JPWO2018225441A1 - 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 capable of forming a cured product having high copper plating adhesion and having excellent resolution. The photosensitive resin composition according to the present invention has photocurability. The photosensitive resin composition comprises a carboxyl group-containing resin (A) having an aromatic ring, an organic filler (B) having an average primary particle diameter of 1 μm or less and a carboxyl group, a silicon atom, an aluminum atom, a titanium atom, And at least one atom selected from the group consisting of and zirconium atoms, and 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 It contains a coupling agent (C) and a silica filler (D) whose average primary particle diameter is in the range of 1 to 150 nm.

Description

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

  Conventionally, for the production of printed wiring boards, various electrically insulating resin compositions are used 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. It is done.

  In recent years, with the demand for higher performance, smaller size, and thinner electronic devices such as communication devices and personal computers, fine through holes and opening patterns are formed in an electrically insulating layer formed from such a resin composition. For example, a photosensitive resin composition is used as a resin composition for forming an electrically insulating layer, because it is necessary to form an electrical insulating layer.

  For example, Patent Document 1 discloses a carboxyl group-containing resin having a weight average molecular weight of 2000 to 40000 and an acid value of 50 to 200 mg KOH / g, which is obtained by reacting (A) a diol compound and a polyvalent carboxylic acid. B) A photosensitive resin composition for an insulating film comprising an unsaturated compound containing at least one or more photopolymerizable ethylenic unsaturated bonds in one molecule, (C) an epoxy compound, and (D) a photopolymerization initiator It is described that the adhesion to a plated metal can be improved by adding a rubber component to the photosensitive resin composition for an insulating film.

  However, in the photosensitive resin composition for insulating films described in Patent Document 1, although the adhesion to the plating metal can be improved to some extent, the cured product of the photosensitive resin composition for insulating films is subjected to a desmearing treatment. The surface roughness of the cured product can not be reduced, and good high frequency characteristics can not be obtained. Further, by adding a rubber component, in the development processing with an aqueous solution containing at least one of an alkali metal salt and an alkali metal hydroxide, the resolution becomes low and a fine through hole or an opening pattern can not be formed. There is a fear. It is not easy to obtain a photosensitive resin composition which has high copper plating adhesion and can form a cured product having low roughness after desmearing and which is excellent in resolution.

Patent No. 4508929

  An object of the present invention is to provide a photosensitive resin composition having high adhesion to copper plating and capable of forming a cured product having low roughness after desmearing and having excellent resolution, and the photosensitive resin composition A printed wiring board comprising a dry film, an interlayer insulating layer comprising a cured product of the photosensitive resin composition, and a printed wiring board comprising a solder resist layer comprising 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, and a carboxyl group-containing resin (A) having an aromatic ring and having an average primary particle diameter of 1 μm or less. And an organic filler (B) having a carboxyl group, and 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, 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 contains.

  The dry film which concerns on one Embodiment of this invention contains the said photosensitive resin composition.

  The 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 including a cured product of the photosensitive resin composition.

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

  The present invention relates to a photosensitive resin composition, a dry film, and a printed wiring board, and more specifically, an electrically insulating layer such as a solder resist layer, a plating resist layer, an etching resist layer, and an interlayer insulating layer on a printed wiring board. Photosensitive resin composition suitable for forming a photosensitive resin composition, a dry film containing the photosensitive resin composition, a printed wiring board having an interlayer insulating layer containing a cured product of the photosensitive resin composition, and the photosensitive resin composition Printed circuit board provided with a solder resist layer containing a cured product of

  A mode for carrying out the present invention will be described. In the following description, "(meth) acrylic" means at least one of "acrylic" and "methacrylic". 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 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, and a carboxyl group, a silicon atom, and aluminum Coupling agent (C) having at least one atom selected from the group consisting of atoms, titanium atoms, and zirconium atoms, and two or more functional groups, and the average primary particle diameter is in the range of 1 to 150 nm And a silica filler (D). The functional group includes 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, 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). Despite containing the organic filler (B), the resin composition has high transparency. Therefore, the resolution improves. In general, when a filler is added to the photosensitive resin composition, the photosensitive resin composition becomes hazy and the transparency is lowered. When the transparency of the photosensitive resin composition is low, light is likely to be scattered when the photosensitive resin composition is exposed, and good resolution can not be obtained. However, 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). Can have high transparency. For this reason, the resolution of the photosensitive resin composition is improved, and fine through holes, opening patterns and the like can be formed in the layer made of the cured product of the photosensitive resin composition. In addition, 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 with low roughness after desmearing. The printed wiring board provided with the layer which consists of this hardened | cured material can have the outstanding high frequency characteristic by reducing the roughness after desmear of hardened | cured material. Furthermore, when a photosensitive resin composition contains a silica filler (D), while raising the glass transition point of the hardened | cured material of the photosensitive resin composition, a thermal expansion coefficient can be reduced. For this reason, since the layer which consists of a hardened | cured material of the photosensitive resin composition is hard to be warped even if the stress by a heat | fever is added, and excellent also in thermal cycle crack resistance, it can be used for the printed wiring board thinned. Moreover, the dielectric loss tangent of the hardened | cured material of the photosensitive resin composition can be reduced because a photosensitive resin composition contains a silica filler (D). For this reason, the high frequency transmission performance of the printed wiring board provided with the layer which consists of a hardened | cured material of the photosensitive resin composition can be improved. Moreover, in the present embodiment, the photosensitive resin composition contains the carboxyl group-containing resin (A), the organic filler (B), the coupling agent (C), and the silica filler (D). The filler (D) interacts with or bonds to the carboxyl group of the carboxyl group-containing resin (A) and the carboxyl group of the organic filler (B) through the coupling agent (C) to form a composite or It is considered to be hybridizing. For this reason, the glass transition point of the hardened | cured material of the photosensitive resin composition further increases, and a thermal expansion coefficient and a dielectric loss tangent are further reduced.

  The photosensitive resin composition has photocurability. Since the photosensitive resin composition has photocurability, the photosensitive resin composition can be irradiated with light to cure the photosensitive resin composition. The photocurability of the photosensitive resin composition is imparted, for example, by the carboxyl group-containing resin (A) having a photopolymerizable unsaturated group. Moreover, the photocurability of the photosensitive resin composition is also provided that the photosensitive resin composition contains an unsaturated compound (E) as described later.

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

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

  The carboxyl group-containing resin (A) preferably contains a resin obtained by the reaction of a polyalcohol resin and at least one compound selected from the group consisting of a polyvalent carboxylic acid and an acid anhydride thereof. In this case, the polyalcohol resin preferably has an aromatic ring, and it is also preferable that at least one compound selected from the group consisting of polyvalent carboxylic acids and their anhydrides have an aromatic ring. More preferably, the carboxyl group-containing resin (A) contains a copolymer obtained by the reaction of a polyalcohol resin and an acid dianhydride. In this case, the polyalcohol resin preferably 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 the reaction of a polyalcohol resin and an acid dianhydride, the photosensitive resin composition is provided with high alkali developability and the photosensitive resin composition It is possible to impart high heat resistance and insulation to the cured product.

  The carboxyl group-containing resin (A) preferably contains a carboxyl group-containing resin having an ethylenically unsaturated group. When 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 provided to the photosensitive resin composition containing carboxyl group-containing resin (A).

  The carboxyl group-containing resin having an ethylenically unsaturated group is, for example, 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), It contains a resin (referred to as a first resin (g)) which is a reaction product with at least one compound (g3) selected from the group of polyvalent carboxylic acids and their anhydrides. The first resin (g) has an aromatic ring derived from at least one of the epoxy compound (g1), the ethylenically unsaturated compound (g2), and the compound (g3). The first resin (g) is, for example, an intermediate having a hydroxyl group obtained by reacting an epoxy group in the epoxy compound (g1) and a carboxyl group in the ethylenically unsaturated compound (g2) with a compound (g3) Obtained by adding). The epoxy compound (g1) can contain an appropriate epoxy resin such as a cresol novolac epoxy resin or a phenol novolac epoxy resin. The epoxy compound (g1) preferably 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 further does not have an epoxy group such as 2- (meth) acryloyloxyethyl phthalate Compound (h2) is contained. The ethylenically unsaturated compound (g2) preferably contains at least one of acrylic acid and methacrylic acid. The compound (g3) contains one or more compounds selected from the group consisting of polyvalent carboxylic acids such as phthalic acid, tetrahydrophthalic acid and methyltetrahydrophthalic acid, and anhydrides of these polyvalent carboxylic acids, for example. . The compound (g3) preferably contains an acid dianhydride. Moreover, it is preferable that acid dianhydride contains the acid dianhydride which has an aromatic ring. In this case, the transparency of the photosensitive resin composition is further improved, and the resolution is further improved accordingly.

  A carboxyl group-containing resin having an ethylenically unsaturated group 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. It may contain a certain resin (referred to as a second resin (i)). 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 group 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 are, for example, acrylic acid, methacrylic acid, ω-carboxy-polycaprolactone (n ≒ 2) monoacrylate, 2- (meth) acryloyloxyethyl phthalate, 2- (meth) acryloyl It contains compounds such as roxyethyl-2-hydroxyethyl phthalate. Ethylenically unsaturated compounds having no carboxyl group are, for example, linear or branched aliphatic or alicyclic (but may have a partially unsaturated bond in the ring) (meth) acrylic acid ester And other compounds. The ethylenically unsaturated compound having an epoxy group preferably contains glycidyl (meth) acrylate.

  The carboxyl group-containing resin (A) preferably has a benzene ring. That is, it is preferable that the aromatic ring which 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 becomes higher, and the photosensitive resin composition has excellent resolution. The carboxyl group-containing resin (A) more preferably includes 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 enhanced, and the photosensitive resin composition has more excellent resolution. The carboxyl group-containing resin (A) further preferably includes a carboxyl group-containing resin having at least one of a biphenyl skeleton and a bisphenol fluorene skeleton, and particularly preferably includes a carboxyl group-containing resin having a bisphenol fluorene skeleton. In this case, 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 the formula (1), a bisphenol fluorene skeleton in which R _{1 to} R ₈ are each independently hydrogen, an alkyl group of 1 to 5 carbon atoms or halogen A carboxyl group which is a reaction product of an acid anhydride (a3) and an intermediate which is a reaction product of an epoxy compound (a1) having a hydroxyl group and a carboxylic acid (a2) containing an unsaturated group-containing carboxylic acid (a2-1) It is preferable to include a group-containing resin (hereinafter referred to as a carboxyl group-containing resin (A1)). 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 an epoxy compound (a1) having a bisphenol fluorene skeleton represented by the following formula (1) with a carboxylic acid (a2) containing an unsaturated group-containing carboxylic acid (a2-1) And the resulting intermediate is reacted with an acid anhydride (a3).

In formula (1), R _{1 to} R ₈ each independently represent hydrogen, an alkyl group having 1 to 5 carbon atoms, or a halogen. That is, each of R _{1 to} R ₈ in the formula (1) may be hydrogen, but may be an alkyl group having 1 to 5 carbon atoms or halogen. Even if the hydrogen in the aromatic ring is substituted with a low molecular weight alkyl group or halogen, the physical properties of the carboxyl group-containing resin (A1) are not adversely affected, but rather the photosensitive resin containing the carboxyl group-containing resin (A1) is substituted. In some cases, the heat resistance or flame retardancy of the cured product of the base resin composition may be improved.

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

  The carboxyl group-containing resin (A1) will be more specifically described. In order to synthesize the carboxyl group-containing resin (A1), first, at least a part of the epoxy group in the epoxy compound (a1) having a bisphenol fluorene skeleton represented by the formula (1) and the unsaturated group-containing carboxylic acid (a2-) An intermediate is synthesized by reacting with a carboxylic acid (a2) containing 1). The synthesis of the intermediate is defined as the first reaction. The intermediate has a secondary hydroxyl group generated by the ring opening addition reaction of an epoxy group and a carboxylic acid (a2) containing an unsaturated group-containing carboxylic acid (a2-1). Next, the secondary hydroxyl group in the intermediate is reacted with the acid anhydride (a3). Thereby, a carboxyl group-containing resin (A1) can be synthesized. The reaction of the intermediate with the acid anhydride (a3) is defined as a second reaction. The acid anhydride (a3) may include an acid monoanhydride and an acid dianhydride. The acid monoanhydride is a compound having one acid anhydride group in which two carboxyl groups in one molecule are dehydrated and condensed. The 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. Further, when the acid anhydride (a3) contains an acid monoanhydride and an acid dianhydride, the carboxyl group-containing resin (A1) is a component in an intermediate, a component in an acid monoanhydride and an acid dianhydride In addition to the reaction with the component in the intermediate, any one of the reaction between the component in the intermediate and the component in the acid monoanhydride, and the reaction of the component in the intermediate with the component in the acid dianhydride One or both may be contained. That is, the carboxyl group-containing resin (A1) may be a mixture containing a plurality of compounds having different structures such as these.

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

  The weight average molecular weight of the carboxyl group-containing resin (A1) is preferably in the range of 700 to 10000. While being able to improve the insulation of the hardened | cured material of the photosensitive resin composition as a weight average molecular weight is 700 or more, a dielectric loss tangent can be reduced. Moreover, the developability by the alkaline aqueous solution of the photosensitive resin composition will improve especially as a weight average molecular weight is 10000 or less. 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.

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

  As for the number average molecular weight and molecular weight distribution of the carboxyl group-containing resin (A1) as described above, the carboxyl group-containing resin (A1) contains the unreacted components in the intermediate, the components in the intermediate and the acid anhydride. Reactant of component with component in acid dianhydride, reactant of component in intermediate with component in acid monoanhydride, reactant of component in intermediate with component in acid dianhydride, etc. This can be achieved by a mixture containing various components appropriately. More specifically, this is achieved by controlling parameters such as the average molecular weight of the epoxy compound (a1), the amount of acid monoanhydride to the epoxy compound (a1), and the amount of acid dianhydride to the epoxy compound (a1) it can.

  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).

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

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

GPC apparatus: Showa Denko SHODEX SYSTEM 11,
Column: Four series of SHODEX KF-800P, KF-005, KF-003, KF-001,
Mobile phase: THF,
Flow rate: 1 ml / min,
Column temperature: 45 ° C,
Detector: RI,
Conversion: polystyrene.

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

  An epoxy compound (a1) has a structure shown, for example to following formula (2). N in Formula (2) is an integer in the range of 0 to 20, for example. In order to appropriately control the molecular weight of the carboxyl group-containing resin (A1), the average of n is particularly preferably in the range of 0-1. When the average of n is in the range of 0 to 1, even when the acid anhydride (a3) contains an acid dianhydride, an increase in excess molecular weight is likely to be suppressed.

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

  The unsaturated group-containing carboxylic acid (a2-1) can contain, for example, a compound having only one ethylenically unsaturated group. More specifically, unsaturated group-containing carboxylic acid (a2-1) is, for example, acrylic acid, methacrylic acid, ω-carboxy-polycaprolactone (n ≒ 2) monoacrylate, crotonic acid, cinnamic acid, 2-acryloyloxy Ethylsuccinic acid, 2-methacryloyloxyethyl succinic acid, 2-acryloyloxyethyl phthalic acid, 2-methacryloyloxyethyl phthalic acid, 2-acryloyloxypropyl phthalic acid, 2-methacryloyloxypropyl phthalic acid, 2-acryloyloxyethylmaleic acid Acid, 2-methacryloyloxyethylmaleic acid, β-carboxyethyl acrylate, 2-acryloyloxyethyl tetrahydrophthalic acid, 2-methacryloyloxyethyl tetrahydrophthalic acid, 2-acryloyloxyethyl hexahydrophthalate It can contain one or more compounds selected from the group consisting of hydrofluoric acid and 2-methacryloyloxyethyl hexahydrophthalic acid. Preferably, the unsaturated group-containing carboxylic acid (a2-1) contains acrylic acid.

  The carboxylic acid (a2) may contain a polybasic acid (a2-2). The polybasic acid (a2-2) is an acid in which two or more hydrogen atoms can be substituted for metal atoms in one molecule. The polybasic acid (a2-2) preferably has two or more carboxyl groups. In this case, the epoxy compound (a1) reacts with both the unsaturated group-containing carboxylic acid (a2-1) and the polybasic acid (a2-2). The cross-linking of the epoxy group present in the two molecules of the epoxy compound (a1) with the polybasic acid (a2-1) results in an increase in molecular weight. Thus, the insulation of the cured product of the photosensitive resin composition can be improved, and the dielectric loss tangent can be reduced.

  The polybasic acid (a2-2) preferably contains a dicarboxylic acid. 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 It can contain one or more compounds selected from the group consisting of acid and terephthalic acid. Preferably, the polybasic acid (a2-2) contains 4-cyclohexene-1,2-dicarboxylic acid.

  For reacting the epoxy compound (a1) with the carboxylic acid (a2), known methods can be adopted. For example, a reactive solution is obtained by adding a carboxylic acid (a2) to a solvent solution of an epoxy compound (a1) and further adding a thermal polymerization inhibitor and a catalyst as needed, and stirring and mixing. The intermediate can be obtained by reacting this reactive solution at a temperature of preferably 60 to 150 ° C., particularly preferably 80 to 120 ° C. in a conventional manner. The solvents include, 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, butyl carbitol acetate, diethylene glycol monoethyl ether It can contain at least one component selected from the group consisting of acetate, acetates such as 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, at least one selected from the group consisting of tertiary amines such as benzyldimethylamine and triethylamine, quaternary ammonium salts such as trimethylbenzylammonium chloride and methyltriethylammonium chloride, triphenylphosphine and triphenylstibin. It can contain one type of ingredient.

  It is preferred that the catalyst comprises in particular triphenylphosphine. That is, it is preferable to react the epoxy compound (a1) with the carboxylic acid (a2) in the presence of triphenyl phosphine. In this case, the ring-opening addition reaction of the epoxy group in the epoxy compound (a1) and the carboxylic acid (a2) is particularly promoted, and a reaction rate (conversion rate) of 95% or more, 97% or more, or almost 100% is achieved. It is possible. In addition, the occurrence of ion migration in the layer containing the cured product of the photosensitive resin composition is suppressed, and the insulation of the layer containing the cured product is improved.

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

  It is also preferable to react the epoxy compound (a1) with the carboxylic acid (a2) under air bubbling. In this case, the addition polymerization reaction of unsaturated groups can be suppressed to suppress the increase in molecular weight of the intermediate and the gelation of the solution of the intermediate. In addition, excessive coloring of the carboxyl group-containing resin (A1), which is the final product, can be suppressed.

  The intermediate thus obtained has a hydroxyl group formed by the reaction of the epoxy group in the epoxy compound (a1) and the carboxyl group in the carboxylic acid (a2).

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

  The acid monoanhydride can contain the anhydride of a dicarboxylic acid. Anhydrides such as 1,2,3,6-tetrahydrophthalic anhydride, phthalic anhydride, succinic anhydride, methylsuccinic anhydride, maleic anhydride, citraconic anhydride, glutaric anhydride, etc. Itaconic anhydride, methyltetrahydrophthalic anhydride, methyl nadic anhydride, hexahydrophthalic anhydride, cyclohexane-1,2,4-tricarboxylic acid-1,2-anhydride, and methyl hexahydrophthalic anhydride And one or more compounds selected from the group consisting of In particular, it is preferable that the acid monoanhydride contains 1,2,3,6-tetrahydrophthalic anhydride. In this case, the insulation of the cured product of the photosensitive resin composition can be improved while securing good developability of the photosensitive resin composition. The amount of 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%, based on the total amount of acid anhydride. However, it is not limited to this.

  The acid anhydride (a3) preferably contains an acid dianhydride. The acid dianhydride is a compound having two acid anhydride groups. The acid dianhydride can contain an anhydride of tetracarboxylic acid. Examples of the acid dianhydride are 1,2,4,5-benzenetetracarboxylic acid dianhydride, benzophenonetetracarboxylic acid dianhydride, methylcyclohexene tetracarboxylic acid dianhydride, tetracarboxylic acid dianhydride, and naphthalene-1. 1,4,5,8-tetracarboxylic acid dianhydride, ethylene tetracarboxylic acid dianhydride, 9,9'-bis (3,4-dicarboxyphenyl) fluorene dianhydride, glycerin bisan hydrotrimellitate mono Acetate, ethylene glycol bisanhydrotrimellitate, 3,3 ′, 4,4′-diphenyl sulfone tetracarboxylic acid dianhydride, 1,3,3a, 4,5,9b-hexahydro-5 (tetrahydro-2, 5-dioxo-3-furanyl) naphtho [1,2-c] furan-1,3-dione, 1,2,3,4-butanetetra Carboxylic acid dianhydride and 3,3 ', may contain at least one compound selected from the group consisting of 4,4'-biphenyl tetracarboxylic acid dianhydride. The acid dianhydride preferably contains an acid dianhydride having an aromatic ring. In particular, the acid dianhydride preferably contains 3,3 ', 4,4'-biphenyltetracarboxylic acid dianhydride. In this case, the insulation of the cured product of the photosensitive resin composition can be improved while securing good developability of the photosensitive resin composition. In addition, the transparency of the photosensitive resin composition is improved, and the resolution is improved accordingly. The amount of 3,3 ′, 4,4′-biphenyltetracarboxylic acid dianhydride is preferably in the range of 20 to 100 mol%, more preferably in the range of 40 to 100 mol%, based on the total amount of the acid dianhydride. Although it is more preferable to be present, it is not limited thereto.

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

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

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

  The carboxyl group-containing resin (A) may contain a carboxyl group-containing resin having an aromatic ring and not having photopolymerization. The carboxyl group-containing resin having an aromatic ring and not having photopolymerizability 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 are acrylic acid, methacrylic acid, ω-carboxy-polycaprolactone (n ≒ 2) monoacrylate, 2- (meth) acryloyloxyethyl phthalate, 2- (meth) acryloyloxy It can contain compounds such as ethyl-2-hydroxyethyl phthalate. The ethylenically unsaturated compound having a carboxyl group can also contain a reaction product of pentaerythritol triacrylate, pentaerythritol trimethacrylate or the like with a dibasic acid anhydride. Ethylenically unsaturated monomers are carboxyl groups such as linear or branched aliphatic or alicyclic (but may have a partially unsaturated bond in the ring) (meth) acrylic acid ester, etc. It may further contain an ethylenically unsaturated compound which does not have.

  The carboxyl group-containing resin (A) may contain only the carboxyl group-containing resin (A1), or may contain the carboxyl group-containing resin (A1) and the carboxyl group-containing resin other than the carboxyl group-containing resin (A1). Only the carboxyl group-containing resin other than the group-containing resin (A1) may be contained. 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) contains 30 mass% of the carboxyl group-containing resin (A1) % Is preferably contained, more preferably 60% by mass or more, and still more preferably 100% by mass.

  The content of the carboxyl group-containing resin (A) is preferably in the range of 5 to 85% by mass, and more preferably in the range of 10 to 75% by mass, with respect to the solid content of the photosensitive resin composition. Preferably, it is more preferably in the range of 26 to 60% by mass, and particularly preferably in the range of 30 to 45% by mass. When the photosensitive resin composition contains a carboxyl group-containing resin (A1), the content of the carboxyl group-containing resin (A1) is in the range of 5 to 85% by mass relative to the solid content of the photosensitive resin composition It is preferably in the range of 10 to 75% by mass, more preferably in the range of 26 to 60% by mass, and particularly preferably in the range of 30 to 45% by mass. preferable. In addition, solid content amount is the total amount of all the components except volatile components, such as a solvent, from the photosensitive resin composition.

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

  The organic filler (B) has a carboxyl group. The carboxyl group of the organic filler (B) is produced, for example, 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, itaconic acid, etc. can get. The organic filler (B) can impart high copper plating adhesion to the cured product of the photosensitive resin composition. Furthermore, the organic filler (B) improves the thixotropy of the photosensitive resin composition and improves the stability (particularly 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, in the case where the photosensitive resin composition contains a crystalline epoxy compound, a crystalline epoxy The compatibility of the compounds can be improved to prevent crystallization. The carboxyl group content of the organic filler (B) is not particularly limited, but the acid value of the organic filler (B) is preferably 1 to 60 mg KOH / g as the acid value determined by acid-base titration. If the acid value is less than 1 mg KOH / g, the stability of the photosensitive resin composition and the developability of the cured product may be reduced. If the acid value is more than 60 mg KOH / g, the moisture resistance reliability of the cured product may be reduced. The acid value of the organic filler (B) is more preferably 3 to 40 mg KOH / g.

  The organic filler (B) also preferably 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 size of the organic filler (B) is 1 μm or less. By the average primary particle diameter of the organic filler (B) being 1 μm or less, the thixotropy of the photosensitive resin composition is efficiently enhanced. Therefore, 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 is preferably 0.001 μm or more, for example. The average primary particle size of the organic filler (B) is measured as D ₅₀ by a laser diffraction type particle size distribution measuring apparatus. The average primary particle size of the organic filler (B) is preferably 0.1 μm or less. In this case, the stability of the photosensitive resin composition is further improved, and the scattering during exposure is suppressed, whereby the resolution is further improved.

  The organic filler (B) is preferably contained in the photosensitive resin composition in a state of a particle diameter of 10 μm or less. The organic filler (B) may contain secondary particles by aggregating in the photosensitive resin composition. In that case, the particle size of the organic filler (B) in the photosensitive resin composition means the particle size of particles 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 of a particle diameter of 10 μm or less, the stability of the photosensitive resin composition is further improved, and scattering at the time of exposure is suppressed. The image quality is further improved. The organic filler (B) is more preferably contained in the photosensitive resin composition in a particle size of 5 μm or less, further preferably in a particle size of 1 μm or less, and more preferably 0.5 μm It is particularly preferable to be contained in the following state. In this case, the stability of the photosensitive resin composition is further improved, and the scattering during exposure is suppressed, whereby the resolution is further improved. The lower limit of the particle size of the organic filler (B) in the photosensitive resin composition is not particularly limited, and may be, for example, 0.01 μm or more.

  The organic filler (B) preferably contains a rubber component. The rubber component can impart flexibility to the cured product of the photosensitive resin composition. 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. In addition, flexibility can be imparted to the cured product of the photosensitive resin composition more effectively by the rubber component. NBR is generally a copolymer of butadiene and acrylonitrile and is classified into nitrile rubber. MBS is generally a copolymer composed of three components of methyl methacrylate, butadiene and styrene, and is classified into butadiene based rubbers. SBR is generally a copolymer of styrene and butadiene and is classified into styrene rubber. As a specific example of the organic filler (B), product number XER-91-MEK manufactured by JSR Corporation can be mentioned. This organic filler is a crosslinked rubber (NBR) having a carboxyl group with an average primary particle diameter of 0.07 μm, and is provided by a methyl ethyl ketone dispersion having a content ratio of crosslinked rubber of 15% by weight, and its acid value is 10.0 mg KOH / g It is. Thus, the organic filler (B) may be blended in a dispersion. The rubber component may be compounded in a dispersion. Further, as a specific example of the organic filler (B), in addition to the above, product numbers XER-32, XER-92 and the like manufactured by JSR Corporation can be mentioned. Moreover, as a dispersion liquid of crosslinked rubber (SBR) which has a carboxyl group and a hydroxyl group, product number XSK-500 etc. by JSR Corporation are mentioned.

  The organic filler (B) may contain particle components other than the rubber component. In this case, the organic filler (B) can contain at least one particle component selected from the group consisting of acrylic resin fine particles having a carboxyl group and cellulose fine particles having a carboxyl group. The acrylic resin fine particle having a carboxyl group can contain at least one particle component selected from the group consisting of non-crosslinked styrene / acrylic resin fine particles and crosslinked styrene / acrylic resin fine particles. 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 Coatings Co., Ltd. can be mentioned. As a specific example of the crosslinked styrene / acrylic resin fine particles, product number MG-351 (average primary particle diameter 1.0 μm) and product number BGK-001 (average primary particle diameter 1.0 μm) manufactured by Nippon Paint Industrial Coatings Co., Ltd. Can be mentioned. In addition, the organic filler (B) may contain a particle component other than the particle component selected from the rubber component, the acrylic resin fine particles, and the cellulose fine particles described above. In this case, the organic filler (B) can contain a particle component having a carboxyl group. That is, the particle component having a carboxyl group may be different from the particle component selected from the rubber component, the fine particles of acrylic resin, and the fine particle of cellulose.

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

  The content of the organic filler (B) is preferably in the range of 1 to 50 parts by mass with respect to 100 parts by mass of the content of the carboxyl group-containing resin (A). The content of the organic filler (B) is at least 1 part by mass with respect to 100 parts by mass of the content of the carboxyl group-containing resin (A), thereby achieving good copper plating adhesion of the cured product of the photosensitive resin composition. You can get Moreover, the outstanding resolution of the photosensitive resin composition can be acquired because content of an organic filler (B) is 50 mass parts or less. In addition, when the content of the organic filler (B) is in the above range, the thixotropy of the photosensitive resin composition is increased, 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 in the range of 10 to 20 parts by mass with respect to 100 parts by mass of the content of the carboxyl group-containing resin (A). It is further preferred that

  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 groups include 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, may have two or more acyloxy groups, and may have two or more alkoxides. In addition, the coupling agent (C) may have two or more different functional groups selected from the group consisting of an alkoxy group, an acyloxy group and an alkoxide. Since the coupling agent (C) enhances the dispersibility of the organic filler (B) and the silica filler (D) in the photosensitive resin composition, the transparency and thixotropy of the photosensitive resin composition can be improved. Thus, the photosensitive resin composition has excellent resolution and stability (particularly 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 are at least one atom selected from the group consisting of a silicon atom, an aluminum atom, a titanium atom, and a zirconium atom Preferably, they are directly bonded.

  When the coupling agent (C) has a silicon atom, examples of the coupling agent (C) are tetraethoxysilane, tetramethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinylmethyldiethoxysilane, vinylmethyldimethoxymethane Silane, 2- (3,4 epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropylmethyldiethoxysilane Cidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, p-styryltrimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl)- 3-aminopropyl Trimethoxysilane, 3-aminopropylmethyldimethoxysilane, 3-aminopropylmethyldiethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3- (2-aminoethylamino) propyltriethoxysilane N, N-dimethyl-3- (trimethoxysilyl) propylamine, 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine, N-phenyl-3-aminopropyltrimethoxysilane, 3 -Mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacrylo Cyclopropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, allyltriethoxysilane, allyltrimethoxysilane, allylchlorodimethylsilane, 3-chloropropyltrimethoxysilane, 3-chloropropyltriethoxysilane, 3-chloro Propyldimethoxymethylsilane, chloromethyltriethoxysilane, chloromethyltrimethoxysilane, 3-chloropropylmethyldiethoxysilane, 3-isocyanatepropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, bis (triethoxysilylpropyl) Tetrasulfide, cyclohexyltrimethoxysilane, methyltriethoxysilane, methyltrimethoxysilane, ethyltriethoxysilane, ethyltrimethoxysilane, Xyltrimethoxysilane, hexyltriethoxysilane, hexadecyltrimethoxysilane, octadecyltriethoxysilane, octadecyltrimethoxysilane, n-octyltriethoxysilane, n-octyltrimethoxysilane, dodecyltriethoxysilane, dodecyltrimethoxysilane, Propyltrimethoxysilane, propyltriethoxysilane, benzyltriethoxysilane, methylphenyldimethoxysilane, methylphenyldiethoxysilane, phenyltriethoxysilane, phenyltrimethoxysilane, p-tolyltrimethoxysilane, 4-vinylphenyltrimethoxysilane 1-Naphthyltrimethoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, 11-pentafluorophenoxyundecyl And trimethoxysilane, pentafluorophenyltrimethoxysilane, 11-azidoundecyltrimethoxysilane, 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 isopropyl tristearoyl titanate, isopropyl tris (dioctyl pyrophosphate) titanate, tetraoctyl bis (ditridecyl phosphate titanate), tetra (2) -2-Diallyloxymethyl-1-butyl) bis (ditridecyl) phosphate titanate, bis (dioctyl pyrophosphate) oxyacetate titanate, and bis (dioctyl pyrophosphate) ethylene titanate.

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

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

  The coupling agent (C) preferably has a silicon atom. That is, the coupling agent (C) is preferably a silane coupling agent. When the coupling agent (C) has a silicon atom, the reactivity with the silica filler (D) is particularly enhanced, and the dispersibility of the silica filler (D) in the photosensitive resin composition is further efficiently enhanced. Therefore, the transparency and stability of the photosensitive resin composition are further improved. Moreover, while a coupling agent (C) has a silicon atom, while further raising the glass transition point of the hardened | cured material of the photosensitive resin composition further, a thermal expansion coefficient can further be reduced.

  The coupling agent (C) preferably has at least one group selected from the group consisting of a methoxy group, an ethoxy group and an acetoxy group. Methoxy and ethoxy are classified as alkoxy. Moreover, an acetoxy group is classified into an acyloxy group. The coupling agent (C) may have only a methoxy group, may have only an ethoxy group, and may have only an acetoxy group. The coupling agent (C) may have two or more different functional groups selected from the group consisting of methoxy group, ethoxy group and acetoxy group. A carboxyl group-containing resin (A) having an aromatic ring, an organic filler (B), and silica having at least one kind of group selected from the group consisting of a methoxy group, an ethoxy group and an acetoxy group by the coupling agent (C) The reactivity between the filler (D) and the coupling agent (C) is improved, and the aggregation of the organic filler (B) and the silica filler (D) in the photosensitive resin composition becomes more difficult to occur. Therefore, the transparency and stability of the photosensitive resin composition are further improved.

  The coupling agent (C) preferably has two to four functional groups selected from the group consisting of an alkoxy group, an acyloxy group and an alkoxide. The coupling agent (C) may have two to four alkoxy groups, may have two to four acyloxy groups, and may have two to four alkoxides. For example, the coupling agent (C) may have two to four methoxy groups, may have two to four ethoxy groups, and may have two to four acetoxy groups. Good. Further, the coupling agent (C) may have two to four different 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) having two to four functional groups selected from the group consisting of an alkoxy group, an acyloxy group and an alkoxide, or It is possible to suppress an excessive crosslinking reaction due to the reaction between the coupling agent (C) and the silica filler (D), and improve the dispersibility of the organic filler (B) and the silica filler (D) in the photosensitive resin composition At the same time, gelation can be suppressed.

  The coupling agent (C) preferably has at least one group selected from the group consisting of an amino group, an epoxy group, a vinyl group, a methacryl 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 is further increased. Efficiently increase. Therefore, 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. Moreover, 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, for example, directly bonded to 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) is As a result, the dispersibility of the organic filler (B) in the photosensitive resin composition is further efficiently enhanced. It is preferred that the coupling agent (C) have an epoxy group or a vinyl group. In this case, the insulating property of the photosensitive resin composition is enhanced, and the stability is further improved.

  The photosensitive resin composition may further contain a coupling agent other than the coupling agent (C). The coupling agent other than the coupling agent (C) may not have at least one atom selected from the group consisting of a silicon atom, an aluminum atom, a titanium atom, and a zirconium atom. The coupling agent other than the coupling agent (C) may not have two or more functional groups 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 obtaining the dispersibility of the organic filler (B) and the silica filler (D) efficiently and from the viewpoint of improving the transparency and stability of the photosensitive resin composition, the photosensitive resin composition is a coupling agent The coupling agent other than (C) may not be included. When the photosensitive resin composition contains a coupling agent (C) and a coupling agent other than the coupling agent (C), the coupling agent (C) and the coupling agent other than the coupling agent (C) It is preferable that content of a coupling agent (C) is 30 mass% or more with respect to the sum total of content of, and it is more preferable that content is 50 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 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). Is preferred. When the content of the coupling agent (C) is in this range, the aggregation of the organic filler (B) and the silica filler (D) in the photosensitive resin composition is prevented, and the dispersibility is improved. The content of the coupling agent (C) is 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). Is more preferred.

  The silica filler (D) has an average primary particle size in the range of 1 to 150 nm. When the average primary particle diameter of the silica filler (D) is in this range, the transparency of the photosensitive resin composition containing the organic filler (B) is efficiently enhanced. Therefore, the resolution of the photosensitive resin composition is further improved. The average primary particle size of the silica filler (D) is measured using a dynamic light scattering method. The average primary particle diameter of the silica filler (D) is more preferably 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 the resolution of the photosensitive resin composition are further improved.

  The silica filler (D) preferably contains silica particles derived from silica sol. In this case, the transparency of the photosensitive resin composition containing the organic filler (B) is further enhanced, and the resolution of the photosensitive resin composition is further enhanced. Examples of silica sols include spherical silica sols and linear silica sols. Specific examples of the silica filler (D) include organosilica sols manufactured by Nissan Chemical Industries, Ltd .: product number 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, M K-ST-L, MEK-ST-ZL, MEK-ST-UP; NANOCRYL manufactured by Hanse-Chemie: Part No. XP0396, XP0596, XP0733, XP0765, XP0765, XP0768, XP0954, XP0945, XP1045; Hanse-Chemie NANOPOX: Part numbers XP0516, XP0525, XP0314 and the like.

  The photosensitive resin composition may further contain an inorganic filler other than the silica filler (D). The inorganic filler other than the silica filler (D) may contain a silica filler whose average primary particle diameter is not in the range of 1 to 150 nm, and may contain an inorganic filler other than the silica filler. Examples of inorganic fillers other than the silica filler (D) include barium sulfate, crystalline silica, nanosilica, 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 or 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 an inorganic filler other than the silica filler (D). When the photosensitive resin composition contains a silica filler (D) and an inorganic filler other than the silica filler (D), the total content of the silica filler (D) and the inorganic filler other than the silica filler (D) On the other hand, the content of the silica filler (D) is preferably 30% by mass or more, and more preferably 50% by mass or more. In this case, good transparency and resolution of the photosensitive resin composition can be obtained.

  The content of the silica filler (D) is preferably in the range of 5 to 200 parts by mass with respect to 100 parts by mass of the content of the carboxyl group-containing resin (A). By the content of the silica filler (D) being 5 parts by mass or more, the transparency of the photosensitive resin composition is further enhanced. Moreover, the photosensitive resin composition may have the further outstanding resolution because content of a silica filler (D) is 200 mass parts or less. In addition, 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 enhanced, and the thermal expansion coefficient and the dielectric loss tangent can be further reduced. Furthermore, the surface roughness of the cured product after desmearing the cured product of the photosensitive resin composition can be further reduced. The content of the silica filler (D) is more preferably in the range of 20 to 150 parts by mass, preferably 40 to 100 parts by mass with respect to 100 parts by mass of the content of the carboxyl group-containing resin (A). Particularly preferred.

  The photosensitive resin composition preferably further contains an unsaturated compound (E) having at least one ethylenically unsaturated bond in one molecule. The unsaturated compound (E) can impart photocurability to the photosensitive resin composition. Unsaturated compounds (E) are, for example, monofunctional (meth) acrylates such as 2-hydroxyethyl (meth) acrylate; and diethylene glycol di (meth) acrylate, trimethylolpropane di (meth) acrylate, trimethylolpropane tri (meth) Acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, ε-caprolactone modified pentaerythritol hexaacrylate, tricyclodecanedihydrate It includes at least one compound selected from the group consisting of polyfunctional (meth) acrylates such as methanol di (meth) acrylate.

  The unsaturated compound (E) preferably contains at least one compound selected from the group consisting of trimethylolpropane tri (meth) acrylate and tricyclodecanedimethanol di (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. The unsaturated compound (E) more preferably contains tricyclodecanedimethanol 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 preferred 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 the aqueous alkaline solution is particularly improved. Examples of trifunctional compounds are, for example, trimethylolpropane tri (meth) acrylate, EO modified trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, ethoxylated isocyanurate tri (meth) acrylate and ε-caprolactone modified And at least one compound selected from the group consisting of tris- (2-acryloxyethyl) isocyanurate and ethoxylated glycerine tri (meth) acrylate.

  It is also preferred 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. The phosphorus-containing unsaturated compound is, for example, 2-methacryloyloxyethyl acid phosphate (as a specific example, product number light ester P-1M and light ester P-2M manufactured by Kyoeisha Chemical Co., Ltd.), 2-acryloyloxyethyl acid phosphate (As a specific example, product number light acrylate P-1A manufactured by Kyoeisha Chemical Co., Ltd.), diphenyl-2-methacryloyloxyethyl phosphate (as a specific example, product number MR-260 manufactured by Daihachi Kogyo Co., Ltd.), and Showa Polymer Co., Ltd. HFA series (specifically, product number HFA-6003 which is an addition reaction product of dipentaerythritol hexaacrylate and HCA, and an addition reaction product of HFA-6007, caprolactone modified dipentaerythritol hexaacrylate and HCA Product number HFA 003, and may contain HFA-6127, etc.) one or more compounds selected from the group consisting of.

  The unsaturated compound (E) may contain a prepolymer. The prepolymer is, for example, at least one selected from the group consisting of a prepolymer obtained by polymerizing a monomer having an ethylenically unsaturated bond and then adding an ethylenically unsaturated group, and an oligo (meth) acrylate prepolymer. Can be contained. Oligo (meth) acrylate prepolymers are, for example, epoxy (meth) acrylate, polyester (meth) acrylate, urethane (meth) acrylate, alkyd resin (meth) acrylate, silicone resin (meth) acrylate, and pyran resin (meth) acrylate And at least one component selected from the group consisting of

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

  The photosensitive resin composition preferably further contains a photopolymerization initiator (F). The photopolymerization initiator (F) includes, for example, an acyl phosphine oxide photopolymerization initiator. That is, the photosensitive resin composition contains, for example, an acylphosphine oxide-based photopolymerization initiator. In this case, when the photosensitive resin composition is exposed, high sensitivity can be imparted to the photosensitive resin composition. In addition, the occurrence of ion migration in the layer containing the cured product of the photosensitive resin composition is suppressed, and the insulation of the layer containing the cured product is further improved.

  Acyl phosphine oxide type photopolymerization initiators are, for example, monoacyl phosphine oxides such as 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, 2,4,6-trimethylbenzoyl-ethyl-phenyl-phosphinate and the like Photopolymerization initiators, as well as bis- (2,6-dichlorobenzoyl) phenyl phosphine oxide, bis- (2,6-dichlorobenzoyl) -2,5-dimethylphenyl phosphine oxide, bis- (2,6- Dichlorobenzoyl) -4-propylphenyl phosphine oxide, bis- (2,6-dichlorobenzoyl) -1-naphthyl phosphine oxide, bis- (2,6-dimethoxy benzoyl) phenyl phosphine oxide, bis- (2, 2, 6 6-Dimethoxybenzoyl) 2,4,4-trimethylpentyl phosphine oxide, bis- (2,6-dimethoxybenzoyl) -2,5-dimethylphenyl phosphine oxide, bis- (2,4,6-trimethyl benzoyl) phenyl phosphine oxide, It includes one or more components selected from the group consisting of bisacylphosphine oxide photopolymerization initiators such as (2,5,6-trimethylbenzoyl) -2,4,4-trimethylpentylphosphine oxide. In particular, it is preferable that the acyl phosphine oxide photopolymerization initiator contains 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, and the acyl phosphine oxide photopolymerization initiator is 2,4,6-trimethyl benzoyl ester. -It may contain only diphenyl-phosphine oxide.

  The photopolymerization initiator (F) preferably contains a hydroxyketone photopolymerization initiator in addition to the acyl phosphine oxide photopolymerization initiator. That is, it is preferable that the photosensitive resin composition contains a hydroxyketone-based photopolymerization initiator. In this case, it is possible to impart higher photosensitivity to the photosensitive resin composition as compared with the case where the hydroxyketone photopolymerization initiator is not contained. Thereby, when it hardens | cures the photosensitive resin composition by exposure, it becomes possible to fully harden over the surface part from the surface of the coating film formed from the photosensitive resin composition. Examples of hydroxyketone-based photopolymerization initiation are 1-hydroxy-cyclohexyl-phenyl-ketone, phenylglyoxyc 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-propan-1-one and 2- Hydroxy-2-methyl-1-phenyl-propan-1-one.

  When the photosensitive resin composition contains an acyl phosphine oxide type photopolymerization initiator and a hydroxy ketone type photo polymerization initiator, the mass ratio of the acyl phosphine oxide type photo polymerization initiator to the hydroxy ketone type photo polymerization initiator is It is preferable to be in the range of 1: 0.01 to 1:10. In this case, the curability in the vicinity of the surface of the coating film formed of the photosensitive resin composition and the curability in the deep portion can be improved in a well-balanced manner.

  It is also preferred that the photoinitiator (F) contains bis (diethylamino) benzophenone. That is, the photosensitive resin composition contains an acyl phosphine oxide type photopolymerization initiator and bis (diethylamino) benzophenone, or an acyl phosphine oxide type photopolymerization initiator, a hydroxy ketone type photopolymerization initiator and a bis (diethyl amino) It is also preferred to contain benzophenone. In this case, when the coating film formed of the photosensitive resin composition is partially exposed and then developed, the curing of the non-exposed part is suppressed, and 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. In particular, when forming an interlayer insulation layer of a multilayer printed wiring board from a photosensitive resin composition and providing a small diameter hole for a through hole in this interlayer insulation layer by photolithography (see FIG. 1), the small diameter hole It becomes possible to form precisely and easily.

  When the photosensitive resin composition contains a bis (diethylamino) benzophenone and an acyl phosphine oxide photopolymerization initiator, the content of bis (diethylamino) benzophenone is 0. 0 to the acyl phosphine oxide photopolymerization initiator. It is preferable to exist in the range of 5-20 mass%. When the content of bis (diethylamino) benzophenone is 0.5% by mass or more, the resolution is particularly high. In addition, when the content of bis (diethylamino) benzophenone is 20% by mass or less, bis (diethylamino) benzophenone is less likely to inhibit the electrical insulation of the cured product of the photosensitive resin composition.

  It is preferable that content of a photoinitiator (F) exists in the range of 0.1-30 mass% with respect to content of carboxyl group-containing resin (A), and it is in the range of 1-25 mass%. It is more preferable that

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

  The 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 crystal. Epoxy resin (specific example: product name YDC-1312 manufactured by Nippon Steel Sumikin Chemical Co., Ltd.), biphenyl type crystalline epoxy resin (specific example: product name YX-4000 manufactured by Mitsubishi Chemical Corporation), diphenyl ether type crystalline epoxy resin (specific example For example, No. YSLV-80 DE manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., crystalline epoxy resin of bisphenol type (example: YSLV-80XY manufactured by Nippon Steel & Sumikin Chemical Co., Ltd. as specific example), crystalline epoxy resin of tetrakisphenol ethane type (example as specific example) Nippon Kayaku Co., Ltd. product number GTR-1800), bisphenol fluorene type crystal Preferably includes one or more components selected from the group consisting of an epoxy resin (epoxy resin having a structure represented by the formula (2) as a specific example).

  The crystalline epoxy resin may have two epoxy groups in one molecule. In this case, it is possible to make the cured product less likely to crack while the temperature change is repeated.

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

  As melting | fusing point of crystalline epoxy resin, 70-180 degreeC is mentioned, for example. In particular, the crystalline epoxy resin preferably contains a crystalline epoxy resin having a melting point of 110 ° C. or less. In this case, the developability by the alkaline aqueous solution of the photosensitive resin composition is particularly improved. The crystalline epoxy resin having a melting point of 110 ° C. or less is, for example, a biphenyl type epoxy resin (as a specific example, product number YX4000 manufactured by Mitsubishi Chemical Co., Ltd.), a biphenyl ether type epoxy resin (as a specific example, as a product number YSLV- manufactured by Nippon Steel Sumikin Chemical Co., Ltd.) 80 DE), and a bisphenol type epoxy resin (specific example, product number YSLV-80XY manufactured by Nippon Steel Sumikin Chemical Co., Ltd.), and a bisphenol fluorene type crystalline epoxy resin (an epoxy resin having a structure shown in Formula (2) as a specific example) It contains at least one component selected.

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

  The amorphous epoxy resin is, for example, a phenol novolac epoxy resin (specifically, product number EPICLON N-775 manufactured by DIC Corporation), a cresol novolac epoxy resin (specifically, product number EPICLON N-695 manufactured by DIC Corporation) Bisphenol A novolac type epoxy resin (Specific example No. EPICLON N-865 manufactured by DIC Corporation), Bisphenol A type epoxy resin (Specific example No. jER1001 manufactured by Mitsubishi Chemical Co., Ltd.), Bisphenol F type epoxy resin (Specific example) As Mitsubishi Chemical Corporation product number jER4004), bisphenol S type epoxy resin (as a specific example product number DIC Corporation product number EPICLON EXA-1514), bisphenol AD type epoxy resin, biphenyl novolac type Propoxy resin (part number NC-3000 manufactured by Nippon Kayaku Co., Ltd. as a specific example), hydrogenated bisphenol A epoxy resin (part number ST-4000D manufactured by Nippon Steel Sumikin Chemical Co., Ltd. as a specific example), naphthalene type epoxy resin (specific example Part No. EPICLON HP-4032, EPICLON HP-4700, EPICLON HP-4770) manufactured by DIC Corporation, Tertiary butyl catechol type epoxy resin (part number EPICLON HP-820 manufactured by DIC Corporation as a specific example), dicyclopentadiene type Epoxy resin (Specific example No. EPICLON HP-7200 manufactured by DIC, adamantane type epoxy resin (Specific example No. ADAMANTATE X-E-201 manufactured by Idemitsu Kosan Co., Ltd. specific example), Special bifunctional epoxy resin (Specific example No. YL7175-500 and YL7175-1000 manufactured by Mitsubishi Chemical Corporation; No. EPICLON TSR-960, EPICLON TER-601, EPICLON TSR-250-80BX, EPICLON 1650-75MPX, EPICLON EXA-4850, manufactured by DIC Corporation EPICLON EXA-4816, EPICLON EXA-4822, and EPICLON EXA-9726; product number YSLV-120TE manufactured by Nippon Steel Sumikin Chemical Co., Ltd., rubber-like core-shell polymer modified bisphenol A epoxy resin (specific example product number MX manufactured by Kaneka Co., Ltd.) -156), and rubber-like core-shell polymer modified bisphenol F-type epoxy resin (specific example, product number MX-136 made by Kaneka Co., Ltd. as a specific example) It is preferable to include one or more components selected from

  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. As a phosphorus containing epoxy resin, phosphoric acid modified bisphenol F type epoxy resin (as a specific example, product number EPICLON EXA-9726 and EPICLON EXA-9710 made by DIC Corporation), product number Epotote FX-305 made by Nippon Steel Sumikin Chemical Co., Ltd., etc. Can be mentioned.

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

  With respect to the content of the epoxy compound (G), the total of the equivalents of epoxy groups contained in the epoxy compound (G) is 0.7 to 2.5 per 1 equivalent of the carboxyl group contained in the carboxyl group-containing resin (A) Is preferably in the range of 0.7 to 2.3, and more preferably in the range of 0.7 to 2.0. Moreover, when an epoxy compound (G) contains a crystalline epoxy resin, the sum total of the equivalent of the epoxy group contained in a crystalline epoxy resin is 0.1 with respect to 1 equivalent of carboxyl groups contained in a carboxyl group-containing resin (A). It is preferably in the range of 7 to 2.5, more preferably in the range of 0.7 to 2.3, and still 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 is enhanced. For this reason, the photosensitive resin composition is particularly suitable as an insulating material for a printed wiring board. In addition, the plating resistance of the cured product of the photosensitive resin composition, that is, the whitening resistance at the time of electroless nickel / gold plating is improved.

  When the photosensitive resin composition contains melamine, it is preferable that the melamine be in the range of 0.1 to 10% by mass with respect to the content of the carboxyl group-containing resin (A), and 0.5 to 5%. More preferably, it is in the range of%.

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

  Examples of the organic solvent include straight-chain, 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 Kinds: Petroleum-based aromatic mixed solvents such as Swazole series (manufactured by Maruzen Petrochemical Co., Ltd.) and Solvesso series (manufactured by Exxon Chemical Co., Ltd.); Cellosolves such as cellosolve and butyl cellosolve; Tol; propylene glycol alkyl ethers such as propylene glycol methyl ether; polypropylene glycol alkyl ethers such as dipropylene glycol methyl ether; ethyl acetate, butyl acetate, cellosolve acetate, carbi Containing and one or more compounds selected from the group consisting of dialkyl glycol ethers; Lumpur acid esters such as acetate.

  When the photosensitive resin composition contains an organic solvent, the amount of the organic solvent is such that the organic solvent volatilizes quickly when the coating film formed from the photosensitive resin composition is dried, that is, the organic solvent is dried. It is preferable to adjust so as not to remain in the membrane. In particular, the organic solvent is preferably in the range of 0 to 99.5% by mass, and more preferably in the range of 15 to 60% by mass with respect to the entire photosensitive resin composition. In addition, since the suitable ratio of the organic solvent changes with coating methods etc., it is preferable that a ratio is suitably adjusted according to a coating method.

  The photosensitive resin composition may further contain components other than the above components as long as the gist of the present invention is not deviated.

  The photosensitive resin composition may further contain known photopolymerization accelerators, sensitizers and the like. For example, photosensitive resin compositions include benzoin and its alkyl ethers; acetophenones such as acetophenone and benzyl dimethyl ketal; anthraquinones such as 2-methylanthraquinone; 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2- Thioxanthones such as isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diisopropylthioxanthone; benzophenones such as benzophenone, 4-benzoyl-4'-methyl diphenyl sulfide; xanthones such as 2,4-diisopropylxanthone; Α-hydroxy ketones such as hydroxy-2-methyl-1-phenyl-propan-1-one; 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-1-propanone It can contain at least one component selected from the group consisting of compounds containing a nitrogen atom. The photosensitive resin composition, together with the photopolymerization initiator (C), is a known tertiary amine such as p-dimethylbenzoic acid ethyl ester, p-dimethylaminobenzoic acid isoamyl ester, 2-dimethylaminoethyl benzoate and the like. You may contain a photopolymerization promoter, a sensitizer, etc. The photosensitive resin composition may optionally contain at least one of a photopolymerization initiator for visible light exposure and a photopolymerization initiator for near infrared light exposure. A photosensitive resin composition contains, together with a photopolymerization initiator (F), a coumarin derivative such as 7-diethylamino-4-methylcoumarin as a sensitizer for laser exposure method, a carbocyanine dye system, a xanthene dye system, etc. May be

  The photosensitive resin composition includes tolylene diisocyanate type, morpholine diisocyanate type, isophorone diisocyanate type and hexamethylene diisocyanate type blocked isocyanates blocked with caprolactam, oxime, malonic acid ester etc .; melamine resin, n-butylated melamine resin Amino resins such as isobutylated melamine resin, butylated urea resin, butylated melamine urea cocondensing resin, benzoguanamine cocondensing resin; various thermosetting resins other than the above; UV curable epoxy (meth) acrylate; bisphenol A type Resins obtained by adding (meth) acrylic acid to epoxy resins such as phenol novolac type, cresol novolac type and alicyclic type; and diallyl phthalate resin, phenoxy resin, urethane resin, fluorine resin, etc. It may contain one or more resins that are selected from the group consisting of a polymer compound.

  When the photosensitive resin composition contains an epoxy compound (G), the photosensitive resin composition may contain a curing agent for curing the epoxy compound (G). Examples of the curing agent include imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, 1- (2 Imidazole derivatives such as -cyanoethyl) -2-ethyl-4-methylimidazole; dicyandiamide, benzyldimethylamine, 4- (dimethylamino) -N, N-dimethylbenzylamine, 4-methoxy-N, N-dimethylbenzylamine, Amine compounds such as 4-methyl-N, N-dimethylbenzylamine; Hydrazine compounds such as adipic acid hydrazide and sebacic acid hydrazide; phosphorus compounds such as triphenylphosphine; acid anhydrides; phenols; mercaptans; Lewis acid amine complexes; And Comprising one or more components selected from the group consisting um salt. As examples of commercial products of these components, 2MZ-A, 2MZ-OK, 2PHZ, 2P4BHZ, 2P4MHZ (all trade names of imidazole compounds) manufactured by Shikoku Kasei Co., Ltd., U-CAT 3503N, U manufactured by San-Apro Co., Ltd. -CAT 3502T (all trade names of blocked isocyanate compounds of dimethylamine), DBU, DBN, U-CATSA 102, U-CAT 5002 (all are bicyclic amidine compounds and salts thereof).

  The photosensitive resin composition may contain an adhesion promoter other than melamine. As the adhesion promoter, for example, guanamine, acetoguanamine, benzoguanamine, and 2,4-diamino-6-methacryloyloxyethyl-S-triazine, 2-vinyl-4,6-diamino-S-triazine, 2-vinyl- S-triazine derivatives such as 4,6-diamino-S-triazine isocyanuric acid adduct, 2,4-diamino-6-methacryloyloxyethyl-S-triazine isocyanuric acid adduct and the like can be mentioned.

  The photosensitive resin composition is a curing accelerator, a colorant, a copolymer such as silicone or acrylate, a leveling agent, an adhesion imparting agent, a thixotropy agent, a polymerization inhibitor, an antihalation agent, a flame retardant, an antifoaming agent, oxidation The composition may contain one or more components selected from the group consisting of an inhibitor, a surfactant, and a polymeric dispersant.

  The content of the amine compound in the photosensitive resin composition is preferably as small as possible. In this case, the electrical insulation of the layer made of the cured product of the photosensitive resin composition is unlikely to be impaired. In particular, the content of the amine compound is preferably 8% by mass or less, more preferably 5% by mass or less, based on the content of the carboxyl group-containing resin (A).

  The photosensitive resin composition can be prepared by blending the raw materials of the photosensitive resin composition as described above and kneading the mixture by a known kneading method using, for example, a triple roll, ball mill, 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., the portion excluding the liquid component, the component having a low viscosity, etc. among the raw materials is first kneaded and the obtained mixture is obtained The photosensitive resin composition may be prepared by adding and mixing a liquid component, a component having a low viscosity, and the like. Further, the photosensitive resin composition may be prepared by stirring and mixing of raw materials, stirring and dissolution, etc., not by kneading.

  In consideration of storage stability and the like, the first agent may be prepared by mixing some of the components of the photosensitive resin composition, and the second agent may be prepared by mixing the rest of the components. That is, the photosensitive resin composition may comprise a first agent and a second agent. In this case, for example, the first agent is prepared by mixing and dispersing a part of the components of the photosensitive resin composition in advance, and the remaining part of the components of the photosensitive resin composition is mixed and dispersed. A second agent may be prepared. In this case, it is possible to prepare a liquid mixture by mixing the first agent and the second agent in a necessary amount, and curing the liquid mixture to obtain a cured product.

  The photosensitive resin composition according to the present embodiment is suitable as an electrically insulating material for printed wiring boards. 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.

  Below, an example of the method of manufacturing a printed wiring board provided with the interlayer insulation layer formed from the photosensitive resin composition by this embodiment is demonstrated with reference to FIG. 1A to FIG. 1E. In this method, through holes are formed in the interlayer insulating layer by photolithography.

  First, as shown in FIG. 1A, the 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 a first conductor wiring 3. As shown to FIG. 1B, the film | membrane 4 is formed from the photosensitive resin composition on the surface in which the 1st conductor wiring 3 of the core material 1 is provided. As a method of forming the film 4, a coating method and a dry film method can be mentioned.

  In the coating method, for example, the photosensitive resin composition is coated 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 such as 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, the wet coated film can be dried, for example, at a temperature in the range of 60 to 120 ° C. to obtain the film 4.

  In the dry film method, a photosensitive resin composition is first applied on a suitable support such as polyester and then dried to form a dry film containing the photosensitive resin composition on the support. Thereby, a dry film with a support provided with the dry film and a support for supporting the dry film is obtained. After the dry film in the dry film with a support is stacked 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 to core the dry film from above the support. Transfer onto material 1 Thereby, the film 4 made of a dry film is provided on the core material 1.

  The film 4 is partially exposed to light, as shown in FIG. 1C. For this purpose, for example, after applying a negative mask to the film 4, the film 4 is irradiated with ultraviolet light through the negative mask. The negative mask includes an exposed portion for transmitting ultraviolet light and a non-exposed portion for shielding ultraviolet light, 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 phototool such as a mask film or a plate. Light sources of ultraviolet light 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-rays (436 nm), h rays (405 nm), i rays (365 nm), and It is selected from the group consisting of a combination of two or more of g-line, h-line and i-line.

  In addition, methods other than the method of using a negative mask may be adopted as the exposure method. For example, the film may be exposed by a direct writing method in which only the portion to be exposed on the film 4 is irradiated with ultraviolet light emitted from a light source. The light source applied to the direct writing method is, for example, a chemical lamp, low pressure mercury lamp, medium pressure mercury lamp, high pressure mercury lamp, super high pressure mercury lamp, xenon lamp, metal halide lamp, LED, 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.

  Further, in the dry film method, after the dry film in the dry film with a support is stacked on the core material 1, the support is allowed to transmit through the support without peeling the support and the film 4 made of the dry film is irradiated. The coating 4 may be exposed to light and subsequently the support may be peeled off the coating 4 prior to development.

  Subsequently, the film 4 is subjected to a developing treatment to remove the unexposed portion 5 of the film 4 shown in FIG. 1C, whereby the hole 6 is formed at the position where the through hole 10 is formed as shown in FIG. Provide In the development process, an appropriate developer can be used according to the composition of the photosensitive resin composition. The developer is, for example, an alkaline aqueous solution containing at least one of an alkali metal salt and an alkali metal hydroxide, or an organic amine. More specifically, the alkaline aqueous solution is, for example, sodium carbonate, potassium carbonate, ammonium carbonate, sodium hydrogencarbonate, potassium hydrogencarbonate, ammonium hydrogencarbonate, sodium hydrogencarbonate, sodium hydroxide, potassium hydroxide, ammonium hydroxide, tetramethylammonium hydroxide and water. It contains at least one component selected from the group consisting of lithium oxide. The solvent in the alkaline aqueous solution may be water alone or a mixture of water and a hydrophilic organic solvent such as lower alcohols. The organic amine contains at least one component selected from the group consisting of, for example, monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine and triisopropanolamine.

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

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

  If necessary, the film 4 may be further irradiated with ultraviolet light before and / or after heating. In this case, 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.

  By the above, on the core material 1, the interlayer insulation layer 7 which consists of hardened | cured material of the photosensitive resin composition is provided. The second conductor wiring 8 and the hole plating 9 can be provided on the interlayer insulating layer 7 by a known method such as an additive method. Thereby, as shown in FIG. 1E, the first conductor wiring 3, the second conductor wiring 8, the interlayer insulating layer 7 interposed between the first conductor wiring 3 and the second conductor wiring 8, and The printed wiring board 11 provided with the through hole 10 for electrically connecting the one conductor wiring 3 and the second conductor wiring 8 is obtained. Although hole plating 9 has a cylindrical shape covering the inner surface of hole 6 in FIG. 1E, hole plating 9 may be filled in the entire inside of hole 6.

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

  First, prepare the core material. The core material comprises, for example, at least one insulating layer and at least one conductor wire. A film is formed from the photosensitive resin composition on the surface of the core material on which the conductor wiring is provided. The coating method and the dry film method are mentioned as a formation method of a film. As the coating method and the dry film method, the same method as in the case of forming the above interlayer insulating layer can be adopted. The film is partially photocured by exposure to light. As the exposure method, the same method as in the case of forming the interlayer insulating layer can be employed. Subsequently, the film is subjected to a development treatment to remove the non-exposed portion of the film, thereby leaving the exposed portion of the film on the core material. Subsequently, the film on the core material is thermally cured by heating. The same developing method and heating method as in the case of forming the interlayer insulating layer can be employed. If necessary, the film may be further irradiated with ultraviolet light before and / or after heating. In this case, 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.

  By the above, the solder resist layer which consists of hardened | cured material of the photosensitive resin composition is provided on a core material. Thus, a printed wiring board is obtained, which includes a core material including the insulating layer and the conductor wiring thereon and a solder resist layer partially covering the surface of the core material on which the conductor wiring is provided.

(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. A bisphenol fluorene type epoxy represented by the formula (2) in a four-necked flask equipped with a reflux condenser, a thermometer, an air blowing tube and a stirrer and all R _{1 to} R ₇ in the formula (2) are hydrogen 250 parts by mass of resin (epoxy equivalent 250 g / eq) 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 methyl hydroquinone 72 parts by mass of acrylic acid .5 parts by weight were added to prepare a mixture. The mixture was heated in a flask at a temperature of 115 ° C. for 12 hours with stirring under air bubbling. This prepared a solution of the intermediate.

  Subsequently, 58.8 parts by mass of 3,3 ′, 4,4′-biphenyltetracarboxylic acid dianhydride, 60.8 parts by mass of tetrahydrophthalic anhydride, and propylene glycol monomethyl are added to the solution of the intermediate in the flask. 38.7 parts by mass of ether acetate was charged, and the mixture was heated at 115 ° C. for 6 hours with stirring under air bubbling, and further heated at 80 ° C. for 1 hour. Thereby, a 65 mass% solution of carboxyl group-containing resin A-1 was obtained. The weight average molecular weight of carboxyl group-containing resin A-1 was 30,96, and the acid value was 105 mg KOH / g.

Synthesis Example A-2
The carboxyl group-containing resin having an aromatic ring of Synthesis Example A-2 was prepared as follows. Biphenyl novolak epoxy resin (Nippon Kayaku Co., Ltd., product number NC-3000-H, epoxy equivalent 288 g / eq) 288 mass in a four-necked flask attached with a reflux condenser, a thermometer, an air blowing tube and a stirrer A mixture was prepared by adding 1 part, 155 parts by mass of diethylene glycol monoethyl ether acetate, 0.2 parts by mass of methyl hydroquinone, 72 parts by mass of acrylic acid, and 3 parts by mass of triphenylphosphine. The mixture was heated in a flask at a temperature of 115 ° C. for 12 hours with stirring under air bubbling. This prepared a solution of the intermediate.

  Subsequently, 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 and heated 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 weight average molecular weight of carboxyl group-containing resin A-2 was 8120, and the acid value was 76 mg KOH / g.

(2) Synthesis of Carboxyl Group-Containing Resin Having No Aromatic Ring:
Synthesis Example B-1
The carboxyl group-containing resin having no aromatic ring of Synthesis Example B-1 was prepared as follows. 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 in a four-necked flask equipped with a reflux condenser, a thermometer, an air blowing tube and a stirrer A mixture was prepared by adding 5 parts by mass. The mixture was heated in a flask under a nitrogen stream at a temperature of 80 ° C. for 5 hours to allow the polymerization reaction to proceed. Thus, a copolymer solution having a concentration of 35% was obtained.

  Subsequently, 0.1 parts by mass of hydroquinone, 50 parts by mass of 3,4-epoxycyclohexylmethyl acrylate, 47 parts by mass of dipropylene glycol monomethyl ether, and 0.8 parts by mass of dimethylbenzylamine are added to the copolymer solution in the flask. The reaction was charged and heated at 110 ° C. for 6 hours to allow the addition reaction to proceed. Thereby, a 38 mass% solution of carboxyl group-containing resin B-1 was obtained. The weight average molecular weight of carboxyl group-containing resin B-1 was 61,324, and the acid value was 132 mg KOH / g.

(3) Synthesis of carboxyl group-free resin having an aromatic ring:
Synthesis Example B-2
The non-carboxyl group-containing resin having an aromatic ring of Synthesis Example B-2 was prepared as follows. A bisphenol fluorene type epoxy represented by the formula (2) in a four-necked flask equipped with a reflux condenser, a thermometer, an air blowing tube and a stirrer and all R _{1 to} R ₇ in the formula (2) are hydrogen 250 parts by mass of resin (epoxy equivalent 250 g / eq), 173 parts by mass of propylene glycol monomethyl ether acetate, 0.2 parts by mass of methyl hydroquinone, 72 parts by mass of acrylic acid, and 1.5 parts by mass of triphenylphosphine Was prepared. The mixture was heated in a flask at a temperature of 115 ° C. for 12 hours with stirring under air bubbling. Thereby, a 65 mass% solution of carboxyl group non-containing resin B-2 was obtained.

(4) Preparation of photosensitive resin composition:
The photosensitive resin compositions of Examples 1 to 18 and Comparative Examples 1 to 5 were prepared as follows. The photosensitive resin composition was obtained by mix | blending the component shown to the table | surface of postscript in a flask, and carrying out stirring mixing at the temperature of 35 degreeC for 2 hours (refer Table 1-Table 3). The photosensitive resin composition was filtered through a 300 mesh filter and then filtered through a filter with a hole diameter of 10 μm.

  In addition, the compounding quantity in a table | surface shows the mass part of solid content of a description component. Moreover, although not described in the table, methyl ethyl ketone is blended in the photosensitive resin composition as a diluent.

The details of the components shown in the table are as follows.
Dispersion of organic filler A: Crosslinked rubber (NBR) having a carboxyl group with an average primary particle diameter of 0.07 μm, manufactured by JSR Corporation, product number XER-91-MEK, methyl ethyl ketone dispersion with content of crosslinked rubber of 15% by weight , Acid value 10.0 mg KOH / g.
Dispersion of organic filler B: Crosslinked rubber (SBR) having carboxyl group and hydroxyl group having an average primary particle diameter of 0.07 μm, manufactured by JSR Co., Ltd., product number XSK-500, methyl ethyl ketone dispersion with content of crosslinked rubber 15% by weight .
Coupling agent A: tetraethoxysilane.
Coupling agent B: methyltrimethoxysilane.
Coupling agent C: 3-glycidoxypropyl trimethoxysilane.
Coupling agent D: N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane.
Coupling agent E: vinyltrimethoxysilane.
Silica filler A: manufactured by Nissan Chemical Industries, Ltd., product number PMA-ST, propylene glycol monomethyl ether acetate dispersed silica sol, solid content concentration 30 mass%, average primary particle diameter 10 to 15 nm.
Silica filler B: manufactured by Nissan Chemical Industries, Ltd., Model No. MEK-EC-2130Y, methyl ethyl ketone dispersed silica sol, grade enhanced 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., Model No. MEK-AC-2140Z, methyl ethyl ketone dispersed silica sol, grade enhanced compatibility with acrylic resin, solid content concentration 40 mass%, average primary particle diameter 10 to 15 nm.
-Silica filler D: Nissan Chemical Industries, Ltd. make, product number MEK-ST-L, methyl ethyl ketone dispersion silica sol, solid content concentration 30 mass%, average primary particle diameter 40-50 nm.
Silica filler E: manufactured by Nissan Chemical Industries, Ltd., Model No. MEK-ST-ZL, methyl ethyl ketone dispersed silica sol, solid content concentration 30 mass%, average primary particle diameter 70 to 100 nm.
Silica filler F: manufactured by Nissan Chemical Industries, Ltd., Model No. MEK-ST-UP, methyl ethyl ketone dispersed linear silica sol, solid content concentration 20 mass%, average primary particle diameter 40 to 100 nm.
Silica filler G: manufactured by Ryumori Co., Ltd., product number Imsil A8, crystalline silica, average primary particle diameter 2 μm.
-Unsaturated compound A: tricyclodecane dimethanol diacrylate.
-Unsaturated compound B: trimethylolpropane triacrylate.
-Unsaturated compound C: A mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate, manufactured by Nippon Kayaku Co., Ltd., part number KAYARAD DPHA.
Photopolymerization initiator A: 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, manufactured by BASF, product number Irgacure TPO.
Photopolymerization initiator B: 1-hydroxy-cyclohexyl-phenyl-ketone, manufactured by BASF, product number Irgacure 184.
Photopolymerization initiator C: 4,4′-bis (diethylamino) benzophenone.
Epoxy compound: bisphenol type crystalline epoxy resin, manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., product number YSLV-80XY, melting point 75-85 ° C., epoxy equivalent 192 g / eq.
Antioxidant: Hindered phenolic antioxidant, manufactured by BASF, product number IRGANOX 1010.
-Surface conditioning agent: DIC Corporation make, part number Megafac F-477.

(5) Production of Test Piece A test piece was produced as follows using the photosensitive resin compositions of the respective Examples and Comparative Examples.

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

A glass epoxy copper clad laminate (FR-4 type) provided with a 17.5 μm thick copper foil was prepared. On this glass epoxy copper clad laminate, a comb-shaped electrode having a line width / space width of 50 μm / 50 μm was formed as a conductor wiring by a subtractive method, to obtain a core material. The conductor wiring was roughened by dissolving and removing the surface layer portion having a thickness of about 1 μm in the conductor wiring of the core material with an etching agent (organic acid micro-etching agent manufactured by MEC Corporation, product number CZ-8101). The dry film was heat-laminated with a vacuum laminator over the entire surface of the core material. The conditions for the heat lamination are 0.5 MPa, 80 ° C., and 1 minute. Thus, a 30 μm-thick film made of a dry film was formed on the core material. 250 mJ / cm through the negative mask with this film directly applied to the film made of polyethylene terephthalate and having a non-exposed area of 30 μm, 40 μm, and 50 μm in diameter. ^The ultraviolet light was irradiated under the conditions of ² . In addition, after exposure and before development, the film made of polyethylene terephthalate was peeled off from the dry film (film). The film after exposure was developed. In the development processing, the film was sprayed with a 1% Na ₂ CO ₃ aqueous solution at 30 ° C. for 90 seconds at a jet pressure of 0.2 MPa. Subsequently, the film was cleaned by injecting pure water at an injection pressure of 0.2 MPa for 90 seconds. This removed the unexposed parts of the film to form holes. Subsequently, the film was heated at 180 ° C. for 60 minutes, and then the film was irradiated with ultraviolet light under the condition of 1000 mJ / cm ² . Thereby, the layer which consists of hardened | cured material (it can be said that it is hardened | cured material of a dry film) of the photosensitive resin composition was formed on the core material. This gave a test piece.

(6) Evaluation Test (6-1) Particle Size Distribution The particle size distribution of the photosensitive resin composition after filtration with a 300 mesh filter was measured using MT3300EXII manufactured by Microtrac Bell Inc. for each Example and Comparative Example. . In Examples 1 to 18 and Comparative Examples 3 and 5, the particle diameter of the photosensitive resin composition measured as D ₅₀ by the laser diffraction / scattering particle size distribution measuring device is 1 μm or less, and the maximum particle diameter is 10 μm or less Met. In Comparative Examples 1, 2, 4, and 6, by laser diffraction scattering particle size distribution measuring apparatus of a photosensitive resin composition, the particle size measured as D ₅₀ of greater than 1 [mu] m, the maximum particle diameter is larger than 10 [mu] m.

(6-2) Transparency The photosensitive resin composition was visually observed about each Example and comparative example, and the result was evaluated as follows.
A: No turbidity is observed and transparency is high.
B: Some turbidity is observed, but it is transparent.
C: Haze is observed, but there is some transparency.
D: Haze is observed and there is no transparency.

(6-3) Stability After storing the photosensitive resin composition at 25 degreeC about each Example and comparative example, the photosensitive resin composition was observed and the result was evaluated as follows.
A: Separation of components did not occur after storage for 4 weeks at 25 ° C.
B: Separation of components did not occur after storage for 3 weeks at 25 ° C., but separation of components occurred after storage for 4 weeks at 25 ° C.
C: After storage for 2 weeks at 25 ° C., separation of the components did not occur, but after storage for 3 weeks at 25 ° C., separation of the components occurred.
D: After storage for 2 weeks at 25 ° C., separation of the components occurred.

(6-4) Developability About each Example and comparative example, in the process of producing a test piece, the non-exposure part of the film after development processing was observed, and the result was evaluated as follows.
A: All the films have been removed.
B: A part of the film remained on the core material.
C: It was not possible to develop.

  About the comparative example 5 whose evaluation of developability is C, evaluation of following (6-5)-(6-11) is not performed. In addition, in Example 17 and Comparative Example 6 in which the evaluation of developability is B, in the evaluation test of roughness after desmearing of (6-6) below, all the film remaining on the unexposed area on the core material is removed. Ru.

(6-5) Opening property About Example 1-18 and Comparative Examples 1-4, the opening formed in the layer which consists of hardened | cured material in a test piece was observed, and the result was evaluated as follows.
A: An opening with a diameter of 30 μm is formed.
B: An opening with a diameter of 35 μm is formed, but an opening with a diameter of 30 μm is not formed.
C: An opening with a diameter of 40 μm is formed, but an opening with a diameter of 35 μm is not formed.
D: An opening of 50 μm in diameter is formed, but an opening of 40 μm in diameter is not formed.
E: An opening with a diameter of 50 μm is not formed.

(6-6) Roughness after desmearing In Examples 1 to 18 and Comparative Examples 1 to 4, the surface of the layer formed of the cured product in the test piece was desmeared as follows based on a known desmearing method. did. Using a commercially available swelling solution (Swelling dip security G, manufactured by Atotech Japan Co., Ltd.) as a swelling solution for desmear, the surface of the layer made of the cured product is subjected to a swelling treatment at 70 ° C. for 15 minutes. The surface of the layer was swollen. The surface of the layer consisting of the swollen cured product was rinsed with hot water. Next, using a commercially available oxidizing agent containing potassium permanganate (Concentrate Compact CP, manufactured by Atotech Japan Co., Ltd.) as a desmear solution, the surface of the layer made of the cured product is roughened at 70 ° C. for 10 minutes. The surface of the layer consisting of the cured product was roughened. The surface of the layer made of the roughened hardened material was rinsed with hot water. Subsequently, the residue of the desmear liquid in the surface of the layer which consists of hardened | cured material was removed at 40 degreeC for 5 minutes using the neutralization liquid (Atotech Japan KK make, reduction solution security g P). Thereafter, the surface of the layer made of the cured product was washed with water. The surface roughness Ra of the surface of the layer consisting of the cured product roughened by desmear treatment was measured using a laser microscope, and the roughness after desmear 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 property About Example 1-18 and Comparative Examples 1-4, 6, the layer which consists of a hardened | cured material of the test piece after the desmear process in the evaluation test of said (6-6) is marketed. The electroless copper plating process was performed using a chemical | medical solution, and the initial stage wiring was formed. The test piece on which the initial wiring was formed was heated at 150 ° C. for 1 hour. Next, electrolytic copper plating was performed using a commercially available chemical solution under a current density of ² A / dm ² to directly deposit copper with a thickness of 33 μm on the initial wiring. The copper-deposited test piece was heated at 180 ° C. for 30 minutes to form a copper plating layer. The adhesion between the copper plating layer and the layer consisting of the cured product on the test piece was evaluated as follows. As for the test piece in which no blister is observed in the test piece at the time of heating both after electroless copper plating treatment and after electrolytic copper plating treatment, the peel strength of the copper plating layer and the layer made of a cured product is JIS-C 6481. It measured according to.
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: Blister occurred at the time of heating after electroless copper plating treatment or at the time of heating after electrolytic copper plating treatment.

(6-8) Insulating Property A test piece is subjected to 130 ° C., 85% R while applying a DC 30 V bias voltage to the conductor wiring (interdigital electrode) in the test pieces of Examples 1 to 18 and Comparative Examples 1 to 4 and 6. . H. Exposure for 100 hours under the test environment of The electrical resistance value between the interdigital electrodes of the layer made of a cured product under the test environment was constantly measured, and the results were evaluated as follows.
A: The electrical resistance value was always maintained at 10 ⁶ Ω or more until 100 hours passed from the start of the test.
B: The electrical resistance was maintained at 10 ⁶ Ω or more until 85 hours after the start of the test, but the electrical resistance became less than 10 ⁶ Ω before 100 hours after the start of the test.
C: The electrical resistance was maintained at 10 ⁶ Ω or more until 70 hours from the start of the test, but the electrical resistance became less than 10 ⁶ Ω before 85 hours from the start of the test.
D: The electrical resistance value was less than 10 ⁶ Ω before 70 hours from the start of the test.

(6-9) Thermal expansion coefficient In the evaluation test of a thermal expansion coefficient, the test piece was produced as follows using the photosensitive resin composition of Examples 1-18 and Comparative Examples 1-4, 6.

The photosensitive resin composition was coated on a polyethylene terephthalate film with an applicator and dried by heating at 95 ° C. for 25 minutes to form a dry film with a thickness of 30 μm on the film. The dry film was heat-laminated on the entire surface of a Teflon (registered trademark) film by a vacuum laminator. The conditions for the heat lamination are 0.5 MPa, 80 ° C., and 1 minute. As a result, a 30 μm-thick film made of a dry film was formed on a Teflon (registered trademark) film. The film was irradiated with ultraviolet light under the condition of 250 mJ / cm ² through the mask in a state in which a mask having a 3 mm × 15 mm rectangular exposure portion was directly applied to the film from a polyethylene terephthalate film. . In addition, after exposure and before development, the film made of polyethylene terephthalate was peeled off from the dry film (film). The film after exposure was developed. In the development processing, the film was sprayed with a 1% Na ₂ CO ₃ aqueous solution at 30 ° C. for 90 seconds at a jet pressure of 0.2 MPa. Subsequently, the film was cleaned by injecting 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 light under the condition of 1000 mJ / cm ² . Thus, a cured product of the photosensitive resin composition was formed on a film made of Teflon (registered trademark). The cured product was peeled off from the Teflon (registered trademark) film to obtain a test piece.

Thermal expansion coefficient of test piece at 30 to 150 ° C. in the second cycle under the conditions of temperature range 25 to 250 ° C., 10 ° C./min, load 5 g using a TMA test apparatus (Thermoplus EVOII TMA 8310, manufactured by Rigaku Corporation) (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 65 ppm / ° C. or more and less than 70 ppm / ° C.
D: CTE is 70 ppm / ° C. or more.

(6-10) Glass transition point In the evaluation test of glass transition point, the photosensitive resin compositions of Examples 1 to 18 and Comparative Examples 1 to 4 and 6 are used, and the method is the same as the above (6 to 9). Test pieces were produced to obtain test pieces.

Using a TMA test device (Thermoplus EVOII TMA 8310, manufactured by Rigaku Corporation), measurement is performed under the conditions of a temperature range of 25 to 250 ° C., a temperature rising / cooling rate of 10 ° C./min, and a load of 5 g. The glass transition point (Tg) of the piece was determined. The results were evaluated as follows.
A: Tg is 160 ° C. or more.
B: Tg is 145 ° C. or more and less than 160 ° C.
C: Tg is 130 degreeC or more and less than 145 degreeC.
D: Tg is less than 130 ° C.

(6-11) Dielectric loss tangent In the evaluation test of dielectric loss tangent, the test piece was produced as follows using the photosensitive resin composition of Examples 1-18 and Comparative Examples 1-4, 6.

The photosensitive resin composition was coated on a polyethylene terephthalate film with an applicator and dried by heating at 95 ° C. for 25 minutes to form a dry film with a thickness of 50 μm on the film. The dry film was heat-laminated on the entire surface of a Teflon (registered trademark) film by a vacuum laminator. The conditions for the heat lamination are 0.5 MPa, 80 ° C., and 1 minute. Thus, a 50 μm-thick film made of a dry film was formed on a Teflon (registered trademark) film. The film was irradiated with ultraviolet light under the condition of 250 mJ / cm ² through the mask in a state in which the film having a 3 mm × 85 mm rectangular exposed portion was directly applied to the film from a polyethylene terephthalate film. . In addition, after exposure and before development, the film made of polyethylene terephthalate was peeled off from the dry film (film). The film after exposure was developed. In the development processing, the film was sprayed with a 1% Na ₂ CO ₃ aqueous solution at 30 ° C. for 90 seconds at a jet pressure of 0.2 MPa. Subsequently, the film was cleaned by injecting 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 light under the condition of 1000 mJ / cm ² . Thus, a cured product of the photosensitive resin composition was formed on a film made of Teflon (registered trademark). The cured product was peeled off from the 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 the cavity resonator method using a dielectric constant measurement apparatus (ADMS 01 O, manufactured by AC Co., Ltd.). The results were evaluated as follows.
A: tan δ is less than 0.020.
B: tan δ is 0.020 or more and less than 0.025.
C: tan δ is 0.025 or more and less than 0.030.
D: tan δ is 0.030 or more.

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

  According to the first aspect, it is possible to form a cured product having high copper plating adhesion and low post-desmear roughness, and to obtain a photosensitive resin composition excellent in resolution.

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

  According to the second aspect, the dispersibility of the silica filler (D) in the photosensitive resin composition is efficiently enhanced, and the transparency and stability of the photosensitive resin composition are improved. While raising the glass transition point of the hardened | cured material of the photosensitive resin composition, a thermal expansion coefficient can be reduced.

  In the photosensitive resin composition according to the third aspect of 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 photosensitive resin composition according to the fourth aspect of 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 the resolution of the photosensitive resin composition are improved. In the photosensitive resin composition according to the fifth aspect of the present invention, any one of the first to fourth aspects. 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 content of the carboxyl group-containing resin (A).

  According to the fifth aspect, good copper plating adhesion of the cured product of the photosensitive resin composition can be obtained. Moreover, the outstanding resolution of the photosensitive resin composition can be obtained. Furthermore, the thixotropy of the photosensitive resin composition is enhanced, and the stability is improved.

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

  According to the sixth aspect, the transparency of the photosensitive resin composition is enhanced, and the photosensitive resin composition may have excellent resolution. Moreover, while raising the glass transition point of the hardened | cured material of the photosensitive resin composition, a thermal expansion coefficient and a dielectric loss tangent can be reduced. Furthermore, the surface roughness of the cured product after desmearing the cured product of the photosensitive resin composition can be further reduced.

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

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

  In the photosensitive resin composition according to the eighth aspect of 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) It is in the range of 0.01-10 mass parts with respect to a total of 100 mass parts with and content of the said silica filler (D).

  According to the eighth aspect, the 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 photosensitive resin composition according to the ninth aspect of the present invention, in any one of the first to eighth aspects, the organic filler (B) has a particle diameter of 10 μm or less in the photosensitive resin composition. It is included in the state of.

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

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

  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 photosensitive resin composition according to the twelfth aspect of 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 is enhanced, and the photosensitive resin composition has excellent resolution.

  In the photosensitive resin composition according to the thirteenth aspect of the present invention, in any one of the first to twelfth aspects, the carboxyl group-containing resin (A) is a reaction between a polyalcohol resin and an acid dianhydride. And copolymers obtained by

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

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

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

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

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

  In the photosensitive resin composition according to the sixteenth aspect of the present invention, in any one of the first to fifteenth aspects, an unsaturated compound (E) having at least one ethylenically unsaturated bond in one molecule is used. And a photopolymerization initiator (F).

  According to the sixteenth aspect, 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 insulation of the layer containing the cured product is improved.

  In the photosensitive resin composition according to the seventeenth aspect of the present invention, in the sixteenth aspect, the unsaturated compound (E) is trimethylolpropane tri (meth) acrylate and tricyclodecanedimethanol di (meth) acrylate. And at least one compound selected from the group consisting of

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

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

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

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

  According to the nineteenth aspect, it is possible to form a cured product having high copper plating adhesion and low roughness after desmearing, and to obtain a dry film excellent in resolution.

  The printed wiring board of the twentieth aspect according to the present invention includes an interlayer insulating layer containing a cured product of the 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 post-desmear roughness.

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

  According to the twenty-first aspect, it is possible to obtain a printed wiring board provided with a solder resist layer having high copper plating adhesion and low post-desmear roughness.

Claims (21)

A photosensitive resin composition having a photocurable property,
A carboxyl group-containing resin (A) having an aromatic ring,
An organic filler (B) having an average primary particle size of 1 μm or less and having a carboxyl group,
A group having 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 a group consisting of an alkoxy group, an acyloxy group and an alkoxide A coupling agent (C) containing at least one group selected from
Containing a silica filler (D) having an average primary particle size in the range of 1 to 150 nm,
Photosensitive resin composition.   The photosensitive resin composition according to claim 1, wherein the coupling agent (C) has a silicon atom.   The photosensitive resin composition according to claim 1, wherein the silica filler (D) contains silica particles derived from silica sol.   The photosensitive resin composition according to any one of claims 1 to 3, wherein the silica filler (D) has an average primary particle diameter in the range of 1 to 60 nm.   The content of the said organic filler (B) is in the range of 1-50 mass parts with respect to 100 mass parts of content of the said carboxyl group-containing resin (A), Any one of Claim 1 to 4 The photosensitive resin composition as described in-.   The content of the said silica filler (D) is in the range of 5-200 mass parts with respect to 100 mass parts of content of the said carboxyl group-containing resin (A), Any one of Claim 1 to 5 The photosensitive resin composition as described in-.   The photosensitive resin composition according to any one of claims 1 to 6, wherein the carboxyl group-containing resin (A) contains a carboxyl group-containing resin having an ethylenically unsaturated group.   The content of the coupling agent (C) is 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). The photosensitive resin composition as described in any one of Claim 1 to 7 which is inside.   The photosensitive resin composition according to any one of claims 1 to 8, wherein the organic filler (B) is contained in a state of a particle diameter of 10 μm or less in the photosensitive resin composition.   The photosensitive resin composition according to any one of claims 1 to 9, wherein the organic filler (B) contains a rubber component.   The photosensitive resin composition according to claim 10, wherein 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 photosensitive resin composition according to any one of claims 1 to 11, wherein the carboxyl group-containing resin (A) contains a carboxyl group-containing resin having a benzene ring.   The photosensitive resin composition according to any one of claims 1 to 12, wherein the carboxyl group-containing resin (A) contains a copolymer obtained by the reaction of a polyalcohol resin and an acid dianhydride.   The photosensitive resin composition according to claim 13, wherein the acid dianhydride contains an acid dianhydride having an aromatic ring.   The photosensitive resin composition according to any one of claims 1 to 14, wherein the carboxyl group-containing resin (A) comprises a carboxyl group-containing resin having at least one of a biphenyl skeleton and a bisphenol fluorene skeleton. An unsaturated compound (E) having at least one ethylenically unsaturated bond in one molecule,
The photosensitive resin composition as described in any one of Claims 1-15 which further contains a photoinitiator (F).   The photosensitivity according to claim 16, wherein the unsaturated compound (E) comprises at least one compound selected from the group consisting of trimethylolpropane tri (meth) acrylate and tricyclodecanedimethanol di (meth) acrylate. Resin composition.   The photosensitive resin composition according to any one of claims 1 to 17, further comprising an epoxy compound (G).   The dry film containing the photosensitive resin composition as described in any one of Claims 1-18.   The printed wiring board provided with the interlayer insulation layer containing the hardened | cured material of the photosensitive resin composition as described in any one of Claims 1-18.   A printed wiring board comprising a solder resist layer containing a cured product of the photosensitive resin composition according to any one of claims 1 to 18.

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