WO2018225441A1

WO2018225441A1 - Photosensitive resin composition, dry film, and printed wiring board

Info

Publication number: WO2018225441A1
Application number: PCT/JP2018/017810
Authority: WO
Inventors: 倫也樋口; 勇佐藤原; 橋本　壯一; 貴荒井; 浩信川里; 真司稲葉
Original assignee: 互応化学工業株式会社; 新日鉄住金化学株式会社
Priority date: 2017-06-09
Filing date: 2018-05-08
Publication date: 2018-12-13
Also published as: JP6733929B2; TWI727175B; CN109791354B; KR102208828B1; KR20200016822A; CN109791354A; TW201902973A; JPWO2018225441A1

Abstract

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

Description

Photosensitive resin composition, dry film, and printed wiring board

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

Conventionally, for the production of printed wiring boards, various electrically insulating resin compositions have been used to form electrically insulating layers such as solder resist layers, plating resist layers, etching resist layers, and interlayer insulating layers. Has been.

In recent years, as electronic devices such as communication devices and personal computers are required to have higher performance, smaller size, and thinner thickness, an electrically insulating layer formed from such a resin composition has fine through holes and opening patterns. For example, a photosensitive resin composition is used as a resin composition for forming an electrically insulating layer.

For example, Patent Document 1 discloses (A) a carboxyl group-containing resin obtained by reacting a diol compound and a polyvalent carboxylic acid, having a weight average molecular weight of 2000 to 40000 and an acid value of 50 to 200 mgKOH / g, B) Photosensitive resin composition for insulating film containing unsaturated compound containing at least one photopolymerizable ethylenically unsaturated bond in one molecule, (C) epoxy compound, and (D) photopolymerization initiator And discloses that the adhesion to the plating 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 film 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 film is subjected to desmear treatment. The surface roughness of the cured product cannot be reduced, and good high frequency characteristics cannot be obtained. In addition, by adding a rubber component, development processing with an aqueous solution containing at least one of an alkali metal salt and an alkali metal hydroxide reduces the resolution and cannot form fine through-holes or opening patterns. There is a fear. It is not easy to obtain a photosensitive resin composition having high copper plating adhesion and capable of forming a cured product having low roughness after desmearing and having excellent resolution.

Japanese Patent No. 4508929

An object of the present invention is to contain a photosensitive resin composition having high copper plating adhesion and having low resolution after desmearing and having excellent resolution, and this photosensitive resin composition. It is intended to provide a printed wiring board provided with a dry film, an interlayer insulating layer containing a cured product of the photosensitive resin composition, and a solder resist layer containing a cured product of the photosensitive resin composition.

The photosensitive resin composition which concerns on one Embodiment of this invention is a photosensitive resin composition which has photocurability, and carboxyl group-containing resin (A) which has an aromatic ring, and an average primary particle diameter are 1 micrometer or less. An organic filler (B) having a carboxyl group, 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, Includes 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.

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

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

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

FIG. 1A is a cross-sectional view showing one step of the steps of manufacturing a multilayer printed wiring board. FIG. 1B is a cross-sectional view showing one step in the steps of manufacturing a multilayer printed wiring board. FIG. 1C is a cross-sectional view showing one step in the process of manufacturing a multilayer printed wiring board. FIG. 1D is a cross-sectional view showing one step in the steps of manufacturing a multilayer printed wiring board. FIG. 1E is a cross-sectional view illustrating 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. A photosensitive resin composition suitable for forming a film, a dry film containing the photosensitive resin composition, a printed wiring board including an interlayer insulating layer containing a cured product of the photosensitive resin composition, and the photosensitive resin composition The present invention relates to a printed wiring board including a solder resist layer containing a cured product.

DETAILED DESCRIPTION Embodiments for carrying out the present invention will be described. In the following description, “(meth) acryl” means at least one of “acryl” and “methacryl”. For example, (meth) acrylate means at least one of acrylate and methacrylate.

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

Since the photosensitive resin composition contains the organic filler (B), the cured product of the photosensitive resin composition has high copper plating adhesion. The photosensitive resin composition contains a carboxyl group-containing resin (A) having an aromatic ring, an organic filler (B), a coupling agent (C), and a silica filler (D). The functional resin composition has high transparency despite containing the organic filler (B). For this reason, resolution improves. Usually, when a filler is mix | blended with the photosensitive resin composition, turbidity will arise in the photosensitive resin composition and transparency will fall. 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 cannot 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). Therefore, it can have high transparency. For this reason, the resolution of the photosensitive resin composition is improved, and a fine through hole, an opening pattern, or the like can be formed in a layer made of a cured product of the photosensitive resin composition. Moreover, the surface roughness of the cured product after the desmear treatment of the cured product of the photosensitive resin composition can be reduced. That is, the photosensitive resin composition can form a cured product having low roughness after desmearing. By reducing the roughness after desmearing of the cured product, a printed wiring board including a layer made of the cured product can have excellent high-frequency characteristics. Furthermore, when the photosensitive resin composition contains the silica filler (D), the glass transition point of the cured product of the photosensitive resin composition can be increased and the thermal expansion coefficient can be reduced. For this reason, since the layer which consists of hardened | cured material of the photosensitive resin composition is hard to warp even if the stress by heat is applied, and it is excellent also in a thermal cycle crack resistance, it can be used for the printed wiring board reduced in thickness. Moreover, the dielectric loss tangent of the hardened | cured material of the photosensitive resin composition can be reduced because the photosensitive resin composition contains a silica filler (D). For this reason, the high frequency transmission performance of a printed wiring board provided with the layer which consists of hardened | cured material of the photosensitive resin composition can be improved. Moreover, in this embodiment, since the photosensitive resin composition contains a carboxyl group-containing resin (A), an organic filler (B), a coupling agent (C), and a silica filler (D), silica The filler (D) interacts with or binds to the carboxyl group of the carboxyl group-containing resin (A) and the carboxyl group of the organic filler (B) via the coupling agent (C) to form a composite or It is thought to be hybridized. For this reason, the glass transition point of the hardened | cured material of the photosensitive resin composition further rises, 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 cured by irradiating the photosensitive resin composition with light. Photocurability of the photosensitive resin composition is imparted, for example, when the carboxyl group-containing resin (A) has a photopolymerizable unsaturated group. Moreover, the photocurability of the photosensitive resin composition is also provided by the photosensitive resin composition containing 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 increased, and the transparency of the photosensitive resin composition is further improved.

The carboxyl group-containing resin (A) preferably includes a resin obtained by a reaction between a polyalcohol resin, a polyvalent carboxylic acid, and at least one compound selected from the group consisting of acid anhydrides thereof. In this case, the polyalcohol resin preferably has an aromatic ring, and at least one compound selected from the group consisting of a polyvalent carboxylic acid and an anhydride thereof preferably has an aromatic ring. More preferably, the carboxyl group-containing resin (A) contains a copolymer obtained by a reaction between a polyalcohol resin and an acid dianhydride. In this case, the polyalcohol resin preferably has an aromatic ring, and the acid dianhydride preferably has an aromatic ring. When the carboxyl group-containing resin (A) contains a copolymer obtained by a reaction between a polyalcohol resin and an acid dianhydride, the photosensitive resin composition is provided with high alkali developability, and the photosensitive resin composition High heat resistance and insulation can be imparted to the cured product.

The carboxyl group-containing resin (A) preferably contains a carboxyl group-containing resin having an ethylenically unsaturated group. Since the carboxyl group-containing resin (A) includes 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 the carboxyl group-containing resin (A).

The carboxyl group-containing resin having an ethylenically unsaturated group is, for example, an intermediate that is a reaction product of an epoxy compound (g1) having two or more epoxy groups in one molecule and an ethylenically unsaturated compound (g2), 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 anhydrides thereof, is contained. 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). For example, the first resin (g) is prepared by combining the compound (g3) with an intermediate having a hydroxyl group obtained by reacting an epoxy group in the epoxy compound (g1) with a carboxyl group in the ethylenically unsaturated compound (g2). ) Is added. 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 a compound (h1) having an epoxy group such as glycidyl (meth) acrylate, or further has no epoxy group such as 2- (meth) acryloyloxyethyl phthalate. Contains compound (h2). 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. . The compound (g3) preferably contains an acid dianhydride. The acid dianhydride preferably contains an acid dianhydride having an aromatic ring. In this case, the transparency of the photosensitive resin composition is further improved, and the resolution is further improved accordingly.

The 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. A certain resin (referred to as second resin (i)) may be contained. The ethylenically unsaturated monomer may further contain an ethylenically unsaturated compound having no carboxyl group. The second resin (i) can be obtained by reacting an ethylenically unsaturated compound having an epoxy group with a part of 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. Examples of the ethylenically unsaturated compound having a carboxyl group include acrylic acid, methacrylic acid, ω-carboxy-polycaprolactone (n≈2) monoacrylate, 2- (meth) acryloyloxyethyl phthalate, and 2- (meth) acryloyl. Contains compounds such as loxyethyl-2-hydroxyethyl phthalate. The ethylenically unsaturated compound having no carboxyl group is, for example, a linear or branched aliphatic or alicyclic (however, the ring may have a partially unsaturated bond) (meth) acrylic acid ester Etc. are contained. 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, the aromatic ring included in the carboxyl group-containing resin (A) is preferably 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 increased, and the photosensitive resin composition has more excellent resolution. The carboxyl group-containing resin (A) further preferably contains a carboxyl group-containing resin having at least one of a biphenyl skeleton and a bisphenol fluorene skeleton, and particularly preferably contains a carboxyl group-containing resin having a bisphenol fluorene skeleton. In this case, the dielectric loss tangent in the cured product of the photosensitive resin composition containing the carboxyl group-containing resin (A) can be further reduced.

The carboxyl group-containing resin (A) is represented by the following formula (1), and in the formula (1), R ₁ to R ₈ are each independently hydrogen, an alkyl group having 1 to 5 carbon atoms, or a bisphenolfluorene skeleton. An intermediate which is a reaction product of an epoxy compound (a1) having a carboxylic acid (a2) containing an unsaturated group-containing carboxylic acid (a2-1) and a carboxylate which is a reaction product of an acid anhydride (a3) It preferably contains a group-containing resin (hereinafter referred to as 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 the epoxy compound (a1) having a bisphenolfluorene skeleton. The carboxyl group-containing resin (A1) has an ethylenically unsaturated group derived from the carboxylic acid (a2) including the unsaturated group-containing carboxylic acid (a2-1). The carboxyl group-containing resin (A1) reacts an epoxy compound (a1) having a bisphenolfluorene skeleton represented by the following formula (1) with a carboxylic acid (a2) containing an unsaturated group-containing carboxylic acid (a2-1). And an intermediate obtained thereby and the acid anhydride (a3) are reacted.

Wherein _{_{(1), R 1 ~ R}} 8 is independently hydrogen, alkyl or halogen having 1 to 5 carbon atoms. That is, each of R ₁ to R ₈ in Formula (1) may be hydrogen, but may be an alkyl group having 1 to 5 carbon atoms or 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. This is because the heat resistance or flame retardancy of the cured product of the conductive resin composition may be improved.

Since the carboxyl group-containing resin (A1) has a bisphenolfluorene skeleton represented by the formula (1) derived from the epoxy compound (a1), it can impart high heat resistance and insulation to the cured product of the photosensitive resin composition. . Moreover, the developability excellent in the photosensitive resin composition can be provided because carboxyl group-containing resin (A1) has a carboxyl group derived from an acid anhydride (a3).

The carboxyl group-containing resin (A1) will be described more specifically. 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 bisphenolfluorene skeleton represented by the formula (1) and an unsaturated group-containing carboxylic acid (a2- An intermediate is synthesized by reacting the 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 a ring-opening addition reaction between 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, carboxyl group-containing resin (A1) can be synthesized. The reaction between the intermediate and the acid anhydride (a3) is defined as the second reaction. The acid anhydride (a3) can 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. An acid dianhydride is a compound having two acid anhydride groups obtained by dehydration condensation of four carboxyl groups in one molecule.

The carboxyl group-containing resin (A1) may contain unreacted components in the intermediate. In the case where the acid anhydride (a3) includes an acid monoanhydride and an acid dianhydride, the carboxyl group-containing resin (A1) includes a component in the intermediate, a component in the acid monoanhydride, and an acid dianhydride. In addition to the reactant with the component in the intermediate, any of the reactant in the intermediate with the component in the acid monoanhydride, and the reactant 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.

The carboxyl group-containing resin (A1) has photoreactivity by having an ethylenically unsaturated group derived from the unsaturated group-containing carboxylic acid (a2-1). For this reason, carboxyl group-containing resin (A1) can provide photosensitivity, specifically, ultraviolet curability, to the photosensitive resin composition. Moreover, carboxyl group-containing resin (A1) has a carboxyl group derived from an acid anhydride (a3), so that the photosensitive resin composition contains at least one of an alkali metal salt and an alkali metal hydroxide. The developability by alkaline aqueous solution can be provided.

The weight average molecular weight of the carboxyl group-containing resin (A1) is preferably in the range of 700 to 10,000. When the weight average molecular weight is 700 or more, the insulating property of the cured product of the photosensitive resin composition can be improved and the dielectric loss tangent can be reduced. Moreover, the developability by the alkaline aqueous solution of the photosensitive resin composition improves especially that a weight average molecular weight is 10,000 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, the developability excellent in the photosensitive resin composition can be provided, ensuring the favorable insulation of the hardened | cured material 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.

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

The polydispersity is the 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 value of the carboxyl group-containing resin (A1) is preferably in the range of 60 to 140 mgKOH / g. In this case, the developability of the photosensitive resin composition is particularly improved. The acid value is more preferably in the range of 80 to 135 mgKOH / g, and the acid value is more preferably in the range of 90 to 130 mgKOH / 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) having an adjusted acid value and molecular weight is obtained. That is, the molecular weight and acid value of the carboxyl group-containing resin (A1) can be easily adjusted by controlling the amount of acid dianhydride contained in the acid anhydride (a3). In addition, the molecular weight of carboxyl group-containing resin (A1) is calculated from the measurement results under the following conditions by gel permeation chromatography.

GPC device: SHODEX SYSTEM 11, manufactured by Showa Denko KK
Column: 4 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 material of the carboxyl group-containing resin (A1) and the reaction conditions during the synthesis of the carboxyl group-containing resin (A1) will be described in detail.

The epoxy compound (a1) has a structure represented by the following formula (2), for example. N in the formula (2) is, for example, an integer in the range of 0-20. 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 excessive increase in molecular weight is likely to be suppressed.

The carboxylic acid (a2) includes an 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 a carboxylic acid other than the unsaturated group-containing carboxylic acid (a2-1) and the unsaturated group-containing carboxylic acid (a2-1).

The unsaturated group-containing carboxylic acid (a2-1) can contain, for example, a compound having only one ethylenically unsaturated group. More specifically, the unsaturated group-containing carboxylic acid (a2-1) is, for example, acrylic acid, methacrylic acid, ω-carboxy-polycaprolactone (n≈2) monoacrylate, crotonic acid, cinnamic acid, 2-acryloyloxy Ethyl succinic acid, 2-methacryloyloxyethyl succinic acid, 2-acryloyloxyethyl phthalic acid, 2-methacryloyloxyethyl phthalic acid, 2-acryloyloxypropyl phthalic acid, 2-methacryloyloxypropyl phthalic acid, 2-acryloyloxyethyl malein Acid, 2-methacryloyloxyethyl maleic acid, β-carboxyethyl acrylate, 2-acryloyloxyethyl tetrahydrophthalic acid, 2-methacryloyloxyethyl tetrahydrophthalic acid, 2-acryloyloxyethyl hexahydrophthal One or more compounds selected from the group consisting of phosphoric acid and 2-methacryloyloxyethyl hexahydrophthalic acid can be contained. 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 capable of substituting two or more hydrogen atoms with 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 polybasic acid (a2-1) cross-links the epoxy groups present in the two molecules of the epoxy compound (a1), thereby increasing the molecular weight. Thereby, while being able to improve the insulation of the hardened | cured material of the photosensitive resin composition, a 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 One or more compounds selected from the group consisting of acid and terephthalic acid can be contained. Preferably, the polybasic acid (a2-2) contains 4-cyclohexene-1,2-dicarboxylic acid.

In reacting the epoxy compound (a1) with the carboxylic acid (a2), a known method may be employed. For example, the reactive solution is obtained by adding the carboxylic acid (a2) to the solvent solution of the epoxy compound (a1), further adding a thermal polymerization inhibitor and a catalyst as necessary, and stirring and mixing. An intermediate can be obtained by reacting this reactive solution at a temperature of preferably 60 to 150 ° C., particularly preferably 80 to 120 ° C., by a conventional method. 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 acetates, acetate esters 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 at least 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 triphenylstibine. A kind of component can be contained.

It is particularly preferable that the catalyst contains triphenylphosphine. That is, it is preferable to react the epoxy compound (a1) and the carboxylic acid (a2) in the presence of triphenylphosphine. In this case, the ring-opening addition reaction between the epoxy group and the carboxylic acid (a2) in the epoxy compound (a1) is particularly accelerated, and a reaction rate (conversion rate) of 95% or more, 97% or more, or almost 100% is achieved. Is possible. Moreover, generation | occurrence | production of the ion migration in the layer containing the hardened | cured material of the photosensitive resin composition is suppressed, and the insulation of the layer containing hardened | cured material improves.

When the epoxy compound (a1) and the carboxylic acid (a2) are reacted, the amount of the carboxylic acid (a2) relative to 1 mol of the epoxy group of the epoxy compound (a1) is in the range of 0.5 to 1.2 mol. Is preferred. In this case, excellent photosensitivity and stability of the photosensitive resin composition can be obtained. From the same viewpoint, the amount of the unsaturated group-containing carboxylic acid (a2-1) relative to 1 mol of the epoxy group of the epoxy compound (a1) is preferably in the range of 0.5 to 1.2 mol. 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-) with respect to 1 mol 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 the polybasic acid (a2-1) relative to 1 mol of the epoxy group of the epoxy compound (a1) is 0.025 to 0.25. It is preferably within 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) and the carboxylic acid (a2) under air bubbling. In this case, the addition polymerization reaction of the unsaturated group can be suppressed, and the increase in the molecular weight of the intermediate and the gelation of the intermediate solution can be suppressed. Moreover, the excessive coloring of carboxyl group-containing resin (A1) which is a final product can be suppressed.

The intermediate obtained in this way has a hydroxyl group produced 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 having one acid anhydride group.

The acid monoanhydride can contain an anhydride of dicarboxylic acid. Examples of the acid monoanhydride include 1,2,3,6-tetrahydrophthalic anhydride, phthalic anhydride, succinic anhydride, methyl succinic anhydride, maleic anhydride, citraconic anhydride, glutaric anhydride, Itaconic anhydride, methyltetrahydrophthalic anhydride, methyl nadic anhydride, hexahydrophthalic anhydride, cyclohexane-1,2,4-tricarboxylic acid-1,2-anhydride, and methylhexahydrophthalic anhydride One or more compounds selected from the group consisting of products can be contained. In particular, the acid monoanhydride preferably contains 1,2,3,6-tetrahydrophthalic anhydride. In this case, the insulating property of the cured product of the photosensitive resin composition can be improved while ensuring good developability of the photosensitive resin composition. 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 entire acid monoanhydride. However, it is not limited to this.

The acid anhydride (a3) preferably contains an acid dianhydride. An acid dianhydride is a compound having two acid anhydride groups. The acid dianhydride can contain an anhydride of tetracarboxylic acid. Examples of the acid dianhydride include 1,2,4,5-benzenetetracarboxylic dianhydride, benzophenone tetracarboxylic dianhydride, methylcyclohexene tetracarboxylic dianhydride, tetracarboxylic dianhydride, naphthalene-1 , 4,5,8-tetracarboxylic dianhydride, ethylenetetracarboxylic dianhydride, 9,9'-bis (3,4-dicarboxyphenyl) fluorene dianhydride, glycerin bisanhydro trimellitate mono Acetate, ethylene glycol bisanhydro trimellitate, 3,3 ′, 4,4′-diphenylsulfone tetracarboxylic 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 dianhydride. In this case, the insulating property of the cured product of the photosensitive resin composition can be improved while ensuring good developability of the photosensitive resin composition. Moreover, the transparency of the photosensitive resin composition is improved, and the resolution is improved accordingly. 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride is preferably in the range of 20 to 100 mol%, and in the range of 40 to 100 mol%, based on the entire acid dianhydride. Although it is more preferable that there is, it is not limited to this.

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

It is particularly preferable that the catalyst contains triphenylphosphine. That is, it is preferable to react the intermediate and the acid anhydride (a3) in the presence of triphenylphosphine. In this case, the reaction between the secondary hydroxyl group and the acid anhydride (a3) in the intermediate is particularly accelerated, and a reaction rate (conversion rate) of 90% or more, 95% or more, 97% or more, or almost 100% is achieved. Is possible. Moreover, generation | occurrence | production of the ion migration in the layer containing the hardened | cured material of the photosensitive resin composition is suppressed, and the insulation of the layer containing hardened | cured material further improves.

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

The carboxyl group-containing resin (A) may include a carboxyl group-containing resin having an aromatic ring and not having photopolymerizability. The carboxyl group-containing resin having an aromatic ring and not having photopolymerizability contains, for example, a polymer of an ethylenically unsaturated monomer including an ethylenically unsaturated compound having a carboxyl group. Ethylenically unsaturated compounds having a carboxyl group include acrylic acid, methacrylic acid, ω-carboxy-polycaprolactone (n≈2) monoacrylate, 2- (meth) acryloyloxyethyl phthalate, 2- (meth) acryloyloxy Compounds such as ethyl-2-hydroxyethyl phthalate can be contained. The ethylenically unsaturated compound having a carboxyl group can also contain a reaction product of pentaerythritol triacrylate, pentaerythritol trimethacrylate and the like with a dibasic acid anhydride. The ethylenically unsaturated monomer is a carboxyl group such as a linear or branched aliphatic or alicyclic (however, the ring may have a partially unsaturated bond) (meth) acrylic acid ester, etc. You may further contain the 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 a carboxyl group-containing resin (A1) and a carboxyl group-containing resin other than the carboxyl group-containing resin (A1). Only a carboxyl group-containing resin other than the group-containing resin (A1) may be included. From the viewpoint of obtaining high transparency of the photosensitive resin composition and reducing the dielectric loss tangent of the cured product of the photosensitive resin composition, the carboxyl group-containing resin (A) is 30 masses of the carboxyl group-containing resin (A1). % Or more, preferably 60% by mass or more, 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, more preferably in the range of 10 to 75% by mass, based on the solid content of the photosensitive resin composition. It is preferably in the range of 26 to 60% by mass, more preferably in the range of 30 to 45% by mass. When the photosensitive resin composition contains the carboxyl group-containing resin (A1), the content of the carboxyl group-containing resin (A1) is in the range of 5 to 85% by mass with respect to the solid content of the photosensitive resin composition. Is preferably within the range of 10 to 75% by mass, more preferably within the range of 26 to 60% by mass, and particularly preferably within the range of 30 to 45% by mass. preferable. In addition, solid content is a total amount of all components remove | excluding volatile components, such as a solvent, from the photosensitive resin composition.

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

Organic filler (B) has a carboxyl group. The carboxyl group of the organic filler (B) can be obtained by, for example, polymerizing or crosslinking a carboxylic acid monomer having a polymerizable unsaturated double bond such as acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid, and itaconic acid. 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) increases 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, the developability of the cured product of the photosensitive resin composition is improved, and when the photosensitive resin composition contains a crystalline epoxy compound, a crystalline epoxy is used. Crystallization can be prevented by improving the compatibility of the compound. 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 mgKOH / g as the acid value by acid-base titration. If the acid value is less than 1 mgKOH / g, the stability of the photosensitive resin composition and the developability of the cured product may be reduced. If the acid value is larger than 60 mgKOH / g, the moisture resistance reliability of the cured product may be lowered. The acid value of the organic filler (B) is more preferably 3 to 40 mgKOH / g.

It is also preferable that the organic filler (B) has a hydroxyl group. When the organic filler (B) has a hydroxyl group, the dispersibility of the organic filler (B) in the photosensitive resin composition is improved.

The average primary particle diameter of the organic filler (B) is 1 μm or less. When the average primary particle diameter of the organic filler (B) is 1 μm or less, the thixotropy of the photosensitive resin composition is efficiently increased. 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 a laser diffraction particle size distribution measuring device, is measured as D _50. The average primary particle diameter of the organic filler (B) is preferably 0.1 μm or less. In this case, the stability of the photosensitive resin composition is further improved and the resolution is further improved since scattering during exposure is suppressed.

The organic filler (B) is preferably contained in the photosensitive resin composition in a state where the particle diameter is 10 μm or less. An organic filler (B) may contain a secondary particle by aggregating in the photosensitive resin composition. In that case, the particle diameter of the organic filler (B) in the photosensitive resin composition means the particle diameter of the 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 particle size distribution analyzer or an optical microscope. If the organic filler (B) is contained in the photosensitive resin composition with a particle size of 10 μm or less, the stability of the photosensitive resin composition is further improved and scattering during exposure is suppressed. The image quality is further improved. The organic filler (B) is more preferably contained in the photosensitive resin composition in a state where the particle diameter is 5 μm or less, more preferably in a state where the particle diameter is 1 μm or less, and 0.5 μm. It is particularly preferable that it is contained in the following state. In this case, the stability of the photosensitive resin composition is further improved and the resolution is further improved since scattering during exposure is suppressed. Although the minimum of the particle diameter of the organic filler (B) in the photosensitive resin composition is not specifically limited, For example, it may be 0.01 micrometer 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 this embodiment can have high resolution even if it contains a rubber component. The rubber component can 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. Moreover, a softness | flexibility can be provided to the hardened | cured material of the photosensitive resin composition effectively with a rubber component. NBR is generally a copolymer of butadiene and acrylonitrile, and is classified as a nitrile rubber. MBS is generally a copolymer composed of three components of methyl methacrylate, butadiene, and styrene, and is classified as a butadiene rubber. SBR is generally a copolymer of styrene and butadiene, and is classified as styrene rubber. Specific examples of the organic filler (B) include product number XER-91-MEK manufactured by JSR Corporation. This organic filler is a crosslinked rubber (NBR) having a carboxyl group having an average primary particle diameter of 0.07 μm, and is provided as a methyl ethyl ketone dispersion having a content of crosslinked rubber of 15% by weight, and its acid value is 10.0 mgKOH / g. It is. Thus, an organic filler (B) may be mix | blended with a dispersion liquid. The rubber component can be blended in a dispersion. In addition to the above, specific examples of the organic filler (B) include product numbers XER-32 and XER-92 manufactured by JSR Corporation. Further, as a dispersion of a crosslinked rubber (SBR) having a carboxyl group and a hydroxyl group, product number XSK-500 manufactured by JSR Corporation may be mentioned.

The organic filler (B) may contain a particle component 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 particles having a carboxyl group can contain at least one particle component selected from the group consisting of non-crosslinked styrene / acrylic resin fine particles and crosslinked styrene / acrylic resin fine particles. As a specific example of the non-crosslinked styrene / acrylic resin fine particles, product number FS-201 (average primary particle size 0.5 μm) manufactured by Nippon Paint Industrial Coatings Co., Ltd. may be mentioned. As specific examples of the crosslinked styrene / acrylic resin fine particles, product number MG-351 (average primary particle size 1.0 μm) and product number BGK-001 (average primary particle size 1.0 μm) manufactured by Nippon Paint Industrial Coatings Co., Ltd. Is mentioned. The organic filler (B) may contain a particle component other than the particle component selected from the rubber component, acrylic resin fine particles, and cellulose fine particles. 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 acrylic resin fine particles, and the cellulose fine particles.

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 the 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) is used. 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 carboxyl group-containing resin (A). Good copper plating adhesion of the cured product of the photosensitive resin composition because the content of the organic filler (B) is 1 part by mass or more with respect to 100 parts by mass of the carboxyl group-containing resin (A). Can be obtained. Moreover, the outstanding resolution of the photosensitive resin composition can be obtained because content of an organic filler (B) is 50 mass parts or less. Moreover, 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 with respect to 100 parts by mass of the carboxyl group-containing resin (A), and is preferably in the range of 10 to 20 parts by mass. More preferably.

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 alkoxy groups, acyloxy groups, and alkoxides. The coupling agent (C) may have two or more alkoxy groups, two or more acyloxy groups, or two or more alkoxides. Moreover, 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) increases 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. Thereby, 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. Direct bonding is preferred.

When the coupling agent (C) has a silicon atom, examples of the coupling agent (C) include tetraethoxysilane, tetramethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinylmethyldiethoxysilane, and vinylmethyldimethoxy. Silane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidyl Sidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, p-styryltrimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl)- 3-aminopro Rutrimethoxysilane, 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-methacrylic Xylpropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, allyltriethoxysilane, allyltrimethoxysilane, allylchlorodimethylsilane, 3-chloropropyltrimethoxysilane, 3-chloropropyltriethoxysilane, 3-chloro Propyldimethoxymethylsilane, chloromethyltriethoxysilane, chloromethyltrimethoxysilane, 3-chloropropylmethyldiethoxysilane, 3-isocyanatopropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, bis (triethoxysilylpropyl) Tetrasulfide, cyclohexyltrimethoxysilane, methyltriethoxysilane, methyltrimethoxysilane, ethyltriethoxysilane, ethyltrimethoxysilane Hexyltrimethoxysilane, 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-pentafluorophenoxyundec Rutrimethoxysilane, pentafluorophenyltrimethoxysilane, 11-azidoundecyltrimethoxysilane, 2-cyanoethyltriethoxysilane, and vinyltriacetoxysilane.

When the coupling agent (C) has an aluminum atom, examples of the coupling agent (C) include acetoalkoxy aluminum diisopropylate, aluminum diisopropoxy monoethyl acetoacetate, and aluminum trisethyl acetoacetate.

When the coupling agent (C) has a titanium atom, examples of the coupling agent (C) include isopropyl tristearoyl titanate, isopropyl tris (dioctyl pyrophosphate) titanate, tetraoctyl bis (ditridecyl phosphate titanate), tetra (2 -2-diallyloxymethyl-1-butyl) bis (ditridecyl) phosphate titanate, bis (dioctylpyrophosphate) oxyacetate titanate, and bis (dioctylpyrophosphate) ethylene titanate.

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

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

The coupling agent (C) preferably has 2 to 4 functional groups selected from the group consisting of alkoxy groups, acyloxy groups and alkoxides. The coupling agent (C) may have 2 to 4 alkoxy groups, may have 2 to 4 acyloxy groups, and may have 2 to 4 alkoxides. For example, the coupling agent (C) may have 2 to 4 methoxy groups, 2 to 4 ethoxy groups, or 2 to 4 acetoxy groups. Good. The coupling agent (C) may have two to four different functional groups selected from the group consisting of alkoxy groups, acyloxy groups, and alkoxides. Since the coupling agent (C) has two to four 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 An excessive crosslinking reaction due to the reaction between the coupling agent (C) and the silica filler (D) can be suppressed, and the dispersibility of the organic filler (B) and the silica filler (D) in the photosensitive resin composition is improved. 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, the carboxyl group contained in the carboxyl group-containing resin (A) and the carboxyl group contained in the organic filler (B) can be reacted, and the dispersibility of the organic filler (B) in the photosensitive resin composition is further increased. Increases efficiently. 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, a coupling agent (C) may have an epoxy group by having a glycidoxy group. When the coupling agent (C) contains a vinyl group, the vinyl group is directly bonded to a silicon atom, for example. Since 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 improved. This increases the dispersibility of the organic filler (B) in the photosensitive resin composition more efficiently. It is preferable that the coupling agent (C) has an epoxy group or a vinyl group. In this case, the insulating property of the photosensitive resin composition is increased 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 containing at least one group selected from the group consisting of an alkoxy group, an acyloxy group, and an alkoxide. However, from the viewpoint of efficiently obtaining the dispersibility of the organic filler (B) and the silica filler (D), and from the viewpoint of improving the transparency and stability of the photosensitive resin composition, the photosensitive resin composition is a coupling agent. Coupling agents 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), a coupling agent other than the coupling agent (C) and the coupling agent (C); The content of the coupling agent (C) is preferably 30% by mass or more, and more preferably 50% by mass or more with respect to the total content. 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 within a range of 0.01 to 10 parts by mass with respect to a total of 100 parts by mass of the content of the organic filler (B) and the content of the silica filler (D). It is preferable. When the content of the coupling agent (C) falls within this range, aggregation of the organic filler (B) and the silica filler (D) in the photosensitive resin composition is prevented, and dispersibility is improved. The content of the coupling agent (C) is 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). It is more preferable.

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

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 increased, and the resolution of the photosensitive resin composition is further improved. Examples of the silica sol include a spherical silica sol and a chain silica sol. Specific examples of the silica filler (D) include organosilica sols manufactured by Nissan Chemical Industries, Ltd .: part numbers MA-ST-M, MA-ST-L, IPA-ST, IPA-ST-ZL, IPA-ST-UP, EG -ST, NPC-ST-30, PGM-ST, DMAC-ST, MEK-ST-40, MIBK-ST, MIBK-ST-L, CHO-ST-M, EAC-ST, TOL-ST, MEK-AC -4130Y, MEK-AC-5140Z, PGM-AC-2140Y, PGM-AC-4130Y, MIBK-AC-2140Z, MIKB-SD-L, MEK-EC-6150P, MEK-EC-7150P, EP-F2130Y, EP -F6140P, EP-F7150P, PMA-ST, MEK-EC-2130Y, MEK-AC-2140Z, M KNOST-L, MEK-ST-ZL, MEK-ST-UP; NANOCRYL manufactured by Hanse-Chemie: Part No. XP0396, XP0596, XP0733, XP0746, XP0765, XP0768, XP0953, XP0954, XPE104h; NANOPOX: product 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 include a silica filler whose average primary particle diameter is not within the range of 1 to 150 nm, or may include an inorganic filler other than the silica filler. Examples of inorganic fillers other than the silica filler (D) include barium sulfate, crystalline silica, nano silica, carbon nanotube, 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 its cured product 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 an inorganic filler other than the silica filler (D) and 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 carboxyl group-containing resin (A). When the content of the silica filler (D) is 5 parts by mass or more, the transparency of the photosensitive resin composition is further increased. Moreover, the photosensitive resin composition can have further excellent resolution because the content of the silica filler (D) is 200 parts by mass or less. Moreover, while content of a silica filler (D) becomes in this range, while further 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 further be reduced. Furthermore, the surface roughness of the cured product after the desmear treatment of 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, and preferably 40 to 100 parts by mass with respect to 100 parts by mass 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. The unsaturated compound (E) is, for example, a monofunctional (meth) acrylate 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, tricyclodecandi It contains 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 tricyclodecane dimethanol 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 tricyclodecane dimethanol di (meth) acrylate. In this case, the dielectric loss tangent of the cured product of the photosensitive resin composition can be further reduced.

It is also 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 with an alkaline aqueous solution is particularly improved. Trifunctional compounds include, for example, trimethylolpropane tri (meth) acrylate, EO modified trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, ethoxylated isocyanuric acid tri (meth) acrylate and ε-caprolactone modified At least one compound selected from the group consisting of tris- (2-acryloxyethyl) isocyanurate and ethoxylated glycerin tri (meth) acrylate.

It is also preferable that the unsaturated compound (E) contains a phosphorus-containing compound (phosphorus-containing unsaturated compound). In this case, the flame retardancy of the cured product of the photosensitive resin composition is improved. Phosphorus-containing unsaturated compounds include, for example, 2-methacryloyloxyethyl acid phosphate (specific examples: product number light ester P-1M and light ester P-2M manufactured by Kyoeisha Chemical Co., Ltd.), 2-acryloyloxyethyl acid phosphate (Specific examples are product number light acrylate P-1A manufactured by Kyoeisha Chemical Co., Ltd.), diphenyl-2-methacryloyloxyethyl phosphate (specific examples are product number MR-260 manufactured by Daihachi Industry Co., Ltd.), and Showa Polymer Co., Ltd. HFA series (specifically, product numbers HFA-6003 and HFA-6007, which are addition reaction products of dipentaerystol hexaacrylate and HCA, are addition reaction products of caprolactone-modified dipentaerystol hexaacrylate and HCA) Part 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 at least one selected from the group consisting of, for example, a prepolymer obtained by polymerizing a monomer having an ethylenically unsaturated bond and then adding an ethylenically unsaturated group, and oligo (meth) acrylate prepolymers These compounds can be contained. Oligo (meth) acrylate prepolymers include, for example, epoxy (meth) acrylate, polyester (meth) acrylate, urethane (meth) acrylate, alkyd resin (meth) acrylate, silicone resin (meth) acrylate, and spirane resin (meth) acrylate 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). Preferably, it is in the range of 10 to 45% by mass, and more preferably in the range of 21 to 40% by mass.

The photosensitive resin composition preferably further contains a photopolymerization initiator (F). A photoinitiator (F) contains an acyl phosphine oxide type photoinitiator, for example. That is, the photosensitive resin composition contains, for example, an acyl phosphine oxide photopolymerization initiator. In this case, when exposing the photosensitive resin composition, high photosensitivity can be imparted to the photosensitive resin composition. Moreover, generation | occurrence | production of the ion migration in the layer containing the hardened | cured material of the photosensitive resin composition is suppressed, and the insulation of the layer containing hardened | cured material further improves.

Acylphosphine oxide photopolymerization initiators include monoacylphosphine oxides such as 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide and 2,4,6-trimethylbenzoyl-ethyl-phenyl-phosphinate. Photopolymerization initiator, bis- (2,6-dichlorobenzoyl) phenylphosphine oxide, bis- (2,6-dichlorobenzoyl) -2,5-dimethylphenylphosphine oxide, bis- (2,6- Dichlorobenzoyl) -4-propylphenylphosphine oxide, bis- (2,6-dichlorobenzoyl) -1-naphthylphosphine oxide, bis- (2,6-dimethoxybenzoyl) phenylphosphine oxide, bis- (2, 6-Dimethoxybenzoyl -2,4,4-trimethylpentylphosphine oxide, bis- (2,6-dimethoxybenzoyl) -2,5-dimethylphenylphosphine oxide, bis- (2,4,6-trimethylbenzoyl) phenylphosphine oxide And 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, the acyl phosphine oxide photopolymerization initiator preferably includes 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, and the acyl phosphine oxide photopolymerization initiator includes 2,4,6-trimethylbenzoyl. Only diphenyl-phosphine oxide may be included.

The photopolymerization initiator (F) preferably contains a hydroxyketone photopolymerization initiator in addition to the acylphosphine oxide photopolymerization initiator. That is, the photosensitive resin composition preferably contains a hydroxyketone photopolymerization initiator. In this case, higher photosensitivity can be imparted to the photosensitive resin composition as compared with the case where no hydroxyketone photopolymerization initiator is contained. Thereby, when hardening the photosensitive resin composition by exposure, it becomes possible to make it fully harden | cure over the deep part from the surface of the coating film formed from the photosensitive resin composition. Examples of hydroxyketone-based photopolymerization initiation include 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- Includes hydroxy-2-methyl-1-phenyl-propan-1-one.

When the photosensitive resin composition contains an acylphosphine oxide photopolymerization initiator and a hydroxyketone photopolymerization initiator, the mass ratio between the acylphosphine oxide photopolymerization initiator and the hydroxyketone photopolymerization initiator is , Preferably 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 from 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 photopolymerization initiator (F) contains bis (diethylamino) benzophenone. That is, the photosensitive resin composition contains an acyl phosphine oxide photopolymerization initiator and bis (diethylamino) benzophenone, or an acyl phosphine oxide photopolymerization initiator, a hydroxyketone photopolymerization initiator, and bis (diethylamino). It is also preferable to contain benzophenone. In this case, when developing after partially exposing the coating film formed from the photosensitive resin composition, the resolution is particularly enhanced by suppressing the curing of the unexposed portion. For this reason, it becomes possible to form a very fine pattern with the hardened | cured material of the photosensitive resin composition. In particular, when an interlayer insulating layer of a multilayer printed wiring board is produced from a photosensitive resin composition and a small-diameter hole for a through hole is provided in the interlayer insulating layer by a photolithography method (see FIG. 1), the small-diameter hole is formed. It becomes possible to form precisely and easily.

When the photosensitive resin composition contains bis (diethylamino) benzophenone and an acyl phosphine oxide photopolymerization initiator, the content of bis (diethylamino) benzophenone is 0. 0 relative to the acyl phosphine oxide photopolymerization initiator. It is preferably in the range of 5 to 20% by mass. When the content of bis (diethylamino) benzophenone is 0.5% by mass or more, the resolution is particularly high. Further, when the content of bis (diethylamino) benzophenone is 20% by mass or less, bis (diethylamino) benzophenone hardly inhibits the electrical insulation of the cured product of the photosensitive resin composition.

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

The photosensitive resin composition preferably further contains an epoxy compound (G). The epoxy compound (G) can impart thermosetting properties to the photosensitive resin composition. The epoxy compound (G) preferably contains a crystalline epoxy resin. The crystalline epoxy resin is an epoxy resin having a melting point. The crystalline epoxy resin can impart thermosetting properties to the photosensitive resin composition. Furthermore, the crystalline epoxy resin improves the heat resistance and 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 (specifically, product name YDC-1312 manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.), biphenyl type crystalline epoxy resin (specifically, product name YX-4000 manufactured by Mitsubishi Chemical Corporation), diphenyl ether type crystalline epoxy resin (specifically For example, Nippon Steel & Sumikin Chemical Co., Ltd., product number YSLV-80DE), bisphenol type crystalline epoxy resin (specifically, Nippon Steel & Sumikin Chemical Co., Ltd. product name YSLV-80XY), tetrakisphenol ethane type crystalline epoxy resin Nippon Kayaku Co., Ltd. product number GTR-1800), bisphenolfluorene type Preferably includes one or more components selected from the group consisting of (epoxy resin having a structure represented by the formula (2) as a specific example) sex epoxy resin.

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

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

Examples of the melting point of the crystalline epoxy resin include 70 to 180 ° C. In particular, the crystalline epoxy resin preferably contains a crystalline epoxy resin having a melting point of 110 ° C. or lower. In this case, the developability of the photosensitive resin composition with an alkaline aqueous solution is particularly improved. Crystalline epoxy resins having a melting point of 110 ° C. or less include, for example, biphenyl type epoxy resins (specifically, product number YX4000 manufactured by Mitsubishi Chemical Corporation), biphenyl ether type epoxy resins (specifically, product number YSLV- manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.) 80DE), and a bisphenol type epoxy resin (part number YSLV-80XY manufactured by Nippon Steel & Sumikin Chemical Co., Ltd. as a specific example), a bisphenol fluorene type crystalline epoxy resin (an epoxy resin having a structure represented by the formula (2) as a specific example). Including at least one component selected.

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

Amorphous epoxy resins include, for example, phenol novolac type epoxy resins (specifically, product number EPICLON N-775 manufactured by DIC Corporation) and cresol novolac type epoxy resins (specific examples, product number EPICLON N-695 manufactured by DIC Corporation). Bisphenol A novolac type epoxy resin (specific example, product number EPICLON N-865 manufactured by DIC Corporation), bisphenol A type epoxy resin (specific example, product number jER1001 manufactured by Mitsubishi Chemical Corporation), bisphenol F type epoxy resin (specific example As product number jER4004P manufactured by Mitsubishi Chemical Co., Ltd.), bisphenol S type epoxy resin (specifically, product number EPICLON EXA-1514 manufactured by DIC Corporation), bisphenol AD type epoxy resin, biphenyl novolac Type epoxy resin (part number NC-3000 manufactured by Nippon Kayaku Co., Ltd.), hydrogenated bisphenol A type epoxy resin (part number ST-4000D manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.), naphthalene type epoxy resin (particular Examples include DIC Corporation part numbers EPICLON HP-4032, EPICLON HP-4700, EPICLON HP-4770), tertiary butyl catechol type epoxy resin (specific examples DIC Corporation part number EPICLON HP-820), dicyclopentadiene. Type epoxy resin (specifically, product number EPICLON HP-7200 manufactured by DIC), adamantane type epoxy resin (specific example, product number ADAMANTATE X-E-201 manufactured by Idemitsu Kosan Co., Ltd.), special bifunctional epoxy resin (tool) For example, product numbers YL7175-500 and YL7175-1000 manufactured by Mitsubishi Chemical Corporation; product numbers EPICLON TSR-960, EPICLON TER-601, EPICLON TSR-250-80BX, EPICLON 1650-75MPX, EPICLON EXA- manufactured by DIC Corporation 4850, EPICLON EXA-4816, EPICLON EXA-4822, and EPICLON EXA-9726; product number YSLV-120TE manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., rubber core-shell polymer modified bisphenol A type epoxy resin (specifically, manufactured by Kaneka Corporation) Product number MX-156), and rubber core-shell polymer modified bisphenol F type epoxy resin (specifically, product number MX-136 manufactured by Kaneka Corporation) It is preferable to include one or more components selected from the group consisting of:

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. Examples of phosphorus-containing epoxy resins include phosphoric acid-modified bisphenol F-type epoxy resins (specific examples of product numbers EPICLON EXA-9726 and EPICLON EXA-9710 manufactured by DIC Corporation), and product number Epototo FX-305 manufactured by Nippon Steel & Sumikin Chemical Co., Ltd. Is mentioned.

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

The content of the epoxy compound (G) is such that the total of equivalents of epoxy groups contained in the epoxy compound (G) is 0.7 to 2.5 with respect to 1 equivalent of carboxyl groups contained in the carboxyl group-containing resin (A). Is preferably in the range of 0.7 to 2.3, more preferably in the range of 0.7 to 2.0. Further, when the epoxy compound (G) contains a crystalline epoxy resin, the total of the equivalents of epoxy groups contained in the crystalline epoxy resin is 0. 0 with respect to 1 equivalent of carboxyl groups contained in the carboxyl group-containing resin (A). It is preferably within the range of 7 to 2.5, more preferably within the range of 0.7 to 2.3, and even more preferably within 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 increased. For this reason, the photosensitive resin composition is particularly suitable as an insulating material for a printed wiring board. Moreover, the plating resistance of the cured product of the photosensitive resin composition, that is, the whitening resistance during the electroless nickel / gold plating process is improved.

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

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, viscosity adjustment, application property adjustment, film formation property adjustment, and the like.

Organic solvents include, for example, linear, branched, secondary or polyhydric alcohols such as ethanol, propyl alcohol, isopropyl alcohol, hexanol and ethylene glycol; ketones such as methyl ethyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene and xylene Petroleum aromatic mixed solvents such as Swazol series (manufactured by Maruzen Petrochemical Co., Ltd.) and Solvesso series (manufactured by Exxon Chemical Co.); cellosolves such as cellosolve and butylcellosolve; Tolls; 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, cal Acetic acid esters such as tall acetate; as well as one or more compounds selected from the group consisting of dialkyl glycol ethers.

When the photosensitive resin composition contains an organic solvent, the amount of the organic solvent is determined so that the organic solvent is volatilized 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 film. 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 an organic solvent changes with application methods etc., it is preferable that a ratio is suitably adjusted according to the application method.

Unless it deviates from the main point of this invention, the photosensitive resin composition may further contain components other than the said component.

The photosensitive resin composition may further contain a known photopolymerization accelerator, sensitizer and the like. For example, the photosensitive resin composition includes benzoin and its alkyl ethers; acetophenones such as acetophenone and benzyldimethyl ketal; anthraquinones such as 2-methylanthraquinone; 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2- Thioxanthones such as isopropylthioxanthone, 4-isopropylthioxanthone and 2,4-diisopropylthioxanthone; benzophenones such as benzophenone and 4-benzoyl-4′-methyldiphenyl sulfide; xanthones such as 2,4-diisopropylxanthone; Α-hydroxyketones 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 is known in combination with a photopolymerization initiator (C), such as tertiary amines such as p-dimethylbenzoic acid ethyl ester, p-dimethylaminobenzoic acid isoamyl ester and 2-dimethylaminoethylbenzoate. You may contain a photoinitiator, a sensitizer, etc. If necessary, the photosensitive resin composition may contain at least one of a photopolymerization initiator for visible light exposure and a photopolymerization initiator for near-infrared exposure. The photosensitive resin composition contains a photopolymerization initiator (F) and a coumarin derivative such as 7-diethylamino-4-methylcoumarin, which is a sensitizer for laser exposure, a carbocyanine dye system, a xanthene dye system, and the like. May be.

Photosensitive resin composition comprising tolylene diisocyanate, morpholine diisocyanate, isophorone diisocyanate and hexamethylene diisocyanate 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 cocondensation resin, benzoguanamine-based cocondensation resin; various other thermosetting resins; ultraviolet curable epoxy (meth) acrylates; , Phenol novolak type, cresol novolak type, alicyclic type and other epoxy resins obtained by adding (meth) acrylic acid; and diallyl phthalate resin, phenoxy resin, urethane resin, fluorine resin 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 hydrazide and sebacic acid hydrazide; phosphorus compounds such as triphenylphosphine; acid anhydrides; phenols; mercaptans; And Comprising one or more components selected from the group consisting um salt. Examples of commercially available products of these components include 2MZ-A, 2MZ-OK, 2PHZ, 2P4BHZ, 2P4MHZ (both trade names of imidazole compounds) manufactured by Shikoku Kasei Co., Ltd., U-CAT3503N, U -CAT3502T (all are trade names of blocked isocyanate compounds of dimethylamine), DBU, DBN, U-CATSA102, U-CAT5002 (all are bicyclic amidine compounds and salts thereof).

The photosensitive resin composition may contain an adhesion-imparting agent other than melamine. Examples of the adhesion-imparting agent include guanamine, acetoguanamine, benzoguanamine, 2,4-diamino-6-methacryloyloxyethyl-S-triazine, 2-vinyl-4,6-diamino-S-triazine, 2-vinyl- Examples thereof include S-triazine derivatives such as 4,6-diamino-S-triazine / isocyanuric acid adduct and 2,4-diamino-6-methacryloyloxyethyl-S-triazine / isocyanuric acid adduct.

Photosensitive resin composition includes a curing accelerator; a colorant; a copolymer such as silicone and acrylate; a leveling agent; an adhesion-imparting agent; a thixotropic agent; a polymerization inhibitor; an antihalation agent; a flame retardant; One or more components selected from the group consisting of an inhibitor; a surfactant; and a polymer dispersant may be contained.

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 a cured product of the photosensitive resin composition is unlikely to be impaired. In particular, the amine compound is preferably 8% by mass or less, and 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 by a known kneading method using, for example, a three roll, ball mill, sand mill or the like. In the case where the raw material of the photosensitive resin composition contains a liquid component, a low viscosity component, etc., the part of the raw material excluding the liquid component, the low viscosity component, etc. is first kneaded, The photosensitive resin composition may be prepared by adding and mixing a liquid component, a component having a low viscosity, and the like. Moreover, you may adjust the photosensitive resin composition not by kneading | mixing but by stirring mixing of a raw material or stirring dissolution.

In consideration of storage stability and the like, the first agent may be prepared by mixing a part 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 include 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 mixed solution by mixing the necessary amount of the first agent and the second agent in a timely manner and curing the mixed solution to obtain a cured product.

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

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

First, a core material 1 is prepared as shown in FIG. 1A. The core material 1 includes, for example, at least one insulating layer 2 and at least one conductor 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. Examples of the method for forming the film 4 include a coating method and a dry film method.

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

In the dry film method, first, a photosensitive resin composition is applied on an appropriate support made of polyester or the like, and then dried to form a dry film containing the photosensitive resin composition on the support. Thereby, the dry film with a support provided with a dry film and the support body which supports a dry film is obtained. In this dry film with a support, the dry film is laminated on the core material 1, then pressure is applied to the dry film and the core material 1, and then the support is peeled off from the dry film, whereby the dry film is cored on the support. Transfer onto material 1. Thereby, the coating 4 made of a dry film is provided on the core material 1.

The film 4 is exposed to light and partially cured as shown in FIG. 1C. For this purpose, for example, a negative mask is applied to the film 4 and then the film 4 is irradiated with ultraviolet rays through the negative mask. The negative mask includes an exposure part that transmits ultraviolet rays and a non-exposure part that blocks ultraviolet rays. The negative mask is a photo tool such as a mask film or a dry plate. Examples of ultraviolet light sources include chemical lamps, low-pressure mercury lamps, medium-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, xenon lamps, metal halide lamps, LEDs, g-line (436 nm), h-line (405 nm), i-line (365 nm), and It is selected from the group consisting of a combination of two or more of g-line, h-line and i-line.

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

In the dry film method, after the dry film in the dry film with the support is stacked on the core material 1, the support 4 is allowed to pass through and the ultraviolet ray is irradiated onto the coating 4 made of the dry film without peeling off the support. Then, the coating 4 may be exposed to light, and then the support may be peeled off from the coating 4 before the development treatment.

Subsequently, the coating 4 is developed to remove the unexposed portion 5 of the coating 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. 1D. Is provided. In the development process, an appropriate developer according to the composition of the photosensitive resin composition can be used. The developer is, for example, an alkaline aqueous solution containing at least one of an alkali metal salt and an alkali metal hydroxide, or an organic amine. More specifically, the alkaline aqueous solution is, for example, sodium carbonate, potassium carbonate, ammonium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, ammonium hydrogen carbonate, sodium hydroxide, potassium hydroxide, ammonium hydroxide, tetramethyl ammonium 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, for example, at least one component selected from the group consisting of 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, and 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 coating 4 is thermally cured by heating. The heating conditions are, for example, within a heating temperature range of 120 to 200 ° C. and a heating time range of 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 coating film 4 may be further irradiated with ultraviolet rays before 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.

Thus, the interlayer insulating layer 7 made of a cured product of the photosensitive resin composition is provided on the core material 1. 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. As a result, 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 first conductor wiring A printed wiring board 11 having a through hole 10 for electrically connecting the first conductor wiring 3 and the second conductor wiring 8 is obtained. In FIG. 1E, the hole plating 9 has a cylindrical shape that covers the inner surface of the hole 6, but the entire inner side of the hole 6 may be filled with the hole plating 9.

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

First, prepare the core material. The core material includes, for example, at least one insulating layer and at least one conductor wiring. A film is formed from the photosensitive resin composition on the surface of the core material where the conductor wiring is provided. Examples of the method for forming the film include a coating method and a dry film method. As the coating method and the dry film method, the same method as that for forming the interlayer insulating layer can be employed. The film is partially photocured by exposure. The exposure method can be the same as the method for forming the interlayer insulating layer. Subsequently, the film is subjected to a development process to remove the unexposed part of the film, whereby the exposed part of the film remains on the core material. Subsequently, the coating on the core material is heated and cured. The developing method and the heating method can be the same as the method for forming the interlayer insulating layer. If necessary, the film may be further irradiated with ultraviolet rays before 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.

As described above, a solderless resist layer made of a cured product of the photosensitive resin composition is provided on the core material. Thereby, a printed wiring board provided with the core material provided with an insulating layer and the conductor wiring on it, and the soldering resist layer which partially covers the surface in which the conductor wiring in a core material is provided is obtained.

(1) Synthesis of carboxyl group-containing resin having an aromatic ring:
[Synthesis Example A-1]
The carboxyl group-containing resin having an aromatic ring of Synthesis Example A-1 was prepared as follows. In a four-necked flask equipped with a reflux condenser, a thermometer, an air blowing tube, and a stirrer, a bisphenolfluorene type epoxy represented by the formula (2) and in which R ₁ to R ₇ in the formula (2) are all 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, and triphenylphosphine 1 A mixture was prepared by adding 5 parts by weight. The mixture was heated in a flask at 115 ° C. for 12 hours with stirring under air bubbling. This prepared an intermediate solution.

Subsequently, the intermediate solution in the flask was charged with 58.8 parts by mass of 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 60.8 parts by mass of tetrahydrophthalic anhydride, and propylene glycol monomethyl. 38.7 parts by mass of ether acetate was added, and the mixture was heated at 115 ° C. for 6 hours while stirring under air bubbling, and further heated at 80 ° C. for 1 hour. This obtained a 65 mass% solution of carboxyl group-containing resin A-1. The weight average molecular weight of the carboxyl group-containing resin A-1 was 3096, and the acid value was 105 mgKOH / g.

[Synthesis Example A-2]
The carboxyl group-containing resin having an aromatic ring of Synthesis Example A-2 was prepared as follows. In a four-necked flask equipped with a reflux condenser, a thermometer, an air blowing tube and a stirrer, biphenyl novolac type epoxy resin (manufactured by Nippon Kayaku Co., Ltd., product number NC-3000-H, epoxy equivalent 288 g / eq) 288 mass Part, 155 parts by mass of diethylene glycol monoethyl ether acetate, 0.2 part by mass of methylhydroquinone, 72 parts by mass of acrylic acid, and 3 parts by mass of triphenylphosphine were added to prepare a mixture. The mixture was heated in a flask at 115 ° C. for 12 hours with stirring under air bubbling. This prepared an intermediate solution.

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

(2) Synthesis of a 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. In a four-necked flask equipped with a reflux condenser, a thermometer, an air blowing tube and a stirrer, 77 parts by weight of methacrylic acid, 123 parts by weight of methyl methacrylate, 370 parts by weight of dipropylene glycol monomethyl ether, and azobisisobutyronitrile 5 parts by weight were added to prepare a mixture. This 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. As a result, 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 were added to the copolymer solution in the flask. The mixture was added and heated at 110 ° C. for 6 hours to allow the addition reaction to proceed. As a result, a 38 mass% solution of the carboxyl group-containing resin B-1 was obtained. The weight average molecular weight of the carboxyl group-containing resin B-1 was 61324, and the acid value was 132 mgKOH / g.

(3) Synthesis of a carboxyl group-free resin having an aromatic ring:
[Synthesis Example B-2]
The carboxyl group-free resin having an aromatic ring in Synthesis Example B-2 was prepared as follows. In a four-necked flask equipped with a reflux condenser, a thermometer, an air blowing tube, and a stirrer, a bisphenolfluorene type epoxy represented by the formula (2) and in which R ₁ to R ₇ in the formula (2) are all 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 methylhydroquinone, 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 115 ° C. for 12 hours with stirring under air bubbling. As a result, a 65 mass% solution of the carboxyl group-free resin B-2 was obtained.

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

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

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 size of 0.07 μm, manufactured by JSR Corporation, product number XER-91-MEK, methyl ethyl ketone dispersion with a content of 15% by weight of crosslinked rubber Acid value 10.0 mg KOH / g.
-Dispersion of organic filler B: Crosslinked rubber (SBR) having an average primary particle size of 0.07 μm and having a carboxyl group and a hydroxyl group, manufactured by JSR Corporation, product number XSK-500, a methyl ethyl ketone dispersion having a content of 15% by weight of crosslinked rubber .
Coupling agent A: tetraethoxysilane.
Coupling agent B: methyltrimethoxysilane.
Coupling agent C: 3-glycidoxypropyltrimethoxysilane.
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 of 30% by mass, average primary particle size of 10 to 15 nm.
Silica filler B: manufactured by Nissan Chemical Industries, Ltd., product number MEK-EC-2130Y, methyl ethyl ketone-dispersed silica sol, grade with improved compatibility with epoxy resin, solid content concentration of 30% by mass, average primary particle size of 10 to 15 nm.
Silica filler C: Nissan Chemical Industries, Ltd., product number MEK-AC-2140Z, methyl ethyl ketone-dispersed silica sol, grade with improved compatibility with acrylic resin, solid content concentration 40 mass%, average primary particle size 10-15 nm.
Silica filler D: manufactured by Nissan Chemical Industries, Ltd., product number MEK-ST-L, methyl ethyl ketone-dispersed silica sol, solid content concentration of 30% by mass, average primary particle size of 40 to 50 nm.
Silica filler E: manufactured by Nissan Chemical Industries, Ltd., product number MEK-ST-ZL, methyl ethyl ketone-dispersed silica sol, solid content concentration of 30% by mass, average primary particle size of 70 to 100 nm.
Silica filler F: manufactured by Nissan Chemical Industries, Ltd., product number MEK-ST-UP, methyl ethyl ketone-dispersed chain silica sol, solid content concentration 20% by mass, average primary particle size 40-100 nm.
Silica filler G: manufactured by Tatsumori Co., Ltd., product number Imsil A8, crystalline silica, average primary particle size 2 μm.
Unsaturated compound A: tricyclodecane dimethanol diacrylate.
Unsaturated compound B: trimethylolpropane triacrylate.
Unsaturated compound C: a mixture of dipentaerystol pentaacrylate and dipentaerystol hexaacrylate, manufactured by Nippon Kayaku Co., Ltd., product 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 to 85 ° C., epoxy equivalent 192 g / eq.
Antioxidant: A hindered phenol antioxidant, manufactured by BASF, product number IRGANOX 1010.
・ Surface conditioner: DIC Corporation, product number MegaFuck F-477.

(5) Preparation of test piece Using the photosensitive resin compositions of the examples and comparative examples, test pieces were prepared as follows.

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

A glass epoxy copper clad laminate (FR-4 type) provided with a copper foil having a thickness of 17.5 μm was prepared. A comb-shaped electrode having a line width / space width of 50 μm / 50 μm was formed as a conductor wiring on this glass epoxy copper clad laminate by a subtractive method, thereby obtaining a core material. The conductor layer was roughened by dissolving and removing the surface layer portion of the core material having a thickness of about 1 μm with an etching agent (organic acid type micro-etching agent, product number CZ-8101 manufactured by MEC Co., Ltd.). A dry film was laminated by heating with a vacuum laminator over the entire surface of the core material. The conditions for 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 the core material. In a state where a negative mask having a non-exposed portion of a pattern including a circular shape having a diameter of 30 μm, 40 μm, and 50 μm is directly applied to this film from a polyethylene terephthalate film, the film is 250 mJ / cm through the negative mask. Ultraviolet rays were irradiated under the conditions of ² . In addition, the film made from a polyethylene terephthalate was peeled from the dry film (coating) after exposure and before development. The exposed film was developed. In the development process, a 1% Na ₂ CO ₃ aqueous solution at 30 ° C. was sprayed onto the film for 90 seconds at a spray pressure of 0.2 MPa. Subsequently, the film was cleaned by spraying pure water with a spray pressure of 0.2 MPa for 90 seconds. Thereby, the part which was not exposed in a film | membrane was removed, and the hole was formed. Subsequently, after heating 60 minutes a film at 180 ° C., an ultraviolet ray was irradiated under the condition of 1000 mJ / cm ² in film. Thereby, the layer which consists of hardened | cured material of the photosensitive resin composition (it can also be said to be hardened | cured material of a dry film) was formed on the core material. As a result, a test piece was obtained.

(6) Evaluation Test (6-1) Particle Size Distribution For each example and comparative example, the particle size distribution of the photosensitive resin composition after being filtered with a 300 mesh filter was measured with MT3300EXII manufactured by Microtrac Bell Co., Ltd. . In Examples 1-18, Comparative Example 3, and 5, by a laser diffraction scattering particle size distribution measuring apparatus of a photosensitive resin composition, the particle size measured as D ₅₀ is at 1μm or less, the maximum particle size of 10μm 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 For each example and comparative example, the photosensitive resin composition was visually observed, and the results were evaluated as follows.
A: Turbidity is not observed and transparency is high.
B: Although some turbidity is observed, it is transparent.
C: Turbidity is observed, but there is some transparency.
D: Turbidity is observed and there is no transparency.

(6-3) Stability For each of the examples and comparative examples, after the photosensitive resin composition was stored at 25 ° C., the photosensitive resin composition was observed, and the results were evaluated as follows.
A: No separation of components occurred after storage at 25 ° C. for 4 weeks.
B: No separation of components occurred after storage at 25 ° C. for 3 weeks, but separation of components occurred after storage at 25 ° C. for 4 weeks.
C: No separation of components occurred after storage at 25 ° C. for 2 weeks, but separation of components occurred after storage at 25 ° C. for 3 weeks.
D: Separation of components occurred after 2 weeks storage at 25 ° C.

(6-4) Developability For each example and comparative example, in the process of preparing test pieces, the unexposed portion of the film after the development treatment was observed, and the results were evaluated as follows.
A: All the films are removed.
B: A part of the film remained on the core material.
C: Development was not possible.

Regarding Comparative Example 5 in which the evaluation of developability is C, the following evaluations (6-5) to (6-11) are not performed. Further, in Example 17 and Comparative Example 6 in which the evaluation of developability is B, in the following (6-6) evaluation test for roughness after post-smear, all of the film remaining on the non-exposed portion on the core material was removed. The

(6-5) Openability With respect to Examples 1 to 18 and Comparative Examples 1 to 4 and 6, the openings formed in the cured layer of the test piece were observed, and the results were evaluated as follows.
A: An opening having a diameter of 30 μm is formed.
B: An opening having a diameter of 35 μm is formed, but an opening having a diameter of 30 μm is not formed.
C: An opening having a diameter of 40 μm is formed, but an opening having a diameter of 35 μm is not formed.
D: An opening having a diameter of 50 μm is formed, but an opening having a diameter of 40 μm is not formed.
E: An opening having a diameter of 50 μm is not formed.

(6-6) Roughness after desmear For Examples 1 to 18 and Comparative Examples 1 to 4 and 6, the surface of the layer made of the cured product in the test piece was treated with desmear as follows based on a known desmear treatment method. did. Using a commercially available swelling liquid (Swelling Dip Securigans P, manufactured by Atotech Japan Co., Ltd.) as a swelling liquid 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 resulting layer was swollen. The surface of the layer made of the swollen cured product was washed with hot water. Next, using a commercially available oxidizing agent containing potassium permanganate (manufactured by Atotech Japan Co., Ltd., Concentrate Compact CP) as a desmear liquid, the surface of the layer made of the cured product is roughened at 70 ° C. for 10 minutes. The surface of the layer made of the cured product was roughened. The surface of the layer made of the roughened cured product was washed with hot water. Subsequently, the residue of the desmear liquid in the surface of the layer which consists of hardened | cured material was removed for 5 minutes at 40 degreeC using the neutralization liquid (Atotech Japan Co., Ltd. product, Reduction Solution Securigant 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 made of the cured product roughened by the desmear treatment was measured using a laser microscope, and the post-desmear roughness was evaluated as follows.
A: Ra is less than 0.2 μm.
B: Ra is 0.2 μm or more and less than 0.25 μm.
C: Ra is 0.25 μm or more and less than 0.3 μm.
D: Ra is 0.3 μm or more.

(6-7) Copper plating adhesion For Examples 1 to 18 and Comparative Examples 1 to 4 and 6, a layer made of a cured product of a test piece after the desmear treatment in the evaluation test of (6-6) above is commercially available. An electroless copper plating process was performed using a chemical solution to form an initial wiring. The test piece on which the initial wiring was formed was heated at 150 ° C. for 1 hour. Next, electrolytic copper plating treatment was performed using a commercially available chemical solution at a current density of ² A / dm ² to directly deposit copper having a thickness of 33 μm on the initial wiring. The test piece on which copper was deposited was heated at 180 ° C. for 30 minutes to form a copper plating layer. The adhesion between the copper plating layer and the layer made of the cured product on the test piece was evaluated as follows. In addition, regarding the test piece in which no blister is observed in the test piece during heating both after the electroless copper plating process and after the electrolytic copper plating process, the peel strength between the copper plating layer and the layer made of the cured product is determined according to JIS-C6481. 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 was generated during heating after the electroless copper plating treatment or during heating after the electrolytic copper plating treatment.

(6-8) Insulation While applying a bias voltage of 30 VDC to the conductor wiring (comb electrode) in the test pieces of Examples 1 to 18 and Comparative Examples 1 to 4 and 6, the test piece was placed at 130 ° C. and 85% R . H. The test environment was exposed for 100 hours. The electrical resistance value between the comb-shaped electrodes of the cured layer in this test environment was constantly measured, and the result was evaluated as follows.
A: The electric resistance value was constantly maintained at 10 ⁶ Ω or more until 100 hours passed from the start of the test.
B: Although the electrical resistance value was always maintained at 10 ⁶ Ω or more until 85 hours passed from the start of the test, the electrical resistance value was less than 10 ⁶ Ω before 100 hours passed from the start of the test.
C: The electric resistance value was always maintained at 10 ⁶ Ω or more until 70 hours passed from the start of the test, but the electric resistance value became less than 10 ⁶ Ω before 85 hours passed from the start of the test.
D: The electrical resistance value was less than 10 ⁶ Ω before 70 hours passed from the start of the test.

(6-9) Thermal expansion coefficient In the thermal expansion coefficient evaluation test, test pieces were prepared as follows using the photosensitive resin compositions of Examples 1 to 18 and Comparative Examples 1 to 4 and 6.

The photosensitive resin composition was coated on a polyethylene terephthalate film with an applicator, and then dried by heating at 95 ° C. for 25 minutes to form a dry film having a thickness of 30 μm on the film. This dry film was heat-laminated with a vacuum laminator over the entire surface of a Teflon (registered trademark) film. The conditions for 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 rays under the condition of 250 mJ / cm ² through the mask in a state where a mask having a 3 mm × 15 mm rectangular exposed portion was directly applied to the film from a polyethylene terephthalate film. . In addition, the film made from a polyethylene terephthalate was peeled from the dry film (coating) after exposure and before development. The exposed film was developed. In the development process, a 1% Na ₂ CO ₃ aqueous solution at 30 ° C. was sprayed onto the film for 90 seconds at a spray pressure of 0.2 MPa. Subsequently, the film was cleaned by spraying pure water with a spray pressure of 0.2 MPa for 90 seconds. Subsequently, after heating the film at 180 ° C. for 60 minutes, the film was irradiated with ultraviolet rays under the condition of 1000 mJ / cm ² . As a result, a cured product of the photosensitive resin composition was formed on a film made of Teflon (registered trademark). The cured product was peeled from the film made of Teflon (registered trademark) to obtain a test piece.

Coefficient of thermal expansion of test piece at 30-150 ° C in the second cycle using TMA test equipment (Thermoplus EVOII TMA8310, manufactured by Rigaku Corporation) under the conditions of temperature range 25-250 ° C, 10 ° C / min, load 5g (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 higher.

(6-10) Glass transition point In the glass transition point evaluation test, the photosensitive resin compositions of Examples 1 to 18 and Comparative Examples 1 to 4 and 6 were used in the same manner as in the above (6-9). A test piece was produced to obtain a test piece.

Using the TMA test equipment (Thermoplus EVOII TMA8310, manufactured by Rigaku Corporation), measurement is performed under the conditions of a temperature range of 25 to 250 ° C., a heating / 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 higher.
B: Tg is 145 ° C. or higher and lower than 160 ° C.
C: Tg is 130 ° C. or higher and lower than 145 ° C.
D: Tg is less than 130 ° C.

(6-11) Dielectric loss tangent In the dielectric loss tangent evaluation test, test pieces were prepared as follows using the photosensitive resin compositions of Examples 1 to 18 and Comparative Examples 1 to 4 and 6.

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

The dielectric loss tangent of the test piece at a frequency of 1 GHz was measured by a cavity resonator method using a dielectric constant measuring apparatus (ADMS01O manufactured by AET 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 is a carboxyl group-containing resin (A ), An organic filler (B) having an average primary particle size of 1 μm or less, 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, A functional group having at least one group selected from the group consisting of an alkoxy group, an acyloxy group, and an alkoxide; and an average primary particle diameter of 1 to 150 nm. 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 roughness after desmearing and having excellent resolution.

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

According to the second aspect, the dispersibility of the silica filler (D) in the photosensitive resin composition is efficiently increased, and the transparency and stability of the photosensitive resin composition are improved. While increasing 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 of the third aspect according to the present invention, in the first or second aspect, the silica filler (D) includes 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 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 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 increased 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 increases, and the photosensitive resin composition can have excellent resolution. In addition, the glass transition point of the cured product of the photosensitive resin composition can be increased, and the thermal expansion coefficient and dielectric loss tangent can be reduced. Furthermore, the surface roughness of the cured product after the desmear treatment of 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, photocurability can be imparted to the photosensitive resin composition.

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). And the content of the silica filler (D) is in the range of 0.01 to 10 parts by mass with respect to 100 parts by mass in total.

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

According to the ninth aspect, the stability of the photosensitive resin composition is improved and the resolution is improved because scattering at the time of exposure is suppressed.

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

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

In the photosensitive resin composition of the eleventh aspect according to 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) includes a carboxyl group-containing resin having a benzene ring.

According to the twelfth aspect, the transparency of the photosensitive resin composition is increased, 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. The copolymer obtained by this is included.

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

According to the fourteenth aspect, 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 fifteenth aspect of the present invention, in any one of the first to fourteenth aspects, the carboxyl group-containing resin (A) is at least one of a biphenyl skeleton and a bisphenolfluorene 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.

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

According to the sixteenth aspect, high photosensitivity can be imparted to the photosensitive resin composition. Moreover, generation | occurrence | production of the ion migration in the layer containing the hardened | cured material of the photosensitive resin composition is suppressed, and the insulation of the layer containing hardened | cured material improves.

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 tricyclodecane dimethanol di (meth) acrylate. 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 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, a cured film having high copper plating adhesion and low desmear roughness can be formed, and a dry film having excellent resolution can be obtained.

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

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

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

According to the twenty-first aspect, a printed wiring board having a solder resist layer having high copper plating adhesion and low roughness after desmearing can be obtained.

Claims

It is a photosensitive resin composition having photocurability,
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, wherein the functional group is an alkoxy group, an acyloxy group, and an alkoxide; A coupling agent (C) containing at least one group selected from:
Silica filler (D) having an average primary particle diameter 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 or 2, 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 organic filler (B) is in the range of 1 to 50 parts by mass with respect to 100 parts by mass of the carboxyl group-containing resin (A). The photosensitive resin composition as described in 2.
The content of the silica filler (D) is in the range of 5 to 200 parts by mass with respect to 100 parts by mass of the carboxyl group-containing resin (A). The photosensitive resin composition as described in 2.
The photosensitive resin composition according to any one of claims 1 to 6, wherein the carboxyl group-containing resin (A) includes 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 a total of 100 parts by mass 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 the photosensitive resin composition in a state of a particle diameter of 10 µm or less.
The photosensitive resin composition according to any one of claims 1 to 9, wherein the organic filler (B) includes a rubber component.
The photosensitive resin composition according to claim 10, wherein the rubber component contains 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) includes 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) includes a copolymer obtained by a reaction between 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) includes a carboxyl group-containing resin having at least one of a biphenyl skeleton and a bisphenolfluorene 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 photosensitive compound according to claim 16, wherein the unsaturated compound (E) includes at least one compound selected from the group consisting of trimethylolpropane tri (meth) acrylate and tricyclodecane dimethanol di (meth) acrylate. Resin composition.
The photosensitive resin composition according to any one of claims 1 to 17, further comprising an epoxy compound (G).
A dry film containing the photosensitive resin composition according to any one of claims 1 to 18.
A printed wiring board comprising an interlayer insulating layer containing a cured product of the photosensitive resin composition according to any one of claims 1 to 18.
A printed wiring board comprising a solder resist layer containing a cured product of the photosensitive resin composition according to any one of claims 1 to 18.