KR20200035008A - Manufacturing method of multilayer printed wiring board and multilayer printed wiring board - Google Patents

Abstract

A method of manufacturing a multilayer printed wiring board capable of achieving high adhesion between an interlayer insulating layer and a conductor layer, even if the interlayer insulating layer is not harmonized or the degree of harmonization is small. In the manufacturing method of the multilayer printed wiring board 20, a film 4 is prepared from the photosensitive resin composition on the printed wiring board 1, and a photocured film is produced to produce a cured film 11, and the cured film 11 is an alkaline solution. After treatment with, a conductor layer 8 is produced. The photosensitive resin composition contains a carboxyl group-containing resin (A), an unsaturated compound (B) having at least one ethylenically unsaturated bond in one molecule, a photopolymerization initiator (C), and an epoxy compound (D). The arithmetic average roughness Ra of the surface contacting the conductor layer 8 in the cured film 11 immediately before the production of the conductor layer 8 is less than 150 nm.

Description

Manufacturing method of multilayer printed wiring board and multilayer printed wiring board

The present invention relates to a method for manufacturing a multilayer printed wiring board and a multilayer printed wiring board.

Conventionally, an electrically insulating resin composition is used to produce an electrically insulating layer such as a solder resist layer, a plating resist layer, an etching resist layer, and an interlayer insulating layer of a printed wiring board. Such a resin composition is a photosensitive resin composition, for example (refer patent document 1).

In the case of producing an interlayer insulating layer, in particular, from a photosensitive resin composition, in order to ensure adhesion between the interlayer insulating layer and a conductor layer produced by a plating method or the like, it is performed to harmonize the interlayer insulating layer (Patent Document) 1). When the interlayer insulating layer is roughened, the high-frequency characteristics of the printed wiring board deteriorate, and therefore the transmission characteristics of the high-speed signal of the printed wiring board deteriorate.

Japanese Patent Publication No. Hei 11-242330

It is an object of the present invention to provide a method for manufacturing a multilayer printed wiring board and a multilayer printed wiring board capable of achieving high adhesion between the interlayer insulating layer and the conductor layer even if the interlayer insulating layer is not harmonized or the degree of harmonization is small.

In the manufacturing method of the multilayer printed wiring board which concerns on one aspect of this invention, a film is produced with a photosensitive resin composition on a printed wiring board. The photosensitive resin composition contains a carboxyl group-containing resin (A), an unsaturated compound (B) having at least one ethylenically unsaturated bond in one molecule, a photopolymerization initiator (C), and an epoxy compound (D). A cured film is produced by photocuring the coating. After treating the cured film with an alkaline solution, a conductor layer in contact with the cured film is prepared. The arithmetic mean roughness Ra defined by JIS B0601-2001 of the surface contacting the conductor layer in the cured film immediately before the production of the conductor layer is less than 150 nm.

The multilayer printed wiring board according to one aspect of the present invention is manufactured by the above manufacturing method.

1 is a cross-sectional view showing a process for manufacturing a multilayer printed wiring board.

The following embodiments relate to a method of manufacturing a multilayer printed wiring board and a multilayer printed wiring board produced by the manufacturing method, and in particular, to a manufacturing method of a multilayer printed wiring board for manufacturing a cured film of a photosensitive resin composition on a printed wiring board and a method of manufacturing the same It relates to a manufactured multilayer printed wiring board.

Hereinafter, one embodiment of the present invention will be described. In addition, in the following description, "(meth) acrylic" means at least one of "acrylic" and "methacryl". For example, (meth) acrylate means at least one of acrylate and methacrylate.

In the manufacturing method of the multilayer printed wiring board 20 according to the present embodiment (see FIG. 1A to FIG. 1E), a film 4 is produced from the photosensitive resin composition on the printed wiring board 1. The photosensitive resin composition contains a carboxyl group-containing resin (A), an unsaturated compound (B) having at least one ethylenically unsaturated bond in one molecule, a photopolymerization initiator (C), and an epoxy compound (D). The cured film 11 is produced by photocuring this film 4. After treating this cured film 11 with an alkaline solution, the conductor layer 8 in contact with the cured film 11 is produced. The arithmetic average roughness Ra defined by JIS B0601-2001 on the surface of the cured film 11 in contact with the conductor layer 8 immediately before the production of the conductor layer 8 is less than 150 nm.

In this embodiment, since the arithmetic average roughness Ra of the cured film 11 is less than 150 nm, even if the conductor layer 8 in contact with the cured film 11 is produced, deterioration of the high-frequency characteristics of the multilayer printed wiring board 20 It is suppressed and the transmission characteristics of the high-speed signal of the multilayer printed wiring board 20 can be maintained satisfactorily.

Further, by treating the cured film 11 with an alkaline solution, the adhesion between the interlayer insulating layer 7 and the conductor layer 8 made of the cured film 11 can be improved. Although the reason is not fully elucidated, when the cured film 11 is treated with an alkali solution, the surface of the cured film 11 is not largely rough, but it is thought that fine unevenness occurs, and this is the interlayer insulating layer 7 It is presumed to be a factor in improving the adhesion between the superconductor layer 8.

Therefore, even if the interlayer insulating layer 7 is not harmonized or the degree of harmonization is small, high adhesion between the interlayer insulating layer 7 and the conductor layer 8 can be achieved.

The photosensitive resin composition used in the present embodiment will be described in detail.

As described above, the photosensitive resin composition contains a carboxyl group-containing resin (A), an unsaturated compound (B) having at least one ethylenically unsaturated bond in one molecule, a photopolymerization initiator (C), and an epoxy compound (D).

It is preferable that the carboxyl group-containing resin (A) contains a carboxyl group-containing resin having an ethylenically unsaturated group. In this case, the carboxyl group-containing resin (A) may have photoreactivity. Therefore, the carboxyl group-containing resin (A) can impart photosensitivity, specifically ultraviolet curability, to the photosensitive resin composition.

It is preferable that the carboxyl group-containing resin (A) contains a carboxyl group-containing resin having an aromatic ring. In this case, high heat resistance and insulation reliability can be imparted to the cured product of the photosensitive resin composition.

It is more preferable that the carboxyl group-containing resin (A) contains a carboxyl group-containing resin having a polycyclic aromatic ring from among a biphenyl skeleton, a naphthalene skeleton, a fluorene skeleton, and an anthracene skeleton. In this case, higher heat resistance and insulation reliability can be imparted to the cured product of the photosensitive resin composition.

It is preferable that the carboxyl group-containing resin (A) contains a carboxyl group-containing resin (A1) having a bisphenol fluorene skeleton. In this case, higher heat resistance and insulation reliability can be imparted to the cured product of the photosensitive resin composition containing the carboxyl group-containing resin (A).

The carboxyl group-containing resin (A1) is, for example, an intermediate that is a reactant of an epoxy compound (a1) and an unsaturated group-containing carboxylic acid (a2), and a reactant of an acid dianhydride (a3) and an acid anhydride (a4). The epoxy compound (a1) has a bisphenol fluorene skeleton. The bisphenol fluorene skeleton 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 halogen.

Each of R ₁ to R ₈ in Formula (1) may be hydrogen, but may be an alkyl group having 1 to 5 carbon atoms or halogen. Because, even if the hydrogen in the aromatic ring is substituted with a low molecular weight alkyl group or halogen, there is no adverse effect on the properties of the carboxyl group-containing resin (A1), but rather the heat resistance or flame retardancy of the cured product of the photosensitive resin composition containing the carboxyl group-containing resin (A1). It is because this may be improved.

When the carboxyl group-containing resin (A1) has a bisphenol fluorene skeleton derived from the epoxy compound (a1), high heat resistance and insulation reliability can be imparted to the cured product of the photosensitive resin composition containing the carboxyl group-containing resin (A1).

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

The carboxyl group-containing resin (A1) may contain unreacted components in the intermediate. In addition, when the acid anhydride (a3) contains an acid anhydride and an acid dianhydride, the carboxyl group-containing resin (A1) includes, in addition to the reactants of the components in the intermediate and the components in the acid and anhydride, the components in the intermediate and the acid and anhydride One or both of the reactants of the components in the medium and the reactants of the components in the intermediate and the acid dianhydride may be contained. That is, the carboxyl group-containing resin (A1) may be a mixture containing a plurality of different compounds having the same structure.

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

The weight average molecular weight of the carboxyl group-containing resin (A1) is preferably in the range of 700 or more and 10000 or less. When the weight average molecular weight is 700 or more, the insulating properties of the cured product of the photosensitive resin composition can be improved, and dielectric loss tangent can be reduced. Moreover, developability by the alkaline aqueous solution of the photosensitive resin composition improves especially when the weight average molecular weight is 10000 or less. The weight average molecular weight is more preferably 900 or more, particularly preferably 1000 or more. Further, the weight average molecular weight is more preferably in the range of 8000 or less, and particularly preferably in the range of 5000 or less.

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

As for the number average molecular weight and molecular weight distribution of the carboxyl group-containing resin (A1), the carboxyl group-containing resin (A1) is an unreacted component in an intermediate, a component in an intermediate and a component in an acid anhydride, and a reactant in an acid in an acid dianhydride It can be achieved by being a mixture containing appropriately various components, such as a reactant of a component in an acid and an acid anhydride, and a reaction between a component in an intermediate and a component in an acid anhydride. More specifically, it can be achieved, for example, by controlling parameters such as the average molecular weight of the epoxy compound (a1), the amount of acid anhydride relative to the epoxy compound (a1), and the amount of acid dianhydride relative to the epoxy compound (a1).

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

The solid acid value of the carboxyl group-containing resin (A1) is preferably within a range of 60 mgKOH / g or more and 140 mgKOH / g or less. In this case, developability of the photosensitive resin composition is particularly improved. It is more preferable if the acid value is in the range of 80 mgKOH / g or more and 135 mgKOH / g or less, and more preferably if the acid value is in the range of 90 mgKOH / g or more and 130 mgKOH / g or less.

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

GPC device: SHODEX SYSTEM 11 manufactured by Showa Denko Corporation

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

Mobile phase: THF

Flow rate: 1 ml / min

Column temperature: 45 ℃

Detector: RI

Converted: Polystyrene

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

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

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

The unsaturated group-containing carboxylic acid (a2-1) can contain, for example, a compound having only one ethylenically unsaturated group. More specifically, the unsaturated group-containing carboxylic acid (a2-1) is, for example, acrylic acid, methacrylic acid, ω-carboxy-polycaprolactone (n ≒ 2) monoacrylate, crotonic acid, cinnamic acid, 2-acrylic. Royloxyethyl succinic acid, 2-methacryloyloxyethyl succinic acid, 2-acryloyloxyethylphthalic acid, 2-methacryloyloxyethylphthalic acid, 2-acryloyloxypropylphthalic acid, 2-methacryloyl Oxypropylphthalic acid, 2-acryloyloxyethylmaleic acid, 2-methacryloyloxyethylmaleic acid, β-carboxyethylacrylate, 2-acryloyloxyethyltetrahydrophthalic acid, 2-methacryloyloxy It may contain one or more compounds selected from the group consisting of ethyl tetrahydrophthalic acid, 2-acryloyloxyethyl hexahydrophthalic acid, and 2-methacryloyloxyethyl hexahydrophthalic acid. Preferably, the unsaturated group-containing carboxylic acid (a2-1) contains acrylic acid.

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

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

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

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

When the epoxy compound (a1) and the carboxylic acid (a2) are reacted, the amount of the carboxylic acid (a2) relative to 1 mol of the epoxy group in the epoxy compound (a1) is preferably within a range of 0.5 mol to 1.2 mol. In this case, excellent photosensitivity and stability of the photosensitive resin composition are obtained. From the same viewpoint, it is preferable that the amount of the unsaturated group-containing carboxylic acid (a2-1) relative to 1 mole of the epoxy group in the epoxy compound (a1) is in the range of 0.5 mol to 1.2 mol. Alternatively, when the carboxylic acid (a2) contains carboxylic acids other than the unsaturated group-containing carboxylic acid (a2-1), the unsaturated group-containing carboxylic acid (a2-1) relative to 1 mole of the epoxy group of the epoxy compound (a1) The amount of may be in the range of 0.5 mol or more and 0.95 mol or less. In addition, when the carboxylic acid (a2) contains a polybasic acid (a2-2), the amount of the polybasic acid (a2-2) to 1 mole of the epoxy group of the epoxy compound (a1) is preferably within the range of 0.025 moles or more and 0.25 moles or less. Do. In this case, excellent photosensitivity and stability of the photosensitive resin composition are obtained.

It is also preferable to react the epoxy compound (a1) and the carboxylic acid (a2) under air bubbling. In this case, it is possible to suppress the addition polymerization reaction of the unsaturated group, thereby suppressing an increase in the molecular weight of the intermediate and gelation of the solution of the intermediate. In addition, it is possible to suppress excessive coloring of the final product, a carboxyl group-containing resin (A1).

The intermediate obtained in this way comprises a hydroxyl group produced by the reaction of the epoxy group in the epoxy compound (a1) with the carboxyl group in the carboxylic acid (a2).

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

The acid anhydride may contain anhydride of dicarboxylic acid. Acid daily anhydrides include, for example, 1,2,3,6-tetrahydrophthalic anhydride, phthalic anhydride, succinic anhydride, methylsuccinic anhydride, maleic anhydride, citraconic anhydride, glutaric anhydride, itaconic anhydride, methyltetra At least one compound selected from the group consisting of hydrophthalic anhydride, methylnadine anhydride, hexahydrophthalic anhydride, cyclohexane-1,2,4-tricarboxylic acid-1,2-anhydride, and methylhexahydrophthalic anhydride It can contain. It is particularly preferable that the acid-anhydride contains 1,2,3,6-tetrahydrophthalic anhydride. In this case, the insulating properties of the cured product of the photosensitive resin composition can be improved while ensuring good developability of the photosensitive resin composition. With respect to the whole acid anhydride, 1,2,3,6-tetrahydrophthalic anhydride is preferably in the range of 20 mol% or more and 100 mol% or less, more preferably in the range of 40 mol% or more and 100 mol% or less, It is not limited to this.

It is preferable that the acid anhydride (a3) contains an acid anhydride. The acid dianhydride is a compound having two acid anhydride groups. The acid dianhydride may contain anhydride of tetracarboxylic acid. Acid dianhydrides are, 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, glycerinbisanhydrotrimellitate monoacetate, ethylene glycol Bishydrohydrotrimellitate, 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-butanetetracarboxylic dianhydride and 3,3 ', 4,4'- It may contain at least one compound selected from the group consisting of biphenyltetracarboxylic dianhydride. It is preferable that an acid dianhydride contains the acid dianhydride which has an aromatic ring. It is particularly preferable that the acid dianhydride contains 3,3 ', 4,4'-biphenyltetracarboxylic acid dianhydride. In this case, the insulating properties of the cured product of the photosensitive resin composition can be improved while ensuring good developability of the photosensitive resin composition. In addition, transparency of the photosensitive resin composition is improved, and resolution is thereby improved. With respect to the whole acid dianhydride, 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride is preferably in the range of 20 mol% or more and 100 mol% or less, and is in the range of 40 mol% or more and 100 mol% or less It is more preferable, but is not limited to this.

In reacting the intermediate with the acid anhydride (a3), a known method can be employed. For example, an acid anhydride (a3) is added to the solvent solution of the intermediate, and a thermal polymerization inhibitor and a catalyst are further added as necessary to stir and mix to obtain a reactive solution. The carboxyl group-containing resin (A1) is obtained by reacting the reactive solution at a temperature of preferably 60 ° C or higher and 150 ° C or lower, particularly preferably 80 ° C or higher and 120 ° C or lower. Suitable solvents, catalysts, and polymerization inhibitors can be used, and solvents, catalysts, and polymerization inhibitors used in the synthesis of intermediates 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 anhydride (a3) in the presence of triphenylphosphine. In this case, the reaction of the secondary hydroxyl group and the acid anhydride (a3) in the intermediate is particularly accelerated, and it is possible to achieve a reaction rate (conversion rate) of 90% or more, 95% or more, 97% or more, or approximately 100%. . In addition, generation of ion migration in the layer containing the cured product of the photosensitive resin composition is suppressed, and the insulating property of the layer containing the cured product is further improved.

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

The carboxyl group-containing resin (A) may include an carboxyl group-containing resin having an aromatic ring and not having photopolymerization. The carboxyl group-containing resin having an aromatic ring and no photopolymerization contains, for example, a polymer of an ethylenically unsaturated monomer containing an ethylenically unsaturated compound having a carboxyl group. The ethylenically unsaturated compound having a carboxyl group is acrylic acid, methacrylic acid, ω-carboxy-polycaprolactone (n ≒ 2) monoacrylate, 2- (meth) acryloyloxyethyl phthalate, 2- (meth) acryloyl And compounds such as oxyethyl-2-hydroxyethyl phthalate. The ethylenically unsaturated compound having a carboxyl group may also contain a reactant with pentaerythritol triacrylate, pentaerythritol trimethacrylate and the like, and a dibasic acid anhydride. The ethylenically unsaturated monomer may further contain an ethylenically unsaturated compound having no carboxyl group, such as a (meth) acrylic acid ester of a linear or branched aliphatic or alicyclic (but may have some unsaturated bond in the ring).

The carboxyl group-containing resin (A) may contain resins other than the carboxyl group-containing resin (A1), that is, a carboxyl group-containing resin having no bisphenol fluorene skeleton (hereinafter also referred to as carboxyl group-containing resin (A2)).

The carboxyl group-containing resin (A2) may contain, for example, a compound having a carboxyl group and having no photopolymerization (hereinafter referred to as (A2-1) component). (A2-1) A component contains the polymer of the ethylenically unsaturated monomer containing the ethylenically unsaturated compound which has a carboxyl group, for example. The ethylenically unsaturated compound having a carboxyl group may contain a compound such as acrylic acid, methacrylic acid, and ω-carboxy-polycaprolactone (n ≒ 2) monoacrylate. The ethylenically unsaturated compound having a carboxyl group may also contain a reactant with pentaerythritol triacrylate, pentaerythritol trimethacrylate and the like, and a dibasic acid anhydride. The ethylenically unsaturated monomer is 2- (meth) acryloyloxyethyl phthalate, 2- (meth) acryloyloxyethyl-2-hydroxyethyl phthalate, linear or branched aliphatic or cycloaliphatic (but partially in the ring) You may further contain the ethylenically unsaturated compound which does not have a carboxyl group, such as (meth) acrylic acid ester of (which may have an unsaturated bond).

The carboxyl group-containing resin (A2) may contain a compound having a carboxyl group and an ethylenically unsaturated group (hereinafter referred to as (A2-2) component). Further, the carboxyl group-containing resin (A2) may contain only the (A2-2) component. The component (A2-2) is selected from, for example, an intermediate that is a reactant of an epoxy compound (x1) having two or more epoxy groups in one molecule and an ethylenically unsaturated compound (x2), and polyhydric carboxylic acid and anhydrides thereof. Contains a resin (referred to as first resin (x)) that is a reactant with at least one compound (x3). The first resin (x) is obtained, for example, by adding a compound (x3) to an intermediate obtained by reacting an epoxy group in the epoxy compound (x1) with a carboxyl group in the ethylenically unsaturated compound (x2). The epoxy compound (x1) may contain a suitable epoxy compound such as cresol novolac-type epoxy compound, phenol novolac-type epoxy compound, and biphenyl novolac-type epoxy compound. In particular, the epoxy compound (x1) preferably contains at least one compound selected from the group of biphenyl novolac-type epoxy compounds and cresol novolac-type epoxy compounds. The epoxy compound (x1) may contain only a biphenyl novolac-type epoxy compound, or may contain only a cresol novolac-type epoxy compound. In this case, since the aromatic ring is contained in the main chain of the epoxy compound (x1), the degree of corrosion of the cured product of the photosensitive resin composition, for example, by an oxidizing agent containing potassium permanganate or the like, can be reduced. The epoxy compound (x1) may contain a polymer of the ethylenically unsaturated compound (z). It contains an ethylenically unsaturated compound (z), for example, a compound (z1) having an epoxy group such as glycidyl (meth) acrylate, or does not have an epoxy group such as 2- (meth) acryloyloxyethylphthalate. Compound (z2) is further contained. It is preferable that ethylenic unsaturated compound (x2) contains at least one of acrylic acid and methacrylic acid. The compound (x3) contains, for example, at least one compound selected from the group consisting of polyvalent carboxylic acids such as phthalic acid, tetrahydrophthalic acid and methyltetrahydrophthalic acid, and anhydrides of these polyhydric carboxylic acids. In particular, it is preferable that the compound (x3) contains at least one polyvalent carboxylic acid selected from the group of phthalic acid, tetrahydrophthalic acid, and methyltetrahydrophthalic acid.

(A2-2) A component may contain the resin (referred to as 2nd resin (y)) which is the reaction material of the polymer of the ethylenically unsaturated monomer containing the ethylenically unsaturated compound which has a carboxyl group, and the ethylenically unsaturated compound which has an epoxy group. . The ethylenically unsaturated monomer may further contain an ethylenically unsaturated compound having no carboxyl group. The second resin (y) is obtained by reacting a part of the carboxyl groups in the polymer with an ethylenically unsaturated compound having an epoxy group. 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 acrylic acid, methacrylic acid, ω-carboxy-polycaprolactone (n (2) monoacrylate, pentaerythritol triacrylate, and pentaerythritol trimethacrylate. Compound. The ethylenically unsaturated compound having no carboxyl group is, for example, 2- (meth) acryloyloxyethylphthalate, 2- (meth) acryloyloxyethyl-2-hydroxyethylphthalate, linear or branched aliphatic or alicyclic It contains compounds, such as (meth) acrylic acid ester of a group (but may have some unsaturated bond in a ring). It is preferable that the ethylenically unsaturated compound having an epoxy group contains glycidyl (meth) acrylate.

The carboxyl group-containing resin (A) contains only a carboxyl group-containing resin (A1), only a carboxyl group-containing resin (A2), or a carboxyl group-containing resin (A1) and a carboxyl group-containing resin (A2). In order to obtain high transparency of the photosensitive resin composition and to reduce the dielectric loss tangent of the cured product of the photosensitive resin composition, the carboxyl group-containing resin (A) preferably contains 30% by mass or more of the carboxyl group-containing resin (A1), and 60 It is more preferable to contain mass% or more, and more preferably to contain 100 mass%.

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

It is preferable that the solid acid value of the carboxyl group-containing resin (A) is in the range of 40 mgKOH / g or more and 160 mgKOH / g or less. In this case, the stability of the photosensitive resin composition is particularly improved. It is more preferable if the acid value is in the range of 60 mgKOH / g or more and 140 mgKOH / g or less, more preferably if the acid value is in the range of 80 mgKOH / g or more and 135 mgKOH / g or less, and if the acid value is in the range of 90 mgKOH / g or more and 130 mgKOH / g or less Especially preferred.

The unsaturated compound (B) can impart photocurability to the photosensitive resin composition. The unsaturated compound (B) includes, for example, monofunctional (meth) acrylates such as 2-hydroxyethyl (meth) acrylate; And diethylene glycol di (meth) acrylate, trimethylolpropane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate , Polyfunctional such as dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, ε-caprolactone-modified pentaerythritol hexaacrylate, tricyclodecanedimethanol di (meth) acrylate It may contain at least one compound selected from the group consisting of (meth) acrylates.

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 in the case of exposing and developing the film 4 formed of the photosensitive resin composition 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, and ethoxyisocyanurate tri (meth) ) Acrylates and ε-caprolactone-modified tris- (2-acryloyloxyethyl) isocyanurate and ethoxylated glycerin tri (meth) acrylate. .

It is also preferable that the unsaturated compound (B) contains a phosphorus-containing compound (phosphorus-containing unsaturated compound). In this case, the flame retardance of the cured product of the photosensitive resin composition is improved. The phosphorus-containing unsaturated compound is, for example, 2-methacryloyloxyethyl acid phosphate (specifically, light ester P-1M manufactured by Kyoeisha Chemical Co., Ltd., light ester P-1M, and light ester P-2M), 2- Acryloyloxyethyl acid phosphate (as a specific example, light acrylate P-1A manufactured by Kyoeisha Chemical Co., Ltd.), diphenyl-2-methacryloyloxyethylphosphate (as a specific example, Daihachi Kogyo Co., Ltd.) Part number MR-260 manufactured by Shiki Corporation and HFA series manufactured by Showa Kobunshi Co., Ltd. [Specifically, dipentaerythritol hexaacrylate and HCA (9,10-dihydro-9-oxa-10-force) Addition reactants of phophenanthrene-10-oxide, part number HFA-6003, and HFA-6007, caprolactone modified dipentaerythritol hexaacrylate and HCA (9,10-dihydro-9-oxa-10-phospho HFA, an addition reactant of phenanthrene-10-oxide) -3003, and HFA-6127, and the like).

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

The photopolymerization initiator (C) contains, for example, an acylphosphine oxide-based photopolymerization initiator. That is, the photosensitive resin composition contains, for example, an acylphosphine oxide-based photopolymerization initiator. In this case, when exposing the photosensitive resin composition to ultraviolet rays, high photosensitivity can be imparted to the photosensitive resin composition. In addition, generation of ion migration in the layer containing the cured product of the photosensitive resin composition is suppressed, and the insulation reliability of the layer containing the cured product of the photosensitive resin composition is further improved.

Further, the acylphosphine oxide-based photopolymerization initiator is difficult to inhibit the electrical insulation of the cured product. Therefore, by exposing and curing the photosensitive resin composition, a cured product having excellent electrical insulation properties is obtained, and the cured product is suitable as an interlayer insulating layer 7.

Acylphosphine oxide-based photopolymerization initiators include monoacylphosphine such as 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide and 2,4,6-trimethylbenzoyl-ethyl-phenyl-phosphinate. Oxide-based photopolymerization initiator, and bis- (2,6-dichlorobenzoyl) phenylphosphine oxide, bis- (2,6-dichlorobenzoyl) -2,5-dimethylphenylphosphine oxide, bis- (2,6-dichloro Benzoyl) -4-propylphenylphosphine oxide, bis- (2,6-dichlorobenzoyl) -1-naphthylphosphine oxide, bis- (2,6-dimethoxybenzoyl) phenylphosphine oxide, bis- (2 , 6-Dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, bis- (2,6-dimethoxybenzoyl) -2,5-dimethylphenylphosphine oxide, bis- (2,4,6 -A group consisting of bisacylphosphine oxide-based photopolymerization initiators such as trimethylbenzoyl) phenylphosphine oxide and (2,5,6-trimethylbenzoyl) -2,4,4-trimethylpentylphosphine oxide. Is selected site may contain a component of at least one. In particular, it is preferable that the acylphosphine oxide-based photopolymerization initiator contains 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, and the acylphosphine oxide-based photopolymerization initiator is 2,4,6-trimethylbenzoyl-diphenyl It is also preferable to contain only phosphine oxide.

It is preferable that the photopolymerization initiator (C) contains a hydroxyketone-based photopolymerization initiator in addition to the acylphosphine oxide-based photopolymerization initiator. That is, it is preferable that the photosensitive resin composition contains a hydroxyketone-based photopolymerization initiator. In this case, it is possible to impart higher photosensitivity to the photosensitive resin composition as compared to the case where the hydroxyketone-based photopolymerization initiator is not contained. Thereby, when the coating film formed from the photosensitive resin composition is cured by irradiating with ultraviolet rays, it is possible to sufficiently cure the coating film from its surface to the core portion. Examples of the hydroxyketone-based photopolymerization initiator include 1-hydroxy-cyclohexyl-phenyl-ketone, phenylglyoxylic 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 -Propan-1-one and 2-hydroxy-2-methyl-1-phenyl-propan-1-one.

The mass ratio of the acylphosphine oxide-based photopolymerization initiator and the hydroxyketone-based photopolymerization initiator is preferably in the range of 1: 0.01 to 1:10. In this case, the curability in the vicinity of the surface of the coating film formed of the photosensitive resin composition and the curability in the core portion can be improved with good balance. Here, when the photosensitive resin composition contains the organic filler (E), the organic filler (E) may sometimes generate light scattering in the photosensitive resin composition during exposure. In this case, there is a possibility that a problem that good developability cannot be obtained in the photosensitive resin composition may occur. From this viewpoint, in order to improve the resolution and obtain good developability in the photosensitive resin composition, the mass ratio of the acylphosphine oxide-based photopolymerization initiator and the hydroxyketone-based photopolymerization initiator is in the range of 1: 0.01 to 1: 1. Especially preferred.

It is also preferable that the photoinitiator (C) contains a photopolymerization initiator having a benzophenone skeleton. That is, the photosensitive resin composition contains an acylphosphine oxide-based photopolymerization initiator and a photopolymerization initiator having a benzophenone skeleton, or an acylphosphine oxide-based photopolymerization initiator, a hydroxyketone photopolymerization initiator, and a photopolymerization initiator having a benzophenone skeleton. It is also preferred. In this case, when developing after partially exposing the coating film formed from the photosensitive resin composition, curing of the unexposed portion is suppressed, so that the resolution is particularly high. Therefore, a cured product of a very fine pattern photosensitive resin composition can be formed. In particular, the interlayer insulating layer 7 of the multi-layer printed wiring board 20 is produced from the photosensitive resin composition, and also a small hole 6 for a via 10 in the interlayer insulating layer 7 When is formed by a photolithography method (see C in Fig. 1 and D in Fig. 1), the small hole 6 can be formed precisely and easily. As a photopolymerization initiator which has a benzophenone skeleton, bis (diethylamino) benzophenone is mentioned, for example.

The amount of the photopolymerization initiator having a benzophenone skeleton to the acylphosphine oxide-based photopolymerization initiator is preferably within a range of 0.5% by mass or more and 20% by mass or less. When the amount of the photopolymerization initiator having a benzophenone skeleton to the acylphosphine oxide-based photopolymerization initiator is 0.5% by mass or more, the resolution is particularly high. In addition, when the amount of the photopolymerization initiator having a benzophenone skeleton relative to an acylphosphine oxide-based photopolymerization initiator is 20% by mass or less, it is difficult to inhibit the electrical insulating properties of the cured product of the photosensitive resin composition from the photopolymerization initiator having a benzophenone skeleton. From the same viewpoint, the amount of bis (diethylamino) benzophenone relative to the acylphosphine oxide-based photopolymerization initiator is preferably within a range of 0.5% by mass or more and 20% by mass or less. Here, when the photosensitive resin composition contains the organic filler (E), the organic filler (E) may sometimes generate light scattering in the photosensitive resin composition during exposure. In this case, there is a possibility that a problem that good developability cannot be obtained in the photosensitive resin composition may occur. From such a viewpoint, in order to obtain good resolution in the photosensitive resin composition, it is particularly preferable that the amount of the photopolymerization initiator having a benzophenone skeleton is within a range of 1% by mass or more and 18% by mass or less with respect to the acylphosphine oxide-based photopolymerization initiator. . From the same viewpoint, the amount of bis (diethylamino) benzophenone is particularly preferably in the range of 1% by mass or more and 18% by mass or less with respect to the acylphosphine oxide-based photopolymerization initiator.

The photopolymerization initiator (C) is not limited to the above preferred examples, and may contain at least one component appropriately selected from known compounds.

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 benzyl dimethyl ketal; Anthraquinones, such as 2-methyl anthraquinone; Thioxanthones such as 2,4-dimethyl thioxanthone, 2,4-diethyl thioxanthone, 2-isopropyl thioxanthone, 4-isopropyl thioxanthone, and 2,4-diisopropyl thioxanthone ; Benzophenones such as benzophenone and 4-benzoyl-4'-methyldiphenyl sulfide; Xanthones such as 2,4-diisopropyl xanthone; And α-hydroxyketones such as 2-hydroxy-2-methyl-1-phenyl-propan-1-one; It may contain at least one component selected from the group consisting of compounds containing nitrogen atoms such as 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-1-propanone. . The photosensitive resin composition, together with the photopolymerization initiator (C), promotes known photopolymerization such as tertiary amines such as p-dimethylbenzoic acid ethyl ester, p-dimethylaminobenzoic acid isoamyl ester, 2-dimethylaminoethylbenzoate, and the like. You may contain a sensitizer or the like. 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 may contain a photopolymerization initiator (C), a coumarin derivative such as 7-diethylamino-4-methylcoumarin, which is a sensitizer for laser exposure, a carbocyanine dye system, a xanthene dye system, or the like.

The epoxy compound (D) can impart thermosetting properties to the photosensitive resin composition. It is preferable that the epoxy compound (D) has at least two epoxy groups in one molecule. The epoxy compound (D) may be a solvent poorly soluble epoxy compound, or a general-purpose solvent may be a soluble epoxy compound. The epoxy compound (D) is a phenol novolac-type epoxy resin (part number EPICLON N-775 manufactured by DIC Corporation as a specific example), a cresol novolac-type epoxy resin (part number EPICLON N-695 manufactured by DIC Corporation as a specific example) ), Bisphenol A novolac type epoxy resin (part number EPICLON N-865 manufactured by DIC Corporation as a specific example), bisphenol A type epoxy resin (part number jER1001 manufactured by Mitsubishi Chemical Co., Ltd. as a specific example), bisphenol F type Epoxy resins (part number jER4004P manufactured by Mitsubishi Chemical Corporation, as a specific example), bisphenol S-type epoxy resins (part number EPICLON EXA-1514 manufactured by DIC Corporation as a specific example), bisphenol AD type epoxy resin, biphenyl type epoxy Resin (part number YX4000, manufactured by Mitsubishi Chemical Corporation, as a specific example), biphenyl novolac type epoxy resin (part number NC, manufactured by Nippon Kayaku Co., Ltd. as a specific example) -3000), hydrogenated bisphenol A-type epoxy resin (Part No. ST-4000D manufactured by Shinnitetsu Sumikin Chemical Co., Ltd.), and naphthalene-type epoxy resin (Part No. EPICLON HP-4032 manufactured by DIC Corporation as a specific example) , EPICLON HP-4700, EPICLON HP-4770), Hydroquinone type epoxy resin (Part No. YDC-1312 manufactured by Shinnitetsu Sumikin Chemical Co., Ltd. as a specific example), tertiary butyl catechol type epoxy resin (DIC as a specific example) Part number EPICLON HP-820 manufactured by Kabuki Kaisha Co., Ltd., dicyclopentadiene type epoxy resin (part number EPICLON HP-7200 manufactured by DIC Co., Ltd.), adamantane type epoxy resin (Idemitsu Kosan Co., Ltd. as specific example) ADAMANTATE XE-201, manufactured by Gaisha Co., Ltd., bisphenol-type epoxy resin (Part No. YSLV-80XY manufactured by Shinnitetsu Sumikin Chemical Co., Ltd. as a specific example), biphenyl ether-type epoxy resin (Cinite as a specific example. Tsu Sumikin Kagaku Co., Ltd. product number YSLV-80DE), tetrakisphenol ethane type epoxy resin (as a specific example, Nippon Kayaku Co., Ltd. product number GTR-1800) epoxy resin having a bisphenol fluorene skeleton (specific As an example, an epoxy resin having a structure (S7)), a rubber-type core shell polymer-modified bisphenol A-type epoxy resin (specifically, Model No. MX-156 manufactured by Kaneka Co., Ltd.), a rubber-type core shell polymer-modified bisphenol F-type epoxy Resin (Part No. MX-136 manufactured by Kaneka Co., Ltd. as a specific example), and special bifunctional epoxy resin (Part No. YL7175-500 manufactured by Mitsubishi Chemical Co., Ltd., YL7175-500, and YL7175-1000; Part number EPICLON TSR-960, EPICLON TER-601, EPICLON TSR-250-80BX, EPICLON 1650-75MPX, EPICLON EXA-4850, EPICLON EXA-4816, EPICLON EXA-4822, and EPICLON EXA-9726; It is preferable to contain at least one component selected from the group consisting of Shinnittetsu Sumkin Chemical Co., Ltd. product number YSLV-120TE).

It is preferable that the epoxy compound (D) contains a crystalline epoxy resin. In this case, developability of the photosensitive resin composition can be improved. In addition, the crystalline epoxy resin is an epoxy resin having a melting point. The crystalline epoxy resin is, for example, triglycidyl isocyanurate (1,3,5-tris (2,3-epoxypropyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione), hydroquinone type crystalline epoxy resin (as a specific example, product name YDC-1312 manufactured by Shinnitetsu Sumikin Chemical Co., Ltd., YDC-1312), biphenyl type crystalline epoxy resin (Mitsubishi Chemical as a specific example) Co., Ltd. product number YX-4000), diphenyl ether type crystalline epoxy resin (as a specific example, Shinnitetsu Sumkin Chemical Co., Ltd. product number YSLV-80DE), bisphenol type crystalline epoxy resin (specific example As Shinnitetsu Sumikin Chemical Co., Ltd. product number YSLV-80XY), tetrakis phenolethane type crystalline epoxy resin (as a specific example, Nippon Kayaku Co., Ltd. product number GTR-1800), bisphenol fluorene type crystal With sex epoxy resin (Epoxy resin having a structure (S7) as a specific example) It may contain at least one component selected from the group consisting of.

The amount of the crystalline epoxy resin for the epoxy compound (D) is preferably in the range of 10% by mass or more and 100% by mass or less, more preferably in the range of 30% by mass or more and 100% by mass or less, more preferably 35% by mass or more and 100% It is more preferable that it is in the range of mass% or less. In this case, in the process before thermosetting of the photosensitive resin composition, the thermosetting reaction of the carboxyl group-containing resin and the epoxy resin is suppressed, and developability can be improved.

In particular, it is preferable that the crystalline epoxy resin contains a crystalline epoxy resin having a melting point of 110 ° C or lower. That is, it is preferable that the epoxy compound (D) contains a crystalline epoxy resin having a melting point of 110 ° C or lower. In this case, developability by the alkaline aqueous solution of the photosensitive resin composition is particularly improved. Crystalline epoxy resins having a melting point of 110 ° C or lower include, for example, biphenyl-type epoxy resins (part number YX4000 manufactured by Mitsubishi Chemical Corporation, as a specific example), and biphenyl ether-type epoxy resins (Synnitets Sumikin as a specific example) At least one component selected from the group consisting of Kagaku Chemical Co., Ltd. product number YSLV-80DE) and bisphenol-type epoxy resin (as a specific example, Shinnittetsu Sumikin Kagaku Chemical Co., Ltd. product number YSLV-80XY). It can contain.

The epoxy compound (D) may contain triglycidyl isocyanurate. The triglycidyl isocyanurate is preferably a β-chain having a structure in which three epoxy groups are bonded in the same direction with respect to the S-triazine ring skeleton surface, or 1 with respect to the β-form and the S-triazine ring skeleton surface. It is preferable that the two epoxy groups are a mixture with an α body having a structure in which different epoxy groups are bonded in different directions.

It is also preferable that the crystalline epoxy resin contains a crystalline epoxy resin having a melting point of less than 100 ° C. That is, it is also preferable that the epoxy compound (D) contains a crystalline epoxy resin having a melting point of less than 100 ° C. In this case, the developability of the photosensitive resin composition can be further improved. In addition, the crystalline epoxy resin having a melting point of less than 100 ° C is highly compatible with components other than the epoxy resin (D) and solvents in the photosensitive resin composition, and is thus easily dispersed and uniform in the photosensitive resin composition. In addition, when the photosensitive resin composition contains a crystalline epoxy resin having a melting point of less than 100 ° C, crystallization is unlikely to occur even at low temperatures. Therefore, high storage stability can be provided to the photosensitive resin composition. Further, at low temperatures, the crosslinking reaction between the carboxyl group and the epoxy group in the photosensitive resin composition is suppressed, so that the photosensitive resin composition can be given high storage stability while maintaining good developability.

The crystalline epoxy resin having a melting point of less than 100 ° C includes, for example, a biphenyl ether type epoxy resin (part number YSLV-80DE manufactured by Shinnitetsu Sumikin Chemical Co., Ltd., as a specific example), and a bisphenol type epoxy resin (as a specific example) At least one component selected from the group consisting of Shinnitetsu Sumkin Chemical Co., Ltd. product number YSLV-80XY) and an epoxy resin having a bisphenol fluorene skeleton (an epoxy resin having a structure (S7) as a specific example) It can contain.

When the epoxy compound (D) contains a crystalline epoxy resin having a melting point of less than 100 ° C, the equivalent of the epoxy group contained in the crystalline epoxy resin having a melting point of less than 100 ° C is equivalent to one equivalent of the carboxyl group contained in the carboxyl group-containing resin (A). On the other hand, if it is in the range of 0.2 or more and 2.0 or less, it is preferable if it is in the range of 0.25 or more and 1.7 or less, and more preferably in the range of 0.3 or more and 1.5 or less.

The epoxy compound (D) may contain a phosphorus-containing epoxy resin. In this case, the flame retardance of the cured product of the photosensitive resin composition is improved. The phosphorus-containing epoxy resin is, for example, a phosphoric acid-modified bisphenol F-type epoxy resin (as a specific example, product numbers EPICLON EXA-9726 and EPICLON EXA-9710 manufactured by DIC Corporation), manufactured by Shinnitetsu Sumkin Chemical Co., Ltd. Part number Etopo FX-305.

It is preferable that the photosensitive resin composition further contains an organic filler (E). In this case, the adhesion between the interlayer insulating layer 7 and the conductor layer 8 is further improved. The organic filler (E) can improve the thixotropy of the photosensitive resin composition, and also improve the stability (especially storage stability).

It is preferable that the organic filler (E) has a polar group. In this case, the adhesion between the interlayer insulating layer 7 and the conductor layer 8 is particularly improved. It is preferable that the polar group contains at least one group selected from the group consisting of carboxyl group, amino group and hydroxyl group. In this case, adhesion is particularly improved.

By improving the developability of the cured product of the photosensitive resin composition when the polar group particularly contains a carboxyl group, and also when the photosensitive resin composition contains a crystalline epoxy compound, the solubility of the crystalline epoxy compound in the photosensitive resin composition is improved, Crystallization can be prevented.

When a polar group contains a hydroxyl group especially, the dispersibility of the organic filler (E) in a photosensitive resin composition improves.

When the polar group particularly contains an amino group, the reactivity of the carboxyl group-containing resin (A) and the epoxy compound (D) can be enhanced, whereby the acid resistance and alkali resistance of the cured film can be improved.

When the polar group of the organic filler (E) contains a carboxyl group, it is preferable that the acid value of the organic filler (E) is in the range of 1 mgKOH / g or more and 60 mgKOH / g or less. When the acid value is less than 1 mgKOH / g, there is a fear that the stability of the photosensitive resin composition and the developability of the cured product are lowered. If the acid value is greater than 60 mgKOH / g, there is a fear that the moisture resistance of the cured product is lowered. The acid value of the organic filler (E) is more preferably 3 mgKOH / g or more, and more preferably 40 mgKOH / g or less.

When the polar group includes a carboxyl group, the organic filler (E) polymerizes a carboxylic acid monomer having a polymerizable unsaturated double bond such as acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid, and itaconic acid, or It is obtained by crosslinking.

The organic filler (E) is blended in the photosensitive resin composition in the form of a dispersion, for example, but is not limited thereto.

It is preferable that the organic filler (E) contains the rubber component which has a polar group. In this case, the polar group contains, for example, a carboxyl group, or a carboxyl group and a hydroxyl group. The rubber component can impart flexibility to the cured product of the photosensitive resin composition.

The rubber component may be composed of resin. It is preferable that the rubber component contains at least one polymer selected from the group consisting of crosslinked acrylic rubber, crosslinked NBR, crosslinked MBS and crosslinked SBR. In this case, the photosensitive resin composition can have high transparency and can improve resolution. In addition, the rubber component can effectively impart flexibility to the cured product of the photosensitive resin composition. NBR is a copolymer of butadiene and acrylonitrile and is classified as a nitrile rubber. MBS is a copolymer composed of three components of methyl methacrylate, butadiene, and styrene, and is classified as a butadiene rubber. SBR is a copolymer of styrene and butadiene and is classified as styrene rubber.

As a specific example of the organic filler (E) provided as a dispersion, JSR Co., Ltd. product number XER-91-MEK (average primary particle diameter of 0.07 μm crosslinked rubber having a carboxyl group (NBR) concentration of 15% by weight of methyl Ethyl ketone dispersion, acid value 10.0 mgKOH / g), dispersion of crosslinked rubber (SBR) having a carboxyl group and hydroxyl group XSK-500 (part number XER-32 and XER-92, manufactured by JSR Corporation, and part number XSK-500, manufactured by JSR Corporation) ).

The organic filler (E) may contain components other than the rubber component. Components other than the rubber component may contain at least one component selected from the group consisting of acrylic resin particles having a carboxyl group and cellulose particles having a carboxyl group. The acrylic resin fine particles having a carboxyl group may contain at least one component selected from the group consisting of non-crosslinked styrene / acrylic resin fine particles and crosslinked styrene / acrylic resin fine particles. Specific examples of the non-crosslinked styrene / acrylic resin fine particles include Nippon Paint / Industrial Coatings Co., Ltd. product number FS-201 (average primary particle diameter 0.5 µm). Specific examples of the crosslinked styrene / acrylic resin fine particles include Nippon Paint and Industrial Coatings Co., Ltd. part number MG-351 (average primary particle diameter 1.0 µm), and part number BGK-001 (average primary particle diameter 1.0 µm) ).

The organic filler (E), when the polar group contains an amino group, for example, melamine, dicyandiamide, imidazole-based compound, acetoguanamine, benzoguanamine, melamine-phenol-formalin resin, triazine compound, ethyl Triazine derivatives such as diamino-S-triazine, 2,4-diamino-S-triazine, and 2,4-diamino-6-xylyl-S-triazine, thiazole-based compounds, and triazole-based Contains at least one component selected from the group consisting of compounds. When the polar group contains an amino group, it is preferable that the organic filler (E) contains melamine particles. When the organic filler (E) contains melamine particles, adhesion between the interlayer insulating layer 7 and the conductor layer 8 is particularly improved.

The organic filler (E) may contain at least one component selected from the group consisting of the components described above. Moreover, the organic filler (E) also contains components having polar groups other than the components described above.

It is preferable that the average primary particle diameter of the organic filler (E) is 1 µm or less. In this case, the thixotropy of the photosensitive resin composition is effectively increased. Therefore, the stability of the photosensitive resin composition is further improved. In addition, the average primary particle diameter of the organic filler (E) is, for example, 0.001 µm or more. The average primary particle diameter of the organic filler (E) is a median diameter (D50) measured by a laser diffraction particle size distribution measuring device. It is preferable that the average primary particle diameter of the organic filler (E) is 0.1 µm or less. In this case, stability of the photosensitive resin composition is further improved, and scattering during exposure is suppressed, so that resolution is further improved.

It is preferable that the particle diameter of the organic filler (E) in a photosensitive resin composition is 10 micrometers or less. The organic filler (E) may contain secondary particles formed by aggregation in the photosensitive resin composition. In that case, the particle diameter of the organic filler (E) in the photosensitive resin composition means the particle diameter of particles containing secondary particles. The particle diameter of the organic filler (E) in the photosensitive resin composition can be measured using a laser diffraction scattering type particle size distribution measuring device or an optical microscope. When the particle diameter of the organic filler (E) in the photosensitive resin composition is 10 µm or less, the organic filler (E) can be favorably dispersed in the photosensitive resin composition and in the interlayer insulating layer (7), whereby the interlayer insulating layer The adhesion between (7) and the conductor layer 8 is particularly improved. In addition, since the stability of the photosensitive resin composition is further improved and scattering during exposure is suppressed, the resolution is further improved. It is more preferable that the particle diameter of the organic filler (E) in the photosensitive resin composition is 5 μm or less, more preferably 1 μm or less, and particularly preferably 0.5 μm or less. In addition, the particle diameter is, for example, 0.01 µm or more.

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

Organic solvents include, for example, straight chain, branched, secondary or polyhydric alcohols such as ethanol, propyl alcohol, isopropyl alcohol, hexanol, and ethylene glycol; Ketones such as methyl ethyl ketone and cyclohexanone; Aromatic hydrocarbons such as toluene and xylene; Petroleum-based aromatic mixed solvents such as Suwasol series (manufactured by Maruzen Sekiyu Chemical Co., Ltd.) and Solvetso series (manufactured by Exxon Chemical Company); Cellosolves such as cellosolve and butyl cellosolve; Carbitols such as carbitol and butyl carbitol; Propylene glycol alkyl ethers such as propylene glycol methyl ether; Polypropylene glycol alkyl ethers such as dipropylene glycol methyl ether; Acetic acid esters such as ethyl acetate, butyl acetate, cellosolve acetate, and carbitol acetate; And it may contain at least one compound selected from the group consisting of dialkyl glycol ethers.

The amount of the components 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 amount of the carboxyl group-containing resin (A) relative to the solid content of the photosensitive resin composition is preferably in the range of 5% by mass or more and 85% by mass or less, more preferably in the range of 10% by mass or more and 75% by mass or less, and more preferably 30% by mass It is more preferable if it is in the range of% to 60 mass%. The amount of the carboxyl group-containing resin (A1) relative to the solid content of the photosensitive resin composition is preferably within a range of 5% by mass to 85% by mass, more preferably within a range of 10% by mass to 75% by mass, It is more preferable if it is in the range of 30 mass% or more and 60 mass% or less.

The amount of the unsaturated compound (B) relative to the carboxyl group-containing resin (A) is preferably 1% by mass or more and 50% by mass or less, more preferably 10% by mass or more and 45% by mass or less, and more preferably 21% by mass It is more preferable if it is in the range of more than 40 mass%.

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

As for the amount of the epoxy compound (D), it is preferable that the sum of the equivalents of the epoxy groups contained in the epoxy compound (D) is within the range of 0.7 or more and 2.5 or less with respect to 1 equivalent of the carboxyl group contained in the carboxyl group-containing resin (A). , It is more preferably in the range of 0.7 or more and 2.3 or less, and more preferably in the range of 0.7 or more and 2.0 or less. Moreover, it is preferable that the sum total of the equivalent of the epoxy group contained in a crystalline epoxy resin is in the range of 0.1 or more and 2.0 or less with respect to 1 equivalent of the carboxyl group contained in the carboxyl group-containing resin (A), and is more than 0.2 or more and 1.9 or less. It is preferable, and more preferably in the range of 0.3 or more and 1.5 or less. Alternatively, the sum of the equivalents of the epoxy groups contained in the crystalline epoxy resin may be in the range of 0.7 or more and 2.5 or less with respect to 1 equivalent of the carboxyl group contained in the carboxyl group-containing resin (A).

It is preferable that the amount of the organic filler (E) is within a range of 1 part by mass to 50 parts by mass with respect to 100 parts by mass of the carboxyl group-containing resin (A). When the amount of the organic filler (E) is 1 part by mass or more, the adhesion between the interlayer insulating layer 7 and the conductor layer 8 is particularly high, and good copper plating adhesion of a cured product of the photosensitive resin composition is obtained. Further, when the amount of the organic filler (E) is 50 parts by mass or less, excellent resolution of the photosensitive resin composition is obtained. In addition, when the content of the organic filler (E) falls within the above range, the thixotropy of the photosensitive resin composition is increased, and stability is improved. The amount of the organic filler (E) is more preferably 5 parts by mass or more, and even more preferably 10 parts by mass or more. Further, the amount of the organic filler (E) is more preferably 30 parts by mass or less, and more preferably 20 parts by mass or less.

When the photosensitive resin composition contains an organic solvent, the amount of the organic solvent is adjusted so that when the coating film formed of the photosensitive resin composition is dried, the organic solvent is rapidly volatilized and disappears, that is, the organic solvent does not remain in the dried film. It is preferred. In particular, the amount of the organic solvent for the entire photosensitive resin composition is preferably in the range of 0% by mass or more and 99.5% by mass or less, and more preferably 15% by mass or more and 60% by mass or less. And since the preferable ratio of an organic solvent differs by a coating method etc., it is preferable that a ratio is suitably adjusted by a coating method.

In addition, solid content means the total amount of all the components except the volatile components, such as a solvent, from a photosensitive resin composition.

The photosensitive resin composition may further contain components other than the above components, as long as the effects of the present embodiment are not inhibited.

The photosensitive resin composition may contain an inorganic filler. In this case, curing shrinkage of the film formed of the photosensitive resin composition is reduced. The inorganic filler contains at least one material selected from the group consisting of, for example, barium sulfate, crystalline silica, nanosilica, carbon nanotubes, talc, bentonite, hydrotalcite, aluminum hydroxide, magnesium hydroxide, and titanium oxide. can do. When the inorganic filler contains a white material such as titanium oxide or zinc oxide, the photosensitive resin composition and its cured product can be whitened with the white material. When the photosensitive resin composition contains an inorganic filler, it is preferable that the amount of the inorganic filler with respect to the carboxyl group-containing resin (A) is more than 0 mass% and less than 300 mass%.

The photosensitive resin composition includes tolylene diisocyanate based, morpholine diisocyanate based, isophorone diisocyanate based and hexamethylene diisocyanate based blocked isocyanate blocked with caprolactam, oxime, malonic acid ester, etc .; Amino resins such as melamine resin, n-butylated melamine resin, isobutylated melamine resin, butylated urea resin, butylated melamine urea co-condensation resin, and benzoguanamine-based co-condensation resin; Various thermosetting resins other than the above; UV curable epoxy (meth) acrylate; Resins obtained by adding (meth) acrylic acid to epoxy resins such as bisphenol A type, phenol novolak type, cresol novolak type, and alicyclic type; And at least one resin selected from the group consisting of polymer compounds such as diallyl phthalate resins, phenoxy resins, urethane resins, and fluorine resins.

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

The photosensitive resin composition may contain an adhesion imparting agent. Examples of the adhesion imparting agent include guanamin, acetoguanamine, benzoguanamine, and 2,4-diamino-6-methacryloyloxyethyl-S-triazine, 2-vinyl-4,6-dia Mino-S-triazine, 2-vinyl-4,6-diamino-S-triazine, isocyanuric acid adduct, 2,4-diamino-6-methacryloyloxyethyl-S-triazine And S-triazine derivatives such as isocyanuric acid adducts.

The photosensitive resin composition may contain a rheology control agent. With the rheology control agent, the viscosity of the photosensitive resin composition becomes easy to apply. As the rheology control agent, for example, urea-modified medium-polar polyamide (product number BYK-430, BYK-431, manufactured by BICCHEMI Japan Corp.), polyhydroxycarboxylic acid amide (manufactured by BICCHEMI Japan Corp.) Product number BYK-405), modified urea (product number BYK-410, BYK-411, BYK-420, manufactured by BIC Chemie Japan Co., Ltd.), polymer urea derivative (product number BYK-415, manufactured by BIC Chemie Japan Ltd. ), Urea-modified urethane (article number BYK-425, manufactured by BIC Chemie Japan Co., Ltd.), polyurethane (article number BYK-428, manufactured by BICKEMI Japan Corp.), castor oil wax, polyethylene wax, polyamide wax, And bentonite, silica, silica gel, kaolin, and clay.

The photosensitive resin composition includes a curing accelerator; coloring agent; Copolymers such as silicone and acrylate; Leveling agents; Adhesion imparting agents such as silane coupling agents; Thixotropic agents; Polymerization inhibitors; Antihalation agents; Flame retardants; Antifoaming agent; Antioxidants; Surfactants; And at least one component selected from the group consisting of polymer dispersants.

The photosensitive resin composition is liquid, for example. When the photosensitive resin composition is a liquid, for example, the raw materials of the photosensitive resin composition as described above are blended, for example, by kneading by a known kneading method using a three roll mill, ball mill, sand mill, etc., the photosensitive resin The composition can be formulated. When the raw material of the photosensitive resin composition contains a liquid component, a low-viscosity component, etc., a portion of the raw material excluding the liquid component, a low-viscosity component, and the like is first kneaded, and the resulting mixture has a liquid component and a viscosity. You may prepare a photosensitive resin composition by adding and mixing a low component. In addition, when any raw material is dispersed in a solvent, for example, the photosensitive resin composition can be prepared by mixing and stirring the raw materials without kneading.

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 remainder of the component. That is, the photosensitive resin composition may contain a first agent and a second agent. In this case, for example, among the components of the photosensitive resin composition, the first agent is prepared by pre-mixing and dispersing a portion of the unsaturated compound (B), an organic solvent, and a thermosetting component, and the remainder of the components of the photosensitive resin composition The second agent may be prepared by mixing and dispersing. In this case, a mixed solution is prepared by mixing the required 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 may be a dry film. The dry film can be produced, for example, by applying a liquid composition such as the above-mentioned liquid photosensitive resin composition onto a suitable support such as a polyester and then drying. Thereby, the laminated body (dry film with a support body) containing a dry film and a support body which supports a dry film is obtained.

It is preferable that the photosensitive resin composition has properties such that even the coating film 4 having a thickness of 25 μm can be developed with an aqueous sodium carbonate solution. In this case, it is possible to produce a sufficiently thick interlayer insulating layer 7 from a photosensitive resin composition by photolithography. Of course, it is also possible to produce an interlayer insulating layer 7 thinner than 25 μm in thickness from the photosensitive resin composition.

Whether the film 4 with a thickness of 25 μm can be developed with an aqueous sodium carbonate solution can be confirmed by the following method. A wet coating film is formed by applying a photosensitive resin composition on a suitable substrate, and the wet coating film is heated at 80 ° C. for 40 minutes to form a film 4 having a thickness of 25 μm. In the state in which a negative mask having a transmissive portion for transmitting ultraviolet rays and a shielding portion for shielding ultraviolet rays is directly applied to the coating film 4, the coating film 4 is irradiated with ultraviolet rays under conditions of 500 mJ / cm 2 to perform exposure. After the exposure, the film 4 is sprayed with a 30% 1% Na ₂ CO ₃ aqueous solution at a spray pressure of 0.2 MPa for 90 seconds, followed by a process of spraying pure water at a spray pressure of 0.2 MPa for 90 seconds. As a result of observing the coating 4 after this treatment, when the portion corresponding to the shielding portion in the coating 4 is removed and residues are not recognized, the coating 4 with a thickness of 25 μm can be developed with an aqueous sodium carbonate solution. You can judge that.

Hereinafter, an example of a method for manufacturing a multilayer printed wiring board 20 including an interlayer insulating layer 7 made from a photosensitive resin composition will be described with reference to FIGS. 1A to 1E.

In this method, the photosensitive resin composition is placed on the printed wiring board 1, and the photosensitive resin composition is photocured to produce a cured film 11. Subsequently, after treating the cured film 11 with an alkaline solution, the conductor layer 8 in contact with the cured film 11 is produced.

Specifically, first, as shown in Fig. 1A, the printed wiring board 1 is prepared. The printed wiring board 1 contains, for example, at least an insulating layer 2 and a conductor wiring 3 thereon.

As shown in B of FIG. 1, the film 4 is produced by placing the photosensitive resin composition on the printed wiring board 1 so as to cover the conductor wiring 3.

In producing the coating 4, when the photosensitive resin composition is liquid, for example, a photosensitive resin composition is coated on the printed wiring board 1 to form a wet coating film. The method for applying the photosensitive resin composition is a known method, for example, dipping, spraying, spin coating, roll coating, curtain coating or screen printing. Subsequently, in order to volatilize the organic solvent in the photosensitive resin composition, for example, the wet coating film is dried at a temperature within a range of 60 ° C to 120 ° C. Thereby, the film 4 can be manufactured.

In producing the coating 4, when the photosensitive resin composition is a dry film, for example, the dry film is superimposed on the printed wiring board 1 in a state supported by the support. In this state, the dry film is transferred from the support to the printed wiring board 1 by applying pressure to the dry film and the printed wiring board 1 and then peeling the support from the dry film. Thereby, the film 4 made of a dry film is formed on the printed wiring board 1.

Next, the cured film 11 is produced by photocuring the film 4. Therefore, for example, by exposing the coating 4, the coating 4 is partially cured as shown in Fig. 1C. Therefore, for example, after applying a negative mask to the coating 4, the coating 4 is irradiated with ultraviolet light. The negative mask includes a transmissive portion that transmits ultraviolet rays and a shielding portion that shields ultraviolet rays, and the shielding portion is formed at a position that matches the position of the via 10. The negative mask is, for example, a photo tool such as a mask film or a dry plate. The ultraviolet light source is, for example, a chemical lamp, a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, an ultra high pressure mercury lamp, a xenon lamp, a metal halide lamp, LED, g line (436 nm), h line (405 nm), i line (365) Nm), and a combination of two or more of g-line, h-line and i-line.

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

When the photosensitive resin composition is a dry film, the dry film in the laminate is superimposed on the printed wiring board 1, and then the ultraviolet ray is irradiated through the support to the coating film 4 made of a dry film without peeling off the support. The coating film 4 may be exposed, and the support may be peeled from the coating film 4 before continuing the development process.

Then, in the case where the via 10 is not formed in the multilayer printed wiring board 20, the film 4 is not partially partially cured, but the entire film 4 is photocured to produce a cured film 11 You may do it.

Subsequently, the cured film 11 is treated with an alkaline solution. When heat-treating the cured film 11 before producing the conductor layer 8, it is preferable to treat the cured film 11 with an alkaline solution before heat-treating.

The alkaline solution is, for example, an alkaline aqueous solution containing either or both of alkali metal salts and alkali metal hydroxides. The alkaline aqueous solution is more specifically, for example, from the group consisting of sodium carbonate, potassium carbonate, ammonium carbonate, sodium hydrogen chloride, potassium hydrogen carbonate, ammonium hydrogen carbonate, sodium hydroxide, potassium hydroxide, ammonium hydroxide, tetramethylammonium hydroxide and lithium hydroxide. It contains at least one component selected. 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. It is preferable that the pH of the alkaline solution is 8.5 or more and 14 or less. The pH of the alkaline solution is more preferably 9 or more, more preferably 9.5 or more, and particularly preferably 10 or more. In addition, the pH of the alkali solution is more preferably 13.5 or less, further preferably 13 or less, and particularly preferably 12.5 or less.

When the film 4 is partially photocured, the cured film 11 is treated with an alkaline solution, and at the same time, the unexposed part 5 of the film 4 is applied from the printed wiring board 1 with the alkaline solution. Can be removed. That is, the cured film 11 can be treated with an alkaline solution, and at the same time, development treatment can be performed with the alkaline solution. Thereby, the hole 6 can be formed in the position where the via 10 is formed as shown in D of FIG. 1.

It is preferable to perform treatment with an alkaline solution in a state in which the reaction rate of the epoxy group based on the coating 4 is 50% or less. The reaction rate of this epoxy group is based on the amount of the epoxy group in the coating 4 before exposure. Treatment with an alkaline solution is more preferably performed in a state in which the reaction rate of the epoxy group is 40% or less, more preferably in a state of 30% or less, and particularly preferably in a state of 20% or less. And the reaction rate of the epoxy group is calculated from the intensity of the peak derived from the epoxy group of 910 cm ^-1 in the IR spectrum obtained by performing infrared spectral analysis of the film 4 and the cured film 11. Specifically, the reaction rate of the epoxy group is a normalized value (S ₀ ) of an area of a peak of 910 cm ^-1 in the IR spectrum obtained by infrared spectral analysis of the film 4 and a cured film 11 after treatment with an alkaline solution. From the normalized value (S ₁ ) of the area of the peak of 910 cm ⁻¹ in the IR spectrum obtained by infrared spectral analysis of (S ₀ -S ₁ ) ÷ S _{0 ×} 100 (%). Then, the values of the normalized value (S ₀ ) and the normalized value (S ₁ ) are based on the area of a peak in the IR spectrum that does not change even when the film 4 is exposed, for example, a peak of 750 cm ^-1 . It is a relative value. That is, the normalized value (S ₀ ), the area measured value (P ₀ ) of the peak at 910 cm ^-1 in the IR spectrum obtained by infrared spectral analysis of the film 4, and the area measured value (R ₀ ) of the peak at 750 cm ^-1 ) Has the relationship of S ₀ = P ₀ / R ₀ . In addition, the normalized value (S ₁ ), the area measured value (P ₁ ) of the peak of 910 cm ^-1 in the IR spectrum obtained by infrared spectral analysis of the cured film 11, and the area measured value (R) of the peak of 750 cm ^-1 ₁ ) is in the relationship of S ₁ = P ₁ / R ₁ .

After the treatment with the alkaline solution, before producing the conductor layer 8, the cured film 11 may be subjected to a cleaner treatment using a known chemical solution. It is preferable that the cleaner treatment is a treatment in which the cured film 11 is not harmonized. In the cleaner treatment, for example, a cleaner solution (Atotech Japan Co., Ltd. Cleaner Secure 902 at a concentration of 40 ml / L, Cleaner Additive 902 at a concentration of 3 ml / L, and NaOH at a concentration of 20 g / L. The cured product 11 is cleaned with the liquid). Subsequently, the cured film 11 is immersed in an aqueous solution containing sodium persulfate at a concentration of 100 g / L and sulfuric acid at a concentration of 10 ml / L, followed by washing with water.

Subsequently, a conductor layer 8 in contact with the cured film 11 is produced. The conductor layer 8 is a conductor wiring made of metal, such as copper. As described above, the arithmetic average roughness Ra defined by JIS B0601-2001 on the surface of the cured film 11 in contact with the conductor layer 8 immediately before the production of the conductor layer 8 is less than 150 nm. to be. This can be easily achieved by producing a cured film 11 from a photosensitive resin composition by a conventional method, for example, a method already described.

If the arithmetic mean roughness Ra is less than 150 nm, the multilayer printed wiring board 20 can have good high-frequency characteristics. The arithmetic mean roughness Ra is preferably less than 100 nm, more preferably less than 80 nm, and particularly preferably less than 30 nm. Moreover, this arithmetic mean roughness Ra is 5 nm or more, for example.

When the hole 6 is formed in the cured film 11, the via 10 is formed by forming a hole plating 9 inside the hole 6. In addition, in Fig. 1E, the hole plating 9 has a cylindrical shape that covers the inner surface of the hole 6, but even if the hole plating 9 is filled in the entire inside of the hole 6 do.

The conductor layer 8 and the hole plating 9 can be produced by a well-known method called an additive method.

It is preferable to heat-treat the cured film 11 after producing the conductor layer 8. In this case, the adhesion between the interlayer insulating layer 7 made of the cured film 11 and the conductor layer 8 can be further improved. The conditions of the heat treatment are, for example, within a range of 120 ° C to 200 ° C in a heating temperature, and within a range of 30 minutes to 120 minutes in a heating time.

The conductor layer 8 can also be produced by performing electroless plating treatment and electrolytic plating treatment on the cured film 11 in this order. In this case, it is preferable to perform the heating treatment between the electroless plating treatment and the electrolytic plating treatment, and further perform the heating treatment after the electrolytic plating treatment. Also in this case, the adhesion between the interlayer insulating layer 7 and the conductor layer 8 made of the cured film 11 can be further improved.

After the cured film 11 is produced, until the conductor layer 8 is produced, the cured film 11 is not subjected to heat treatment, or the heating temperature is 200 ° C or less and the heating time is 150 minutes or less. It is preferable to perform a heat treatment that satisfies either or both. That is, after producing the cured film 11, until the conductor layer 8 is produced, it is preferable not to heat-treat the cured film 11, and even when performing heat treatment, the conditions are It is preferable that either or both of the heating temperature is 200 ° C or less and the heating time is 150 minutes or less. The heating temperature is more preferably 180 ° C. or less, more preferably 160 ° C. or less, and particularly preferably 140 ° C. or less. The heating time is more preferably 120 minutes or less, even more preferably 90 minutes or less, and particularly preferably 60 minutes or less.

Moreover, it is preferable to perform heat processing so that the reaction rate of the epoxy group based on the coating 4 in the cured film 11 after heat processing may be less than 95%. The reaction rate of this epoxy group is based on the amount of the epoxy group in the coating 4 before exposure. The heat treatment is more preferably performed such that the reaction rate of the epoxy group is less than 90%, more preferably less than 85%, and particularly preferably less than 80%. Then, the reaction rate of the epoxy group is calculated from the peak intensity derived from the 910 cm ^-1 epoxy group in the IR spectrum obtained by performing infrared spectral analysis of the coating film 4 and the cured film 11 after heat treatment. Specifically, the reaction rate of the epoxy group is the normalized value (S ₀ ) of the area of the peak of 910 cm ^-1 in the IR spectrum obtained by infrared spectral analysis of the film 4, and the infrared spectroscopy of the cured film 11 after heat treatment. From the normalized value (S ₂ ) of the area of the peak of 910 cm ⁻¹ in the IR spectrum obtained by analysis, it is calculated by the formula (S ₀ -S ₂ ) ÷ S ₀ × 100 (%). Then, the values of the normalized value (S ₀ ) and the normalized value (S ₂ ) are based on the area of a peak in the IR spectrum that does not change even when the film 4 is exposed, for example, a peak of 750 cm ^-1 . It is a relative value. That is, the normalized value (S ₀ ), the area measured value (P ₀ ) of the peak at 910 cm ^-1 in the IR spectrum obtained by infrared spectral analysis of the film 4, and the area measured value (R ₀ ) of the peak at 750 cm ^-1 ) Has the relationship of S ₀ = P ₀ / R ₀ . In addition, the normalized value (S ₂ ), the area measured value (P ₂ ) of the peak of 910 ccm ^-1 in the IR spectrum obtained by infrared spectral analysis of the cured film 11, and the area measured value (R) of the peak of 750 cm ^-1 ₂ ) has the relationship of S ₂ = P ₂ / R ₂ .

In this case, the adhesion between the interlayer insulating layer 7 and the conductor layer 8 can be particularly improved. Although the reason is not fully elucidated, even if it does not heat-process, and it does, when the conditions are in the said range, compared with the case where it is not, the component in the photosensitive resin composition is in the surface of the cured film 11 There are many functional groups derived from, and it is presumed that the interaction between the functional group and the conductor layer 8 contributes to the improvement of adhesion.

After the cured film 11 is produced, it is preferable that the cured film 11 is not treated with an oxidizing agent until the conductor layer 8 is produced. In this case, the cured film 11 is prevented from being roughened by the oxidizing agent, and it is easy to achieve that the arithmetic average roughness Ra of the cured film 11 is less than 150 nm. Even when the treatment with an oxidizing agent is performed, it is preferable that the cured film 11 has a degree of arithmetic average roughness Ra of less than 150 nm.

In addition, in the case where the hole 6 is formed in the cured film 11, it is the hole 6 that is subjected to a desmear treatment using an oxidizing agent to the cured film 11 before producing the conductor layer 8 It is useful to remove smear within. However, in the present embodiment, since the photosensitive resin composition can have excellent developability and resolution, smear is hardly left even if the hole 6 is formed in the cured film 11. Therefore, even when the treatment with the oxidizing agent is not performed or the treatment with the oxidizing agent is easily performed, the problem caused by smear is unlikely to occur.

As described above, the multilayer printed wiring board 20 including the interlayer insulating layer 7 made of the cured film 11 and the conductor layer 8 in contact with the interlayer insulating layer 7 can be manufactured. The thickness of the interlayer insulating layer 7 is, for example, within a range of 3 µm to 50 µm. In this multilayer printed wiring board 20, as described above, even if the interlayer insulating layer 7 is not harmonized or the degree of harmonization is small, high adhesion between the interlayer insulating layer 7 and the conductor layer 8 can be achieved. have.

<Example>

Hereinafter, specific examples of the present invention will be described. And, the present invention is not limited to the following examples.

[Examples, Comparative Examples and Reference Examples]

(1) Synthesis of carboxyl group-containing resin

[Synthesis Example A-1]

In a four-necked flask equipped with a reflux cooler, thermometer, air intake tube, and stirrer, bisphenol fluorene-type epoxy resins represented by formula (2), wherein R ₁ to R ₇ in formula (2) are all hydrogen (epoxy equivalent: 250 g / eq) 250 parts by mass, propylene glycol monomethyl ether acetate 60 parts by mass, diethylene glycol monoethyl ether acetate 140 parts by mass, methyl hydroquinone 0.2 parts by mass, acrylic acid 72 parts by mass, and triphenylphosphine 1.5 parts by mass , The mixture was prepared. The mixture was heated in a flask under air bubbling at a temperature of 115 ° C. for 12 hours. Thereby, a solution of the intermediate was prepared.

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

[Synthesis Example A-2]

The carboxyl group-containing resin having the aromatic ring of Synthesis Example A-2 was adjusted as follows. 288 parts by mass of a biphenyl novolac-type epoxy resin (manufactured by Nippon Kayaku Co., Ltd., NC-3000-H, epoxy equivalent: 288 g / eq) in a four-necked flask equipped with a reflux cooler, thermometer, air intake tube, and stirrer , Diethylene glycol monoethyl ether acetate 155 parts by weight, methyl hydroquinone 0.2 parts by weight, acrylic acid 72 parts by weight, and triphenylphosphine 3 parts by weight to prepare a mixture. The mixture was heated in a flask under air bubbling at a temperature of 115 ° C. for 12 hours. Thereby, a solution of the intermediate was prepared.

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

(2) Preparation of photosensitive resin composition (Composition Examples 1 to 9)

The components shown in Table 1 were blended in a flask and stirred and mixed at a temperature of 35 ° C. for 2 hours to obtain photosensitive resin compositions of Composition Examples 1 to 9 (see Table). The photosensitive resin compositions of Composition Examples 1 to 9 were filtered through a 300 mesh filter, and further filtered through a filter having a pore diameter of 10 µm. When the particle diameter of the organic filler contained in the photosensitive resin compositions of Composition Examples 1 to 9 was confirmed by a laser diffraction scattering type particle size distribution measuring device, the maximum particle diameter was 10 µm or less.

In addition, the compounding quantity in Table 1 shows the mass part of the solid content of the indicated component. In addition, although not described in the table, methyl ethyl ketone is blended as a diluent in the photosensitive resin composition.

The details of the components shown in Table 1 are as follows.

Organic filler A (dispersed liquid) having a polar group: methyl ethyl ketone dispersion containing crosslinked rubber (NBR) having a carboxyl group having an average primary particle diameter of 0.07 µm in a proportion of 15% by weight, manufactured by JSR Corporation, product number XER -91-MEK, acid value 10.0mgKOH / g

Organic filler B (dispersed liquid) having a polar group: methyl ethyl ketone dispersion containing a crosslinked rubber (SBR) having a carboxyl group and a hydroxyl group having an average primary particle diameter of 0.07 µm in a ratio of 15% by weight, manufactured by JSR Corporation, Article number XSK-500

Organic filler C (dispersed liquid) having a polar group: Nissan Chemical Industry Co., Ltd., 1.5 parts by weight of finely divided melamine, prepared by dispersing 3.5 parts by weight of tricyclodecane dimethanol diacrylate with a bead mill, dispersion varnish of finely divided melamine, The maximum particle diameter of finely divided melamine is 5㎛ or less

Organic filler without a polar group (dispersion): 1.5 parts by weight of glycidyl-modified acrylonitrile-butadiene rubber having an average primary particle diameter of 0.3 µm in a powder form, dispersed in 2.5 parts by weight of tricyclodecane dimethanol diacrylate in a beads mill Dispersion varnish of glycidyl-modified acrylonitrile-butadiene rubber

Coupling agent: 3-glycidoxypropyl trimethoxysilane

Silica: Nissan Chemical Industry Co., Ltd. product number MEK-EC-2130Y, methyl ethyl ketone dispersed silica sol, grade with improved compatibility with epoxy resin, solid content concentration 30 mass%, average primary particle diameter 10 nm 15 nm or more

Unsaturated compound A: tricyclodecane dimethanol diacrylate (including tricyclodecane dimethanol diacrylate derived from a dispersion of an organic filler)

Unsaturated compound B: trimethylolpropane triacrylate

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

Photopolymerization initiator A: 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, manufactured by BASF, product number Irgacure TPO

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

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

Epoxy compound: biphenyl-type crystalline epoxy resin, manufactured by Mitsubishi Chemical Corporation, part number YX4000, epoxy equivalent 186 g / eq

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

Surface adjuster: manufactured by DIC Corporation, product number Megapack F-477

[Table 1]

(3) Preparation of test cylinders (Examples 1 to 29, Comparative Examples 1 to 27, and Reference Examples 1 to 18)

Using the photosensitive resin compositions of Composition Examples 1 to 9, test cylinders were prepared as follows. The summary of each Example, Comparative Example and Reference Example is shown in Tables 2-10.

(3-1) Preparation of cured film

The photosensitive resin compositions of Composition Examples 1 to 9 were applied onto a film made of polyethylene terephthalate with an applicator and then dried by heating at 95 ° C. for 25 minutes to form a dry film having a thickness of 30 μm on the film.

A glass epoxy copper clad laminate (FR-4 type) having a copper foil having a thickness of 17.5 μm was prepared. A comb-shaped electrode having a line width / space width of 50 µm / 50 µm as a conductor wiring was formed on this glass epoxy copper-clad laminate as a subtractive method, thereby obtaining a printed wiring board.

Conductor wiring was harmonized by dissolving and removing the surface layer portion having a thickness of about 1 µm in the conductor wiring of the printed wiring board with an etchant (an organic acid-based microetching agent manufactured by Mec., Part number CZ-8101).

The dry film was heated and laminated on the entire surface of one side of the printed wiring board with a vacuum laminator. The conditions of the heating laminate were 0.5 MPa, 80 ° C, and 1 minute. Thereby, a film having a film thickness of 30 µm made of a dry film was formed on the printed wiring board so as to cover the conductor wiring.

Infrared spectroscopy analysis of the coating was conducted to obtain an IR spectrum.

Subsequently, on the film, from a film made of polyethylene terephthalate, a circular shield having a diameter of 30 µm, 45 µm, and 60 µm, and a stripe-shaped shield having a line width / space width of 40 µm / 40 µm. The eggplant was directly put on a negative mask, and the exposed portion of the film was cured by irradiating the film with UV light at a condition of 300 mJ / cm 2 through the negative mask to produce a cured film. A film made of polyethylene terephthalate was peeled from the cured film.

Subsequently, in each of Examples and Reference Examples 1 to 9, the cured film was treated with an alkaline solution, and the unexposed portion of the film was removed with the alkaline solution. In the treatment, a 1% Na ₂ CO ₃ aqueous solution (pH11) at 30 ° C. was sprayed onto the cured film at a spray pressure of 0.2 MPa for 90 seconds. Subsequently, the cured film was cleaned by spraying pure water at an injection pressure of 0.2 MPa for 90 seconds. Thereby, an opening was formed in a position where the unexposed portion of the cured film was removed. On the other hand, in each of Comparative Examples and Reference Examples 10 to 18, the cured film was not treated with an alkaline solution.

(3-2) Heat treatment of cured film

In Examples 1-27, each comparative example, and each reference example, the cured film was heated at 150 degreeC for 50 minutes. In Example 28, the cured film was heated at 160 ° C for 120 minutes. In Example 29, the cured film was heated at 180 ° C for 120 minutes.

Subsequently, infrared spectral analysis of the cured film was performed to obtain an IR spectrum.

From of the 910cm ^-1 in the IR spectrum peak area of the film standardized value (S ₀₎ of the normalized value and a cured film of the IR 910cm ^-1 in the spectrum peak area _{(S 2), (S 0} -S 2 ) ÷ S _{0 ×} 100 (%), the reaction rate (percentage) of the epoxy group was calculated. Then, the standardization value S ₀ is S ₀ = P from the area measurement value P ₀ of the peak at 910 cm ⁻¹ in the IR spectrum of the film, and the area measurement value R ₀ of the peak at 750 cm ⁻¹ . ₀ / R, and the value calculated by the formula _0, normalized value (S ₂₎ is, the cured film IR area of a peak of the actually measured value of the 910cm ^-1 in the spectrum (P ₂₎ and the actually measured value of the peak area of the 750cm ^-1 ( From R ₂ ), S ₂ = P ₂ / R ₂ . In addition, the first digit of the decimal point of the calculation result of the reaction rate of the epoxy group was rounded.

From this result, the reaction rate of the epoxy group was classified as follows.

A: The reaction rate of the epoxy group is less than 85%

B: The reaction rate of the epoxy group is 85% or more, and less than 90%

C: The reaction rate of the epoxy group is 90% or more, and less than 95%

D: The reaction rate of the epoxy group is 95% or more

Subsequently, in each example, each comparative example, and each reference example, ultraviolet rays of 1000 mJ / cm 2 were irradiated to the cured film using a high pressure mercury lamp.

(3-3) Surface treatment of cured film

(3-3-1) Examples 1 to 9, Examples 28 to 29 and Comparative Examples 1 to 9 (no harmonization)

The cured film was subjected to a cleaner treatment in the following manner. 60 占 폚 of the cured film in a cleaner solution (Atotech Japan Co., Ltd. Cleaner Security 902 at a concentration of 40 ml / L, Cleaner Additive 902 at a concentration of 3 ml / L, NaOH at a concentration of 20 g / L) Soak for 5 minutes at. Subsequently, the cured film was immersed in an aqueous solution of 0.1 g / L of SnCl ₂ for 3 minutes, and then washed with water. Subsequently, the cured film was immersed in a solution containing sodium persulfate at a concentration of 100 g / L and sulfuric acid at a concentration of 10 ml / L for 1 minute at 25 ° C, followed by washing with water.

(3-3-2) Examples 10 to 18 and Comparative Examples 10 to 18 (low harmonic)

The cured film was immersed in a swelling solution for desmear at 50 ° C (Atotech Japan Co., Ltd., Swelling Dip Security P, at a concentration of 500 mL / L and NaOH at a concentration of 3 g / L) for 15 minutes. After swelling by immersion, the cured film was washed. Subsequently, the cured film was added to a desmear solution containing 50 ° C potassium permanganate (Atotech Japan Co., Ltd., Concentrate Compact CP at a concentration of 580 mL / L and NaOH at a concentration of 40 g / L). The surface of the cured film was adjusted by immersion for 10 minutes, and then washed. Subsequently, the cured film was added to a neutralizing solution at 40 ° C (Atotech Japan Co., Ltd., a solution containing Reduction Solution Security P500 at a concentration of 70 mL / L and sulfuric acid (98%) at a concentration of 50 mL / L). The residue of the desmear liquid on the surface of the cured film was removed by immersion for 5 minutes, and then washed with water. Subsequently, the cured film was subjected to a cleaner treatment in the same manner as in the above (4-1).

(3-3-3) In the case of Examples 19-27 and Comparative Examples 19-27 (medium harmony)

The surface of the cured film was applied to a swelling solution for desmear at 80 ° C (Atotech Japan Co., Ltd., Swelling Dip Security P, at a concentration of 500 mL / L and NaOH at a concentration of 3 g / L). After swelling by immersion for 5 minutes, the cured film was washed. Subsequently, the cured film was added to a desmear solution containing potassium permanganate at 60 ° C (Atotech Japan Co., Ltd., Concentrate Compact CP at a concentration of 580 mL / L and NaOH at a concentration of 40 g / L). The surface of the cured film was roughened by immersion for 5 minutes, and then washed. Subsequently, the cured film was added to a neutralizing solution at 40 ° C (Atotech Japan Co., Ltd., a solution containing Reduction Solution Security P500 at a concentration of 70 mL / L and sulfuric acid (98%) at a concentration of 50 mL / L). The residue of the desmear liquid on the surface of the cured film was removed by immersion for 5 minutes, and then washed with water. Subsequently, the cured film was subjected to a cleaner treatment in the same manner as in the above (4-1).

(3-3-4) In the case of Reference Examples 1 to 18 (high harmony)

The surface of the cured film is 7.5 in a swelling solution for desmear at 70 ° C (manufactured by Atotech Japan, Swelling Dip Security Guns P at a concentration of 500 mL / L and NaOH at a concentration of 3 g / Ln) 7.5 After swelling by immersion for a minute, the cured film was washed. Subsequently, the cured film was added to a desmear solution containing potassium permanganate at 70 ° C (Atotech Japan Co., Ltd., Concentrate Compact CP at a concentration of 580 mL / L and NaOH at a concentration of 40 g / L). The surface of the cured film was adjusted by immersion for 7.5 minutes, and then washed. Subsequently, the cured film was added to a neutralizing solution at 40 ° C (Atotech Japan Co., Ltd., a solution containing Reduction Solution Security P500 at a concentration of 70 mL / L and sulfuric acid (98%) at a concentration of 50 mL / L). The residue of the desmear liquid on the surface of the cured film was removed by immersion for 5 minutes, and then washed with water. Subsequently, the cured film was subjected to a cleaner treatment in the same manner as in the above (4-1).

The surface roughness (arithmetic mean roughness (Ra)) of the cured film in the test cylinder after the surface treatment was measured with a laser microscope. The results were classified as follows. The results are shown in the table.

A: The arithmetic mean roughness (Ra) is less than 30 nm

B: The arithmetic mean roughness (Ra) is 30 nm or more and less than 80 nm

C: The arithmetic mean roughness (Ra) is 80 nm or more and less than 150 nm

D: The arithmetic mean roughness (Ra) is 150 nm or more

(4) Evaluation test

The following tests were performed for the test cylinders of each Example, Comparative Example, and Reference Example. The results are shown in Tables 2-10.

(4-1) Copper plating adhesion

The cured film was subjected to electroless copper plating treatment (MV Plus treatment by Atotech Japan), followed by heating at 150 ° C. for 1 hour, followed by electrolytic copper plating treatment under a current density of 2 A / dm 2. A copper film with a thickness of 33 µm was formed, and the test cylinder was then heated at 180 ° C for 30 minutes. Thereby, a copper plating layer was formed on the cured film. The peel strength of the copper plated layer to the cured film was measured in accordance with JIS C6481, except when blistering occurred in at least one of the case of heating after the electroless copper plating treatment and during heating after the electrolytic copper plating treatment. . From this result, the adhesion of the copper plating layer was evaluated as follows.

A: The peeling strength of the copper plating layer is 0.2 kN / m or more.

B: The peeling strength of the copper plating layer is 0.1 kN / m or more and less than 0.2 kN / m

C: The peeling strength of the copper plating layer was less than 0.1 kN / m

D: Blisters occurred on at least one side during heating after the electroless copper plating treatment and during heating after the electrolytic copper plating treatment.

(4-2) Electrical insulation

After heating the test cylinder at 150 ° C for 1 hour and heating at 180 ° C for 30 minutes, the test cylinder was 130 ° C and 85% RH while applying a bias voltage of DC 30V between the comb electrodes in the conductor wiring in the test cylinder. Was exposed for 100 hours under the test environment. Under the test environment, the electrical resistance value of the cured film between the comb electrodes was always measured, and the results were evaluated as follows.

A: From the start of the test until 100 hours elapsed, the electrical resistance value was always maintained at 10 ⁶ Ω or higher.

B: The electrical resistance value was always maintained at 10 ⁶ Ω or more from the start of the test until 85 hours elapsed, but the electrical resistance value was less than 10 ⁶ Ω before 100 hours from the start of the test.

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

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

(4-3) Openness

The circular opening corresponding to the circular-shaped shield of the negative mask of the cured film in the test cylinders of the Examples, Comparative Examples, and Reference Examples was observed and evaluated as follows.

A: All openings corresponding to shields having a diameter of 30 μm, 45 μm, and 60 μm are formed.

B: An opening corresponding to a shield having a diameter of 30 μm is not formed, but an opening corresponding to a shield having a diameter of 45 μm and 60 μm is formed.

C: An opening corresponding to a shielding portion having a diameter of 30 μm and 45 μm is not formed, but an opening corresponding to a shielding portion having a diameter of 60 μm is formed.

D: All openings corresponding to shielding portions having a diameter of 30 µm, 45 µm, and 60 µm are not formed.

(4-4) Resolution

The stripe-shaped openings corresponding to the stripe-shaped shielding portions of the cured films in the test cylinders of the Examples, Comparative Examples, and Reference Examples were observed and evaluated as follows.

A: There is no looseness in the contour of the opening, and it exhibits clear and clear resolution.

B: There is some looseness in the contour of the opening, but it exhibits a clear resolution.

C: The looseness of the outline of the opening is seen, and the resolution is slightly inferior.

D: The looseness of the outline of the opening is large, and the resolution is poor.

[Table 2]

[Table 3]

[Table 4]

[Table 5]

[Table 6]

[Table 7]

[Table 8]

[Table 9]

Table 10

As is apparent from the above-described embodiment, in the method for manufacturing the multilayer printed wiring board 20 of the first aspect of the present invention, the coating 4 is produced on the printed wiring board 1 with a photosensitive resin composition. The photosensitive resin composition contains a carboxyl group-containing resin (A), an unsaturated compound (B) having at least one ethylenically unsaturated bond in one molecule, a photopolymerization initiator (C), and an epoxy compound (D). The cured film 11 is produced by photocuring the coating 4. After treating the cured film 11 with an alkaline solution, a conductor layer 8 in contact with the cured film 11 is produced. The arithmetic average roughness Ra defined by JIS B0601-2001 of the surface of the cured film 11 in contact with the conductor layer 8 immediately before the production of the conductor layer 8 is less than 150 nm.

According to the first aspect, even if the interlayer insulating layer 7 made of the cured film 11 is not harmonized or the degree of harmonization is small, high adhesion between the interlayer insulating layer 7 and the conductor layer 8 can be achieved. A multilayer printed wiring board 20 can be obtained.

In the method for manufacturing the multilayer printed wiring board 20 of the second aspect of the present invention, in the first aspect, the arithmetic average roughness Ra is less than 80 nm.

According to the second aspect, the multilayer printed wiring board 20 can have good high-frequency characteristics.

In the method for manufacturing the multilayer printed wiring board 20 of the third aspect of the present invention, in the first or second aspect, after the cured film 11 is produced, until the conductor layer 8 is produced, curing is performed. The heat treatment is not performed on the membrane 11 or the reaction rate of the epoxy group based on the coating 4 is less than 95%.

According to the third aspect, adhesion between the interlayer insulating layer 7 and the conductor layer 8 made of the cured film 11 can be improved.

In the manufacturing method of the multilayer printed wiring board 20 of the 4th aspect which concerns on this invention, in any one of the 1st-3rd, the photosensitive resin composition is a dry film.

According to the fourth aspect, even if the interlayer insulating layer 7 made of the cured film 11 is not harmonized or the degree of harmonization is small, high adhesion between the interlayer insulating layer 7 and the conductor layer 8 can be achieved. A multilayer printed wiring board 20 can be obtained.

In the manufacturing method of the multilayer printed wiring board 20 of 5th aspect which concerns on this invention, in any one of the 1st-4th, the photosensitive resin composition further contains the organic filler (E).

According to the fifth aspect, adhesion between the interlayer insulating layer 7 made of the cured film 11 and the conductor layer 8 is improved.

In the manufacturing method of the multilayer printed wiring board 20 of the 6th aspect which concerns on this invention, in a 5th aspect, the organic filler E has a polar group.

According to the sixth aspect, the adhesion between the interlayer insulating layer 7 made of the cured film 11 and the conductor layer 8 is further improved.

In the manufacturing method of the multilayer printed wiring board 20 of the 7th aspect which concerns on this invention, in a 6th aspect, a polar group contains at least 1 sort (s) group chosen from the group which consists of a carboxyl group, an amino group, and a hydroxyl group.

According to the seventh aspect, adhesion between the interlayer insulating layer 7 and the conductor layer 8 made of the cured film 11 is particularly improved.

In the manufacturing method of the multilayer printed wiring board 20 of the 8th aspect which concerns on this invention, in any one of the 5th-7th aspect, the particle diameter of the organic filler E in the photosensitive resin composition is 10 micrometers or less. to be. The adhesion between the interlayer insulating layer 7 made of the cured film 11 and the conductor layer 8 is particularly improved.

According to the eighth aspect, adhesion between the interlayer insulating layer 7 and the conductor layer 8 made of the cured film 11 is particularly improved.

In the manufacturing method of the multilayer printed wiring board 20 of the ninth aspect according to the present invention, in any one of the first to eighth aspects, after producing the cured film 11, the conductor layer 11 is produced. Until now, the cured film 11 is not treated with an oxidizing agent.

According to the ninth aspect, the cured film 11 is prevented from being roughened by an oxidizing agent, and it is easy to achieve that the arithmetic average roughness Ra of the cured film 11 is less than 150 nm.

The multilayer printed wiring board 20 of the tenth aspect of the present invention is manufactured by any one of the first to ninth aspects of the manufacturing method.

According to the tenth aspect, a multilayer printed wiring board 20 having high adhesion between the interlayer insulating layer 7 and the conductor layer 8 can be obtained.

1: Printed wiring board
4: film
7: Interlayer insulation layer
8: conductor layer
11: cured film
20: multilayer printed wiring board

Claims (10)

A film was prepared from the photosensitive resin composition on the printed wiring board,
The photosensitive resin composition,
Carboxyl group-containing resin (A),
An unsaturated compound (B) having at least one ethylenically unsaturated bond in one molecule,
Photopolymerization initiator (C), and
It contains an epoxy compound (D),
A cured film is produced by photocuring the coating,
After treating the cured film with an alkaline solution, a conductor layer in contact with the cured film is prepared,
The arithmetic average roughness Ra defined by JIS B0601-2001 of the surface of the cured film contacting the conductor layer immediately before the production of the conductor layer is less than 150 nm,
Method for manufacturing a multilayer printed wiring board. According to claim 1,
The arithmetic mean roughness Ra is less than 80 nm, a method of manufacturing a multilayer printed wiring board. The method according to claim 1 or 2,
After producing the cured film, until the conductor layer is produced, the cured film is not subjected to heat treatment, or heat-treated so that the reaction rate of the epoxy group based on the film is less than 95%, Method for manufacturing a multilayer printed wiring board. The method according to any one of claims 1 to 3,
The said photosensitive resin composition is a dry film, The manufacturing method of a multilayer printed wiring board. The method according to any one of claims 1 to 4,
The said photosensitive resin composition further contains the organic filler (E), The manufacturing method of a multilayer printed wiring board. The method of claim 5,
The organic filler (E) has a polar group, a method of manufacturing a multilayer printed wiring board. The method of claim 6,
The polar group includes at least one group selected from the group consisting of a carboxyl group, an amino group, and a hydroxyl group, and the method for manufacturing a multilayer printed wiring board. The method according to any one of claims 5 to 7,
The particle diameter of the said organic filler (E) in the said photosensitive resin composition is 10 micrometers or less, The manufacturing method of a multilayer printed wiring board. The method according to any one of claims 1 to 8,
A method of manufacturing a multilayer printed wiring board, wherein after producing the cured film, until the conductor layer is produced, the cured film is not treated with an oxidizing agent. A multilayer printed wiring board manufactured by the manufacturing method according to any one of claims 1 to 9.

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