than the coupling agent (C) and the coupling agent (C), with respect to the sum of the contents of the coupling agent (C) and the coupling agent other than the coupling agent (C), the coupling agent ( The content of C) 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) in 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 in total of the content of the organic filler (B) and the content of the silica filler (D). When the content of the coupling agent (C) falls within this range, aggregation of the organic filler (B) and the silica filler (D) in the photosensitive resin composition is prevented, and dispersibility is improved. The content of the coupling agent (C) is more preferably in the range of 0.05 to 5 parts by mass with respect to 100 parts by mass in total of the content of the organic filler (B) and the content of the silica filler (D).

The silica filler (D) has an average primary particle diameter 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) is effectively increased. For this reason, the resolution of the photosensitive resin composition is further improved. The average primary particle diameter of the silica filler (D) is measured using a dynamic light scattering method. As for the silica filler (D), it is more preferable that the average primary particle diameter is in the range of 1 to 60 nm, and still more preferably in the range of 1 to 30 nm. In this case, the transparency and resolution of the photosensitive resin composition are further improved.

It is preferable that the silica filler (D) contains silica particles derived from silica sol. In this case, the transparency of the photosensitive resin composition containing the organic filler (B) is further increased, and the resolution of the photosensitive resin composition is further improved. Examples of the silica sol include spherical silica sol and chain silica sol. As a specific example of the silica filler (D), organo silica sol manufactured by Nissan Chemical Industry Co., Ltd.: part numbers MA-ST-M, MA-ST-L, IPA-ST, IPA-ST- ZL, IPA-ST-UP, EG-ST, NPC-ST-30, PGM-ST, DMAC-ST, MEK-ST-40, MIBK-ST, MIBK-ST-L, CHO-ST-M, EAC- ST, 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; NANOCRYL manufactured by Hanse-Chemie: Article numbers XP0396, XP0596, XP0733, XP0746, XP0765, XP0768, XP0953, XP0954, XP1045; NANOPOX manufactured by Hanse-Chemie: Product numbers XP0516, XP0525, XP0314, and the like are exemplified.

The photosensitive resin composition may further contain inorganic fillers other than the silica filler (D). Inorganic fillers other than the silica filler (D) may contain a silica filler whose average primary particle diameter is not within the range of 1 to 150 nm, or may contain inorganic fillers other than the silica filler. Examples of inorganic fillers 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. However, 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 silica filler (D). When the photosensitive resin composition contains inorganic fillers other than the silica filler (D) and the silica filler (D), with respect to the sum of the contents of the inorganic fillers other than the silica filler (D) and the silica filler (D), the silica filler ( It is preferable that the content of D) is 30 mass% or more, and it is more preferable to contain 50 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 with respect to 100 parts by mass of the carboxyl group-containing resin (A). When the content of the silica filler (D) is 5 parts by mass or more, the transparency of the photosensitive resin composition further increases. Moreover, when the content of the silica filler (D) is 200 parts by mass or less, the photosensitive resin composition may have more excellent resolution. Further, when the content of the silica filler (D) falls 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. Further, the surface roughness of the cured product after desmear treatment of the cured product of the photosensitive resin composition can be made smaller. The content of the silica filler (D) is more preferably in the range of 20 to 150 parts by mass, and particularly preferably 40 to 100 parts by mass with respect to 100 parts by mass of the carboxyl group-containing resin (A).

It is preferable that the photosensitive resin composition further contains an unsaturated compound (E) which has at least one ethylenically unsaturated bond per molecule. The unsaturated compound (E) can impart photocurability to the photosensitive resin composition. Examples of the unsaturated compound (E) include monofunctional (meth)acrylates such as 2-hydroxyethyl (meth)acrylate; And diethylene glycol di(meth)acrylate, trimethylolpropanedi(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate , Dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, ε-caprolactone modified pentaerythritol hexaacrylate, tricyclodecane dimethanol di (meth) acrylate, etc. It contains at least one compound selected from the group consisting of (meth)acrylates.

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

It is also preferable that the unsaturated compound (E) contains a trifunctional compound, that is, a compound having three unsaturated bonds in one molecule. In this case, the resolution of the photosensitive resin composition is further improved, and the developability of the photosensitive resin composition by an alkaline aqueous solution is particularly improved. The trifunctional compound is, for example, trimethylolpropane tri(meth)acrylate, EO-modified trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, ethoxylated isocyanuric acid tri( And at least one compound selected from the group consisting of meth)acrylate and ε-caprolactone-modified tris-(2-acryloxyethyl)isocyanurate and ethoxylated glycerin tri(meth)acrylate.

It is also preferable that the unsaturated compound (E) contains a phosphorus-containing compound (phosphorus-containing unsaturated compound). In this case, the flame retardancy of the cured product of the photosensitive resin composition is improved. Phosphorus-containing unsaturated compounds are, for example, 2-methacryloyloxyethyl acid phosphate (as a specific example, light ester P-1M manufactured by Kyoeisha Chemical Co., Ltd., and light ester). P-2M), 2-acryloyloxyethyl acid phosphate (as a specific example, light acrylate P-1A manufactured by Kyoeisha Chemical Co., Ltd.), diphenyl-2-methacryl Royloxyethyl phosphate (as a specific example, product number MR-260 manufactured by Daihachi Industries, Ltd.), and the HFA series manufactured by Showa Polymer Corporation (dipentaerythritol hexa as a specific example) Selected from the group consisting of product numbers HFA-6003, which is an addition reaction product of acrylate and HCA, and HFA-6007, product number HFA-3003, which is an addition reaction product of caprolactone-modified paper pentaerythritol hexaacrylate and HCA, and HFA-6127, etc. It may contain one or more compounds.

The unsaturated compound (E) may contain a prepolymer. The prepolymer may contain, for example, a prepolymer obtained by polymerizing a monomer having an ethylenically unsaturated bond and then adding an ethylenically unsaturated group, and at least one compound selected from the group consisting of oligo(meth)acrylate prepolymers. I can. Oligo (meth) acrylate prepolymers are, for example, epoxy (meth) acrylate, polyester (meth) acrylate, urethane (meth) acrylate, alkyd resin (meth) acrylate, silicone resin (meth) acrylic It may contain at least one component selected from the group consisting of rate and spiran 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 10 to 45% by mass, based on the content of the carboxyl group-containing resin (A). It is more preferable to exist in the range of %, and it is still more preferable to exist in the range of 21 to 40 mass %.

It is preferable that the photosensitive resin composition further contains a photoinitiator (F). The photoinitiator (F) contains, for example, an acylphosphine oxide-based photoinitiator. That is, the photosensitive resin composition contains, for example, an acylphosphine oxide-based photopolymerization initiator. In this case, when exposing the photosensitive resin composition to light, high photosensitivity can be imparted to the photosensitive resin composition. In addition, the occurrence of ion migration in the layer containing the cured product of the photosensitive resin composition is suppressed, and the insulating property of the layer containing the cured product is further improved.

The acylphosphine oxide-based photoinitiator is, for example, monoacylphos, such as 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide and 2,4,6-trimethylbenzoyl-ethyl-phenyl-phosphinate. Pin oxide-based photopolymerization initiator, and bis-(2,6-dichlorobenzoyl)phenylphosphine oxide, bis-(2,6-dichlorobenzoyl)-2,5-dimethylphenylphosphine oxide, bis-(2,6- Dichlorobenzoyl)-4-propylphenylphosphine oxide, bis-(2,6-dichlorobenzoyl)-1-naphthylphosphine oxide, bis-(2,6-dimethoxybenzoyl)phenylphosphine oxide, bis-( 2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide, bis-(2,6-dimethoxybenzoyl)-2,5-dimethylphenylphosphine oxide, bis-(2,4, One selected from the group consisting of bisacylphosphine oxide-based photopolymerization initiators such as 6-trimethylbenzoyl)phenylphosphine oxide and (2,5,6-trimethylbenzoyl)-2,4,4-trimethylpentylphosphine oxide It contains the above ingredients. In particular, it is preferable that the acylphosphine oxide-based photopolymerization initiator contains 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, and the acylphosphine oxide-based photopolymerization initiator is 2,4,6-trimethylbenzoyl-di It may also contain only phenyl-phosphine oxide.

It is preferable that the photoinitiator (F) contains a hydroxyketone system photoinitiator in addition to an acylphosphine oxide system photoinitiator. That is, it is preferable that the photosensitive resin composition contains a hydroxyketone type photoinitiator. In this case, higher photosensitivity can be imparted to the photosensitive resin composition as compared to the case where the hydroxyketone-based photoinitiator is not contained. Thereby, when curing the photosensitive resin composition by exposure, it becomes possible to sufficiently cure from the surface to the core of the coating film formed of the photosensitive resin composition. Examples of the initiation of hydroxyketone photopolymerization are 1-hydroxy-cyclohexyl-phenyl-ketone, phenylglyoxic acid methyl ester, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy -2-Methyl-1-propan-1-one, 2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propionyl)-benzyl]phenyl}-2-methyl-propane 1-one and 2-hydroxy-2-methyl-1-phenyl-propan-1-one.

When the photosensitive resin composition contains an acylphosphine oxide photopolymerization initiator and a hydroxy ketone photopolymerization initiator, the mass ratio of the acylphosphine oxide photopolymerization initiator and the hydroxy ketone photopolymerization initiator is in the range of 1:0.01 to 1:10 It is desirable to be internal. In this case, the curability in the vicinity of the surface of the coating film formed from the photosensitive resin composition and the curability in the core can be improved in a good balance.

It is also preferable that the photoinitiator (F) contains bis(diethylamino)benzophenone. That is, the photosensitive resin composition contains an acylphosphine oxide photopolymerization initiator and bis(diethylamino)benzophenone, or an acylphosphine oxide photopolymerization initiator, a hydroxy ketone photopolymerization initiator and bis(diethylamino)benzophenone It is also preferable to contain. In this case, when developing after partially exposing the coating film formed of the photosensitive resin composition, curing of the unexposed portion is suppressed, so that the resolution becomes particularly high. For this reason, it becomes possible to form a very fine pattern by the hardened|cured material of a photosensitive resin composition. Particularly, when an interlayer insulating layer of a multilayer printed wiring board is prepared with a photosensitive resin composition, and a small diameter hole for a through hole is provided in the interlayer insulating layer by a photolithography method (see Fig. 1), a small diameter hole It becomes possible to form precisely and easily.

When the photosensitive resin composition contains bis(diethylamino)benzophenone and an acylphosphine oxide-based photopolymerization initiator, the content of bis(diethylamino)benzophenone is 0.5 to 20 mass with respect to the acylphosphine oxide-based photopolymerization initiator. It is preferably within the range of %. When the content of bis(diethylamino)benzophenone is 0.5% by mass or more, the resolution becomes particularly high. In addition, when the content of bis(diethylamino)benzophenone is 20% by mass or less, it is difficult for bis(diethylamino)benzophenone to inhibit the electrical insulation of the cured product of the photosensitive resin composition.

The content of the photoinitiator (F) is preferably in the range of 0.1 to 30 mass%, more preferably in the range of 1 to 25 mass% with respect to the content of the carboxyl group-containing resin (A).

It is preferable that the photosensitive resin composition further contains an epoxy compound (G). The epoxy compound (G) can impart thermosetting property to the photosensitive resin composition. It is preferable that the epoxy compound (G) contains a crystalline epoxy resin. Crystalline epoxy resin is an epoxy resin having a melting point. The crystalline epoxy resin can impart thermosetting property to the photosensitive resin composition. Further, the crystalline epoxy resin improves the heat resistance and developability of the cured product.

Crystalline epoxy resin is, for example, 1,3,5-tris (2,3-epoxypropyl)-1,3,5-triazine-2,4,6 (1H,3H,5H)-trione , Hydroquinone type crystalline epoxy resin (as a specific example, product name YDC-1312 manufactured by Shinnittetsu Sumikin Chemical Co., Ltd.), biphenyl type crystalline epoxy resin (as a specific example, Mitsubishi Chemical Corporation) Product name YX-4000 manufactured by Shiki Corporation), diphenyl ether type crystalline epoxy resin (as a specific example, product number YSLV-80DE manufactured by Shinnittetsu Sumikin Chemical Co., Ltd.), bisphenol type crystalline epoxy resin (as a specific example YSLV-80XY manufactured by Shin-Nitetsu Sumikin Chemical Co., Ltd.), tetrakisphenolethane type crystalline epoxy resin (as a specific example, part number GTR-1800 manufactured by Nippon Kayaku Corporation), It is preferable to contain at least one component selected from the group consisting of a bisphenol fluorene type crystalline epoxy resin (a specific example, an epoxy resin having a structure shown in formula (2)).

The crystalline epoxy resin may have two epoxy groups in one molecule. In this case, it is possible to prevent cracks from easily occurring in the cured product while the temperature change is repeated.

It is preferable that the crystalline epoxy resin has an epoxy equivalent of 150 to 300 g/eq. This epoxy equivalent is the gram weight of the crystalline epoxy resin containing 1 gram equivalent of an epoxy group.

As a melting point of a crystalline epoxy resin, 70-180 degreeC is mentioned, for example. In particular, it is preferable that the crystalline epoxy resin contains a crystalline epoxy resin having a melting point of 110°C or less. In this case, developability of the photosensitive resin composition by an alkaline aqueous solution is particularly improved. Crystalline epoxy resins having a melting point of 110°C or less are, for example, biphenyl-type epoxy resins (part number YX4000 manufactured by Mitsubishi Chemical Corporation as a specific example), and biphenyl ether-type epoxy resins (as a specific example, Shinnittetsusumi YSLV-80DE manufactured by Kin Chemical Co., Ltd.), bisphenol type epoxy resin (as a specific example, YSLV-80XY manufactured by Shinnittetsu Sumikin Chemical), bisphenol fluorene type crystalline epoxy resin (formula as a specific example) It contains at least one component selected from the group consisting of (epoxy resin having the structure shown in (2)).

The epoxy compound (G) may contain an epoxy compound other than a crystalline epoxy resin. Epoxy compounds other than the crystalline epoxy resin contain an amorphous epoxy resin. The amorphous epoxy resin is an epoxy resin that does not have a melting point. The amorphous epoxy resin can impart thermosetting property to the photosensitive resin composition. It is preferable that the amorphous epoxy resin has at least two epoxy groups in one molecule.

The amorphous epoxy resin is, for example, a phenolic rock-type epoxy resin (part number EPICLON N-775 manufactured by DIC Corporation as a specific example), a cresol novolak-type epoxy resin (as a specific example, manufactured by DIC Corporation. Part number EPICLON N-695), bisphenol A novolak type epoxy resin (as a specific example, product number EPICLON N-865 manufactured by DIC Corporation), bisphenol A type epoxy resin (as a specific example, manufactured by Mitsubishi Chemical Co., Ltd. Part number jER1001), bisphenol F type epoxy resin (as a specific example, product number jER4004P manufactured by Mitsubishi Chemical Co., Ltd.), bisphenol S type epoxy resin (specific example, product number EPICLON EXA-1514 manufactured by DIC Corporation), bisphenol AD type epoxy resin, biphenyl novolak type epoxy resin (as a specific example, product number NC-3000 manufactured by Nippon Kayaku Co., Ltd.), hydrogenated bisphenol A type epoxy resin (as a specific example, Shinnittetsu Sumikin Chemical Product number ST-4000D manufactured by Co., Ltd.), naphthalene type epoxy resin (as a specific example, product number EPICLON HP-4032, EPICLON HP-4700, EPICLON HP-4770 manufactured by DIC Corporation), tert-butylcatechol type epoxy Resin (as a specific example, part number EPICLON HP-820 manufactured by DIC Corporation), dicyclopentadiene type epoxy resin (as a specific example, part number EPICLON HP-7200 manufactured by DIC), adamantane type epoxy resin (as a specific example ADAMANTATE XE-201 manufactured by Idemitsukosan Co., Ltd.), a special bifunctional epoxy resin (as a specific example, product numbers YL7175-500 manufactured by Mitsubishi Chemical Co., Ltd., and YL7175-1000; Part number EPICLON TSR-960, EPICLON TER-601, EPICLON TSR-250-80BX, EPICLON 1650-75MPX, EPICLON EXA-4850, EPICLON EXA-4816, EPICLON manufactured by DIC Corporation EXA-4822, and EPICLON EXA-9726; YSLV-120TE manufactured by Shinnittetsu Sumikin Chemical Co., Ltd.), rubber-type core-shell polymer-modified bisphenol A-type epoxy resin (as a specific example, product number MX-156 manufactured by Kaneka Corporation), and rubber-type core It is preferable to contain at least one component selected from the group consisting of a shell polymer-modified bisphenol F-type epoxy resin (part number MX-136 manufactured by Kaneka Corporation as a specific example).

The epoxy compound (G) may contain a phosphorus-containing epoxy resin. In this case, the flame retardancy of the cured product of the photosensitive resin composition is improved. Phosphorus-containing epoxy resins include phosphoric acid-modified bisphenol F-type epoxy resins (specific examples, part numbers EPICLON EXA-9726 and EPICLON EXA-9710 manufactured by DIC Corporation), and product numbers manufactured by Shinnittetsu Sumikin Chemical Co., Ltd. Examples include epotohto FX-305.

It is preferable that the epoxy compound (G) contains only a crystalline epoxy resin, or 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, and even more preferably 50% by mass. In this case, 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 in the range of 0.7 to 2.5, with respect to 1 equivalent of carboxyl groups contained in the carboxyl group-containing resin (A), the sum of the equivalents of the epoxy group contained in the epoxy compound (G), 0.7 to It is more preferable to exist in the range of 2.3, and it is still more preferable to exist in the range of 0.7 to 2.0. In addition, when the epoxy compound (G) contains a crystalline epoxy resin, the sum of the equivalents of the epoxy groups contained in the crystalline epoxy resin is in the range of 0.7 to 2.5 with respect to 1 equivalent of the carboxyl groups contained in the carboxyl group-containing resin (A). It is preferably in the range, more preferably in the range of 0.7 to 2.3, and even more preferably in the range of 0.7 to 2.0.

The photosensitive resin composition may contain melamine. In this case, the adhesion between the cured product of the photosensitive resin composition and a metal such as copper increases. For this reason, the photosensitive resin composition is particularly suitable as an insulating material for a printed wiring board. Further, the plating resistance of the cured product of the photosensitive resin composition, that is, the whitening resistance during electroless nickel/plating treatment is improved.

When the photosensitive resin composition contains melamine, the melamine is preferably in the range of 0.1 to 10 mass%, more preferably in the range of 0.5 to 5 mass% with respect 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 the purpose of liquefying or varnishing the photosensitive resin composition, adjusting viscosity, adjusting coating properties, and adjusting film forming properties.

Examples of the organic solvent include linear, branched, secondary or polyhydric alcohols such as ethanol, propyl alcohol, isopropyl alcohol, hexanol, and ethylene glycol; Ketones such as methyl ethyl ketone and cyclohexanone; Aromatic hydrocarbons such as toluene and xylene; Petroleum-based aromatic mixed solvents such as Suwasol series (manufactured by Maruzen Petrochemical Co., Ltd.) and Sorbiso series (manufactured by Exxon Chemical Co., Ltd.); Cellosolves such as cellosolve and butyl cellosolve; Carbitols such as carbitol and butylcarbitol; Propylene glycol alkyl ethers such as propylene glycol methyl ether; Polypropylene glycol alkyl ethers such as dipropylene glycol methyl ether; Acetic acid esters such as ethyl acetate, butyl acetate, cellosolve acetate, and carbitol acetate; And one or more compounds selected from the group consisting of dialkyl glycol ethers.

When the photosensitive resin composition contains an organic solvent, the amount of the organic solvent is preferably adjusted so that the organic solvent evaporates quickly when drying the coating film formed of the photosensitive resin composition, that is, so that the organic solvent does not remain in the dried film. Do. In particular, it is preferable that the organic solvent is in the range of 0 to 99.5 mass%, more preferably in the range of 15 to 60 mass% with respect to the photosensitive resin composition as a whole. In addition, since the preferred ratio of the organic solvent differs depending on the application method or the like, it is preferable that the ratio is appropriately adjusted by the application method.

The photosensitive resin composition may further contain components other than the above-described components, unless departing from the gist of the present invention.

The photosensitive resin composition may further contain a known photopolymerization accelerator, a sensitizer, and the like. For example, the photosensitive resin composition includes benzoin and its alkyl ethers; Acetophenones such as acetophenone and benzyl dimethyl chemical; Anthraquinones such as 2-methylanthraquinone; Thioxanthones such as 2,4-dimethyl thioxanthone, 2,4-diethyl thioxanthone, 2-isopropyl thioxanthone, 4-isopropyl thioxanthone, and 2,4-diisopropyl thioxanthone ; Benzophenones such as benzophenone and 4-benzoyl-4'-methyldiphenyl sulfide; Xanthones such as 2,4-diisopropylxanthone; And α-hydroxyketones such as 2-hydroxy-2-methyl-1-phenyl-propan-1-one; It may contain at least one component selected from the group consisting of compounds containing nitrogen atoms such as 2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-1-propanone. . The photosensitive resin composition, together with the photoinitiator (C), is a known photopolymerization accelerator such as a tertiary amine system such as p-dimethylbenzoic acid ethyl ester, p-dimethylaminobenzoic acid isoamyl ester, and 2-dimethylaminoethylbenzoate. It may contain a sensitizer or the like. If necessary, the photosensitive resin composition may contain at least one of a photopolymerization initiator for exposure to visible light and a photopolymerization initiator for near-infrared exposure. The photosensitive resin composition may contain, together with the photoinitiator (F), a coumarin derivative such as 7-diethylamino-4-methylcoumarin which is a sensitizer for a laser exposure method, a carbocyanine dye, a xanthene dye, and the like.

The photosensitive resin composition includes blocked isocyanates of trilened diisocyanate-based, morpholine diisocyanate-based, isophorone diisocyanate-based and hexamethylene diisocyanate-based blocked isocyanates with caprolactam, oxime, malonic acid ester, and the like; Amino resins such as melamine resin, n-butylated melamine resin, isobutylated melamine resin, butylated urea resin, butylated melamine urea cocondensation resin, and benzoguanamine-based cocondensation resin; Various thermosetting resins other than those described above; UV curable epoxy (meth)acrylate; Resins obtained by adding (meth)acrylic acid to epoxy resins such as bisphenol A type, phenol novolak type, cresol novolak type, and alicyclic type; And one or more resins selected from the group consisting of polymer compounds such as diarylphthalate resins, phenoxy resins, urethane resins, and fluorine resins.

When the photosensitive resin composition contains the epoxy compound (G), the photosensitive resin composition may contain a curing agent for curing the epoxy compound (G). The curing agent is, for example, imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1 -Imidazole derivatives such as cyanoethyl-2-phenylimidazole and 1-(2-cyanoethyl)-2-ethyl-4-methylimidazole; Amines such as dicyandiamide, benzyldimethylamine, 4-(dimethylamino)-N,N-dimethylbenzylamine, 4-methoxy-N,N-dimethylbenzylamine, and 4-methyl-N,N-dimethylbenzylamine compound; Hydrazine compounds such as adipic acid hydrazide and sebacic acid hydrazide; Phosphorus compounds such as triphenylphosphine; Acid anhydride; phenol; Mercaptan; Lewis acid amine complex; And at least one component selected from the group consisting of onium salts. As examples of commercially available products of these ingredients, 2MZ-A, 2MZ-OK, 2PHZ, 2P4BHZ, 2P4MHZ (all brand names of imidazole-based compounds) manufactured by Shikoku Hwaseong Co., Ltd., from San Apro Co., Ltd. Prepared U-CAT3503N, U-CAT3502T (all are trade names of dimethylamine block isocyanate compounds), DBU, DBN, U-CATSA102, and U-CAT5002 (all bicyclic amidine compounds and salts thereof) are mentioned.

The photosensitive resin composition may contain an adhesive imparting agent other than melamine. As the adhesion imparting agent, for example, guanamine, acetoguanamine, benzoguanamine, and 2,4-diamino-6-methacryloyloxyethyl-S-triazine, 2-vinyl-4,6- Diamino-S-triazine, 2-vinyl-4,6-diamino-S-triazine/isocyanuric acid adduct, 2,4-diamino-6-methacryloyloxyethyl-S-tri There are S-triazine derivatives such as azine/isocyanuric acid adducts.

The photosensitive resin composition is a curing accelerator; coloring agent; Copolymers such as silicone and acrylate; Leveling agents; Adhesion imparting agent; Thixotropic agents; Polymerization inhibitors; Antihalation agents; Flame retardant; Antifoaming agent; Antioxidants; Surfactants; And it may contain one or more components selected from the group consisting of a polymer dispersant.

It is preferable that the content of the amine compound in the photosensitive resin composition is as small as possible. In this case, the electrical insulation properties of the layer made of the cured product of the photosensitive resin composition are unlikely to be impaired. Particularly, the amine compound is preferably 8% by mass or less, and more preferably 5% by mass or less with respect to the content of the carboxyl group-containing resin (A).

The photosensitive resin composition can be prepared by mixing the raw materials of the photosensitive resin composition as described above and kneading by a known kneading method using, for example, a 3-roll, mixing grinder, sand mill, or the like. When the raw material of the photosensitive resin composition contains a liquid component, a component having a low viscosity, etc., a portion of the raw material excluding a liquid component and a component having a low viscosity, etc., is first kneaded, and the resulting mixture has a liquid component and viscosity. A photosensitive resin composition can also be prepared by adding and mixing a low component etc. Moreover, the photosensitive resin composition can also be adjusted by stirring mixing of raw materials, stirring dissolution, etc., not by kneading.

In consideration of storage stability and the like, the first agent may be prepared by mixing a part of the component dnk of the photosensitive resin composition, and the second agent may be prepared by mixing the remainder of the component. That is, the photosensitive resin composition may also include a 1st agent and a 2nd agent. In this case, for example, a first agent may be prepared by mixing and dispersing some of the components of the photosensitive resin composition in advance, and a second agent may be prepared by mixing and dispersing the remainder of the components of the photosensitive resin composition. In this case, the required amount of the first agent and the second agent are mixed in a timely manner to prepare a mixed solution, and the mixed solution is cured to obtain a cured product.

The photosensitive resin composition according to the present embodiment is suitable as an electrical insulating material for a printed wiring board. In particular, the photosensitive resin composition is suitable for forming an electrically insulating layer such as a solder resist layer, a plating resist layer, an etching resist layer, and an interlayer insulating layer.

Hereinafter, an example of a method of manufacturing a printed wiring board including an interlayer insulating layer formed of the photosensitive resin composition according to the present embodiment will be described with reference to FIG. 1A to FIG. 1E. In this method, through holes are formed in the interlayer insulating layer by a photolithography method.

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

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

In the dry film method, a dry film containing a photosensitive resin composition is formed on the support by first applying a photosensitive resin composition onto an appropriate support such as a polyester and then drying. Thereby, a dry film with a support body provided with the support body which supports a dry film and a dry film can be obtained. After superimposing the dry film in the dry film with a support on the core material 1, pressure is applied to the dry film and the core material 1, and then the support is peeled from the dry film, thereby removing the dry film from the support. Transfer (轉寫) onto the material (1). Thereby, on the core material 1, the coating 4 made of a dry film is provided.

By exposing the film 4 to light, it is partially photocured as shown in Fig. 1C. To this end, for example, after a negative mask is abutted against the film 4, ultraviolet rays are irradiated to the film 4 through the negative mask. The negative mask includes an exposed portion that transmits ultraviolet rays and a non-exposed portion that shields ultraviolet rays, and the non-exposed portion is provided at a position coincident with the position of the through hole 10. The negative mask is, for example, a photo tool such as a mask film and a dry plate. UV light sources include, for example, chemical lamps, low pressure mercury lamps, medium pressure mercury lamps, high pressure mercury lamps, ultra-high pressure mercury lamps, xenon lamps, metal halide lamps, LEDs, g-line (436 nm), h-line (405 nm), i-line (365 nm) , And a combination of two or more of g-line, h-line and i-line.

And, as the exposure method, a method other than a method of using a negative mask may be employed. For example, the film may be exposed by a direct drawing method in which ultraviolet rays generated from a light source are irradiated only on a portion to be exposed on the film 4. Light sources applied to the direct drawing method are, for example, chemical lamps, low pressure mercury lamps, medium pressure mercury lamps, high pressure mercury lamps, ultra-high pressure mercury lamps, xenon lamps, metal halide lamps, LEDs, g-line (436 nm), h-line (405 nm), i It is selected from the group consisting of a line (365 nm), and a combination of two or more of g-line, h-line, and i-line.

Further, in the dry film method, after the dry film of the dry film with a support is superimposed on the core material 1, the support is not peeled off, and the support is passed through, and ultraviolet rays are irradiated to the film 4 made of the dry film. After (4) is exposed, the support body can also be peeled off from the film|membrane 4 before subsequent development processing.

Subsequently, by performing a development treatment on the film 4, the unexposed portion 5 of the film 4 shown in Fig. 1C is removed, whereby the through hole 10 as shown in Fig. 1D. Install the hole (6) at the location where) is formed. In the developing treatment, an appropriate developer according to the composition of the photosensitive resin composition can be used. The developer is, for example, an alkaline aqueous solution containing at least one of an alkali metal salt and an alkali metal hydroxide, or an organic amine. The alkaline aqueous solution is, for example, sodium carbonate, potassium carbonate, ammonium carbonate, sodium hydrogen chloride, potassium hydrogen carbonate, ammonium hydrogen carbonate, sodium hydroxide, potassium hydroxide, ammonium hydroxide, tetramethylammonium hydroxide and lithium hydroxide. It contains at least one component selected from the group. The solvent in the alkaline aqueous solution may be water alone 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 achieve an improvement in the working environment and a reduction in the burden of waste treatment.

Subsequently, the film 4 is heat-cured. Heating conditions are, for example, within the range of a heating temperature of 120 to 200°C and a heating time of 30 to 150 minutes. When the film 4 is thermally cured in this manner, the strength, hardness, and chemical resistance of the interlayer insulating layer 7 are improved.

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

The thickness of the interlayer insulating layer 7 is not particularly limited, but may be in the range of 10 to 50 µm.

As described above, the interlayer insulating layer 7 made of a cured product of the photosensitive resin composition is provided on the core material 1. On this interlayer insulating layer 7, the second conductor wiring 8 and the hole plating 9 can be provided by a known method such as an additive method. Thereby, as shown in E of FIG. 1, an interlayer insulating layer interposed between the first conductor wiring 3, the second conductor wiring 8, the first conductor wiring 3 and the second conductor wiring 8 ( 7), and a through hole 10 for electrically connecting the first conductor wiring 3 and the second conductor wiring 8 to each other, and a printed wiring board 11 can be obtained. In Fig. 1E, the hole plating 9 has a cylindrical shape covering the inner surface of the hole 6, but even if the hole plating 9 is filled in the entire inner surface of the hole 6 do.

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

First, a core material is prepared. The core material includes, for example, at least one insulating layer and at least one conductor wiring. On the surface of the core material on which the conductor wiring is provided, a film is formed from the photosensitive resin composition. As a method of forming a film, a coating method and a dry film method are exemplified. As the coating method and the dry film method, the same method as in the case of forming the above-described interlayer insulating layer can be adopted. It is partially photocured by exposing the film. As for the exposure method, the same method as in the case of forming the above-described interlayer insulating layer can be employed. Subsequently, development treatment is performed on the film to remove the unexposed portion of the film, whereby the exposed portion of the film remains on the core material. Subsequently, the film on the core material is heated to cause heat curing. As for the developing method and the heating method, the same method as in the case of forming the above-described interlayer insulating layer can be employed. If necessary, the film may be further irradiated with ultraviolet rays either or both before heating and 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, but may be in the range of 10 to 50 µm.

Thereby, a solder resist layer made of a cured product of the photosensitive resin composition is provided on the core material. Thereby, a printed wiring board including a core material including an insulating layer and conductor wiring thereon, and a solder resist layer partially covering the surface of the core material on which the conductor wiring is provided is obtained.

Example

(1) Synthesis of carboxyl group-containing resin having an aromatic ring:

[Synthesis Example A-1]

The carboxyl group-containing resin having an aromatic ring of Synthesis Example A-1 was prepared as follows. In a four-necked flask equipped with a reflux cooler, thermometer, air intake pipe, and stirrer, represented by formula (2), wherein R ₁ to R ₇ in formula (2) are all hydrogen bisphenol fluorene-type epoxy resin (epoxy equivalent 250 g /eq) 250 parts by mass, 60 parts by mass of propylene glycol monomethyl ether acetate, 140 parts by mass of diethylene glycol monoethyl 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 added, A mixture was prepared. This mixture was heated in a flask at a temperature of 115° C. for 12 hours while stirring under air bubbling. Thereby, a solution of the intermediate was prepared.

Next, 58.8 parts by mass of 3,3',4,4'-biphenyltetracarboxylic dianhydride, 60.8 parts by mass of tetrahydrophthalic anhydride, and 38.7 parts by mass of propylene glycol monomethyl ether acetate were added to the solution of the intermediate in the flask. It heated at 115 degreeC for 6 hours, stirring under air bubbling, and it heated at 80 degreeC for 1 hour more. Thereby, a 65 mass% solution of carboxyl group-containing resin A-1 was obtained. The carboxyl group-containing resin A-1 had a weight average molecular weight of 3096 and an acid value of 105 mgKOH/g.

[Synthesis Example A-2]

The carboxyl group-containing resin having an aromatic ring of Synthesis Example A-2 was adjusted as follows. In a 4-neck flask equipped with a reflux cooler, thermometer, air intake pipe and stirrer, biphenyl novolak type epoxy resin (manufactured by Nippon Kayaku Corporation, part number NC-3000-H, epoxy equivalent 288g/ 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 were added to prepare a mixture. This mixture was heated in a flask at a temperature of 115° C. for 12 hours while stirring under air bubbling. Thereby, a solution of the intermediate was prepared.

Next, 91.2 parts by mass of tetrahydrophthalic anhydride and 90 parts by mass of diethylene glycol monoethyl ether acetate were added to the solution of the intermediate in the flask, followed by heating at 90° C. for 4 hours while stirring under air bubbling. Thereby, a 65 mass% solution of carboxyl group-containing resin A-2 was obtained. The carboxyl group-containing resin A-2 had a weight average molecular weight of 8120 and an acid value of 76 mgKOH/g.

(2) Synthesis of carboxyl group-containing resin that does not have an aromatic ring:

[Synthesis Example B-1]

The carboxyl group-containing resin having no aromatic ring of Synthesis Example B-1 was adjusted as follows. In a four-necked flask equipped with a reflux condenser, thermometer, air intake pipe and 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 azobisisobutyronitrile 5 parts by mass was added to prepare a mixture. This mixture was heated in a flask at a temperature of 80° C. for 5 hours under a nitrogen stream to advance the polymerization reaction. Thereby, a copolymer solution having a concentration of 35% was obtained.

Then, to the copolymer solution in the flask, 0.1 parts by mass of hydroquinone, 50 parts by mass of 3,4-epoxycyclohexylethyl acrylate, 47 parts by mass of dipropylene glycol monomethyl ether, and 0.8 parts by mass of dimethylbenzylamine were added, and 110 It heated at °C for 6 hours, and the addition reaction proceeded. Thereby, a 38 mass% solution of carboxyl group-containing resin B-1 was obtained. The carboxyl group-containing resin B-1 had a weight average molecular weight of 61324 and an acid value of 132 mgKOH/g.

(3) Synthesis of carboxyl group-free resin having an aromatic ring:

[Synthesis Example B-2]

The carboxyl group-free resin having an aromatic ring of Synthesis Example B-2 was adjusted as follows. In a four-necked flask equipped with a reflux cooler, thermometer, air intake pipe, and stirrer, represented by formula (2), wherein R ₁ to R ₇ in formula (2) are all hydrogen bisphenol fluorene-type epoxy resin (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 added to prepare a mixture. This mixture was heated in a flask at a temperature of 115° C. for 12 hours while stirring under air bubbling. Thereby, a 65 mass% solution of the carboxyl group-free resin B-2 was obtained.

(4) Preparation of photosensitive resin composition:

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

In addition, the blending amount in the table represents the mass part of the solid content amount of the indicated component. In addition, although not described in the table, methyl ethyl ketone is blended as a diluent in the photosensitive resin composition.

The details of the components shown in the table are as follows.

Dispersion of organic filler A: cross-linked rubber (NBR) having a carboxyl group having an average primary particle diameter of 0.07 μm, manufactured by JSR, part number XER-91-MEK, a methyl ethyl ketone dispersion having a content ratio of 15% by weight of the crosslinked rubber , Acid value 10.0mgKOH/g.

Dispersion of organic filler B: crosslinked rubber (SBR) having a carboxyl group and hydroxyl group having an average primary particle diameter of 0.07㎛, manufactured by JSR Corporation, product number XSK-500, a methylethylketone dispersion having a content ratio of 15% by weight of the crosslinked rubber .

-Coupling agent A: tetraethoxysilane.

-Coupling agent B: methyltrimethoxysilane.

-Coupling agent C: 3-glycidoxypropyltrimethoxysilane.

Coupling agent D: N-(2-amino ethyl)-3-aminopropylmethyldimethoxysilane.

-Coupling agent E: vinyl trimethoxysilane.

Silica filler A: manufactured by Nissan Chemical Industries, Ltd., part number PMA-ST, propylene glycol monomethyl ether acetate dispersed silica sol, solid content concentration 30% by mass, average primary particle diameter 10 to 15 nm.

Silica filler B: manufactured by Nissan Chemical Industries, Ltd., part number MEK-EC-2130Y, silica sol dispersed in methyl ethyl ketone, grade with improved compatibility with epoxy resin, solid content concentration 30 Mass%, average primary particle diameter 10 to 15 nm.

Silica filler C: manufactured by Nissan Chemical Industries, Ltd., part number MEK-AC-2140Z, methyl ethyl ketone dispersed silica sol, grade with improved compatibility with acrylic resin, solid content concentration 40% by mass, average Primary particle diameter 10-15 nm.

Silica filler D: manufactured by Nissan Chemical Industries, Ltd., part number MEK-ST-L, methyl ethyl ketone-dispersed silica sol, solid content concentration 30% by mass, average primary particle diameter 40-50 nm.

Silica filler E: manufactured by Nissan Chemical Industries, Ltd., part number MEK-ST-ZL, methyl ethyl ketone-dispersed silica sol, solid content concentration of 30 mass%, average primary particle diameter of 70 to 100 nm.

Silica filler F: manufactured by Nissan Chemical Industries, Ltd., product number MEK-ST-UP, methyl ethyl ketone dispersed chain silica sol, solid content concentration of 20% by mass, average primary particle diameter of 40 to 100 nm.

Silica filler G: manufactured by Tatsumori Co., Ltd., article number IMSIL A8, crystalline silica, average primary particle diameter of 2 µm.

Unsaturated compound A: tricyclodecanedimethanol diacrylate.

Unsaturated compound B: trimethylolpropane triacrylate.

Unsaturated compound C: a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate, manufactured by Nippon Kayaku Co., Ltd., product number KAYARAD DPHA.

Photoinitiator A: 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, manufactured by BASF, part number Irgacure TPO.

Photopolymerization initiator B: 1-hydroxy-cyclohexyl-phenyl-ketone, manufactured by BASF, part number Irgacure 184.

Photopolymerization initiator C: 4,4'-bis(diethylamino)benzophenone.

Epoxy compound: Bisphenol type crystalline epoxy resin, manufactured by Shinnittetsu Sumikin Chemical Co., Ltd., part number YSLV-80XY, melting point 75 to 85°C, epoxy equivalent 192 g/eq.

Antioxidant: Hindered phenyl antioxidant, manufactured by BASF, part number IRGANOX 1010.

·Surface modifier: manufactured by DIC Corporation, part number Megapack F-477.

(5) Preparation of test piece

Test pieces were prepared as follows using the photosensitive resin composition of each Example and Comparative Example.

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

A glass epoxy copper clad laminate (FR-4 type) provided with a copper foil having a thickness of 17.5 μm was prepared. A comb-shaped electrode having a line width/space width of 50 µm/50 µm as a conductor wiring was formed on this glass epoxy copper clad laminate by a subtractive method, thereby obtaining a core material. The conductor wiring is roughened by dissolving and removing the surface layer portion of the core material having a thickness of about 1 μm in the conductor wiring with an etching agent (organic acid-based micro-etchant manufactured by Meck Co., Ltd., part number CZ-8101). did. A dry film was heated and laminated with a vacuum laminator on the entire surface of the core material. The conditions of the heating lamination are 0.5 MPa, 80 degreeC, and 1 minute. Thereby, a 30 µm-thick film made of a dry film was formed on the core material. To this film, a negative mask having an unexposed portion of a pattern including a circular shape having a diameter of 30 µm, 40 µm, and 50 µm from a film made of polyethylene terephthalate was directly abutted to the film through the negative mask at 250 mJ. UV rays were irradiated under the conditions of /cm ² . And after exposure, before development, the film made of polyethylene terephthalate was peeled from the dry film (coating). Development treatment was performed on the film after exposure. During the development treatment, a 30° C. 1% Na ₂ CO ₃ aqueous solution was sprayed onto the film for 90 seconds at an injection pressure of 0.2 MPa. Subsequently, the film was washed by spraying pure water at an injection pressure of 0.2 MPa for 90 seconds. Thereby, the unexposed part of the film was removed to form a hole. Subsequently, the film was heated at 180° C. for 60 minutes, and then the film was irradiated with ultraviolet rays under conditions of 1000 mJ/cm ² . As a result, a layer made of a cured product of the photosensitive resin composition (also referred to as a cured product of a dry film) was 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 after filtering with a 300 mesh filter was measured by MT3300EXII manufactured by Micro Track Bell Co., Ltd. In Examples 1 to 18 and Comparative Examples 3, and 5, the particle diameter measured as D ₅₀ was 1 μm or less, and the maximum particle diameter was 10 μm or less by a laser diffraction scattering particle size distribution measuring device of the photosensitive resin composition. . In Comparative Examples 1, 2, 4, and 6, the particle diameter measured as D ₅₀ was larger than 1 μm and the maximum particle diameter was larger than 10 μm by the laser diffraction scattering type particle size distribution measuring device of the photosensitive resin composition.

(6-2) Transparency

For each Example and Comparative Example, the photosensitive resin composition was observed by visual observation, and the result was evaluated as follows.

A: No turbidity was observed, and transparency was high.

B: Some turbidity is observed, but there is transparency.

C: Cloudiness is observed, but there is some transparency.

D: Cloudiness is observed, and there is no transparency.

(6-3) stability

With respect to each of the Examples and Comparative Examples, after storing the photosensitive resin composition at 25°C, the photosensitive resin composition was observed, and the results were evaluated as follows.

A: After storage at 25°C for 4 weeks, separation of components did not occur.

B: After storage at 25°C for 3 weeks, separation of components did not occur, but after storage at 25°C for 4 weeks, separation of components occurred.

C: After storage at 25°C for 2 weeks, separation of components did not occur, but after storage at 25°C for 3 weeks, separation of components occurred.

D: After storage at 25°C for 2 weeks, separation of components occurred.

(6-4) Developability

For each of the Examples and Comparative Examples, in the process of producing the test piece, the unexposed portion of the film after the development treatment was observed, and the results were evaluated as follows.

A: All of the film has been removed.

B: A part of the film remained on the core material.

C: It could not be developed.

About Comparative Example 5 in which the evaluation of developability is C, evaluations of the following (6-5) to (6-11) were not performed. In addition, about Example 17 and Comparative Example 6 in which the evaluation of developability is B, in the evaluation test of roughness after desmearing of the following (6-6), all the coatings remaining on the non-exposed portion on the core material were removed.

(6-5) openness

For Examples 1 to 18 and Comparative Examples 1 to 4 and 6, the openings formed in the layer made of the cured product in the test piece were observed, and the results were evaluated as follows.

A: An opening with a diameter of 30 µm is formed.

B: An opening having a diameter of 35 µm is formed, but an opening having a diameter of 30 µm is not formed.

C: An opening having a diameter of 40 µm is formed, but an opening having a diameter of 35 µm is not formed.

D: An opening having a diameter of 50 µm is formed, but an opening having a diameter of 40 µm is not formed.

E: No openings having a diameter of 50 µm are formed.

(6-6) Roughness after desmear

In Examples 1 to 18 and Comparative Examples 1 to 4 and 6, the surface of the layer made of the cured product in the test piece was subjected to a desmear treatment as follows based on a known desmear treatment method. A commercially available swelling liquid (Swelling Dip Securiganth P, manufactured by Atotech Japan Co., Ltd.) is used as a swelling liquid for desmear, and the surface of the layer made of a cured product is at 70°C for 15 The swelling treatment was performed for a minute, and the surface of the layer made of the cured product was swollen. The surface of the layer made of the swollen cured product was washed with hot water. Next, using a commercially available oxidizing agent containing potassium permanganate (manufactured by Atotech Japan Co., Ltd., Concentrate Compact CP) as a desmear solution, roughening treatment at 70°C for 10 minutes was performed on the surface of the layer made of the cured product. And roughened the surface of the layer made of the cured product. The surface of the layer consisting of the harmonized cured product was washed with hot water. Next, using a neutralizing liquid (manufactured by Atotech Japan Co., Ltd., Reduction Solution Securigans P), the residue of the desmear liquid on the surface of the layer made of the cured product was removed at 40°C for 5 minutes. After that, the surface of the layer made of the cured product was washed with water. The surface roughness Ra of the surface of the layer made of the cured product roughened by the desmear treatment was measured using a laser microscope, and the roughness after desmearing was evaluated as follows.

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 Examples 1 to 18 and Comparative Examples 1 to 4 and 6, electroless using a commercially available chemical solution was applied to the layer made of the cured product of the test piece after desmear treatment in the evaluation test of (6-6). Copper plating treatment was performed, and initial wiring was formed. The test piece on which the initial wiring was formed was heated at 150°C for 1 hour. Next, an electrolytic copper plating treatment was performed under a current density of ² A/dm ² using a commercially available chemical solution, and copper having a thickness of 33 µm was directly deposited on the initial wiring. The test piece in which copper was deposited was heated at 180° C. for 30 minutes to form a copper plating layer. The adhesion between the copper plating layer and the layer formed of the cured product on the test piece was evaluated as follows. And, when heating both after the electroless copper plating treatment and after the electrolytic copper plating treatment, for a test piece in which a blister is not observed on the test piece, a peel between the copper plating layer and the layer made of a cured product. ) The strength was measured according to JIS-C6481.

A: The peel strength of the copper plating layer is 0.4 kN/m or more.

B: The peel strength of the copper plating layer is 0.3 kN/m or more and less than 0.4 kN/m.

C: The peel strength of the copper plating layer is less than 0.3 kN/m.

D: At the time of heating after the electroless copper plating treatment or at the time of heating after the electrolytic copper plating treatment, blisters occurred.

(6-8) Insulation

While applying a bias voltage of DC 30V to the conductor wiring (comb electrode) in the test pieces of Examples 1 to 18 and Comparative Examples 1 to 4 and 6, the test piece was exposed under a test atmosphere of 130°C and 85%RH for 100 hours. did. The electrical resistance value between the comb-shaped electrodes of the layer made of the cured product under this test atmosphere was constantly measured, and the result was evaluated as follows.

A: From the start of the test to the lapse of 100 hours, the electrical resistance value was always maintained at 10 ⁶ Ω or more.

B: From the start of the test to 85 hours, the electrical resistance value always maintained 10 ⁶ Ω or more, but the electrical resistance value became less than 10 ⁶ Ω before 100 hours from the start of the test.

C: The electrical resistance value always maintained 10 ⁶ Ω or more from the start of the test until 70 hours elapsed, but the electrical resistance value became less than 10 ⁶ Ω before 85 hours elapsed from the start of the test.

D: The electrical resistance value became less than 10 ⁶ Ω before 70 hours elapsed from the start of the test.

(6-9) Coefficient of thermal expansion

In the evaluation test of the coefficient of thermal expansion, a test piece was produced as follows using the photosensitive resin compositions of Examples 1 to 18 and Comparative Examples 1 to 4 and 6.

The photosensitive resin composition was applied on a polyethylene terephthalate film with an applicator and then dried by heating at 95° C. for 25 minutes to form a dry film having a thickness of 30 μm on the film. This dry film was laminated by heating with a vacuum laminator on the entire surface of a Teflon (registered trademark) film. The conditions of the heating lamination are 0.5 MPa, 80 degreeC, and 1 minute. Thereby, a 30 µm-thick film made of a dry film was formed on the Teflon (registered trademark) film. To this film, a mask having a rectangular exposed portion of 3 mm x 15 mm was directly abutted on a polyethylene terephthalate film, and ultraviolet rays were irradiated to the film through the mask under conditions of 250 mJ/cm ² . And after exposure, before development, the film made of polyethylene terephthalate was peeled from the dry film (coating). Development treatment was performed on the film after exposure. During the development treatment, a 30° C. 1% Na ₂ CO ₃ aqueous solution was sprayed onto the film for 90 seconds at an injection pressure of 0.2 MPa. Subsequently, the film was washed by spraying pure water at an injection pressure of 0.2 MPa for 90 seconds. Subsequently, the film was heated at 180°C for 60 minutes, and then the film was irradiated with ultraviolet rays under conditions of 1000 mJ/cm ² . Thereby, a cured product of the photosensitive resin composition was formed on a film made of Teflon (registered trademark). This cured product was peeled off from a Teflon (registered trademark) film to obtain a test piece.

Using a TMA testing device (manufactured by Thermoplus EVOII TMA8310, Inc.), under the conditions of a temperature range of 25 to 250°C, 10°C/min, and a load of 5 g, test pieces at 30 to 150°C at the second cycle The coefficient of thermal expansion (CTE) was measured. The results were evaluated as follows.

A: CTE is less than 60 ppm/°C.

B: CTE is 60 ppm/°C or more and less than 65 ppm/°C.

C: CTE is not less than 65 ppm/°C and less than 70 ppm/°C.

D: CTE is 70 ppm/°C or more.

(6-10) glass transition point

In the evaluation test of the glass transition point, using the photosensitive resin compositions of Examples 1 to 18 and Comparative Examples 1 to 4 and 6, a test piece was prepared in the same manner as in (6-9), and a test piece was obtained.

Using a TMA test apparatus (manufactured by Thermoplus EVOII TMA8310, Inc.), measurements were performed 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, and from the measurement result of the second cycle The glass transition point (Tg) of the test piece was determined. The results were evaluated as follows.

A: Tg is 160°C or higher.

B: Tg is 145°C or more and less than 160°C.

C: Tg is 130°C or more and less than 145°C.

D: Tg is less than 130 degreeC.

(6-11) Genetic loss tangent

In the evaluation test of the dielectric loss tangent, test pieces were prepared as follows using the photosensitive resin compositions of Examples 1 to 18 and Comparative Examples 1 to 4 and 6.

The photosensitive resin composition was applied on a polyethylene terephthalate film with an applicator, and then dried by heating at 95° C. for 25 minutes to form a dry film having a thickness of 50 μm on the film. This dry film was laminated by heating with a vacuum laminator on the entire surface of a Teflon (registered trademark) film. The conditions of the heating lamination are 0.5 MPa, 80 degreeC, and 1 minute. Thereby, a 50 µm-thick film made of a dry film was formed on the Teflon (registered trademark) film. The film was irradiated with ultraviolet rays under conditions of 250 mJ/cm ^{2 to} the film through the mask in a state where a mask having a rectangular exposed portion of 3 mm x 85 mm was directly abutted on a polyethylene terephthalate film. And after exposure, before development, the film made of polyethylene terephthalate was peeled from the dry film (coating). Development treatment was performed on the film after exposure. During the development treatment, a 1% Na ₂ CO ₃ aqueous solution was sprayed onto the film at 30°C for 90 seconds at an injection pressure of 0.2 MPa. Subsequently, the film was washed by spraying pure water at an injection pressure of 0.2 MPa for 90 seconds. Subsequently, after heating the film at 180° C. for 60 minutes, the film was irradiated with ultraviolet rays under conditions of 1000 mJ/cm ² . Thereby, a cured product of the photosensitive resin composition was formed on a film made of Teflon (registered trademark). This cured product was peeled off from a Teflon (registered trademark) film to obtain a test piece.

The dielectric loss tangent of the test piece at a frequency of 1 GHz was measured by a cavity resonance method using a dielectric constant measuring device (manufactured by ADMS01O). The results were evaluated as follows.

A: tan δ is less than 0.020.

B: tan delta is 0.020 or more and less than 0.025.

C: tan delta is 0.025 or more and less than 0.030.

D: tan delta is 0.030 or more.

[Table 1]

[Table 2]

[Table 3]

As revealed from the above-described embodiment, the photosensitive resin composition of the first aspect of the present invention is a photosensitive resin composition having photocurability, and has a carboxyl group-containing resin (A) having an aromatic ring, and an average primary particle diameter It is 1 μm or less and has at least one atom selected from the group consisting of an organic filler (B) having a carboxyl group, a silicon atom, an aluminum atom, a titanium atom, and a zirconium atom, and two or more functional groups, and the functional group, A coupling agent (C) containing at least one group selected from the group consisting of an alkoxy group, an acyloxy group and an alkoxide, and a silica filler (D) having an average primary particle diameter in the range of 1 to 150 nm are contained.

According to the first aspect, a cured product having high copper plating adhesion and low roughness after desmearing can be formed, and a photosensitive resin composition having excellent resolution can be obtained.

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

According to the second aspect, the dispersibility of the silica filler (D) in the photosensitive resin composition is improved with good efficiency, and the transparency and stability of the photosensitive resin composition are improved. The glass transition point of the cured product of the photosensitive resin composition can be increased and the coefficient of thermal expansion can be reduced.

In the third solar photosensitive resin composition according to the present invention, 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 is increased, and the resolution of the photosensitive resin composition is improved.

In the fourth solar photosensitive resin composition according to the present invention, in any one of the first to third aspects, the silica filler (D) has an average primary particle diameter in the range of 1 to 60 nm.

According to the fourth aspect, the transparency and resolution of the photosensitive resin composition are improved. In the fifth solar photosensitive resin composition according to the present invention, in any one of the first to fourth aspects, the content of the organic filler (B) is based on 100 parts by mass of the content of the carboxyl group-containing resin (A), It is within the range of 1 to 50 parts by mass.

According to the fifth aspect, good copper plating adhesion of the cured product of the photosensitive resin composition can be obtained. Moreover, excellent resolution of the photosensitive resin composition can be obtained. In addition, thixotropy of the photosensitive resin composition is increased, and stability is improved.

In the sixth solar photosensitive resin composition according to the present invention, in any one of the first to fifth aspects, the content of the silica filler (D) is based on 100 parts by mass of the content of the carboxyl group-containing resin (A), It is in the range of 5 to 200 parts by mass.

According to the sixth aspect, the transparency of the photosensitive resin composition becomes high, and the photosensitive resin composition can have excellent resolution. In addition, it is possible to increase the glass transition point of the cured product of the photosensitive resin composition and to reduce the thermal expansion coefficient and the dielectric loss tangent. Further, the surface roughness of the cured product after desmear treatment of the cured product of the photosensitive resin composition can be made smaller.

In the seventh solar photosensitive resin composition according to the present invention, in any one of the first to sixth aspects, the carboxyl group-containing resin (A) contains a carboxyl group-containing resin having an ethylenically unsaturated group.

According to the seventh aspect, photocurability can be imparted to the photosensitive resin composition.

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

According to the eighth aspect, aggregation of the organic filler (B) and the silica filler (D) in the photosensitive resin composition is prevented, and the dispersibility is improved.

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

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

In the tenth solar photosensitive resin composition according to the present invention, in any one of the first to ninth aspects, 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 the eleventh solar photosensitive resin composition according to the present invention, in the tenth aspect, the rubber component contains at least one polymer selected from the group consisting of crosslinked acrylic rubber, crosslinked NBR, crosslinked MBS, and crosslinked SBR.

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

In the twelfth solar photosensitive resin composition according to the present invention, in any one of the first to eleventh aspects, the carboxyl group-containing resin (A) contains a carboxyl group-containing resin having a benzene ring.

According to the twelfth aspect, the transparency of the photosensitive resin composition becomes high, and the photosensitive resin composition has excellent resolution.

In the thirteenth solar photosensitive resin composition according to the present invention, in any one of the first to twelve aspects, the carboxyl group-containing resin (A) contains a copolymer obtained by reaction of a polyalcohol resin and an acid dianhydride. .

According to the thirteenth aspect, it is possible to impart high alkali developability to the photosensitive resin composition and provide high heat resistance and insulation properties to the cured product of the photosensitive resin composition.

In the fourteenth solar photosensitive resin composition according to the present invention, in the thirteenth aspect, the acid dianhydride contains an acid dianhydride having an aromatic ring.

According to the fourteenth aspect, it is possible to impart high alkali developability to the photosensitive resin composition, and to impart high heat resistance and insulation properties to the cured product of the photosensitive resin composition.

In the fifteenth solar photosensitive resin composition according to the present invention, in any one of the first to fourteenth aspects, the carboxyl group-containing resin (A) is a carboxyl group-containing resin having at least one of a biphenyl skeleton and a bisphenol fluorene skeleton. Includes.

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

The sixteenth solar photosensitive resin composition according to the present invention, in any one of the first to fifteenth aspects, comprises an unsaturated compound (E) having at least one ethylenically unsaturated bond per molecule, and a photopolymerization initiator (F). It contains more.

According to the 16th aspect, high photosensitivity can be imparted to the photosensitive resin composition. Further, generation of ion migration in the layer containing the cured product of the photosensitive resin composition is suppressed, and the insulating property of the layer containing the cured product is improved.

In the seventeenth solar photosensitive resin composition according to the present invention, in the sixteenth aspect, the unsaturated compound (E) is a group consisting of trimethylolpropane tri(meth)acrylate and tricyclodecanedimethanoldi(meth)acrylate At least one compound selected from is included.

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

The eighteenth solar photosensitive resin composition according to the present invention further contains an epoxy compound (G) in any one of the first to seventeenth aspects.

According to the 18th aspect, thermosetting can be imparted to the photosensitive resin composition.

The nineteenth solar dry film according to the present invention contains the photosensitive resin composition of any one of the first to eighteenth aspects.

According to the 19th aspect, a cured product having high copper plating adhesion and low roughness after desmearing can be formed, and a dry film excellent in resolution can be obtained.

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

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

The 21st solar printed wiring board which concerns on this invention is provided with the soldering resist layer containing the photosensitive resin composition hardened|cured material of any one of 1st-13th aspect.

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 desmearing.

Claims (21)

As a photosensitive resin composition having photocurability,
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,
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 is at least one selected from the group consisting of an alkoxy group, an acyloxy group and an alkoxide A coupling agent (C) containing a group of, and
It contains a silica filler (D) having an average particle diameter in the range of 1 to 70 nm as measured using the dynamic light scattering method,
The coupling agent (C) has at least one group selected from the group consisting of an amino group, an epoxy group, a vinyl group, a methacrylic group, a mercapto group, an isocyanate group and a sulfide group,
Photosensitive resin composition. The method of claim 1,
The coupling agent (C) has a silicon atom, the photosensitive resin composition. The method according to claim 1 or 2,
The silica filler (D) is measured using a dynamic light scattering method. The photosensitive resin composition in which the average particle diameter is in the range of 1 to 60 nm. The method according to claim 1 or 2,
The photosensitive resin composition, wherein the content of the organic filler (B) is in the range of 1 to 50 parts by mass with respect to 100 parts by mass of the carboxyl group-containing resin (A). The method according to claim 1 or 2,
The content of the silica filler (D) is in the range of 5 to 200 parts by mass with respect to 100 parts by mass of the carboxyl group-containing resin (A). The method according to claim 1 or 2,
The photosensitive resin composition, wherein the carboxyl group-containing resin (A) contains a carboxyl group-containing resin having an ethylenically unsaturated group. The method according to claim 1 or 2,
The content of the coupling agent (C) is in a range of 0.01 to 10 parts by mass with respect to 100 parts by mass of the total of the content of the organic filler (B) and the content of the silica filler (D). The method according to claim 1 or 2,
The organic filler (B) contains a rubber component, photosensitive resin composition. The method of claim 8,
The rubber component comprises at least one polymer selected from the group consisting of crosslinked acrylic rubber, crosslinked NBR, crosslinked MBS, and crosslinked SBR. The method according to claim 1 or 2,
The said carboxyl group-containing resin (A) contains a carboxyl group-containing resin which has a benzene ring, and the photosensitive resin composition. The method according to claim 1 or 2,
The said carboxyl group-containing resin (A) contains a copolymer obtained by reaction of a polyalcohol resin and an acid dianhydride, The photosensitive resin composition. The method of claim 11,
The acid dianhydride contains an acid dianhydride having an aromatic ring, photosensitive resin composition. The method according to claim 1 or 2,
The photosensitive resin composition, wherein the carboxyl group-containing resin (A) contains a carboxyl group-containing resin having at least one of a biphenyl skeleton and a bisphenol fluorene skeleton. The method according to claim 1 or 2,
An unsaturated compound (E) having at least one ethylenically unsaturated bond per molecule, and
A photosensitive resin composition further containing a photoinitiator (F). The method of claim 14,
The unsaturated compound (E) contains at least one compound selected from the group consisting of trimethylolpropane tri(meth)acrylate and tricyclodecanedimethanoldi(meth)acrylate. The method according to claim 1 or 2,
The photosensitive resin composition further containing an epoxy compound (G). A dry film containing the photosensitive resin composition according to claim 1 or 2. A printed wiring board comprising an interlayer insulating layer comprising a cured product of the photosensitive resin composition according to claim 1 or 2. A printed wiring board comprising a solder resist layer comprising a cured product of the photosensitive resin composition according to claim 1 or 2. As a method for producing the photosensitive resin composition according to claim 1 or 2,
Mixing the carboxyl group-containing resin (A), the organic filler (B), the coupling agent (C), and the silica filler (D),
At least a part of the silica filler (D) is derived from silica,
A method for producing a photosensitive resin composition. delete

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