JP6172816B2 - Photosensitive resin composition, dry film, printed wiring board, and method for producing photosensitive resin composition - Google Patents

Description

  The present invention relates to a photosensitive resin composition, a dry film, a printed wiring board, and a method for producing a photosensitive resin composition, and more specifically, to a printed wiring board, a solder resist layer, a plating resist layer, an etching resist layer, an interlayer insulating layer, and the like A photosensitive resin composition suitable for forming an electrically insulating layer, a dry film containing the photosensitive resin composition, a printed wiring board comprising an interlayer insulating layer containing a cured product of the photosensitive resin composition, The present invention relates to a printed wiring board including a solder resist layer containing a cured product of the photosensitive resin composition, and a method for producing the photosensitive resin composition.

  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 give high heat resistance to the layer formed from the photosensitive resin composition, it has been proposed to add a carboxyl group-containing resin having a bisphenolfluorene skeleton to the photosensitive resin composition. For example, Patent Document 1 discloses the use of a carboxyl group-containing resin having a bisphenolfluorene skeleton obtained by reacting fluorene epoxy (meth) acrylate with a polyvalent carboxylic acid or an anhydride thereof.

  In recent years, since the use of a developer containing an organic amine has been avoided for the purpose of improving the working environment and reducing the burden of waste disposal, the photosensitive resin composition is made of an alkali metal salt and an alkali metal. There is a strong demand for development with an alkaline aqueous solution containing at least one of the hydroxides.

  Furthermore, when using the hardened | cured material of the photosensitive resin composition as a permanent resist layer etc. of a printed wiring board, it is requested | required that a sufficient effect should be exhibited in the reliability test represented by the thermal cycle test. That is, high thermal shock resistance is required for the cured product of the photosensitive resin composition.

Japanese Patent No. 4508929

  The present invention has been made in view of the above reasons, can be a cured product having excellent thermal shock resistance, and further has a bisphenolfluorene skeleton, while having a developability with an alkaline aqueous solution, the photosensitive resin composition, A dry film containing a photosensitive resin composition, a printed wiring board provided with an interlayer insulating layer containing a cured product of the photosensitive resin composition, and a printed wiring board provided with a solder resist layer containing a cured product of the photosensitive resin composition And it aims at providing the manufacturing method of the photosensitive resin composition.

The photosensitive resin composition according to the present invention comprises 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). The carboxyl group-containing resin (A) is represented by the following formula (1), and in the formula (1), R _{1 to} R ₈ are each independently hydrogen, a C 1-5 alkyl group, or a bisphenolfluorene skeleton. The carboxyl group-containing resin (A1) which is a reaction product of an intermediate product which is a reaction product of the epoxy compound (a1) having an unsaturated group-containing carboxylic acid (a2) and an acid anhydride. The epoxy compound (D) comprises a bisphenol-type structural unit (d1) obtained by removing terminal OH groups from bisphenol, a linear hydrocarbon structural unit having 4 to 20 carbon atoms, and an ether oxygen atom number of 3 to 20 And an epoxy compound (d) having at least one structural unit (d2) selected from the group consisting of polyalkylene ether structural units. The acid anhydride contains an acid dianhydride.

  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.

The manufacturing method of the photosensitive resin composition which concerns on this invention is shown by following formula (1), and R < ₁ > -R < ₈ > is hydrogen, a C1-C5 alkyl group, or halogen each independently in Formula (1). The epoxy compound (a1) having a bisphenolfluorene skeleton and the unsaturated group-containing carboxylic acid (a2) are reacted, and the intermediate obtained thereby is reacted with the acid anhydride, thereby containing a carboxyl group. A resin (A1), a carboxyl group-containing resin (A) containing the carboxyl group-containing resin (A1), an unsaturated compound (B) having at least one ethylenically unsaturated bond in one molecule; Mixing a photoinitiator (C) and an epoxy compound (D) is included. The epoxy compound (D) comprises a bisphenol-type structural unit (d1) obtained by removing terminal OH groups from bisphenol, a linear hydrocarbon structural unit having 4 to 20 carbon atoms, and an ether oxygen atom number of 3 to 20 And an epoxy compound (d) having at least one structural unit (d2) selected from the group consisting of polyalkylene ether structural units. The acid anhydride contains an acid dianhydride.

  According to the present invention, a cured product having excellent thermal shock resistance can be obtained. Further, the photosensitive resin composition has excellent developability with an alkaline aqueous solution while having a bisphenolfluorene skeleton, and contains the photosensitive resin composition. Printed wiring board provided with a dry film, an interlayer insulation layer containing a cured product of the photosensitive resin composition, a printed wiring board provided with a solder resist layer containing a cured product of the photosensitive resin composition, and the photosensitive resin composition The manufacturing method 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).

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

  The carboxyl group-containing resin (A1) is synthesized by reacting the epoxy compound (a1) with the unsaturated group-containing carboxylic acid (a2), and reacting the resulting intermediate with an acid anhydride. The Examples of the acid anhydride include acid dianhydride (a3) and acid monoanhydride (a4). The acid anhydride preferably contains an acid dianhydride (a3), more preferably at least one selected from an acid dianhydride (a3) and an acid monoanhydride (a4). When the acid anhydride contains the acid dianhydride (a3), tackiness of a film formed from the photosensitive resin composition can be further suppressed. Hereinafter, the case where an acid anhydride consists of an acid dianhydride (a3) and an acid monoanhydride (a4) is demonstrated.

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, the carboxyl group-containing resin (A1) has a bisphenolfluorene skeleton represented by the formula (1) derived from the epoxy compound (a1), so that the photosensitive resin composition containing the carboxyl group-containing resin (A1). High heat resistance and insulation reliability can be imparted to the cured product.

  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 group-containing carboxylic acid (a2). The intermediate has a structure represented by the following formula (3) generated by a ring-opening addition reaction between an epoxy group and an unsaturated group-containing carboxylic acid (a2). That is, the intermediate has a secondary hydroxyl group generated by a ring-opening addition reaction between an epoxy group and an unsaturated group-containing carboxylic acid (a2) in the structure represented by the formula (3). In Formula (3), A is an unsaturated group-containing carboxylic acid residue.

  Next, a part of the secondary hydroxyl group in the intermediate is reacted with acid dianhydride (a3), and another part of the secondary hydroxyl group in the intermediate is reacted with acid monoanhydride ( a4) is reacted. Thereby, carboxyl group-containing resin (A1) can be synthesized. Therefore, the carboxyl group-containing resin (A1) has a bisphenolfluorene skeleton represented by the formula (1), a structure represented by the following formula (4), and a structure represented by the following formula (5).

  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 monoanhydride (a4). In Formula (4), A is an unsaturated group-containing carboxylic acid residue, and B is an acid monoanhydride residue.

  The structure represented by the formula (5) is generated by the reaction between two acid anhydride groups in the acid dianhydride (a3) and two secondary hydroxyl groups in the intermediate. That is, the structure shown in Formula (5) is produced by crosslinking two secondary hydroxyl groups with acid dianhydride (a3). 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 an unsaturated group-containing carboxylic acid residue, and D is an acid dianhydride residue.

  The carboxyl group-containing resin (A1) may further have a structure represented by the following formula (6). The structure represented by the formula (6) occurs when only one of the two acid anhydride groups in the acid dianhydride (a3) reacts with the secondary hydroxyl group in the intermediate. In Formula (6), A is an unsaturated group-containing carboxylic acid residue, and D is an acid dianhydride 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, in this embodiment, by optimizing the reaction conditions during the synthesis of the carboxyl group-containing resin (A1), the structure shown in the formula (2) in the carboxyl group-containing resin (A1) and the formula (6) It is possible to reduce or almost eliminate the structure shown.

  As described above, the carboxyl group-containing resin (A1) has the bisphenolfluorene skeleton represented by the formula (1), the structure represented by the formula (4), and the structure represented by the 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 may have a structure produced by reaction of at least one of acid dianhydride (a3) and acid dianhydride (a4).

  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 (a3) react, as described above, two secondary hydroxyl groups present in one molecule of the intermediate are acid dianhydrides (a3). There may be a case where two secondary hydroxyl groups respectively present in two molecules of the intermediate are crosslinked with an acid dianhydride (a3). 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). For this reason, carboxyl group-containing resin (A1) can provide photosensitivity, specifically, ultraviolet curability, to the photosensitive resin composition. The carboxyl group-containing resin (A1) has a carboxyl group derived from the acid dianhydride (a3) and the acid monoanhydride (a4), so that the photosensitive resin composition has an alkali metal salt and an alkali metal water. The developability by the alkaline aqueous solution containing at least one of the oxides can be imparted. Furthermore, the molecular weight of the carboxyl group-containing resin (A1) is adjusted by crosslinking with the acid dianhydride (a3). For this reason, the carboxyl group-containing resin (A1) in which the acid value and the molecular weight are appropriately adjusted is obtained. That is, by controlling the amount of the acid dianhydride (a3) and the acid monoanhydride (a4) and the amount of the acid dianhydride (a4) relative to the acid dianhydride (a3), the carboxyl group-containing resin (A1 ) Can be easily adjusted.

  The weight average molecular weight of the carboxyl group-containing resin (A1) is preferably in the range of 1000 to 5000. When the weight average molecular weight is 1000 or more, tackiness of a film formed from the photosensitive resin composition can be further suppressed, and 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 5000 or less.

  Moreover, it is preferable that the solid content acid value of carboxyl group-containing resin (A1) exists in the range of 60-140 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 weight average molecular weight (Mw) of the carboxyl group-containing resin (A1) is calculated from the molecular weight measurement result by gel permeation chromatography. The molecular weight measurement by gel permeation chromatography can be performed, for example, under the following conditions.

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 a number within 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 due to the addition of acid dianhydride (a3) is likely to be suppressed.

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

  In reacting the epoxy compound (a1) with the unsaturated group-containing carboxylic acid (a2), a known method may be employed. For example, a reactive solution is obtained by adding an unsaturated group-containing carboxylic acid (a2) to a solvent solution of the epoxy compound (a1), and 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, butyl carbitol acetate, propylene glycol monomethyl ether acetate, diethylene glycol mono It can contain at least one component selected from the group consisting of acetates such as ethyl ether acetate and dialkyl glycol ethers. The thermal polymerization inhibitor contains, for example, at least one of methyl hydroquinone, 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) with the unsaturated group-containing carboxylic acid (a2) in the presence of triphenylphosphine. In this case, the ring-opening addition reaction between the epoxy group and the unsaturated group-containing carboxylic acid (a2) in the epoxy compound (a1) is particularly accelerated, and the reaction rate (conversion) is 95% or more, 97% or more, or almost 100%. Rate). 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 unsaturated group-containing carboxylic acid (a2) are reacted, the amount of the unsaturated group-containing carboxylic acid (a2) relative to 1 mol of the epoxy group of the epoxy compound (a1) is 0.8 to 1. It is preferably within a range of 2 moles. In this case, excellent photosensitivity and storage stability of the photosensitive resin composition can be obtained.

  It is also preferable to react the epoxy compound (a1) and the unsaturated group-containing 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 unsaturated group-containing carboxylic acid (a2).

  The acid dianhydride (a3) is a compound having two acid anhydride groups. The acid dianhydride (a3) can contain an anhydride of tetracarboxylic acid. Acid dianhydride (a3) is, for example, 1,2,4,5-benzenetetracarboxylic dianhydride, benzophenone tetracarboxylic dianhydride, methylcyclohexene tetracarboxylic dianhydride, tetracarboxylic dianhydride, Naphthalene-1,4,5,8-tetracarboxylic dianhydride, ethylenetetracarboxylic dianhydride, 9,9'-bis (3,4-dicarboxyphenyl) fluorene dianhydride, glycerin bisanhydrotri Melitate monoacetate, ethylene glycol bisanhydro trimellitate, 3,3 ′, 4,4′-diphenylsulfone tetracarboxylic dianhydride, 1,3,3a, 4,5,9b-hexahydro-5 (tetrahydro -2,5-dioxo-3-furanyl) naphtho [1,2-c] furan-1,3-dione, 1,2,3,4-buta Tetracarboxylic 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 (a3) 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, the tackiness of the film formed from the photosensitive resin composition is further suppressed, and the film formed from the photosensitive resin composition is exposed and developed. In this case, the resolution is improved. Furthermore, the insulation reliability and plating resistance of the cured product are further improved. The total amount of 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride is preferably in the range of 20 to 100 mol%, and preferably 40 to 100 mol%, based on the entire acid dianhydride (a3). Although it is more preferable to be within the range, it is not limited to this.

  The acid monoanhydride (a4) is a compound having one acid anhydride group. The acid monoanhydride (a4) can contain an anhydride of a dicarboxylic acid. Examples of the acid monoanhydride (a4) include phthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylnadic acid anhydride, hexahydrophthalic anhydride, methylhexa It may contain one or more compounds selected from the group consisting of hydrophthalic anhydride, succinic anhydride, methyl succinic anhydride, maleic anhydride, citraconic anhydride, glutaric anhydride, and itaconic anhydride . In particular, it is preferable that the acid monoanhydride (a4) 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. . It is preferable that 1,2,3,6-tetrahydrophthalic anhydride is in the range of 20 to 100 mol%, and in the range of 40 to 100 mol%, based on the entire acid monoanhydride (a4). Is more preferable, but not limited to this.

  In reacting the intermediate with the acid dianhydride (a3) and the acid monoanhydride (a4), a known method may be employed. For example, the acid dianhydride (a3) and the acid monoanhydride (a4) are added to the solvent solution of the intermediate, and a thermal polymerization inhibitor and a catalyst are added as necessary, followed by stirring and mixing to obtain a reactive solution. . The carboxyl group-containing resin (A1) can be obtained by reacting this reactive solution at a temperature of preferably 60 to 150 ° C., particularly preferably 80 to 120 ° C., 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 with acid monoanhydride (a4) and acid dianhydride (a3) in the presence of triphenylphosphine. In this case, the reaction of the secondary hydroxyl group in the intermediate with acid monoanhydride (a4) and acid dianhydride (a3) is particularly promoted, and is 90% or more, 95% or more, 97% or more, or almost 100%. It is possible to achieve a reaction rate (conversion rate) of For this reason, the carboxyl group-containing resin (A1) having the structure represented by the formula (4) and the structure represented by the formula (5) can be 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.

  It is also preferred to react the intermediate with acid monoanhydride (a4) and acid dianhydride (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).

  When the intermediate is reacted with the acid monoanhydride (a4) and the acid dianhydride (a3), the amount of the acid dianhydride (a3) with respect to 1 mol of the epoxy group of the epoxy compound (a1) is: It is preferably in the range of 0.05 to 0.24 mol. Moreover, it is preferable that the quantity of acid monoanhydride (a4) exists in the range of 0.3-0.7 mol with respect to 1 mol of epoxy groups of an epoxy compound (a1). In this case, the carboxyl group-containing resin (A1) in which the acid value and the molecular weight are appropriately adjusted can be easily obtained. Moreover, 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) of this embodiment may contain only the carboxyl group-containing resin (A1), or a carboxyl group-containing resin other than the carboxyl group-containing resin (A1) (hereinafter referred to as carboxyl group-containing resin (F). ))) May be further contained.

  The carboxyl group-containing resin (F) can contain, for example, a compound having a carboxyl group and not having photopolymerizability (hereinafter referred to as (F1) component).

  (F1) 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 (F) may contain a compound having a carboxyl group and an ethylenically unsaturated group (hereinafter referred to as (F2) component). The component (F2) 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 its anhydride. 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 substances. 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 (F2) 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. (I)) may be contained. The ethylenically unsaturated monomer may further contain an ethylenically unsaturated compound having no carboxyl group. The second resin (i) can be obtained by reacting an ethylenically unsaturated compound having an epoxy group with a part of the carboxyl group in the polymer. The 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) contains only the carboxyl group-containing resin (A1) or the carboxyl group-containing resin (A1) and the carboxyl group-containing resin (F). The carboxyl group-containing resin (A) preferably contains 30% by mass or more of the carboxyl group-containing resin (A1), more preferably 50% 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.

  Components other than the carboxyl group-containing resin (A) in the photosensitive resin composition will be described.

  As described above, the photosensitive resin composition 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).

  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) Multifunctional (such as acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, ε-caprolactone modified pentaerythritol hexaacrylate It can contain at least one compound selected from the group consisting of (meth) acrylate and tricyclodecane dimethanol 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-3 03, and it may contain one or more compounds selected from the group consisting of HFA-6127, etc.).

  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, although the photosensitive resin composition contains the carboxyl group-containing resin (A1), high photosensitivity can be imparted to the photosensitive resin composition when the photosensitive resin composition is exposed to ultraviolet rays. 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 has at least two epoxy groups in one molecule. The epoxy compound (D) may be a solvent-insoluble epoxy compound or a general-purpose solvent-soluble epoxy compound.

The epoxy compound (D) contains an epoxy compound (d) having a bisphenol type structural unit (d1) and a structural unit (d2). When the epoxy compound (D) contains the epoxy compound (d), the thermal shock resistance of the cured product of the photosensitive resin composition can be improved.

Examples of the bisphenol type structural unit (d1) include structural units derived from bisphenol A, bisphenol F, and bisphenol S. The bisphenol type structural unit (d1), specifically, units represented by these terminal OH groups excluding units and the following equation (8) below. Moreover, a part of phenylene group and phenyl group in the unit represented by the formula (8) may be hydrogenated. Furthermore, the phenylene group and the phenyl group in the unit represented by the formula (8) may have a substituent such as a hydrocarbon group, an alkoxyl group, an aryl group, an aryloxy group, or a hydroxyl group.

The structural unit (d2) is composed of at least one selected from the group consisting of a linear hydrocarbon structural unit having 4 to 20 carbon atoms and a polyalkylene ether structural unit having 3 to 20 ether oxygen atoms.

The linear hydrocarbon structural unit having 4 to 20 carbon atoms in the structural unit (d2) is a structural unit in which _{y of} — (CH ₂ ) _y — is 4 to 20. y is preferably 4 to 10. Incidentally, _- (CH ₂₎ y - may have a substituent such as a hydroxyl group in place y is a hydrogen atom in the structural unit is 4 or more 20 or less. Furthermore, at least one hydrogen atom in the structural unit in which _{y of} — (CH ₂ ) _y — is 4 or more and 20 or less may be substituted with a hydrocarbon group, an alkoxyl group, an aryl group, an aryloxy group, or the like. . The hydrocarbon and alkoxyl groups as the substituent preferably have 4 or less carbon atoms. The aryl group in the aryl group and aryloxy group is preferably a phenyl group. 20 following linear hydrocarbon structural unit having 4 or more carbon atoms in the structural unit (d2) is, these substituents may have a range that does not impair the flexibility of the structural units (d2).

The polyalkylene ether structural unit in the structural unit (d2) has 3 to 20 ether oxygen atoms, preferably 3 to 10 ether atoms. Specific examples of the polyalkylene ether structural unit in the structural unit (d2) include one or more alkylene oxides selected from ethylene oxide, propylene oxide, butylene oxide, isobutylene oxide, neopentylene oxide, tetramethylene oxide, and the like. Examples include structural units derived from polymers. One or more hydrogen atoms of the alkylene oxide may be substituted with, for example, a hydroxyl group, an alkoxyl group, an aryl group, an aryloxy group, a hydrocarbon group, or the like. The hydrocarbon and alkoxyl groups as the substituent preferably have 4 or less carbon atoms. The aryl group in the aryl group and aryloxy group is preferably a phenyl group. Polyalkylene ether structural units in the structural units (d2) is, these substituents may have a range that does not impair the flexibility of the structural units (d2).

The molar ratio between the structural unit (d1) and the structural unit (d2) is preferably 10: 1 to 1: 5, and more preferably 5: 1 to 1: 3. When the molar ratio of the structural unit (d1) is higher than the above range, the epoxy compound (d) does not have sufficient flexibility and the cured product of the photosensitive resin composition may be easily cracked. Moreover, when the molar ratio of the structural unit (d1) is lower than the above range, the Tg of the epoxy compound (d) is too low, and the heat resistance of the cured product of the photosensitive resin composition may be lowered.

  Specifically, the epoxy compound (d) preferably has one or more structures represented by the following structural formulas (9-i) to (9-iv). Further, a plurality of hydroxyl groups in the structural formula shown below may undergo a crosslinking reaction, and the oxygen atom of the hydroxyl group may knot an unspecified structure.

In the structural formulas (9-i) to (9-iv), Ar ₁ and Ar ₂ are hydrogenated or optionally substituted bisphenol-type structural units (d1). Ar ₁ and Ar ₂ may be the same or different. X is at least one selected from the group consisting of a linear hydrocarbon group having 4 to 20 carbon atoms and a polyalkylene ether structure having 1 to 18 ether oxygen atoms. When X is a linear hydrocarbon group having 4 to 20 carbon atoms, X constitutes the structural unit (d2). When X is a polyalkylene ether structure having 1 to 18 ether oxygen atoms, —O—X—O— constitutes the structural unit (d2). Moreover, n is an average value of a repeating unit and is 1-30.

  Examples of a method for obtaining such an epoxy compound (d) include a method of curing a predetermined epoxy resin using a curing agent.

As this predetermined epoxy resin, a method using an epoxy compound having structural units (d1) and (d2) as described above; an epoxy compound having structural unit (d1) and an epoxy compound having structural unit (d2) And an epoxy compound having the structural unit (d1) and a chain extender that can impart the structural unit (d2) to the epoxy compound by a reaction.

  Specific examples of the epoxy compound (d) include product numbers EPICLON EXA4816 and EPICLON EXA4822 manufactured by DIC Corporation, and product numbers YL7175-500 and YL7175-1000 manufactured by Mitsubishi Chemical Corporation.

The epoxy equivalent of the epoxy compound having the bisphenol type structural unit (d1) and the structural unit (d2) is preferably 200 to 800 g / eq, and more preferably 350 to 650 g / eq.

  The epoxy compound (D) may further contain a compound other than the epoxy compound (d). The compound is a phenol novolac type epoxy resin (specifically, product number EPICLONN-775 manufactured by DIC Corporation), a cresol novolak type epoxy resin (specifically, product number EPICLON N-695 manufactured by DIC Corporation), bisphenol A novolac type epoxy resin. (As a specific example, product number EPICLONN-865 manufactured by DIC Corporation), bisphenol A type epoxy resin (as a specific example, product number jER1001 manufactured by Mitsubishi Chemical Corporation), bisphenol F type epoxy resin (as a specific example, product number manufactured by Mitsubishi Chemical Corporation) jER4004P), bisphenol S type epoxy resin (specifically, product number EPICLONEXA-1514 manufactured by DIC Corporation), bisphenol AD type epoxy resin, biphenyl type epoxy resin (specifically, Mitsubishi Chemical) (Product number YX4000 manufactured by Nippon Kayaku Co., Ltd.), biphenyl novolac type epoxy resin (specifically, product number NC-3000 manufactured by Nippon Kayaku Co., Ltd.), hydrogenated bisphenol A type epoxy resin (specifically, product number ST manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.) -4000D), naphthalene type epoxy resins (specific examples: product numbers EPICLONP-4032, EPICLON HP-4700, EPICLON HP-4770, manufactured by DIC Corporation), hydroquinone type epoxy resins (specifications, product number YDC- manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.) 1312), tertiary butyl catechol type epoxy resin (specific example, product number EPICLONP-820 manufactured by DIC Corporation), dicyclopentadiene type epoxy resin (specific example, product number EPICLON HP-7200 manufactured by DIC), ADA Tantalum type epoxy resin (part number ADAMANTEX-E-201 manufactured by Idemitsu Kosan Co., Ltd.), bisphenol type epoxy resin (part number YSLV-80XY manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.), biphenyl ether type epoxy resin (specific example Nippon Steel & Sumikin Chemical Co., Ltd. product number YSLV-80DE), epoxy resin having a bisphenolfluorene skeleton (an epoxy resin having a structure represented by formula (7) as a specific example), tetrakisphenolethane type epoxy resin (as a specific example, Nippon Kayaku Product number GTR-1800 manufactured by Co., Ltd.) and special bifunctional epoxy resin (specific examples: product numbers EPICLONTSR-960, EPICLON TER-601, EPICLON TSR-250-80BX, EPICLON manufactured by DIC Corporation) 1650-75MPX, EPICLON EXA-4850 and EPICLONEXA-9726; product number YSLV-120TE manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., rubber-like core-shell polymer-modified bisphenol A type epoxy resin (as a specific example, product number MX-156 manufactured by Kaneka Corporation) In addition, it is preferable to contain one or more components selected from the group consisting of rubber-like core-shell polymer-modified bisphenol F-type epoxy resins (specifically, product number MX-136 manufactured by Kaneka Corporation).

  In particular, the epoxy compound (D) preferably contains a crystalline epoxy resin having two epoxy groups in one molecule. A crystalline epoxy resin is an epoxy resin having a melting point. In this case, the developability of the photosensitive resin composition with the alkaline aqueous solution is particularly improved, and the thermal shock resistance of the cured product of the photosensitive resin composition is improved. Crystalline epoxy resins having two epoxy groups in one molecule are, for example, hydroquinone type epoxy resin (specifically, product number YDC-1312 manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.), biphenyl type epoxy resin (specifically, Mitsubishi Chemical Corporation). Manufactured product number YX4000), biphenyl ether type epoxy resin (specifically, product number YSLV-80DE manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.), bisphenol type epoxy resin (specific example, product number YSLV-80XY manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.), and bisphenolfluorene It can contain at least one component selected from the group consisting of epoxy resins having a skeleton (an epoxy resin having a structure represented by formula (7) as a specific example).

  The epoxy compound (D) may contain triglycidyl isocyanurate. The triglycidyl isocyanurate is preferably a β-form having a structure in which three epoxy groups are bonded in the same direction with respect to the S-triazine ring skeleton plane, or 1 for the β-form and the S-triazine ring skeleton plane. A mixture with an α-isomer having a structure in which one epoxy group is bonded to a different direction from the other two epoxy groups is preferable.

  The epoxy compound (D) 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 (specifically, product numbers EPICLON EXA-9726 and EPICLON EXA-9710 manufactured by DIC Corporation), and product number Epototo FX-305 manufactured by Nippon Steel & Sumikin Chemical Co., Ltd. Is mentioned.

  The photosensitive resin composition may contain melamine (E). 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 within a range of 5 to 85% by mass, more preferably within a range of 10 to 75% by mass with respect to the solid content of the photosensitive resin composition, and more preferably 15 to 70. If it is in the range of mass%, it is still more preferable, and if it exists in the range of 30-60 mass%, it is especially preferable.

  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.

  The epoxy compound (d) is preferably in the range of 5 to 100% by mass relative to the epoxy compound (D), more preferably in the range of 10 to 80% by mass, and in the range of 20 to 70% by mass. If it is in, it is more preferable. If the content rate of an epoxy compound (d) exists in the said range, the developability of the photosensitive resin composition can be improved, and also the thermal shock resistance of the hardened | cured material of the photosensitive resin composition can be improved.

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

  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. 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 (E). 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 curing accelerator; colorant; copolymer such as silicone and acrylate; leveling agent; adhesion imparting agent such as silane coupling agent; thixotropic agent; polymerization inhibitor; antihalation agent; One or more components selected from the group consisting of: an antifoaming agent, an antioxidant, a surfactant, and a polymer dispersant.

  The content of the amine compound in the photosensitive resin composition is preferably as small as possible. In this case, the electrical insulation of the layer made of a cured product of the photosensitive resin composition is unlikely to be 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 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 the condition of 500 mJ / cm ² . A 1% Na ₂ CO ₃ aqueous solution at 30 ° C. is sprayed for 90 seconds at an injection pressure of 0.2 MPa on the film after exposure, and then pure water is sprayed 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 containing the hardened | cured material of 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 light and a non-exposure part that blocks ultraviolet light, and the non-exposure part is provided at a position that matches the position of the through hole 10. 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, for example, a chemical lamp, a low-pressure mercury lamp, a medium-pressure mercury lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a xenon lamp, and a metal halide lamp.

  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 allowed to pass through and the ultraviolet ray is irradiated onto the coating 4 made of the dry film without peeling off the support. Then, the coating 4 may be exposed to light, and then the support may be peeled off from the coating 4 before the development treatment.

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

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

  Subsequently, the coating 4 is thermally cured by heating. The heating conditions are, for example, within a heating temperature range of 120 to 200 ° C. and 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.

  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 having a solder resist layer containing a cured product of the photosensitive resin composition according to the present embodiment will be described.

  First, a core material is prepared. The core material includes, for example, at least one insulating layer and at least one conductor wiring. 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.

  By the above, the soldering 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 Into a four-necked flask equipped with a reflux condenser, a thermometer, an air blowing tube, and a stirrer, the components shown in the “First Reaction” column of Table 1 were added. A mixture was prepared by stirring under air bubbling. 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. Subsequently, with the exception of Synthesis Example B-1, the mixture was heated at the reaction temperature and reaction time shown in the column “Reaction Conditions (2)” while 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. The molar ratio between the components is also shown in Table 1.

In addition, the detail of the component shown in the (a1) 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: epoxy equivalent 279 g represented by the formula (7), wherein R ₁ and R ₅ in the formula (7) are all methyl groups, and R _{2 to} R ₄ and R _{6 to} R ₈ are all hydrogen / Eq bisphenolfluorene type epoxy compound.

(2) Preparation of photosensitive resin composition The components shown in Tables 2 to 4 below are kneaded with three rolls, and then dissolved or stirred in the flask to obtain a photosensitive resin composition. It was. In addition, the detail of the component shown by Tables 2-4 is as follows. The crystalline epoxy compound was previously pulverized with a jet mill or a mortar so that the average particle size was 20 μm or less.
Unsaturated compound A: trimethylolpropane triacrylate Unsaturated compound B: ε-caprolactone modified pentaerythrole hexaacrylate, manufactured by Nippon Kayaku Co., Ltd., part number DPCA-60
Unsaturated compound C: Tricyclodecane dimethanol diacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd., product number A-DCP
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: 1,3,5-tris (2,3-epoxypropyl) -1,3,5-triazine-2, 4,6 (1H, 3H, 5H) -trione (high melting type), melting point 150-158 ° C., epoxy equivalent 99 g / eq
Crystalline epoxy resin B: Hydroquinone type crystalline epoxy resin, product name YDC-1312 manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., melting point 138-145 ° C., epoxy equivalent 176 g / eq
Crystalline epoxy resin C: Biphenyl type crystalline epoxy resin, product name YX-4000 manufactured by Mitsubishi Chemical Corporation, melting point 105 ° C., epoxy equivalent 187 g / eq
Crystalline epoxy resin D: Biphenyl ether type crystalline epoxy resin, manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., product number YSLV-80DE, melting point 80-90 ° C., epoxy equivalent 163 g / eq
Crystalline epoxy resin E: Bisphenol type crystalline epoxy resin. Product name YSLV-80XY manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., melting point 75-85 ° C., 192 g / eq
Amorphous epoxy resin solution A: Cresol novolak type epoxy resin, manufactured by DIC, product number EPICLON N-695, softening point 90-100 ° C., epoxy equivalent 214 g / eq dissolved in diethylene glycol monoethyl ether acetate at a solid content of 75% Solution (epoxy equivalent of 75% solid content is 285 g / eq)
Amorphous epoxy resin solution B: Amorphous biphenyl novolac type epoxy resin, Nippon Kayaku Co., Ltd. product name NC-3000, softening point 53-63 ° C., epoxy equivalent 280 g / eq at a solid content of 80%, diethylene glycol Solution dissolved in monoethyl ether acetate (epoxy equivalent in terms of solid content of 80% is 350 g / eq)
Epoxy resin solution A having a specific structure: long-chain carbon chain-containing bisphenol A type epoxy resin (manufactured by DIC, part number EPICLON EXA-4816, liquid resin, epoxy equivalent 410 g / eq, structural unit (d1): bisphenol A skeleton, structure A solution of unit (d2): containing a straight-chain hydrocarbon having 6 carbon atoms dissolved in diethylene glycol monoethyl ether acetate at a solid content of 90% (epoxy equivalent in terms of solid content of 90% is 455.56 g / eq)
Amorphous epoxy resin solution B having a specific structure: long-chain carbon chain-containing bisphenol A type epoxy resin (manufactured by DIC, product number EPICLON EXA-4822, liquid resin, epoxy equivalent 389 g / eq, structural unit (d1): bisphenol A Solution in which skeleton, structural unit (d2): polyethylene glycol, ether oxygen atom number: 4) is dissolved in 85% solid content diethylene glycol monoethyl ether acetate (epoxy equivalent in terms of solid content 85% is 457.65 g / eq)
Melamine (E): manufactured by Nissan Chemical Industries, Ltd., fine powdered melamine, antioxidant: hindered phenol antioxidant, manufactured by BASF, product number IRGANOX 1010
-Blue pigment: phthalocyanine blue-Yellow pigment: 1,1 '-[(6-phenyl-1,3,5-triazine-2,4-diyl) bis (imino)] bis (9,10-anthracenedione)
Barium sulfate: manufactured by Sakai Chemical Industry Co., Ltd., product number Variace B31
-Talc: manufactured by Nippon Talc Co., Ltd., part number SG-2000
Bentonite: manufactured by Leox, part number Benton SD-2
Antifoaming agent: manufactured by Shin-Etsu Silicone Co., Ltd.
・ Surfactant: manufactured by DIC, part number MegaFuck F-477
-Rheology control agent: manufactured by Big Chemie Japan, part number BYK-430
-Solvent A: Diethylene glycol monoethyl ether acetate-Solvent B: Methyl ethyl ketone (3) Preparation of test piece When using the photosensitive resin compositions of Examples and Comparative Examples other than Example 20, test pieces were as follows. Was made.

A glass epoxy copper clad laminate (FR-4 type) provided with a 35 μm thick copper foil 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 wire of the core material with a product number CZ-8100 manufactured by MEC Co., Ltd. A wet paint film was formed by applying the photosensitive resin composition to the entire surface of the core material by screen printing. This wet coating film was heated at 80 ° C. for 40 minutes and preliminarily dried to form a film having a thickness of 25 μm. In a state where a negative mask having a non-exposed portion having a pattern including a circular shape with a diameter of 50 μm was directly applied to this film, the film was irradiated with ultraviolet rays through the negative mask under the condition of 500 mJ / cm ² . 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 heated at 160 ° C. for 60 minutes and further irradiated with ultraviolet rays under the condition of 1000 mJ / cm ² . Thereby, the layer which consists of hardened | cured material of the photosensitive resin composition was formed on the core material. As a result, a test piece was obtained.

  When using the photosensitive resin composition of Example 20, the test piece was produced 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 25 μm on the film.

  A glass epoxy copper clad laminate (FR-4 type) provided with a 35 μm thick copper foil 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 wire of the core material with a product number CZ-8100 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 25 μm-thick film made of a dry film was formed on the core material. The film was exposed, developed and irradiated with ultraviolet light under the same conditions as described above. In addition, the film made from the polyethylene terephthalate which consists of a dry film (film | membrane) was peeled after exposure and before image development. 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) Tackiness For each of the examples and comparative examples except Example 20, when producing a test piece, the degree of adhesiveness of the film when removing the negative mask from the film after exposure of the film, Evaluation was performed as follows.
A: Resistance is not felt when removing the negative mask from the film, and no sticking marks are observed on the film after the negative mask is removed.
B: Resistance was felt when the negative mask was removed from the film, and sticking marks were observed on the film after the negative mask was removed.
C: It was difficult to remove the negative mask from the film, and the film was damaged when the negative mask was forcibly removed.

  In addition, about Comparative Examples 8 and 9 whose tackiness evaluation is C, (4-3) to (4-8) are not evaluated. Moreover, about Example 20, since the membrane | film | coat was formed from the dry film, tackiness evaluation was not performed.

(4-2) Developability For each of Examples and Comparative Examples except Example 20, a wet coating film was formed by applying the photosensitive resin composition to the entire surface of the printed wiring board by a screen printing 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.

  For Comparative Examples 4, 5, 6, and 7 where the evaluation of developability is C, the evaluations of (4-3) to (4-8) are not performed. Moreover, about Example 20, since the membrane | film | coat was formed from the dry film, developability evaluation was not performed. In Example 20, development was possible without problems in the development step after exposure.

(4-3) 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 40 μm or more.
B: The diameter of the bottom of the hole is 25 μm or more and less than 40 μm.
C: The diameter of the bottom of the hole is less than 25 μm, or no clear hole is formed.

(4-4) 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.

(4-5) Insulation between lines While applying a bias voltage of DC 30 V to the conductor wiring (comb electrode) in the test pieces of the examples and comparative examples, the test piece was set at 121 ° C. and 97% R.D. H. The test environment was exposed for 150 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 150 hours passed from the start of the test.
B: The electric resistance value was always 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 150 hours passed from the start of the test.
C: The electric resistance value was less than 10 ⁶ Ω before 100 hours passed from the start of the test.

(4-6) Interlayer insulation The conductive tape was affixed 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 50 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 electric resistance value was less than 10 ⁶ Ω before 50 hours passed from the start of the test.

(4-7) Pressure cooker test (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 cured film 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.

(4-8) Thermal shock resistance (cooling cycle)
After holding the test piece of each Example and Comparative Example for 10 minutes at a temperature condition of −65 ° C., the test piece was immediately transferred to a temperature condition of 150 ° C. and held for 10 minutes. This cool heat treatment is defined as one cycle, and a test piece subjected to 500 cycles of cool heat treatment (hereinafter referred to as test piece (500 cycles)) and a test piece subjected to 1000 cycles of cool heat treatment (hereinafter referred to as test piece (1000 cycles)). Got. About these test pieces, the external appearance of the film was evaluated according to the following evaluation criteria.
A: No crack was observed in the film of the test piece (1000 cycles).
B: Although no crack was found in the film of the test piece (500 cycles), a crack was found in the film of the test piece (1000 cycles).
C: Cracks were observed in the film of the test piece (500 cycles).

Claims (10)

Contains a carboxyl group-containing resin (A), an unsaturated compound (B) containing at least one ethylenically unsaturated bond in one molecule, a photopolymerization initiator (C), and an epoxy compound (D). ,
The carboxyl group-containing resin (A) is represented by the following formula (1), and in the formula (1), R _{1 to} R ₈ are each independently hydrogen, an alkyl group having 1 to 5 carbon atoms, or bisphenolfluorene. Containing an intermediate which is a reaction product of the epoxy compound (a1) having a skeleton and an unsaturated group-containing carboxylic acid (a2), and a carboxyl group-containing resin (A1) which is a reaction product of an acid anhydride,

The epoxy compound (D) comprises a bisphenol-type structural unit (d1) obtained by removing a terminal OH group from bisphenol, a linear hydrocarbon structural unit having 4 to 20 carbon atoms, and an ether oxygen atom number of 3 to 20 An epoxy compound (d) having at least one structural unit (d2) selected from the group consisting of the following polyalkylene ether structural units ;
The photosensitive resin composition in which the said acid anhydride contains an acid dianhydride.   The photosensitive resin composition according to claim 1, wherein the epoxy compound (D) further contains a crystalline epoxy resin.   The photosensitive resin composition according to claim 1 or 2, wherein the acid dianhydride contains 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride.   The photosensitive resin composition according to any one of claims 1 to 3, wherein the carboxyl group-containing resin (A1) has a weight average molecular weight in the range of 1000 to 5000.   The photosensitive resin composition of any one of Claims 1 thru | or 4 whose solid content acid value of the said carboxyl group-containing resin (A1) exists in the range of 60-140 mgKOH / g.   The photosensitive resin composition according to claim 1, wherein the acid anhydride contains 1,2,3,6-tetrahydrophthalic anhydride.   The dry film containing the photosensitive resin composition as described in any one of Claims 1 thru | or 6.   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 6.   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 6. An epoxy compound (a1) having a bisphenolfluorene skeleton represented by the following formula (1), wherein R _{1 to} R ₈ are each independently hydrogen, an alkyl group having 1 to 5 carbon atoms, or halogen; By reacting the unsaturated group-containing carboxylic acid (a2) and reacting the resulting intermediate with an acid anhydride, a carboxyl group-containing resin (A1) is synthesized,
A carboxyl group-containing resin (A) containing the carboxyl group-containing resin (A1), an unsaturated compound (B) having at least one ethylenically unsaturated bond in one molecule, a photopolymerization initiator (C), Mixing with the epoxy compound (D),

The epoxy compound (D) comprises a bisphenol-type structural unit (d1) obtained by removing a terminal OH group from bisphenol, a linear hydrocarbon structural unit having 4 to 20 carbon atoms, and an ether oxygen atom number of 3 to 20 An epoxy compound (d) having at least one structural unit (d2) selected from the group consisting of the following polyalkylene ether structural units ;
The manufacturing method of the photosensitive resin composition in which the said acid anhydride contains an acid dianhydride.

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