JP2017161659A - Photosensitive resin composition, dry film, and printed wiring board - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photosensitive resin composition which prevents aggregation of an organic filler and is excellent in resolution, flexibility, thixotropy, plating resistance, and thermal shock resistance.SOLUTION: The photosensitive resin composition contains a carboxyl group-containing resin (A), an unsaturated compound (B) having at least one ethylenically unsaturated bond in one molecule, a photopolymerization initiator (C), an epoxy compound (D), an organic filler (E), and a coupling agent (F). The organic filler (E) contains an organic filler (E1) having a carboxyl group with an average primary particle diameter of 1 μm or less. The coupling agent (F) contains a coupling agent (F1) containing atoms selected from silicon atoms, aluminum atoms, titanium atoms, and zirconia atoms and further containing two or more functional groups selected from an alkoxy group, an acyloxy group, and an alkoxide.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a photosensitive resin composition, a dry film, and a printed wiring board. Specifically, an electrically insulating layer such as a solder resist layer, a plating resist layer, an etching resist layer, or an interlayer insulating layer is formed on the printed wiring board. Suitable photosensitive resin composition, dry film containing the photosensitive resin composition, printed wiring board including an interlayer insulating layer containing a cured product of the photosensitive resin composition, and curing of the photosensitive resin composition The present invention relates to a printed wiring board provided with a solder resist layer containing an object.

  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. For example, a photosensitive resin composition is used as the resin composition.

  In order to suppress the occurrence of cracks in the cured product obtained from the photosensitive resin composition and increase the physical strength, it is known to add an organic filler to the photosensitive resin composition (Patent Document 1).

Japanese Patent No. 5564144

  However, in many cases, sufficient dispersibility cannot be obtained only by adding an organic filler to the photosensitive resin composition. Thus, for example, Patent Document 1 discloses that a coupling agent is added to a resin composition containing a carboxyl group-containing resin, a photopolymerization initiator, and an organic filler. The dispersibility of an organic filler can be improved by mix | blending a coupling agent with a resin composition.

  However, in Patent Document 1, an organic filler whose surface is coated with silica must be used. It is not easy to obtain a photosensitive resin composition that prevents aggregation of organic fillers and is excellent in resolution, flexibility, thixotropy, plating resistance, and thermal shock resistance.

  The present invention has been made in view of the above-mentioned reasons, and prevents the aggregation of organic fillers, and is a photosensitive resin composition excellent in resolution, flexibility, thixotropy, plating resistance, and thermal shock resistance, and the photosensitive resin. Printed circuit board comprising a dry film containing a photosensitive resin composition, 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 purpose is to provide.

  The photosensitive resin composition according to the present invention includes a carboxyl group-containing resin (A), an unsaturated compound (B) having at least one ethylenically unsaturated bond in one molecule, a photopolymerization initiator (C), And an epoxy compound (D), an organic filler (E), and a coupling agent (F). The said organic filler (E) contains the organic filler (E1) which has a carboxyl group whose average primary particle diameter is 1 micrometer or less. The coupling agent (F) contains an atom selected from a silicon atom, an aluminum atom, a titanium atom, and a zirconia atom, and further contains two or more functional groups selected from an alkoxy group, an acyloxy group, and an alkoxide. Contains agent (F1).

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

  The printed wiring board which concerns on this invention is equipped with the interlayer insulation layer containing the hardened | cured material of the said photosensitive resin composition.

  The printed wiring board which concerns on this invention is equipped with the soldering resist layer containing the hardened | cured material of the said photosensitive resin composition.

  According to the present invention, by incorporating an organic filler having a carboxyl group and a coupling agent, aggregation of the organic filler is prevented, and the resolution, flexibility, thixotropy, plating resistance, and thermal shock resistance are excellent. A photosensitive resin composition, 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 a cured product of the photosensitive resin composition A printed wiring board provided with a solder resist layer is obtained.

1A to 1E are cross-sectional views showing a process of manufacturing a multilayer printed wiring board.

  A mode 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 this embodiment includes a carboxyl group-containing resin (A), an unsaturated compound (B) having at least one ethylenically unsaturated bond in one molecule, and a photopolymerization initiator (C). And an epoxy compound (D), an organic filler (E), and a coupling agent (F). An organic filler (E) contains the organic filler (E1) which has a carboxyl group whose average primary particle diameter is 1 micrometer or less. The coupling agent (F) contains an atom selected from a silicon atom, an aluminum atom, a titanium atom, and a zirconia atom, and further contains two or more functional groups selected from an alkoxy group, an acyloxy group, and an alkoxide. (F1) is included. When the photosensitive resin composition contains the organic filler (E1), the thixotropy of the photosensitive resin composition is increased, and the stability of the photosensitive resin composition is improved. Moreover, even if the temperature change is repeated in the cured product, cracks in the cured product can be made difficult to occur. Furthermore, the dispersibility of an organic filler (E1) increases because a photosensitive resin composition contains a coupling agent (F1), and the thixotropy and stability of a photosensitive resin composition improve.

  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) has an ethylenically unsaturated group, it has photoreactivity. For this reason, the carboxyl group-containing resin (A) can impart photosensitivity, specifically, ultraviolet curability, to the photosensitive resin composition.

  The carboxyl group-containing resin (A) preferably contains a carboxyl group-containing resin having an aromatic ring. When the carboxyl group-containing resin (A) contains an aromatic ring, high heat resistance and insulation reliability can be imparted to the cured product of the photosensitive resin composition containing the carboxyl group-containing resin (A). It is more preferable that the carboxyl group-containing resin (A) includes a carboxyl group-containing resin having any polycyclic aromatic ring among a biphenyl skeleton, a naphthalene skeleton, a fluorene skeleton, and an anthracene skeleton. The photosensitive resin composition containing carboxyl group-containing resin (A) because carboxyl group-containing resin (A) contains any polycyclic aromatic ring among biphenyl skeleton, naphthalene skeleton, fluorene skeleton, and anthracene skeleton. Higher heat resistance and insulation reliability can be imparted to the cured product. More preferably, the carboxyl group-containing resin (A) includes a carboxyl group-containing resin having a bisphenolfluorene skeleton. When the carboxyl group-containing resin (A) includes a bisphenolfluorene skeleton, higher heat resistance and insulation reliability can be imparted to the cured product of the photosensitive resin composition containing the carboxyl group-containing resin (A).

The carboxyl group-containing resin (A) preferably contains a carboxyl group-containing resin (A1). The carboxyl group-containing resin (A1) is represented by the following formula (1), and in the formula (1), R _{1 to} R ₈ are each independently hydrogen, a C 1-5 alkyl group, or a bisphenolfluorene skeleton. It is a reaction product of an intermediate which is a reaction product of an epoxy compound (a1) having carboxylic acid (a2) containing an unsaturated group-containing carboxylic acid (a2-1) and an acid anhydride (a3). 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.

In formula (1), R _{1 to} R ₈ are each independently hydrogen, an alkyl group having 1 to 5 carbon atoms, or halogen. That is, each of R _{1 to} R ₈ in Formula (1) may be hydrogen, but may be an alkyl group having 1 to 5 carbon atoms or a halogen. Even if 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.

  In this embodiment, since the carboxyl group-containing resin (A1) has a bisphenolfluorene skeleton represented by the formula (1) derived from the epoxy compound (a1), the cured product of the photosensitive resin composition has high heat resistance and insulation. Reliability can be given. 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). Furthermore, thermosetting property can be provided to the photosensitive resin composition because the photosensitive resin composition contains an epoxy resin.

  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 (see formula (2)) in the epoxy compound (a1) having a bisphenolfluorene skeleton represented by formula (1) and unsaturated An intermediate is synthesized by reacting the carboxylic acid (a2) containing the group-containing carboxylic acid (a2-1). The synthesis of the intermediate is defined as the first reaction. The intermediate has a structure represented by the following formula (3) generated by the ring-opening addition reaction between the epoxy group and the carboxylic acid (a2). That is, the intermediate is 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) in the structure represented by the formula (3). Have In formula (3), A is a carboxylic acid residue. This A includes an unsaturated group-containing carboxylic acid residue.

  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.

  When the acid anhydride (a3) contains an acid monoanhydride, the carboxyl group-containing resin (A1) has a bisphenolfluorene skeleton represented by the formula (1) and a structure represented by the following formula (4).

  The structure represented by the formula (4) is generated by the reaction between the secondary hydroxyl group in the structure represented by the formula (3) of the intermediate and the acid anhydride group in the acid anhydride (a3). In formula (4), A is a carboxylic acid residue and B is an acid monoanhydride residue. This A includes an unsaturated group-containing carboxylic acid residue.

  Further, the acid anhydride (a3) may contain both an acid monoanhydride and an acid dianhydride. For example, a part of the secondary hydroxyl group in the intermediate is reacted with acid monoanhydride, and another part of the secondary hydroxyl group in the intermediate is reacted with acid dianhydride. Also good. In this case, the synthesized carboxyl group-containing resin (A1) has a bisphenolfluorene skeleton represented by the formula (1), a structure represented by the above formula (4), and a structure represented by the following formula (5).

  The structure represented by the formula (5) is generated by the reaction between the acid anhydride group in the acid dianhydride and the two secondary hydroxyl groups in the intermediate. That is, the structure shown in Formula (5) is produced by crosslinking of two secondary hydroxyl groups with an acid dianhydride. In addition, the case where two secondary hydroxyl groups present in one molecule of the intermediate are crosslinked and the case where two secondary hydroxyl groups present in each of the two molecules of the intermediate are crosslinked It is possible. When two secondary hydroxyl groups present in the two molecules of the intermediate are cross-linked, an increase in molecular weight is obtained. In formula (5), A is a carboxylic acid residue and D is an acid dianhydride residue. This A includes an unsaturated group-containing carboxylic acid residue.

  The carboxyl group-containing resin (A1) may further have a structure represented by the following formula (6). The structure represented by formula (6) occurs when only one of the two acid anhydride groups in the acid dianhydride reacts with the secondary hydroxyl group in the intermediate. In formula (6), A is a carboxylic acid residue and D is an acid dianhydride residue. This A includes an unsaturated group-containing carboxylic acid residue.

  When some of the epoxy groups in the epoxy compound (a1) remain unreacted during the synthesis of the intermediate, the carboxyl group-containing resin (A1) may have a structure represented by the formula (2), that is, an epoxy group. sell. In addition, when a part of the structure represented by the formula (3) in the intermediate body remains unreacted, the carboxyl group-containing resin (A1) may have a structure represented by the formula (3).

  However, by optimizing the reaction conditions during the synthesis of the carboxyl group-containing resin (A1), the structure shown in the formula (2) and the structure shown in the formula (6) in the carboxyl group-containing resin (A1) are reduced. Or it can be almost eliminated.

  As described above, the carboxyl group-containing resin (A1) can have a bisphenolfluorene skeleton represented by the formula (1) and a structure represented by the formula (4). Furthermore, the carboxyl group-containing resin (A1) can also have a structure shown in Formula (5). Furthermore, the carboxyl group-containing resin (A1) may have at least one of the structure shown in Formula (2), the structure shown in Formula (3), and the structure shown in Formula (6).

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

  In addition, the structure of the above-mentioned carboxyl group-containing resin (A1) is reasonably inferred based on the common general technical knowledge, and the structure of the carboxyl group-containing resin (A1) cannot be identified by analysis. The reason is as follows. When the epoxy compound (a1) itself has a secondary hydroxyl group (for example, when n is 1 or more in the formula (7)), the carboxyl group-containing resin depends on the number of secondary hydroxyl groups in the epoxy compound (a1). The structure of (A1) changes greatly. When the intermediate and the acid dianhydride react, as described above, when two secondary hydroxyl groups present in one molecule of the intermediate are cross-linked with the acid dianhydride, There may be a case where two secondary hydroxyl groups respectively present in the two molecules of the intermediate are crosslinked with an acid dianhydride. For this reason, the carboxyl group-containing resin (A1) finally obtained contains a plurality of molecules having different structures, and even when the carboxyl group-containing resin (A1) is analyzed, the structure cannot be identified.

  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 tackiness of the film formed from the photosensitive resin composition can be further suppressed, and the insulation reliability and plating resistance of the cured product can be further improved. 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, it was excellent in the photosensitive resin composition while ensuring good insulation reliability and plating resistance (for example, resistance to whitening during electroless nickel / gold plating) of the cured product formed from the photosensitive resin composition. Developability can be imparted. The polydispersity of the carboxyl group-containing resin (A1) is more preferably 1.1 to 4.0, and further preferably 1.2 to 2.8. The polydispersity is a value (Mw / Mn) of the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) of the carboxyl group-containing resin (A1).

  The solid content acid 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 (7), for example. N in Formula (7) is an integer in the range of 0-20, for example. In order to appropriately control the molecular weight of the carboxyl group-containing resin (A1), the average of n is particularly preferably in the range of 0-1. If the average of n is in the range of 0 to 1, an excessive increase in molecular weight is likely to be suppressed even when the acid anhydride (a3) contains an acid dianhydride.

  The carboxylic acid (a2) includes an unsaturated group-containing carboxylic acid (a2-1). The carboxylic acid (a2) may contain only the unsaturated group-containing carboxylic acid (a2-1). Or carboxylic acid (a2) may contain carboxylic acid other than unsaturated group containing carboxylic acid (a2-1) and 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, 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) crosslinks the epoxy groups present in the two molecules of the epoxy compound (a1), whereby an increase in molecular weight is obtained. As a result, the tackiness of the film formed from the photosensitive resin composition can be further controlled, and the insulation reliability and plating resistance of the cured product can be further improved.

  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 preferred 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. For this reason, the intermediate which has a structure shown in Formula (3) is obtained with a high yield. 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 reliability of the layer containing hardened | cured material further 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 mole. Moreover, when carboxylic acid (a2) contains polybasic acid (a2-1), the quantity of polybasic acid (a2-1) with respect to 1 mol of epoxy groups of epoxy compound (a1) is 0.025-0.25. 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. That is, it is preferable that B in Formula (4) includes an acid monoanhydride residue.

  The acid monoanhydride can contain an anhydride of a 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, methylnadic acid 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. That is, it is preferable that B in Formula (4) contains a 1,2,3,6-tetrahydrophthalic anhydride residue. In this case, while ensuring good developability of the photosensitive resin composition, it is possible to further suppress the tackiness of a film formed from the photosensitive resin composition and further improve the insulation reliability and plating resistance of the cured product. . 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, and 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′-diphenylsulfonetetracarboxylic 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. In particular, the acid dianhydride preferably contains 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride. That is, it is preferable that D in Formula (5) and Formula (6) includes a 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride residue. In this case, while ensuring good developability of the photosensitive resin composition, it is possible to further suppress the tackiness of a film formed from the photosensitive resin composition and further improve the insulation reliability and plating resistance of the cured product. . 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. The carboxyl group-containing resin (A1) can be obtained by reacting this reactive solution at a temperature of preferably 60 to 150 ° C., particularly preferably 80 to 120 ° C., 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 preferred that the catalyst contains triphenylphosphine. That is, it is preferable to react the intermediate and the acid anhydride (a3) in the presence of triphenylphosphine. In this case, the reaction between the secondary hydroxyl group and the acid anhydride (a3) in the intermediate is particularly accelerated, and a reaction rate (conversion rate) of 90% or more, 95% or more, 97% or more, or almost 100% is achieved. Is possible. For this reason, the carboxyl group-containing resin (A1) having the structure represented by the formula (4) can be obtained with high yield. 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 reliability of the layer containing hardened | cured material further improves.

  It is also preferable to react an intermediate and an 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 contain only the carboxyl group-containing resin (A1) or only a carboxyl group-containing resin other than the carboxyl group-containing resin (A1), and the carboxyl group-containing resin (A1) and the carboxyl group-containing resin. You may contain carboxyl group-containing resin other than resin (A1). The carboxyl group-containing resin other than the carboxyl group-containing resin (A1) includes a carboxyl group-containing resin having no bisphenolfluorene skeleton (hereinafter also referred to as a carboxyl group-containing resin (A2)).

  The carboxyl group-containing resin (A2) can contain, for example, a compound having a carboxyl group and not having photopolymerizability (hereinafter referred to as (A2-1) component). (A2-1) A component contains the polymer of the ethylenically unsaturated monomer containing the ethylenically unsaturated compound which has a carboxyl group, for example. The ethylenically unsaturated compound having a carboxyl group can contain compounds such as acrylic acid, methacrylic acid, and ω-carboxy-polycaprolactone (n≈2) monoacrylate. 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 2- (meth) acryloyloxyethyl phthalate, 2- (meth) acryloyloxyethyl-2-hydroxyethyl phthalate, linear or branched aliphatic or alicyclic (provided that It may further contain an ethylenically unsaturated compound having no carboxyl group, such as (meth) acrylic acid ester (which may partially have an unsaturated bond in the ring).

  The carboxyl group-containing resin (A2) may contain a compound having a carboxyl group and an ethylenically unsaturated group (hereinafter referred to as “component (A2-2)”). The component (A2-2) includes, 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 polyvalent carboxylic acid, and It contains a resin (referred to as a first resin (g)) that is a reaction product with at least one compound (g3) selected from the group of anhydrides. For example, the first resin (g) is obtained by adding the compound (g3) to an intermediate obtained by reacting the epoxy group in the epoxy compound (g1) with the carboxyl group in the ethylenically unsaturated compound (g2). Can be obtained. 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) 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 component (A2-2) is a resin (second resin) that is a reaction product of a polymer of an ethylenically unsaturated monomer containing an ethylenically unsaturated compound having a carboxyl group and an ethylenically unsaturated compound having an epoxy group. Of resin (i)). 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 ethylenically unsaturated monomer may further contain an ethylenically unsaturated compound having no carboxyl group. Examples of the ethylenically unsaturated compound having a carboxyl group include compounds such as acrylic acid, methacrylic acid, ω-carboxy-polycaprolactone (n≈2) monoacrylate, pentaerythritol triacrylate, and pentaerythritol trimethacrylate. Examples of the ethylenically unsaturated compound having no carboxyl group include 2- (meth) acryloyloxyethyl phthalate, 2- (meth) acryloyloxyethyl-2-hydroxyethyl phthalate, linear or branched aliphatic or oil It contains a compound such as a (meth) acrylic acid ester of a cyclic group (however, it may have some unsaturated bonds in the ring). The ethylenically unsaturated compound having an epoxy group preferably contains glycidyl (meth) acrylate.

  The carboxyl group-containing resin (A) can contain only the carboxyl group-containing resin (A1), only the carboxyl group-containing resin (A2), or the carboxyl group-containing resin (A1) and the carboxyl group-containing resin (A2). The carboxyl group-containing resin (A) preferably contains 30% by mass or more of the carboxyl group-containing resin (A1), more preferably 60% by mass or more, and still more preferably 100% by mass. In this case, the heat resistance and insulation reliability of the cured product of the photosensitive resin composition can be particularly improved. Moreover, the tack property of the film | membrane formed from the photosensitive resin composition can fully be suppressed. Furthermore, the developability by the alkaline aqueous solution of the photosensitive resin composition can be ensured.

  The unsaturated compound (B) can impart photocurability to the photosensitive resin composition. The unsaturated compound (B) 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, etc. It can contain at least one compound selected from the group consisting of polyfunctional (meth) acrylates such as candimethanol di (meth) acrylate.

  In particular, the unsaturated compound (B) preferably contains a trifunctional compound, that is, a compound having three unsaturated bonds in one molecule. In this case, the resolution when the film formed from the photosensitive resin composition is exposed and developed is 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 It can contain at least one compound selected from the group consisting of tris- (2-acryloxyethyl) isocyanurate and ethoxylated glycerin tri (meth) acrylate.

  It is also preferred that the unsaturated compound (B) 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 (as specific examples, product number light ester P-1M and light ester P-2M manufactured by Kyoeisha Chemical Co., Ltd.), 2-acryloyloxyethyl acid phosphate (As a specific example, product number light acrylate P-1A manufactured by Kyoeisha Chemical Co., Ltd.), diphenyl-2-methacryloyloxyethyl phosphate (as a specific example, product number MR-260 manufactured by Daihachi Kogyo Co., Ltd.), and Showa Polymer Co., Ltd. HFA series (particularly HFA-6003, which is an addition reaction product of dipentaerystol hexaacrylate and HCA, and HFA-6007, an addition reaction product 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 (B) 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:

  The photopolymerization initiator (C) contains, for example, an acyl phosphine oxide photopolymerization initiator (C1). That is, the photosensitive resin composition contains, for example, an acyl phosphine oxide photopolymerization initiator (C1). In this case, when exposing the photosensitive resin composition with ultraviolet rays, 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 reliability of the layer containing hardened | cured material further improves.

  Acylphosphine oxide photopolymerization initiator (C1) is, for example, monoacyl such as 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, 2,4,6-trimethylbenzoyl-ethyl-phenyl-phosphinate Phosphine oxide 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-dimethoxyben Yl) -2,4,4-trimethylpentylphosphine oxide, bis- (2,6-dimethoxybenzoyl) -2,5-dimethylphenylphosphine oxide, bis- (2,4,6-trimethylbenzoyl) phenylphosphine Contains one or more components selected from the group consisting of bisacylphosphine oxide photopolymerization initiators such as fin oxide and (2,5,6-trimethylbenzoyl) -2,4,4-trimethylpentylphosphine oxide it can. In particular, the acylphosphine oxide photopolymerization initiator (C1) preferably contains 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, and the acylphosphine oxide photopolymerization initiator (C1) is 2, It is also preferred to contain only 4,6-trimethylbenzoyl-diphenyl-phosphine oxide.

  The photopolymerization initiator (C) preferably contains a hydroxyketone photopolymerization initiator (C2) in addition to the acylphosphine oxide photopolymerization initiator (C1). That is, it is preferable that the photosensitive resin composition contains a hydroxyketone photopolymerization initiator (C2). In this case, higher photosensitivity can be imparted to the photosensitive resin composition as compared with the case where the hydroxyketone photopolymerization initiator (C2) is not contained. Thereby, when irradiating and hardening an ultraviolet-ray to the coating film formed from the photosensitive resin composition, it becomes possible to fully harden a coating film over the deep part from the surface. Examples of the hydroxyketone photopolymerization initiator (C2) include 1-hydroxy-cyclohexyl-phenyl-ketone, phenylglyoxyc acid methyl ester, and 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy. 2-methyl-1-propan-1-one, 2-hydroxy-1- {4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] phenyl} -2-methyl-propane-1- On and 2-hydroxy-2-methyl-1-phenyl-propan-1-one.

  The mass ratio of the acylphosphine oxide photopolymerization initiator (C1) and the hydroxyketone photopolymerization initiator (C2) 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 (C) contains bis (diethylamino) benzophenone (C3). That is, the photosensitive resin composition contains an acyl phosphine oxide photopolymerization initiator (C1) and bis (diethylamino) benzophenone (C3), or an acyl phosphine oxide photopolymerization initiator (C1), a hydroxyketone type. It is also preferable to contain a photopolymerization initiator (C2) and bis (diethylamino) benzophenone (C3). 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 prepared 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.

  Bis (diethylamino) benzophenone (C3) is preferably in the range of 0.5 to 20% by mass with respect to the acylphosphine oxide photopolymerization initiator (C1). When bis (diethylamino) benzophenone (C3) is 0.5% by mass or more, the resolution is particularly high. Further, when the content of bis (diethylamino) benzophenone (C3) is 20% by mass or less, it is difficult for bis (diethylamino) benzophenone (C3) to inhibit the electrical insulation of the cured product of the photosensitive resin composition.

  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 together 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 (C) and a coumarin derivative such as 7-diethylamino-4-methylcoumarin that is a sensitizer for laser exposure, a carbocyanine dye system, a xanthene dye system, and the like. May be.

  The epoxy compound (D) can impart thermosetting properties to the photosensitive resin composition. The epoxy compound (D) 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 (product name YDC-1312 manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.), biphenyl type crystalline epoxy resin (product name YX-4000 manufactured by Mitsubishi Chemical Co., Ltd.), diphenyl ether type crystalline epoxy resin (specific example) As an example, NS Nippon Kayaku Co., Ltd. product number GTR-1800), bisphenolfluorene type crystal Preferably it contains one or more components selected from the group consisting of an epoxy resin (epoxy resin having a structure represented by the formula (7) as a specific example).

  The crystalline epoxy resin may have two epoxy groups in one molecule. In this case, it is possible to further prevent 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.

  As melting | fusing point of crystalline epoxy resin, 70-180 degreeC is mentioned, for example. In particular, the crystalline epoxy resin preferably contains a crystalline epoxy resin having a melting point of 110 ° C. or 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 resin (specifically, product number YX4000 manufactured by Mitsubishi Chemical Corporation), biphenyl ether type epoxy resin (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 as a specific example), a bisphenol fluorene type crystalline epoxy resin (specifically, an epoxy resin having a structure represented by formula (7)). It can contain at least one selected component.

  The epoxy compound (D) 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.

  The amorphous epoxy resin is, for example, a phenol novolac type epoxy resin (specifically, product number EPICLON N-775 manufactured by DIC Corporation), or a cresol novolac type epoxy resin (specific example, product number EPICLON N-695 manufactured by DIC Corporation). Bisphenol A novolac type epoxy resin (specifically, product number EPICLON N-865 manufactured by DIC Corporation), bisphenol A type epoxy resin (specifically, product number jER1001 manufactured by Mitsubishi Chemical Corporation), bisphenol F type epoxy resin (specific example) As product number jER4004P manufactured by Mitsubishi Chemical Corporation), bisphenol S type epoxy resin (specifically, product number EPICLON EXA-1514 manufactured by DIC Corporation), bisphenol AD type epoxy resin, biphenyl novolak type Poxy 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 example) DIC Corporation product numbers EPICLON HP-4032, EPICLON HP-4700, EPICLON HP-4770), tertiary butyl catechol type epoxy resin (specifically, product number EPICLON HP-820 manufactured by DIC Corporation), dicyclopentadiene type Epoxy resin (part number EPICLON HP-7200 manufactured by DIC as a specific example), adamantane type epoxy resin (part number ADAMANATE X-E-201 manufactured by Idemitsu Kosan Co., Ltd.), special bifunctional type epoxy resin (specific example , Mitsubishi Chemical Corporation part numbers YL7175-500 and YL7175-1000; DIC Corporation part numbers EPICLON TSR-960, EPICLON TER-601, EPICLON TSR-250-80BX, EPICLON 1650-75MPX, EPICLON EXA-4850, EPICLON EXA-4816, EPICLON EXA-4822, and EPICLON EXA-9726; Nippon Steel & Sumikin Chemical Co., Ltd. product number YSLV-120TE), rubber core-shell polymer modified bisphenol A type epoxy resin (specifically, product number MX manufactured by Kaneka Corporation) 156), and a rubbery core-shell polymer-modified bisphenol F type epoxy resin (as a specific example, product number MX-136 manufactured by Kaneka Corporation) It is preferable to contain one or more components selected from the above.

  The epoxy compound (crystalline or amorphous epoxy compound) as described above 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.

  It is preferable that an epoxy compound (D) contains only a crystalline epoxy resin or a crystalline epoxy resin and an amorphous epoxy resin. The epoxy compound (D) 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 reliability of the cured product of the photosensitive resin composition can be particularly improved.

  The organic filler (E) includes an organic filler (E1). The organic filler (E1) has a carboxyl group. The carboxyl group of the organic filler (E1) is obtained by polymerizing or crosslinking a carboxylic acid monomer having a polymerizable unsaturated double bond such as acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid, and itaconic acid. can get. The organic filler (E1) increases the thixotropy of the photosensitive resin composition and improves the stability (particularly storage stability). Furthermore, since the organic filler (E1) has a carboxyl group, it can improve the developability of the cured product, improve the compatibility of the crystalline epoxy resin, and prevent crystallization. The carboxyl group content of the organic filler (E1) is not particularly limited, but the acid value of the organic filler (E1) is preferably 1 to 60 mgKOH / g 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 (E1) is more preferably 3 to 40 mgKOH / g.

  The organic filler (E1) also preferably has a hydroxyl group. When the organic filler (E1) has a hydroxyl group, the dispersibility of the organic filler (E1) in the photosensitive resin composition is improved.

The average primary particle diameter of the organic filler (E1) is 1 μm or less. When the average primary particle diameter of the organic filler (E1) 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 by a laser diffraction particle size distribution measuring device, is measured as D _50. The average primary particle diameter of the organic filler (E1) is preferably 0.4 μm or less, and more 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 because scattering during exposure is suppressed.

The organic filler (E1) is preferably dispersed with a maximum particle size of 1.0 μm or less, more preferably 0.5 μm or less in the photosensitive resin composition. Maximum particle diameter, by laser diffraction type particle size distribution measuring device, is measured as D _50. Alternatively, the maximum particle size is measured by observing the cured product with a transmission electron microscope (TEM). The organic filler (E1) may aggregate in the photosensitive resin composition (for example, can form secondary particles). In this case, the maximum particle diameter means the size of the particles after aggregation. When the maximum particle diameter of the organic filler (E1) in the dispersed state is within the above range, the stability of the photosensitive resin composition is further improved and the resolution is further improved because scattering during exposure is suppressed. . When particle aggregation occurs, the maximum particle size is usually larger than the average primary particle size.

  The organic filler (E1) preferably contains a rubber component. The rubber component can impart flexibility to the cured product of the photosensitive resin composition. The rubber component can be composed of a resin. The rubber component preferably contains at least one polymer selected from crosslinked acrylic rubber, crosslinked NBR, crosslinked MBS, and crosslinked SBR. In this case, the rubber component effectively imparts flexibility to the cured product of the photosensitive resin composition, so that cracks can hardly be caused while the temperature change is repeated. 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 (E1) 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 size of 0.07 μm and is provided as a methyl ethyl ketone dispersion having a content of 15% by weight of the crosslinked rubber, and its acid value is 10.0 mgKOH / g. It is. Thus, an organic filler (E1) 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 (E1) include product numbers XER-32 and XER-92 manufactured by JSR Corporation. Moreover, 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 (E1) may contain a particle component other than the rubber component. In this case, the organic filler (E1) can contain at least one particle component selected from the group consisting of acrylic resin fine particles having a carboxyl group and cellulose fine particles having a carboxyl group. The acrylic resin fine particles having a carboxyl group 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 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 (E1) may contain a particle component other than the particle component selected from the rubber component, the acrylic resin fine particles, and the cellulose fine particles. In this case, the organic filler (E1) can contain a particle component having a carboxyl group. That is, the particle component having a carboxyl group may be different from the particle component selected from the rubber component, the acrylic resin fine particles, and the cellulose fine particles.

  The organic filler (E) may further contain an organic filler other than the organic filler (E1). Organic fillers other than the said organic filler (E1) do not need to have a carboxyl group. The organic filler other than the organic filler (E1) may have an average primary particle size larger than 1 μm. However, from the viewpoint of efficiently obtaining thixotropy, the viewpoint of improving the compatibility of the crystalline epoxy resin, and the viewpoint of obtaining high resolution, the photosensitive resin composition contains an organic filler other than the organic filler (E1). It does not have to be included.

  The organic filler (E) contains only the organic filler (E1) or an organic filler other than the organic filler (E1) and the organic filler (E1). The organic filler (E) preferably contains 30% by mass or more, more preferably 50% by mass or more, and still more preferably 100% by mass of the organic filler (E1). In this case, the stability of the photosensitive resin composition can be particularly improved.

  The coupling agent (F) includes a coupling agent (F1). The coupling agent (F1) contains an atom selected from a silicon atom, an aluminum atom, a titanium atom, and a zirconia atom. The coupling agent (F1) further contains two or more functional groups selected from alkoxy groups, acyloxy groups and alkoxides. The coupling agent (F1) may contain two or more alkoxy groups, may contain two or more acyloxy groups, and may contain two or more alkoxides. The coupling agent (F1) may contain two or more different functional groups selected from an alkoxy group, an acyloxy group, and an alkoxide. The coupling agent (F1) has the dispersibility of the organic filler (E1) in the photosensitive resin composition by reaction or interaction with the carboxyl group contained in the carboxyl group-containing resin (A) and the organic filler (E1). In order to enhance, the thixotropy and stability (especially storage stability) of the photosensitive resin composition are improved. The functional group selected from an alkoxy group, an acyloxy group, and an alkoxide is preferably directly bonded to an atom selected from a silicon atom, an aluminum atom, a titanium atom, and a zirconia atom.

  When the coupling agent (F1) contains a silicon atom, examples of the coupling agent (F1) include tetraethoxysilane, tetramethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinylmethyldiethoxysilane, and vinylmethyl. Dimethoxysilane, 2- (3,4 epoxy cyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3- Glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, p-styryltrimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3 Aminopropyltrimethoxysilane, 3-aminopropylmethyldimethoxysilane, 3-aminopropylmethyldiethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3- (2-aminoethylamino) propyltri Ethoxysilane, 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, -Methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, allyltriethoxysilane, allyltrimethoxysilane, allylchlorodimethylsilane, 3-chloropropyltrimethoxysilane, 3-chloropropyltriethoxysilane, 3 -Chloropropyldimethoxymethylsilane, chloromethyltriethoxysilane, chloromethyltrimethoxysilane, 3-chloropropylmethyldiethoxysilane, 3-isocyanatopropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, bis (triethoxysilyl) Propyl) tetrasulfide, cyclohexyltrimethoxysilane, methyltriethoxysilane, methyltrimethoxysilane, ethyltriethoxysilane, ethyltrimethyl Xysilane, hexyltrimethoxysilane, hexyltriethoxysilane, hexadecyltrimethoxysilane, octadecyltriethoxysilane, octadecyltrimethoxysilane, n-octyltriethoxysilane, n-octyltrimethoxysilane, dodecyltriethoxysilane, dodecyltrimethoxysilane Silane, propyltrimethoxysilane, propyltriethoxysilane, benzyltriethoxysilane, methylphenyldimethoxysilane, methylphenyldiethoxysilane, phenyltriethoxysilane, phenyltrimethoxysilane, p-tolyltrimethoxysilane, 4-vinylphenyltri Methoxysilane, 1-naphthyltrimethoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, 11-pentafluoropheno Examples thereof include xylundecyltrimethoxysilane, pentafluorophenyltrimethoxysilane, 11-azidoundecyltrimethoxysilane, 2-cyanoethyltriethoxysilane, and vinyltriacetoxysilane.

  When the coupling agent (F1) contains an aluminum atom, examples of the coupling agent (F1) include acetoalkoxy aluminum diisopropylate, aluminum diisopropoxy monoethyl acetoacetate, aluminum trisethyl acetoacetate and the like. .

  When the coupling agent (F1) contains a titanium atom, examples of the coupling agent (F1) 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, bis (dioctylpyrophosphate) ethylene titanate and the like.

  When the coupling agent (F1) contains a zirconia atom, examples of the coupling agent (F1) include zirconium tetranormal propoxide and zirconium tetranormal butoxide.

  The coupling agent (F1) preferably contains a silicon atom. When the coupling agent (F1) contains a silicon atom, the dispersibility of the organic filler (E1) in the photosensitive resin composition is efficiently increased. Therefore, the thixotropy and stability of the photosensitive resin composition are further improved. The coupling agent (F1) may be a silane coupling agent.

  The coupling agent (F1) preferably contains a functional group selected from 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 (F1) may contain only a methoxy group, may contain only an ethoxy group, or may contain only an acetoxy group. Further, the coupling agent (F1) may contain different functional groups selected from a methoxy group, an ethoxy group, and an acetoxy group. Since the coupling agent (F1) contains a functional group selected from a methoxy group, an ethoxy group, and an acetoxy group, the reactivity between the organic filler (E1) and the coupling agent (F1) is improved, and a photosensitive resin. Aggregation of the organic filler (E1) in the composition is less likely to occur. Therefore, the thixotropy and stability of the photosensitive resin composition are further improved. Moreover, the favorable resolution of the photosensitive resin composition is obtained.

  The coupling agent (F1) preferably contains two to four functional groups selected from an alkoxy group, an acyloxy group, and an alkoxide. The coupling agent (F1) may contain 2 to 4 alkoxy groups, may contain 2 to 4 acyloxy groups, and may contain 2 to 4 alkoxides. For example, the coupling agent (F1) may contain 2 to 4 methoxy groups, 2 to 4 ethoxy groups, or 2 to 4 acetoxy groups. Good. Further, the coupling agent (F1) may contain two to four different functional groups selected from an alkoxy group, an acyloxy group, and an alkoxide. The coupling agent (F1) contains two to four functional groups selected from an alkoxy group, an acyloxy group and an alkoxide, so that excessive crosslinking is caused by a reaction between the organic filler (E1) and the coupling agent (F1). Reaction can be suppressed and the dispersibility of the organic filler (E1) in the photosensitive resin composition can be improved, and at the same time, gelation can be suppressed.

  The coupling agent (F1) preferably contains at least one functional group selected from an amino group, an epoxy group, a vinyl group, a methacryl group, a mercapto group, an isocyanate group, and a sulfide group. The coupling agent (F1) contains at least one functional group selected from an amino group, an epoxy group, a vinyl group, a methacryl group, a mercapto group, an isocyanate group, and a sulfide group, and thus included in the organic filler (E1). The dispersibility of the organic filler (E1) in the photosensitive resin composition can be further efficiently increased. Therefore, the thixotropy, stability and resolution of the photosensitive resin composition are further improved.

  When the coupling agent (F1) contains an amino group, the amino group is introduced by, for example, an aminoalkyl group. Moreover, when a coupling agent (F1) contains an epoxy group, an epoxy group is introduce | transduced by a glycidoxy group, for example. When the coupling agent (F1) contains a vinyl group, the vinyl group is directly bonded to a silicon atom, for example. When the coupling agent (F1) contains an amino group, an epoxy group, or a vinyl group, the reactivity with the organic filler (E1) increases, and the dispersibility of the organic filler (E1) in the photosensitive resin composition further increases. Increases efficiently. The coupling agent (F1) preferably has an epoxy group or a vinyl group. When the coupling agent (F1) has an epoxy group or a vinyl group, the insulating property between lines of the photosensitive resin composition is increased, and the stability is further improved.

  The coupling agent (F) may further contain a coupling agent other than the coupling agent (F1). The coupling agent other than the coupling agent (F1) may not contain an atom selected from a silicon atom, an aluminum atom, a titanium atom, and a zirconia atom. The coupling agent other than the coupling agent (F1) may not contain two or more functional groups selected from an alkoxy group, an acyloxy group, and an alkoxide. However, from the viewpoint of efficiently obtaining the dispersibility of the organic filler (E1) and from the viewpoint of improving the thixotropy and stability of the photosensitive resin composition, the photosensitive resin composition is other than the coupling agent (F1). A coupling agent may not be included.

  The coupling agent (F) contains only the coupling agent (F1) or a coupling agent other than the coupling agent (F1) and the coupling agent (F1). The coupling agent (F) preferably contains 30% by mass or more of the coupling agent (F1), more preferably contains 50% by mass or more, and still more preferably contains 100% by mass. In this case, the dispersibility of the organic filler (E) in the photosensitive resin composition can be particularly improved.

  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.

  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, carb It can contain, as well as one or more compounds selected from the group consisting of dialkyl glycol ethers; Lumpur acid esters such as acetate.

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

  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, and more preferably in the range of 30 to 60% with respect to the solid content of the photosensitive resin composition. It is more preferable if it is within the range of mass%. Further, the carboxyl group-containing resin (A1) is preferably in the range of 5 to 85% by mass, more preferably in the range of 10 to 75% by mass with respect to the solid content of the photosensitive resin composition, 30 More preferably, it is in the range of ˜60 mass%.

  The unsaturated compound (B) is preferably in the range of 1 to 50% by mass, more preferably in the range of 10 to 45% by mass with respect to the carboxyl group-containing resin (A), and more preferably 21 to 40% by mass. If it is in the range, it is more preferable.

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

  Regarding the amount of the epoxy compound (D), the total equivalent of the epoxy groups contained in the epoxy compound (D) is 0.7 to 2.5 with respect to 1 equivalent of the carboxyl group contained in the carboxyl group-containing resin (A). Is preferably within the range of 0.7 to 2.3, more preferably within the range of 0.7 to 2.0. Moreover, when an epoxy compound (D) contains a crystalline epoxy resin, the sum total of the equivalent of the epoxy group contained in a crystalline epoxy resin is 0.00 with respect to 1 equivalent of carboxyl groups contained in a 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 content of the organic filler (E) is preferably in the range of 1 to 40 parts by mass when the content of the carboxyl group-containing resin (A) is 100 parts by mass. When the content of the organic filler (E) is within this range, the thixotropy of the photosensitive resin composition is increased and the stability is improved. The content of the organic filler (E) is more preferably in the range of 5 to 20 parts by mass, when the content of the carboxyl group-containing resin (A) is 100 parts by mass, More preferably within the range. Moreover, it is preferable that content of an organic filler (E1) exists in the range of 1-40 mass parts, when content of carboxyl group-containing resin (A) is 100 mass parts. When the content of the organic filler (E1) is within this range, the thixotropy of the photosensitive resin composition is efficiently increased, and the stability is effectively improved. The content of the organic filler (E1) is more preferably in the range of 5 to 20 parts by mass, when the content of the carboxyl group-containing resin (A) is 100 parts by mass, More preferably within the range.

  The content of the coupling agent (F) is preferably in the range of 0.01 to 7 parts by mass when the content of the organic filler (E) is 100 parts by mass. When the content of the coupling agent (F) falls within this range, aggregation of the organic filler (E) in the photosensitive resin composition is prevented and dispersibility is improved. The content of the coupling agent (F) is more preferably in the range of 0.05 to 5 parts by mass when the content of the organic filler (E) is 100 parts by mass. Moreover, it is preferable that content of a coupling agent (F1) exists in the range of 0.01-7 mass parts, when content of an organic filler (E1) is 100 mass parts. When the content of the coupling agent (F1) is within this range, aggregation of the organic filler (E1) in the photosensitive resin composition is efficiently prevented, and dispersibility is effectively improved. The content of the coupling agent (F1) is more preferably in the range of 0.05 to 5 parts by mass when the content of the organic filler (E1) is 100 parts by mass.

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

  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.

  In addition, solid content is a total amount of all components remove | excluding volatile components, such as a solvent, from the photosensitive resin composition.

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

  For example, the photosensitive resin composition may contain an inorganic filler (inorganic filler). In this case, the curing shrinkage of the film formed from the photosensitive resin composition is reduced. The inorganic filler can contain, for example, one or more materials selected from the group consisting of barium sulfate, crystalline silica, nano silica, carbon nanotubes, talc, bentonite, aluminum hydroxide, magnesium hydroxide, and titanium oxide. You may whiten the photosensitive resin composition and its hardened | cured material by making an inorganic filler contain white materials, such as a titanium oxide and a zinc oxide. Although the ratio of the inorganic filler in the photosensitive resin composition is appropriately set, it is preferably in the range of 0 to 300% by mass with respect to the carboxyl group-containing resin (A).

  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 cocondensation resin; various other thermosetting resins; ultraviolet curable epoxy (meth) acrylate; bisphenol A type , Resins obtained by adding (meth) acrylic acid to phenolic novolac type, cresol novolac type, alicyclic type epoxy resins; and diallyl phthalate resin, phenoxy resin, urethane resin, fluorine resin, etc. It may contain one or more resins that are selected from the group consisting of a polymer compound.

  The photosensitive resin composition may contain a curing agent for curing the epoxy compound (D). 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 It may contain 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 manufactured by San Apro Co., Ltd. -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, 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 not easily impaired. In particular, the amine compound is preferably 6% by mass or less, more preferably 4% by mass or less, based on the carboxyl group-containing resin (A).

  The raw material of the photosensitive resin composition as described above is blended, and the photosensitive resin composition can be prepared by 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, and the resulting mixture is The photosensitive resin composition may be prepared by adding and mixing a liquid component, a component having a low viscosity, and the like.

  In blending the organic filler (E1) having a carboxyl group, it is preferable to disperse the organic filler (E1) by stirring in the presence of the carboxyl group-containing resin (A) and the coupling agent (F1) in advance. Moreover, it is preferable to couple | bond and hybridize carboxyl group-containing resin (A) and the organic filler (E1) which has a carboxyl group through a coupling agent (F1). At this time, it is preferable to stir under acidic conditions or alkaline conditions. Under acidic conditions, the hydrolysis rate of the coupling agent (F1) increases, and under alkaline conditions, the condensation reaction rate of the coupling agent (F1) increases.

  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 previously mixing and dispersing the unsaturated compound (B), a part of the organic solvent, and the thermosetting component among the components of the photosensitive resin composition. You may prepare a 2nd agent by mixing and disperse | distributing the remainder among the components of a composition. 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.

  When the photosensitive resin composition is formed into a film having a thickness of 25 μm, the film is preferably developable with an aqueous sodium carbonate solution. In this case, since a sufficiently thick electrically insulating layer can be produced from the photosensitive resin composition by photolithography, the photosensitive resin composition is used as an interlayer insulating layer or solder resist in a printed wiring board. Widely applicable for producing layers and the like. Of course, it is also possible to produce an electrically insulating layer having a thickness of less than 25 μm from the photosensitive resin composition.

It can be confirmed by the following method that the film can be developed with an aqueous sodium carbonate solution. A wet paint film is formed by applying the photosensitive resin composition on a suitable substrate, and this wet paint film is heated at 80 ° C. for 40 minutes to form a film having a thickness of 25 μm. In a state where a negative mask having an exposed portion that transmits ultraviolet rays and a non-exposed portion that blocks ultraviolet rays is directly applied to the coating, the coating is irradiated with ultraviolet rays through the negative mask under a condition of 500 mJ / cm ² . A 1% Na ₂ CO ₃ aqueous solution at 30 ° C. is jetted for 90 seconds at an injection pressure of 0.2 MPa on the film after exposure, and then pure water is jetted for 90 seconds at an injection pressure of 0.2 MPa. As a result of observing the film after this treatment, it can be determined that development is possible when a portion corresponding to the non-exposed part of the film is removed and no residue is observed.

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

  First, the 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 coating 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. The ultraviolet light source is selected from the group consisting of chemical lamps, low-pressure mercury lamps, medium-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, xenon lamps, and metal halide lamps, for example.

  As an exposure method, a method other than a method using a negative mask may be employed. 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. The light source applied to the direct drawing method is, for example, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a metal halide lamp, g-line (436 nm), h-line (405 nm), i-line (365 nm), and g-line, h-line, and i-line. It is selected from the group consisting of two or more kinds of combinations.

  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 transmitted through the support 4 without irradiating the film 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 within a heating time range of 30 to 120 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 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.

  As described above, the interlayer insulating layer 7 made of a cured product of the photosensitive resin composition is provided on the core material 1. 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, a core material is prepared. 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.

  By the above, the solderless resist layer which consists of hardened | cured material of the photosensitive resin composition is provided on a 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:
The carboxyl group-containing resins of Synthesis Examples A-1 to A-3 were prepared as follows. The details are shown in Table 1 below. The components shown in the “First Reaction” column of Table 1 are added to a four-necked flask equipped with a reflux condenser, thermometer, air blowing tube and stirrer, and the mixture is stirred by air bubbling. Was prepared. While stirring this mixture in the flask under air bubbling, the mixture was heated at the reaction temperature and reaction time shown in the “Reaction Conditions” column. This prepared an intermediate solution.

  Subsequently, the components shown in the “second reaction” column of Table 1 were added to the intermediate solution in the flask, and the reaction temperature and reaction time shown in the “reaction conditions (1)” column were stirred while air bubbling. Heated. In Synthesis Example A-1, the mixture was further heated at the reaction temperature and reaction time shown in the “Reaction Conditions (2)” column with stirring under air bubbling. This obtained a 65 mass% solution of carboxyl group-containing resin. The weight average molecular weight and acid value of the carboxyl group-containing resin are as shown in Table 1. For Synthesis Example A-1, the molar ratio between the components is also shown in Table 1. Further, the polydispersity of Synthesis Example A-1 was 2.15.

In addition, the detail of the component shown in the (a1) and (g1) column of Table 1 is as follows.
Epoxy compound 1: A bisphenolfluorene type epoxy compound having an epoxy equivalent of 250 g / eq represented by the formula (7) and in which R _{1 to} R ₈ in the formula (7) are all hydrogen.
Epoxy compound 2: biphenyl novolac type epoxy resin (manufactured by Nippon Kayaku Co., Ltd., product number NC-3000-H, epoxy equivalent 288 g / eq).
Epoxy compound 3: Cresol novolac type epoxy resin (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., product number YDC-700-5, epoxy equivalent 203 g / eq).

(2) Preparation of photosensitive resin composition:
The photosensitive resin compositions of Examples 1-20 and Comparative Examples 1-5 were prepared as follows. A photosensitive resin composition was obtained by stirring and mixing the components shown in the table below (see Tables 2 to 4). The photosensitive resin composition was filtered under pressure with a filter having a hole diameter of 30 μm.

  The photosensitive resin composition of Comparative Example 6 was prepared as follows. While stirring a 65% solution of a carboxyl group-containing resin and a coupling agent shown in the table below and a coupling agent in a flask, a part of other components are kneaded with three rolls and then added to the flask. All of the remainder was added and stirred and mixed in the flask to obtain a photosensitive resin composition (see Table 4). The photosensitive resin composition was filtered under pressure with a filter having a hole diameter of 30 μm.

Details of the components shown in the table are as follows.
Unsaturated compound A: trimethylolpropane triacrylate.
Unsaturated compound B: ε-caprolactone-modified dipentaerystol hexaacrylate, manufactured by Nippon Kayaku Co., Ltd., product number KAYARAD DPCA-20.
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
Crystalline epoxy resin A: Biphenyl type crystalline epoxy resin, manufactured by Mitsubishi Chemical Corporation, product number YX-4000, melting point 105 ° C., epoxy equivalent 187 g / eq.
Crystalline epoxy resin B: 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.
-Dispersion of organic filler A: cross-linked 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 cross-linked 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, carboxyl group and hydroxyl group, manufactured by JSR Corporation, product number XSK-500, methyl ethyl ketone dispersion having a content of 15% by weight of crosslinked rubber .
Organic filler C: Epoxy group-containing organic filler powder: glycidyl-modified acrylonitrile butadiene rubber having an average primary particle size of 0.3 μm.
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.
Antioxidant: A hindered phenol antioxidant, manufactured by BASF, product number IRGANOX 1010.
Colorant: Color pigment dispersion varnish containing a color index Pigment Blue 15: 3 and a color index Pigment Yellow 147 in a weight ratio of 1: 2.5 in total 15% by weight.
Surfactant: manufactured by DIC, product number MegaFuck F-477.
-Rheology control agent: Product number BYK-430 manufactured by Big Chemie Japan Co., Ltd.
Melamine dispersed varnish: A fine melamine dispersed varnish manufactured by Nissan Chemical Industries, Ltd. Disperse 1.5 parts fine melamine and 3.5 parts unsaturated compound trimethylolpropane triacrylate in a bead mill.
Solvent: methyl ethyl ketone.

(3) 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 a surface layer portion having a thickness of about 1 μm in the conductor wiring of the core material 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. With this film directly exposed to a negative mask having a non-exposed portion of a pattern including a circular shape with a diameter of 60 μm from a polyethylene terephthalate film, ultraviolet rays are applied to the film through the negative mask under the condition of 250 mJ / cm ^2. Was irradiated. 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, the film was irradiated with ultraviolet rays under the condition of 1000 mJ / cm ² , and then the film was heated at 180 ° C. for 60 minutes. 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.

(4) Evaluation test (4-1) Dispersibility For each example and comparative example, the particle size distribution of the photosensitive resin composition was measured with MT3300EXII manufactured by Microtrack Bell Co., Ltd., and the results were evaluated as follows. did.
A: The maximum particle size was 0.5 μm or less by particle size distribution measurement.
B: The maximum particle size was larger than 0.5 μm and 1.0 μm or less by particle size distribution measurement.
C: The maximum particle size was larger than 1.0 μm and 20 μm or less by particle size distribution measurement.
D: The maximum particle size was larger than 20 μm by particle size distribution measurement.

  However, since Examples 17 to 19 are affected by the colorant and melamine, a composition in which the colorant and the melamine dispersion varnish are not blended in the compositions of Examples 17 to 19 in Table 3 is prepared. The particle size distribution was measured as an evaluation of 17-19.

(4-2) Stability About each Example and a comparative example, after storing the photosensitive resin composition in a refrigerator (4 degreeC) for 1 week, the photosensitive resin composition was observed, and the result was evaluated as follows. did.
A: Separation of components in the photosensitive resin composition did not occur, and a uniform state was maintained.
B: Some turbidity was seen in the photosensitive resin composition, but no precipitate was seen.
C: Separation occurred in the components in the photosensitive resin composition, and precipitates were observed.

(4-3) Uniformity of coating film For each example and comparative example, a dry film having a thickness of 30 μm formed on the film was observed, and the result was evaluated as follows.
A: Aggregates and voids (bubbles) were not observed, and the surface state was uniform.
B: Some aggregates and / or voids (bubbles) were observed.
C: Many aggregates and / or voids (bubbles) were observed, and the surface state was not uniform, or a uniform film thickness was not obtained.

(4-4) Developability About each Example and the comparative example, the wet paint film was formed by apply | coating the photosensitive resin composition to the whole surface of the printed wiring board by the spin coat method. This wet coating film was heated at 80 ° C. for 40 minutes or 60 minutes to form a film having a thickness of 25 μm. This film was developed without exposure. In the development process, a 1% Na ₂ CO ₃ aqueous solution at 30 ° C. was jetted for 90 seconds at a jet pressure of 0.2 MPa, and then pure water was jetted for 90 seconds at a jet pressure of 0.2 MPa. The printed wiring board after the treatment was observed, and the result was evaluated as follows.
A: The film was completely removed regardless of whether the heating time of the wet coating film was 40 minutes or 60 minutes.
B: When the heating time of the wet coating film was 40 minutes, all the coating film was removed, but at 60 minutes, a part of the coating film remained on the printed wiring board.
C: A part of the film remained on the printed wiring board regardless of whether the heating time of the wet coating film was 40 minutes or 60 minutes.

(4-5) Resolution About each Example and the comparative example, the hole formed in the layer which consists of hardened | cured material in a test piece was observed, and the result was evaluated as follows.
A: The diameter of the bottom of the hole is 53 μm or more.
B: The diameter of the bottom of the hole is 50 μm or more and less than 53 μm.
C: The diameter of the bottom of the hole is 40 μm or more and less than 50 μm.
D: The diameter of the bottom of the hole is less than 40 μm, or no clear hole is formed.

(4-6) Plating resistance After a nickel plating layer is formed using a commercially available electroless nickel plating bath on the portion of the conductor wiring of the test piece of each example and comparative example that is exposed to the outside, it is commercially available. A gold plating layer was formed using an electroless gold plating bath. This formed the metal layer which consists of a nickel plating layer and a gold plating layer. The layer and metal layer which consisted of hardened | cured material were observed visually. Moreover, the cellophane adhesive tape peeling test was done with respect to the layer which consists of hardened | cured material. The results were evaluated as follows.
A: No abnormality was observed in the appearance of the layer made of the cured product and the metal layer, and peeling of the layer made of the cured product by the cellophane adhesive tape peeling test did not occur.
B: Although discoloration was recognized in the layer which consists of hardened | cured materials, peeling of the layer which consists of hardened | cured materials by the cellophane adhesive tape peeling test did not arise.
C: Lifting of the layer made of the cured product was observed, and peeling of the layer made of the cured product by the cellophane adhesive tape peeling test occurred.

(4-7) Insulation between lines While applying a bias voltage of DC 30 V to the conductor wiring (comb electrode) in the test pieces of each Example and Comparative Example, the test piece was 121 ° C. and 97% R.D. H. The test environment was exposed for 120 hours. The electrical resistance value between the comb-type electrodes of the cured product layer in this test environment was constantly measured, and the result was evaluated according to the following evaluation criteria.
A: The electric resistance value was constantly maintained at 10 ⁶ Ω or more until 120 hours passed from the start of the test.
B: The electric resistance value was constantly maintained at 10 ⁶ Ω or more until 100 hours passed from the start of the test, but the electric resistance value became less than 10 ⁶ Ω before 120 hours passed from the start of the test.
C: The electric resistance value was always maintained at 10 ⁶ Ω or more until 80 hours passed from the start of the test, but the electric resistance value became less than 10 ⁶ Ω before 100 hours passed from the start of the test.
D: The electric resistance value was less than 10 ⁶ Ω before 80 hours passed from the start of the test.

(4-8) Interlayer insulation The conductive tape was stuck on the layer which consists of hardened | cured material in the test piece of each Example and a comparative example. While applying a bias voltage of DC 100 V to the conductive tape, the test piece was placed at 121 ° C. and 97% R.D. H. The test environment was exposed for 60 hours. The electrical resistance value between the conductive wiring of the layer made of the cured product and the conductive tape in this test environment was constantly measured, and the result was evaluated according to the following evaluation criteria.
A: The electric resistance value was constantly maintained at 10 ⁶ Ω or more until 60 hours passed from the start of the test.
B: The electric resistance value was always maintained at 10 ⁶ Ω or more until 45 hours passed from the start of the test, but the electric resistance value became less than 10 ⁶ Ω before 60 hours passed from the start of the test.
C: The electrical resistance value was less than 10 ⁶ Ω before 45 hours passed from the start of the test.

(4-9) PCT
The test piece of each Example and Comparative Example was 121 ° C., 100% R.D. H. After being allowed to stand for 100 hours in this environment, the appearance of the layer made of the cured product was evaluated according to the following evaluation criteria.
A: No abnormality was found in the layer made of the cured product.
B: Discoloration was observed in the layer made of the cured product.
C: A large discoloration was observed in the layer made of the cured product, and partial swelling occurred.

(4-10) Cooling cycle resistance The test piece of each Example and Comparative Example was changed in temperature, and passed through -65 ° C for 10 minutes (low temperature condition) and 150 ° C for 10 minutes (high temperature condition) as one cycle. , 750 cycle and 1000 cycle temperature cycle tests were conducted. Then, the external appearance of the layer which consists of hardened | cured material was evaluated by the following evaluation criteria.
A: No crack was observed after 1000 cycles.
B: Cracks were not observed at 750 cycles, but cracks were observed at 1000 cycles.
C: Cracks were observed at 750 cycles.

  The results of the above evaluation tests are shown in Tables 2 to 4 below.

Claims (14)

A carboxyl group-containing resin (A);
An unsaturated compound (B) having at least one ethylenically unsaturated bond in one molecule;
A photopolymerization initiator (C);
An epoxy compound (D);
An organic filler (E);
A coupling agent (F),
The organic filler (E) includes an organic filler (E1) having a carboxyl group with an average primary particle size of 1 μm or less,
The coupling agent (F) contains an atom selected from a silicon atom, an aluminum atom, a titanium atom, and a zirconia atom, and further contains two or more functional groups selected from an alkoxy group, an acyloxy group, and an alkoxide. Containing agent (F1),
Photosensitive resin composition.   The photosensitive resin composition of Claim 1 in which the said organic filler (E1) is disperse | distributed with the particle diameter of 1 micrometer or less.   The photosensitive resin composition of Claim 1 or 2 in which the said coupling agent (F1) contains a silicon atom.   The coupling agent (F1) according to claim 3, further comprising at least one functional group selected from an amino group, an epoxy group, a vinyl group, a methacryl group, a mercapto group, an isocyanate group, and a sulfide group. Photosensitive resin composition.   The content of the organic filler (E1) is in the range of 1 to 40 parts by mass when the content of the carboxyl group-containing resin (A) is 100 parts by mass. The photosensitive resin composition of one term.   The photosensitive resin composition as described in any one of Claims 1 thru | or 5 in which the said carboxyl group-containing resin (A) contains the carboxyl group-containing resin which has an ethylenically unsaturated group.   The content of the coupling agent (F1) is in the range of 0.01 to 7 parts by mass, when the content of the organic filler (E1) is 100 parts by mass. A photosensitive resin composition according to claim 1.   The average primary particle diameter of the organic filler (E1) is 0.1 μm or less, and the organic filler (E1) is dispersed with a particle diameter of 0.5 μm or less. The photosensitive resin composition as described.   The photosensitive resin composition as described in any one of Claims 1 thru | or 8 in which the said organic filler (E1) contains a rubber component.   The photosensitive resin composition of Claim 9 in which the said rubber component contains at least 1 polymer chosen from crosslinked acrylic rubber, crosslinked NBR, crosslinked MBS, and crosslinked SBR.   The photosensitive resin composition according to any one of claims 1 to 10, wherein the carboxyl group-containing resin (A) includes a carboxyl group-containing resin having a bisphenolfluorene skeleton.   The dry film containing the photosensitive resin composition as described in any one of Claims 1 thru | or 11.   A printed wiring board provided with the interlayer insulation layer containing the hardened | cured material of the photosensitive resin composition as described in any one of Claims 1 thru | or 11.   A printed wiring board provided with the soldering resist layer containing the hardened | cured material of the photosensitive resin composition as described in any one of Claims 1 thru | or 11.

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