TW201910137A - Manufacturing method of multi-layered printed wiring board and multi-layered printed wiring board - Google Patents

Abstract

Provided is a method for producing a multilayer printed wiring board, which is capable of achieving high adhesion between an interlayer insulating layer and a conductor layer even if the interlayer insulating layer is not roughened or the roughening degree of the interlayer insulating layer is low. According to this method for producing a multilayer printed wiring board (20), a cured film (11) is produced by forming a coating film (4) from a photosensitive resin composition on a printed wiring board (1) and photocuring the coating film (4), and a conductor layer (8) is produced after processing the cured film (11) with an alkaline solution. The photosensitive resin composition contains a carboxyl group-containing resin (A), an unsaturated compound (B) that has at least one ethylenically unsaturated bond in each molecule, a photopolymerization initiator (C) and an epoxy compound (D). A surface of the cured film (11), said surface coming into contact with the conductor layer (8), has an arithmetic mean roughness Ra of less than 150 nm immediately before the formation of the conductor layer (8).

Description

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

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

Conventionally, in order to produce an electrically insulating layer such as a solder resist layer, a plating resist layer, an etchant resist layer, and an interlayer insulating layer of a printed wiring board, an electrically insulating resin composition has been used. Such a resin composition is, for example, a photosensitive resin composition (see Patent Document 1).

In particular, when an interlayer insulating layer is formed from a photosensitive resin composition, the interlayer insulating layer is roughened in order to ensure the adhesion between the interlayer insulating layer and the conductor layer produced thereon by plating or the like (Refer to Patent Document 1). If the interlayer insulating layer is roughened, the high-frequency characteristics of the printed wiring board will deteriorate, so the transmission characteristics of the high-speed signal of the printed wiring board will deteriorate. [Prior Art Literature] (Patent Literature)

Patent Document 1: Japanese Patent Laid-Open No. 11-242330

An object of the present invention is to provide a method for manufacturing a multilayer printed wiring board and a multilayer printed wiring board. This method can achieve a gap between the interlayer insulating layer and the conductor layer even if the interlayer insulating layer is not roughened or the roughness is small High adhesion.

In one aspect of the present invention, a method for manufacturing a multilayer printed wiring board is to produce a film from a photosensitive resin composition on the printed wiring board. The aforementioned 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 photo-hardening of the aforementioned film is used to produce a cured film. First, the cured film is treated with an alkaline solution, and then a conductor layer in contact with the cured film is prepared. Immediately before the production of the conductive layer, the arithmetic average roughness Ra of the surface of the cured film in contact with the conductive layer specified by Japanese Industrial Standard (JIS) B0601-2001 is less than 150 nm.

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

The following embodiments relate to a method of manufacturing a multilayer printed wiring board and a multilayer printed wiring board manufactured by the manufacturing method, in particular to a method of manufacturing a multilayer printed wiring board and manufactured by the manufacturing method A multilayer printed wiring board. This manufacturing method produces a cured film of a photosensitive resin composition on a printed wiring board.

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

The manufacturing method of the multilayer printed wiring board 20 of this embodiment (refer to FIGS. 1A to 1E) is to form a film 4 on the printed wiring board 1 from 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). By photocuring this film 4, a cured film 11 is produced. The cured film 11 is first treated with an alkaline solution, and then the conductor layer 8 in contact with the cured film 11 is produced. Immediately before the conductor layer 8 is produced, the arithmetic mean roughness Ra of the surface of the cured film 11 in contact with the conductor layer 8 specified by JIS B0601-2001 is less than 150 nm.

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

Further, by treating the cured film 11 with an alkaline solution, the adhesion between the interlayer insulating layer 7 and the conductor layer 8 composed of the cured film 11 can be improved. The reason is not clear enough, but it is considered that if the cured film 11 is treated with an alkaline solution, the surface of the cured film 11 will not be significantly roughened, but fine irregularities will occur, which is presumed to be interlayer insulation One of the reasons that the adhesion between the layer 7 and the conductor layer 8 is improved.

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

The photosensitive resin composition used in this 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).

The carboxyl group-containing resin (A) preferably contains a carboxyl group-containing resin having an ethylenically unsaturated group. At this time, the carboxyl group-containing resin (A) can have photoreactivity. Therefore, the carboxyl group-containing resin (A) can impart photosensitivity to the photosensitive resin composition, and specifically, can impart purple line curability to the photosensitive resin composition.

The carboxyl group-containing resin (A) preferably contains a carboxyl group-containing resin having an aromatic ring. In this case, it is possible to impart high heat resistance and insulation reliability to the cured product of the photosensitive resin composition.

The carboxyl group-containing resin (A) is more preferably a carboxyl group-containing resin having a polycyclic aromatic ring having any one of a biphenyl skeleton, a naphthalene skeleton, a stilbene skeleton and an anthracene skeleton. In this case, it is possible to impart higher heat resistance and insulation reliability to the cured product of the photosensitive resin composition.

The carboxyl group-containing resin (A) preferably contains a carboxyl group-containing resin (A1) having a bisphenol fusi skeleton. In this case, the cured product of the photosensitive resin composition containing the carboxyl group-containing resin (A) can be given further higher heat resistance and insulation reliability.

Carboxy group-containing resin (A1), for example, a reaction product of an intermediate with an acid dianhydride (a3) and an acid monoanhydride (a4), the intermediate is an epoxy compound (a1) and an unsaturated group-containing carboxylic acid (a2) Reactant. The epoxy compound (a1) has a bisphenol fusi skeleton. The bisphenol stilbene skeleton is represented by the following formula (1). In the formula (1), R ₁ to R ₈ are each independently hydrogen, an alkyl group having 1 to 5 carbon atoms, or a halogen.

Each of R ₁ to R ₈ in formula (1) may be hydrogen, or may be a C 1-5 alkyl group or halogen. The reason is that even if the hydrogen in the aromatic ring is replaced by a low-molecular-weight alkyl group or halogen, it will not adversely affect the physical properties of the carboxyl-containing resin (A1), but may sometimes increase the The heat resistance or flame resistance of the cured product of the photosensitive resin composition.

If the carboxyl group-containing resin (A1) has a bisphenol fusi 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).

More specifically, the carboxyl group-containing resin (A1) will be described. In order to synthesize the carboxyl group-containing resin (A1), first, by using at least a part of epoxy groups in the epoxy compound (a1) having a bisphenol fusi skeleton represented by the formula (1), and an unsaturated group-containing carboxylic acid The carboxylic acid (a2) of (a2-1) is reacted to synthesize an intermediate. The synthesis of intermediates is defined as the first reaction. The intermediate has a secondary hydroxyl group, which is generated by the ring-opening addition reaction of the epoxy group and the carboxylic acid (a2) containing the unsaturated group-containing carboxylic acid (a2-1). Then, the secondary hydroxyl group in the intermediate is reacted with the acid anhydride (a3). With this, the carboxyl group-containing resin (A1) can be synthesized. The reaction of the intermediate with the acid anhydride (a3) is defined as the second reaction. The acid anhydride (a3) can contain an acid monoanhydride and an acid dianhydride. Acid monoanhydride refers to a compound having one acid anhydride group, which is formed by dehydration condensation of two carboxyl groups in one molecule. Acid dianhydride refers to a compound having two acid anhydride groups, which is formed by dehydration condensation of 4 carboxyl groups in one molecule.

The carboxyl group-containing resin (A1) may contain unreacted components in the intermediate. In addition, when the acid anhydride (a3) contains an acid monoanhydride and an acid dianhydride, the carboxyl group-containing resin (A1), except for the reactant containing the component in the intermediate, the component in the acid monoanhydride and the component in the acid dianhydride, It may contain either or both of the reactant of the component in the intermediate and the component in the acid monoanhydride, and the reactant of the component in the intermediate and the component in the acid dianhydride. That is, the carboxyl group-containing resin (A1) may be a mixture containing plural compounds of different structures like this.

The carboxyl group-containing resin (A1) has 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 to the photosensitive resin composition, specifically, it can impart 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) to impart developability to the photosensitive resin composition by an alkaline aqueous solution containing an alkali metal salt and alkali metal hydrogen At least one of the oxides.

The weight average molecular weight of the carboxyl group-containing resin (A1) is preferably in the range of 700 or more and 10,000 or less. If the weight average molecular weight is 700 or more, the insulation of the cured product of the photosensitive resin composition can be improved, and the dielectric loss tangent can be reduced. In addition, if the weight average molecular weight is 10,000 or less, the developability of the photosensitive resin composition by the alkaline aqueous solution can be particularly improved. The weight average molecular weight is further preferably 900 or more, and particularly preferably 1000 or more. In addition, the weight average molecular weight is still more preferably in the range of 8,000 or less, and particularly preferably in the range of 5,000 or less.

It is preferable that the polydispersity of the carboxyl group-containing resin (A1) is in the range of 1.0 or more and 4.8 or less. In this case, it is possible to ensure good insulation of the cured product formed of the photosensitive resin composition, and to impart excellent developability to the photosensitive resin composition. More preferably, the polydispersity of the carboxyl group-containing resin (A1) is 1.1 or more and 4.0 or less, and still more preferably 1.2 or more and 2.8 or less.

The number average molecular weight and molecular weight distribution of the carboxyl group-containing resin (A1) as described above can be achieved by making the carboxyl group-containing resin (A1) a mixture containing appropriately the following components: unreacted components in the intermediate; intermediate The reactants of the components in the body, the components in the acid monoanhydride and the components in the acid dianhydride; the reactants of the components in the intermediate and the components in the acid monoanhydride; the components in the intermediate and the components in the acid dianhydride Of reactants. More specifically, it can be achieved by controlling, for example, the following parameters: the average molecular weight of the epoxy compound (a1), the amount of acid monoanhydride relative to the epoxy compound (a1), and the acid dianhydride relative to the epoxy compound (a1 ) Amount.

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

The acid value of the solid component of the carboxyl group-containing resin (A1) is preferably in the range of 60 mgKOH / g or more and 140 mgKOH / g or less. In this case, the developability of the photosensitive resin composition can be 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; 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 of the acid dianhydride. At this time, a carboxyl group-containing resin (A1) having adjusted acid value and molecular weight can be obtained. That is, by controlling the amount of 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. Furthermore, the molecular weight of the carboxyl group-containing resin (A1) is calculated based on the measurement results obtained by colloidal permeation chromatography (Gel Permeation Chromatography, GPC) under the following conditions. GPC device: manufactured by Showa Denko Co., Ltd., trade name: SHODEX SYSTEM 11; column: 4 series of SHODEX KF-800P, KF-005, KF-003, KF-001 in series; mobile phase: tetrahydrofuran (THF); flow rate: 1ml / Min; column temperature: 45 ° C; detector: refractive index (RI) detector; conversion: polystyrene.

The raw materials of the carboxyl group-containing resin (A1) and the reaction conditions when synthesizing the carboxyl group-containing resin (A1) are explained in detail.

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

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

The unsaturated group-containing carboxylic acid (a2-1) may contain, for example, a compound having only one ethylenically unsaturated group. More specifically, the unsaturated group-containing carboxylic acid (a2-1) can contain, for example, one or more compounds selected from the group consisting of acrylic acid, methacrylic acid, ω-carboxy-polycaprolactone (n ≒ 2) Monoacrylate, crotonic acid, cinnamic acid, succinic acid mono (2-propenyloxyethyl) ester, succinic acid mono (2-methacryloyloxyethyl) ester, phthalic acid Mono (2-propenyloxyethyl) formate, mono (2-methacryloxyethyl) phthalate, mono (2-propenyloxypropyl) phthalate, Phthalic acid mono (2-methacryloxypropyl) ester, maleic acid mono (2-propenyloxyethyl) ester, maleic acid mono (2-methacryloxyethyl) ) Ester, β-carboxyethyl acrylate, tetrahydrophthalic acid mono (2-propenyloxyethyl) ester, tetrahydrophthalic acid mono (2-methacryloxyethyl) ester, Hexahydrophthalic acid mono (2-propenyloxyethyl) ester, and hexahydrophthalic acid mono (2-methacryloxyethyl) ester. The unsaturated group-containing carboxylic acid (a2-1) preferably contains acrylic acid.

The carboxylic acid (a2) may contain a polybasic acid (a2-2). The polyacid (a2-2) is an acid in which two or more hydrogen atoms in one molecule can be substituted with metal atoms. The polyacid (a2-2) preferably has two or more carboxyl groups. At this time, the epoxy compound (a1) can react with both the unsaturated group-containing carboxylic acid (a2-1) and the polybasic acid (a2-2). By crosslinking the epoxy group and the polybasic acid (a2-1) existing in two molecules of the epoxy compound (a1), the molecular weight can be increased. With this, the insulation of the cured product of the photosensitive resin composition can be improved, and the dielectric loss tangent can be reduced.

The polyacid (a2-2) preferably contains a dicarboxylic acid. The polyacid (a2-2) can contain, for example, one or more compounds selected from the group consisting of 4-cyclohexene-1,2-dicarboxylic acid, oxalic acid, malonic acid, succinic acid, and pentane Diacid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, maleic acid, fumaric acid, phthalic acid, isophthalic acid, terephthalic acid. It is preferred that the polyacid (a2-2) contains 4-cyclohexene-1,2-dicarboxylic acid.

When the epoxy compound (a1) and the carboxylic acid (a2) are reacted, a known method can be used. 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, and the mixture is stirred and mixed, thereby obtaining a reactive solution. The intermediate can be obtained by the following method: according to a conventional method, it is more preferable to react the reactive solution at a temperature of 60 ° C or more and 150 ° C or less, particularly preferably at a temperature of 80 ° C or more and 120 ° C or less This reactive solution reacts. The solvent can contain, for example, at least one component selected from the group consisting of: ketones such as methyl ethyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene and xylene; ethyl acetate and butyl acetate , Cellosolve acetate, butyl cellosolve acetate, carbitol acetate, butyl carbitol acetate, diethylene glycol monoethyl ether ether Acetates, propylene glycol monomethyl ether acetate and other acetates; and, dioxane glycol ethers. The thermal polymerization inhibitor contains, for example, at least one of hydroquinone and hydroquinone monomethyl ether. The catalyst can contain, for example, at least one component selected from the group consisting of tertiary amines such as benzyldimethylamine and triethylamine; trimethylbenzyl ammonium chloride, methyl alcohol Quaternary ammonium salts such as triethylammonium chloride; triphenylphosphine; and, triphenyl antimony (triphenyl stibine).

In particular, it is preferred that the catalyst contains triphenylphosphine. That is, it is preferable that the epoxy compound (a1) and the carboxylic acid (a2) be reacted in the presence of triphenylphosphine. At this time, the ring-opening addition reaction of the epoxy group in the epoxy compound (a1) and the carboxylic acid (a2) can be particularly promoted, thereby achieving a reaction rate (conversion rate) of 95% or more, 97% or more, or approximately 100% . In addition, the layer containing the cured product of the photosensitive resin composition can suppress the occurrence of ion migration, thereby improving the insulation of the layer containing the cured product.

When the epoxy compound (a1) and the carboxylic acid (a2) are reacted, the amount of the carboxylic acid (a2) is preferably 0.5 mol or more with respect to 1 mol epoxy group of the epoxy compound (a1) And within 1.2 moles. At this time, excellent sensitivity and stability of the photosensitive resin composition can be obtained. From the same viewpoint, the amount of unsaturated group-containing carboxylic acid (a2-1) is preferably 0.5 mol or more and 1.2 mol or less with respect to 1 mol of epoxy group of epoxy compound (a1) In the range. Alternatively, when the carboxylic acid (a2) contains a carboxylic acid other than the unsaturated group-containing carboxylic acid (a2-1), the unsaturated group-containing carboxylic acid is 1 mole of epoxy based on the epoxy compound (a1) The amount of (a2-1) may be in the range of 0.5 moles or more and 0.95 moles or less. Furthermore, when the carboxylic acid (a2) contains a polybasic acid (a2-2), the amount of the polybasic acid (a2-2) is preferably 0.025 mol with respect to 1 mol epoxy group of the epoxy compound (a1) Within the range of above ear and below 0.25 mole. At this time, excellent sensitivity and stability of the photosensitive resin composition can be obtained.

It is also preferable that the epoxy compound (a1) and the carboxylic acid (a2) be reacted in a state where air is foamed. In this case, it is possible to suppress the addition polymerization reaction of the unsaturated group, thereby suppressing the increase in the molecular weight of the intermediate body and the gelation of the intermediate solution. In addition, excessive coloration of the final product, that is, the carboxyl group-containing resin (A1) can be suppressed.

The intermediate obtained in this way has a hydroxyl group which is generated by the reaction of the epoxy group in the epoxy compound (a1) and the carboxyl group in the carboxylic acid (a2).

The acid anhydride (a3) preferably contains an acid monoanhydride. Acid monoanhydride is a compound with one acid anhydride group.

The acid monoanhydride can contain an anhydride of a dicarboxylic acid. Acid monoanhydride can contain, for example, one or more compounds selected from the group consisting of 1,2,3,6-tetrahydrophthalic anhydride, phthalic anhydride, succinic anhydride, methyl Succinic anhydride, maleic anhydride, citraconic anhydride, glutaric anhydride, itaconic anhydride, methyltetrahydrophthalic anhydride, methyl nadic acid anhydride, hexahydrophthalic anhydride, cyclic Hexane-1,2,4-tricarboxylic acid-1,2-anhydride and methylhexahydrophthalic anhydride. In particular, it is preferred that the acid monoanhydride contains 1,2,3,6-tetrahydrophthalic anhydride. In this case, good developability of the photosensitive resin composition can be ensured, and the insulation of the cured product of the photosensitive resin composition can be improved. Relative to all acid monoanhydrides, 1,2,3,6-tetrahydrophthalic anhydride is preferably in the range of 20 mol% or more and 100 mol% or less, more preferably 40 mol % Or more and 100 mol% or less, but not limited to these ranges.

The acid anhydride (a3) preferably contains an acid dianhydride. Acid dianhydride is a compound with two acid anhydride groups. The acid dianhydride can contain an anhydride of tetracarboxylic acid. The acid dianhydride can contain, for example, at least one compound selected from the group consisting of 1,2,4,5-pyromellitic dianhydride, diphenyl ketone tetracarboxylic dianhydride, methylcyclohexene Tetracarboxylic dianhydride, tetracarboxylic dianhydride, naphthalene-1,4,5,8-tetracarboxylic dianhydride, ethylenetetracarboxylic dianhydride, 9,9'-bis (3,4-dicarboxyphenyl) stilbene dianhydride , Glycerol bis (trimellitic anhydride) monoacetate, ethylene glycol bis (trimellitic anhydride), 3,3 ', 4,4'-diphenylbenzene tetracarboxylic dianhydride, 1, 3,3a, 4,5,9b-hexahydro-5 (tetrahydro-2,5-bi- pendant-3-furanyl) naphtho [1,2-c] furan-1,3-dione, 1,2,3,4-butanetetracarboxylic dianhydride and 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride. The acid dianhydride preferably contains an acid dianhydride having an aromatic ring. In particular, it is preferable that the acid dianhydride contains 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride. In this case, good developability of the photosensitive resin composition can be ensured, and the insulation of the cured product of the photosensitive resin composition can be improved. In addition, the transparency of the photosensitive resin composition can be improved to improve the resolution. Relative to all acid dianhydrides, 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride is preferably in the range of 20 mol% or more and 100 mol% or less, more preferably 40 mol% Ear% or more and 100 mole% or less, but not limited to these ranges.

When the intermediate is reacted with the acid anhydride (a3), a known method can be used. 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, and they are stirred and mixed, thereby obtaining a reactive solution. The carboxyl group-containing resin (A1) can be obtained by the following method: according to a conventional method, it is more preferable to react the reactive solution at a temperature of 60 ° C. or more and 150 ° C. or less, particularly preferably 80 ° C. or more and 120 ° C. The following temperature makes this reactive solution react. As the solvent, catalyst, and polymerization inhibitor, an appropriate solvent, catalyst, and polymerization inhibitor can be used, or the solvent, catalyst, and polymerization inhibitor used when synthesizing the intermediate can be directly used.

In particular, it is preferred that the catalyst contains triphenylphosphine. That is, it is preferable to react the intermediate with the acid anhydride (a3) in the presence of triphenylphosphine. At this time, the reaction between the secondary hydroxyl group in the intermediate and the acid anhydride (a3) can be particularly promoted, and a reaction rate (conversion rate) of 90% or more, 95% or more, 97% or more, or approximately 100% can be achieved. In addition, the layer containing the cured product of the photosensitive resin composition can suppress the occurrence of ion migration, thereby further improving the insulation of the layer containing the cured product.

It is also preferable to react the intermediate with the acid anhydride (a3) in a state where air is bubbling. At this time, it is possible to suppress an excessive increase in the molecular weight of the generated carboxyl group-containing resin (A1), and thereby it is possible to particularly improve the developability of the photosensitive resin composition by the alkaline aqueous solution.

The carboxyl group-containing resin (A) may contain a carboxyl group-containing resin having an aromatic ring and not having photopolymerizability. The carboxyl group-containing resin having an aromatic ring and not having photopolymerizability contains, for example, a polymer of an ethylenically unsaturated monomer including an ethylenically unsaturated compound having a carboxyl group. An ethylenically unsaturated compound with a carboxyl group can contain the following compounds: acrylic acid, methacrylic acid, ω-carboxy-polycaprolactone (n ≒ 2) monoacrylate, 2- (meth) acryloyl phthalate Ethyloxyethyl, 2- (meth) acryloyloxyethyl phthalate 2-hydroxyethyl, etc. The ethylenically unsaturated compound having a carboxyl group can also contain pentaerythritol triacrylate, pentaerythritol trimethacrylate, and the reactant with a dibasic acid anhydride. Ethylene unsaturated monomers, which may further contain a linear or branched aliphatic or alicyclic (wherein a part of the ring may have an unsaturated bond) such as (meth) acrylic esters without ethylenic unsaturation of carboxyl group Compound.

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

The carboxyl group-containing resin (A2) can contain, for example, a compound having a carboxyl group and no photopolymerization (hereinafter referred to as (A2-1) component). The component (A2-1) contains, for example, a polymer of an ethylenically unsaturated monomer including an ethylenically unsaturated compound having a carboxyl group. The ethylenically unsaturated compound having a carboxyl group can contain the following compounds: acrylic acid, methacrylic acid, ω-carboxy-polycaprolactone (n ≒ 2) monoacrylate, and the like. The ethylenically unsaturated compound having a carboxyl group can also contain pentaerythritol triacrylate, pentaerythritol trimethacrylate, and the reactant with a dibasic acid anhydride. The ethylenically unsaturated monomer may further contain the following ethylenically unsaturated compounds having no carboxyl group: 2- (meth) acryloyloxyethyl phthalate, 2- (meth) acrylic phthalate Acetyloxyethyl 2-hydroxyethyl, linear or branched aliphatic or alicyclic (wherein a part of the ring may have an unsaturated bond) (meth) acrylate, etc.

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). In addition, the carboxyl group-containing resin (A2) may contain only the (A2-2) component. The component (A2-2) contains a resin (hereinafter referred to as the first resin (x)), which is, for example, a reactant of an intermediate and a compound (x3), which has two or more rings in one molecule A reactant of an epoxy compound (x1) of an oxygen group and an ethylenically unsaturated compound (x2), the compound (x3) is at least one selected from the group of polycarboxylic acids and their anhydrides. The first resin (x) can, for example, react the epoxy group in the epoxy compound (x1) with the carboxyl group in the ethylenically unsaturated compound (x2), and then add the compound (x3) to the obtained intermediate obtain. The epoxy compound (x1) can contain an appropriate epoxy compound such as a cresol novolac type epoxy compound, a phenol novolac type epoxy compound, a biphenol novolac type epoxy compound. In particular, the epoxy compound (x1) preferably contains at least one compound selected from the group of biphenol novolac-type epoxy compounds and cresol novolac-type epoxy compounds. The epoxy compound (x1) may contain only the biphenol novolac type epoxy compound, or may contain only the cresol novolac type epoxy compound. At this time, since the main chain of the epoxy compound (x1) contains an aromatic ring, it is possible to significantly reduce the degree of corrosion of the cured product of the photosensitive resin composition by an oxidizing agent containing potassium permanganate or the like. The epoxy compound (x1) may contain a polymer of an ethylenically unsaturated compound (z). The ethylenically unsaturated compound (z) contains, for example, a compound having an epoxy group (z1) such as glycidyl (meth) acrylate, or further contains 2- (meth) acryloyloxyethyl phthalate, etc. Compound (z2) without epoxy group. The ethylenically unsaturated compound (x2) preferably contains at least one of acrylic acid and methacrylic acid. The compound (x3) contains, for example, one or more compounds selected from the group consisting of polycarboxylic acids such as phthalic acid, tetrahydrophthalic acid, and methyltetrahydrophthalic acid; and, Anhydrides of these polycarboxylic acids. In particular, the compound (x3) preferably contains at least one polycarboxylic acid selected from the group of phthalic acid, tetrahydrophthalic acid, and methyltetrahydrophthalic acid.

(A2-2) The component may also contain a resin (called a second resin (y)) which is a reactant of a polymer of an ethylenically unsaturated monomer and an ethylenically unsaturated compound having an epoxy group, The ethylenically unsaturated monomer contains an ethylenically unsaturated compound having a carboxyl group. The ethylenically unsaturated monomer may further contain an ethylenically unsaturated compound having no carboxyl group. The second resin (y) can be obtained by reacting an ethylenically unsaturated compound having an epoxy group with a part of carboxyl groups in the polymer. The ethylenically unsaturated monomer may further contain an ethylenically unsaturated compound having no carboxyl group. Ethylene unsaturated compound having a carboxyl group, containing, for example, the following compounds: acrylic acid, methacrylic acid, ω-carboxy-polycaprolactone (n ≒ 2) monoacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, etc. . An ethylenically unsaturated compound that does not have a carboxyl group and contains, for example, the following compounds: 2- (meth) acryloyloxyethyl phthalate, 2- (meth) acryloyloxyethyl phthalate 2 -Hydroxyethyl ester, linear or branched aliphatic or alicyclic (wherein a part of the ring may have an unsaturated bond) (meth) acrylate, etc. The ethylenically unsaturated compound having an epoxy group preferably contains glycidyl (meth) acrylate.

The carboxyl group-containing resin (A) contains only the carboxyl group-containing resin (A1), only the carboxyl group-containing resin (A2), or the carboxyl group-containing resin (A1) and the 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 ), More preferably contains 60% by mass or more, further more preferably contains 100% by mass.

The content of the carboxyl group-containing resin (A) relative to the solid content of the photosensitive resin composition is preferably in the range of 5 mass% or more and 85% by mass or less, more preferably 10 mass% or more and 75 mass% Within the following range, it is still more preferably within a range of 26% by mass or more and 60% by mass or less, and particularly preferably within a range of 30% by mass or more and 45% by mass or less. The solid content refers to the total amount of all components remaining after removing volatile components such as solvents from the photosensitive resin composition.

The acid value of the solid component of the carboxyl group-containing resin (A) is preferably 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 can be particularly improved. It is better if the acid value is in the range of 60 mgKOH / g or more and 140 mgKOH / g or less; if the acid value is in the range of 80 mgKOH / g or more and 135 mgKOH / g or less, the acid value is more than 90 mgKOH / g and It is particularly preferable in the range of 130 mgKOH / g or less.

The unsaturated compound (B) can impart photocurability to the photosensitive resin composition. The unsaturated compound (B) can contain, for example, at least one compound selected from the group consisting of: monofunctional (meth) acrylates such as 2-hydroxyethyl (meth) acrylate; and, diethylenedioxide Alcohol di (meth) acrylate, trimethylolpropane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) Acrylic ester, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, ε-caprolactone modified pentaerythritol hexaacrylate, tricyclodecane dimethanol di (meth) acrylate, etc. Functional (meth) acrylate.

In particular, the unsaturated compound (B) preferably contains a trifunctional compound, that is, a compound having three unsaturated bonds in one molecule. At this time, when the film 4 formed of the photosensitive resin composition is exposed and developed, the resolution can be improved, and the developability of the photosensitive resin composition by the alkaline aqueous solution can be particularly improved. The trifunctional compound can contain, for example, at least one compound selected from the group consisting of trimethylolpropane tri (meth) acrylate, ethylene oxide (EO) modified trimethylolpropane tri (meth Base) acrylate, pentaerythritol tri (meth) acrylate, ethoxylated isocyanurate tri (meth) acrylate, ε-caprolactone modified ginseng (2-propenyloxyethyl) iso Cyanurate, and ethoxylated glycerol tri (meth) acrylate.

The unsaturated compound (B) also preferably contains a phosphorus-containing compound (a phosphorus-containing unsaturated compound). In this case, the flame retardancy of the cured product of the photosensitive resin composition can be improved. The phosphorus-containing unsaturated compound can contain, for example, at least one compound selected from the group consisting of: 2-methacryloyloxyethyl phosphate (as a specific example, a product manufactured by Kyoeisha Chemical Co., Ltd. Models LIGHT ESTER P-1M, and LIGHT ESTER P-2M), 2-propenyloxyethyl phosphate (as a specific example, product model LIGHT ACRYLATE P-1A manufactured by Kyoeisha Chemical Co., Ltd.), diphenyl phosphate Ethyl-2-methacryloyloxyethyl (as a specific example, product model MR-260 manufactured by Daeba Industries Co., Ltd.), and the HFA series manufactured by Showa Polymer Co., Ltd. (as a specific example, dipentaerythritol The addition reactant of hexaacrylate and HCA (9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide) is also the product model HFA-6003 and HFA-6007, caprolactone modification (The addition reaction of high-quality dipentaerythritol hexaacrylate and HCA (9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide) is also the product models HFA-3003 and HFA-6127, etc.) .

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 first polymerizing a monomer having an ethylenically unsaturated bond and then adding an ethylenically unsaturated group ; And, oligomeric (meth) acrylate prepolymers. The oligomeric (meth) acrylate prepolymers can contain, for example, at least one component selected from the group consisting of epoxy (meth) acrylate, polyester (meth) acrylate, Aminoester (meth) acrylate, alkyd resin (meth) acrylate, silicone resin (meth) acrylate, and spirale resin (meth) acrylate.

The photopolymerization initiator (C) contains, for example, an acrylphosphine oxide-based photopolymerization initiator. That is, the photosensitive resin composition contains, for example, an acyl phosphine oxide-based photopolymerization initiator. At this time, when the photosensitive resin composition is exposed to ultraviolet rays, high sensitivity can be imparted to the photosensitive resin composition. In addition, the layer containing the cured product of the photosensitive resin composition can suppress the occurrence of ion migration, thereby further improving the insulation reliability of the layer.

In addition, the acylphosphine oxide-based photopolymerization initiator is not likely to hinder the electrical insulation of the cured product. Therefore, by exposure-curing the photosensitive resin composition, a cured product excellent in electrical insulation can be obtained, and this cured product is suitable as the interlayer insulating layer 7.

The acylphosphine oxide-based photopolymerization initiator can contain, for example, at least one component selected from the group consisting of 2,4,6-trimethylbenzyl-diphenyl-phosphine oxide, 2,4,6-Trimethylbenzyl-phenyl-phosphonic acid ethyl ester and other mono-acylphosphine oxide-based photopolymerization initiators; and, bis- (2,6-dichlorobenzyl) Phenylphosphine oxide, bis- (2,6-dichlorobenzyl) -2,5-dimethylphenylphosphine oxide, bis- (2,6-dichlorobenzyl) -4-propane Phenyl phosphine oxide, bis- (2,6-dichlorobenzyl) -1-naphthylphosphine oxide, bis- (2,6-dimethoxybenzyl) phenylphosphine oxide, bis -(2,6-dimethoxybenzyl) -2,4,4-trimethylpentylphosphine oxide, bis- (2,6-dimethoxybenzyl) -2,5 -Dimethylphenylphosphine oxide, bis- (2,4,6-trimethylbenzyl) phenylphosphine oxide, (2,5,6-trimethylbenzyl) -2,4 , 4-trimethylpentyl phosphine oxide and other bis acetyl phosphine oxide photopolymerization initiator. In particular, it is preferable that the acyl phosphine oxide-based photopolymerization initiator contains 2,4,6-trimethylbenzyl-diphenyl-phosphine oxide, and it is also preferable that the acyl phosphine oxide-based photopolymerization initiator The agent contains only 2,4,6-trimethylbenzyl-diphenyl-phosphine oxide.

The photopolymerization initiator (C) preferably contains a hydroxy ketone-based photopolymerization initiator in addition to an acyl phosphine oxide-based photopolymerization initiator. That is, the photosensitive resin composition preferably contains a hydroxyketone-based photopolymerization initiator. In this case, the photosensitive resin composition can be provided with higher sensitivity than when the hydroxyketone-based photopolymerization initiator is not contained. By this, when the coating film formed of the photosensitive resin composition is irradiated with ultraviolet rays to harden it, the coating film can be sufficiently cured from the surface to the deep part. Examples of the hydroxyketone-based photopolymerization initiator include 1-hydroxy-cyclohexyl-phenyl-ketone, methyl phenylglyoxylate, 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 to the hydroxyketone-based photopolymerization initiator is preferably in the range of 1: 0.01 to 1:10. In this case, the curability near the surface of the coating film formed of the photosensitive resin composition and the curability in the deep portion can be improved in a balanced manner. Here, since the photosensitive resin composition contains the organic filler (E), the organic filler (E) may cause light scattering in the photosensitive resin composition during exposure. At this time, a problem may arise that the photosensitive resin composition cannot obtain good developability. From such a viewpoint, in order to improve the resolution and obtain good developability by the photosensitive resin composition, the mass ratio of the acetylphosphine oxide-based photopolymerization initiator to the hydroxyketone-based photopolymerization initiator is particularly preferably Within the range of 1: 0.01 to 1: 1.

The photopolymerization initiator (C) also preferably contains a photopolymerization initiator having a diphenyl ketone skeleton. That is, it is also preferable that the photosensitive resin composition contains an acyl phosphine oxide-based photopolymerization initiator and a photopolymerization initiator having a diphenyl ketone skeleton, or the photosensitive resin composition contains an acyl phosphine oxide-based system A photopolymerization initiator, a hydroxyketone photopolymerization initiator and a photopolymerization initiator having a diphenyl ketone skeleton. At this time, when the coating film formed of the photosensitive resin composition is partially exposed and then developed, the hardening of the unexposed portion is suppressed, so the resolution becomes particularly high. Therefore, it is possible to form a very fine pattern of the cured product of the photosensitive resin composition. In particular, when the interlayer insulating layer 7 of the multilayer printed wiring board 20 is made of a photosensitive resin composition, and a small diameter hole 6 for the through hole 10 is provided in the interlayer insulating layer 7 by photolithography At this time (refer to FIGS. 1C and 1D), the hole 6 with a small diameter can be formed precisely and easily. Examples of the photopolymerization initiator having a diphenyl ketone skeleton include bis (diethylamino) diphenyl ketone.

The amount of the photopolymerization initiator having a diphenyl ketone skeleton relative to the acetylphosphine oxide-based photopolymerization initiator is preferably within a range of 0.5% by mass or more and 20% by mass or less. If the amount of the photopolymerization initiator having a diphenyl ketone skeleton is 0.5% by mass or more with respect to the acetylphosphine oxide-based photopolymerization initiator, the resolution becomes particularly high. In addition, if the amount of the photopolymerization initiator having a diphenyl ketone skeleton is 20% by mass or less relative to the acetylphosphine oxide-based photopolymerization initiator, the photopolymerization initiator having a diphenyl ketone skeleton It is less likely to hinder the electrical insulation of the cured product of the photosensitive resin composition. From the same viewpoint, the amount of bis (diethylamino) diphenyl ketone is preferably in the range of 0.5% by mass or more and 20% by mass or less with respect to the acetylphosphine oxide-based photopolymerization initiator. Inside. Here, since the photosensitive resin composition contains the organic filler (E), the organic filler (E) may cause light scattering in the photosensitive resin composition during exposure. At this time, a problem may arise that the photosensitive resin composition cannot obtain good developability. From such a viewpoint, in order to obtain good developability with the photosensitive resin composition, the amount of the photopolymerization initiator having a diphenyl ketone skeleton relative to the acetylphosphine oxide-based photopolymerization initiator is particularly preferable. It is within the range of 1% by mass or more and 18% by mass or less. From the same point of view, the amount of bis (diethylamino) diphenyl ketone is particularly preferably in the range of 1% by mass or more and 18% by mass relative to the acetylphosphine oxide-based photopolymerization initiator Inside.

The photopolymerization initiator (C) is not limited to the above-mentioned preferred examples, and can 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. The photosensitive resin composition can contain, for example, at least one component selected from the group consisting of benzoin and its alkyl ethers; acetophenone, acetophenone and other acetophenones; 2 -Anthraquinones such as methylanthraquinone; 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diisopropyl thioxanthone and other thioxanthones; thioxanthone; diphenyl ketone, 4-benzoyl-4'-methyldiphenyl sulfide and other diphenyl ketones; 2 , 4-diisopropyldibenzopiperone and other dibenzopiperones (xanthone); and, 2-hydroxy-2-methyl-1-phenyl-propan-1-one and other α-hydroxyl Ketones; 2-methyl-1- [4- (methylthio) phenyl] -2- (N-morpholinyl) -1-acetone and other compounds containing nitrogen atoms. The photosensitive resin composition, in addition to the photopolymerization initiator (C), may also contain ethyl p-dimethylbenzoate, isoamyl p-dimethylaminobenzoate, 2-dimethylamine benzoate Known photopolymerization accelerators or sensitizers such as tertiary amines such as ethyl ethyl ester. 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 as needed. The photosensitive resin composition, in addition to the photopolymerization initiator (C), may also contain a sensitizer used in the laser exposure method, that is, 7-diethylamino-4-methyl coumarin, etc. Bean derivatives, carbocyanine pigments, xanthene pigments, etc.

The epoxy compound (D) can impart thermosetting properties to the photosensitive resin composition. The epoxy compound (D) preferably has at least 2 epoxy groups in one molecule. The epoxy compound (D) may be a solvent-insoluble epoxy compound or a general-purpose solvent-soluble epoxy compound. The epoxy compound (D) preferably contains, for example, one or more components selected from the group consisting of: phenol novolac-type epoxy resin (as a specific example, the product model EPICLON N manufactured by DIC Corporation) -775), cresol novolac epoxy resin (as a specific example, product model EPICLON N-695 manufactured by DIC Corporation), bisphenol A novolac epoxy resin (as a specific example, manufactured by DIC Corporation) Product model EPICLON N-865), bisphenol A epoxy resin (as a specific example, product model jER1001 manufactured by Mitsubishi Chemical Corporation), bisphenol F epoxy resin (as a specific example, Mitsubishi Chemical Corporation) Manufactured product model number jER4004P), bisphenol S type epoxy resin (as a specific example, product model EPICLON EXA-1514 manufactured by DIC Corporation), bisphenol AD type epoxy resin, biphenyl type epoxy resin (as specific For example, Mitsubishi Chemical Corporation's product model YX4000), biphenol novolac-type epoxy resin (as a specific example, Nippon Pharmaceutical Co., Ltd. product model NC-3000), hydrogenated double Type A epoxy resin (as a specific example, product model ST-4000D manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd.), naphthalene type epoxy resin (as a specific example, product model EPICLON HP-4032 made by DIC Corporation, EPICLON HP-4700, EPICLON HP-4770), hydroquinone type epoxy resin (as a specific example, product model YDC-1312 manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd.), tertiary butyl catechol type epoxy resin Resin (as a specific example, product model EPICLON HP-820 manufactured by DIC Corporation), dicyclopentadiene type epoxy resin (as a specific example, product model EPICLON HP-7200 manufactured by DIC Corporation), adamantane type Epoxy resin (as a specific example, product model ADAMANTATE XE-201 manufactured by Idemitsu Kosei Co., Ltd.), bisphenol-type epoxy resin (as a specific example, product model YSLV-80XY manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd.) ), Biphenyl ether type epoxy resin (as a specific example, product model YSLV-80DE manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd.), and (hydroxyphenyl) ethane type crystalline epoxy resin (as a specific example ,Japan Product model GTR-1800 manufactured by Chemical Pharmaceutical Co., Ltd., epoxy resin with bisphenol fusi skeleton (as a specific example, epoxy resin with structure (S7)), rubber-like core-shell polymer modified bisphenol A Type epoxy resin (as a specific example, product model MX-156 manufactured by Zhonghua Co., Ltd.), rubber-like core-shell polymer modified bisphenol F type epoxy resin (as a specific example, manufactured by Zhonghua Co., Ltd. Product model MX-136), and special difunctional epoxy resin (as specific examples, product models YL7175-500 and YL7175-1000 manufactured by Mitsubishi Chemical Corporation; product model EPICLON TSR-960 manufactured by DIC Corporation) , EPICLON TER-601, EPICLON TSR-250-80BX, EPICLON 1650-75MPX, EPICLON EXA-4850, EPICLON EXA-4816, EPICLON EXA-4822, and EPICLON EXA-9726; products manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd. Model YSLV-120TE).

The epoxy compound (D) preferably contains a crystalline epoxy resin. In this case, the developability of the photosensitive resin composition can be improved. In addition, crystalline epoxy resin means the epoxy resin which has a melting point. The crystalline epoxy resin can contain, for example, at least one component selected from the group consisting of triglycidyl isocyanurate (1,3,5-ginseng (2,3-epoxypropyl ) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione), hydroquinone type crystalline epoxy resin (as a specific example, manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd.) Product name YDC-1312), biphenyl type crystalline epoxy resin (as a specific example, product model YX4000 manufactured by Mitsubishi Chemical Corporation), diphenyl ether type crystalline epoxy resin (as a specific example, Xinri Product model YSLV-80DE manufactured by Tetsumi Gold Chemical Co., Ltd., bisphenol-type crystalline epoxy resin (as a specific example, product name YSLV-80XY manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.), hydroxyphenyl (hydroxyphenyl) ) Ethane-type crystalline epoxy resin (as a specific example, the product model GTR-1800 manufactured by Nippon Kayaku Co., Ltd.), bisphenol stilbene-type crystalline epoxy resin (as a specific example, having a ring of structure (S7) Oxygen resin).

The amount of the crystalline epoxy resin relative to 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 It is even more preferably in the range of 35% by mass or more and 100% by mass or less. In this case, in the step until the photosensitive resin composition is thermally cured, the thermal curing reaction of the carboxyl group-containing resin and the epoxy resin can be suppressed, and the developability can be improved.

In particular, the crystalline epoxy resin preferably contains a crystalline epoxy resin having a melting point of 110 ° C or lower. That is, the epoxy compound (D) preferably contains a crystalline epoxy resin having a melting point of 110 ° C or lower. In this case, the developability of the photosensitive resin composition by the alkaline aqueous solution can be particularly improved. The crystalline epoxy resin having a melting point of 110 ° C. or lower can contain, for example, at least one component selected from the group consisting of: biphenyl type epoxy resin (as a specific example, a product model manufactured by Mitsubishi Chemical Corporation) YX4000), biphenyl ether type epoxy resin (as a specific example, product model YSLV-80DE manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd.), and bisphenol type epoxy resin (as a specific example, Nippon Steel & Sumitomo Chemical Product model YSLV-80XY manufactured by a joint stock company).

The epoxy compound (D) may contain triglycidyl isocyanurate. In particular, the triglycidyl isocyanurate is preferably a β-body having a structure in which three epoxy groups are bonded in the same direction with respect to the skeleton surface of the s-triazine ring; or , Preferably: a mixture of the β body and the α body, the α body has one epoxy group bonded to the s-triazine ring skeleton plane in a direction different from the other two epoxy groups structure.

The crystalline epoxy resin also preferably contains a crystalline epoxy resin having a melting point of less than 100 ° C. That is, the epoxy compound (D) preferably 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 has high compatibility with components other than the epoxy resin (D) or the solvent in the photosensitive resin composition, so it is easily dispersed in the photosensitive resin composition Medium and uniform. Furthermore, if 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, it is possible to impart high storage stability to the photosensitive resin composition. Furthermore, the crosslinking reaction between the carboxyl group and the epoxy group in the photosensitive resin composition can be suppressed at a low temperature, so that the good developability of the photosensitive resin composition can be maintained, and the photosensitive resin composition can be given high storage stability .

A crystalline epoxy resin with a melting point of less than 100 ° C can contain, for example, at least one component selected from the group consisting of: biphenyl ether type epoxy resin (as a specific example, Nippon Steel & Sumitomo Chemical Co., Ltd. Product model YSLV-80DE manufactured by the company, bisphenol-type epoxy resin (as a specific example, product model YSLV-80XY manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd.), and epoxy resin with bisphenol fusel skeleton (as Specific example, epoxy resin with structure (S7)).

When the epoxy compound (D) contains a crystalline epoxy resin having a melting point of less than 100 ° C, the crystalline epoxy resin having a melting point of less than 100 ° C contains 1 equivalent of carboxyl groups contained in the carboxyl group-containing resin (A). The equivalent of the epoxy group of is preferably in the range of 0.2 or more and 2.0 or less, more preferably in the range of 0.25 or more and 1.7 or less, and even more preferably in the range of 0.3 or more and 1.5 or less.

Epoxy compound (D) may contain phosphorus-containing epoxy resin. In this case, the flame retardancy of the cured product of the photosensitive resin composition can be improved. Phosphorus-containing epoxy resin, such as phosphoric acid-modified bisphenol F-type epoxy resin (as specific examples, the product models EPICRON EXA-9726 and EPICRON EXA-9710 manufactured by DIC Corporation), Nippon Steel & Sumitomo Chemical Co., Ltd. Product model Epotohto FX-305 manufactured by the company.

The photosensitive resin composition preferably further contains an organic filler (E). At this time, the adhesion between the interlayer insulating layer 7 and the conductor layer 8 can be further improved. The organic filler (E) can also improve the shakeability of the photosensitive resin composition and improve stability (especially storage stability).

The organic filler (E) preferably has a polar group. In this case, the adhesion between the interlayer insulating layer 7 and the conductor layer 8 can be particularly improved. In particular, the polar group preferably contains at least one group selected from the group consisting of carboxyl group, amine group and hydroxyl group. In this case, the adhesion can be particularly improved.

Especially when the polar group contains a carboxyl group, the developability of the cured product of the photosensitive resin composition can be improved, and when the photosensitive resin composition contains a crystalline epoxy compound, the crystalline epoxy compound can be improved in the photosensitive resin Solubility in the composition and prevent crystallization.

In particular, when the polar group contains a hydroxyl group, the dispersibility of the organic filler (E) in the photosensitive resin composition can be improved.

In particular, when the polar group contains an amine group, the reactivity of the carboxyl group-containing resin (A) and the epoxy compound (D) can be improved, thereby improving the acid resistance and alkali resistance of the cured film.

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. If the acid value is less than 1 mgKOH / g, the stability of the photosensitive resin composition and the developability of the cured product may decrease. If the acid value is greater than 60 mgKOH / g, the moisture resistance reliability of the hardened product may decrease. The acid value of the organic filler (E) is more preferably 3 mgKOH / g or more, and still more preferably 40 mgKOH / g or less.

When the polar group contains a carboxyl group, the organic filler (E) can be obtained by, for example, making acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, etc., polymerizable unsaturated Carboxylic acid monomers with double bonds undergo polymerization or crosslinking.

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

The organic filler (E) preferably contains a rubber component having a polar group. At this time, the polar group includes, for example, a carboxyl group, or includes 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 can be composed of resin. The rubber component preferably contains at least one polymer selected from the group consisting of: cross-linked acrylic rubber, cross-linked butadiene-acrylonitrile rubber (cross-linked NBR), cross-linked methacrylic acid Ester-butadiene-styrene (crosslinked MBS) and crosslinked styrene-butadiene rubber (crosslinked SBR). At this time, the photosensitive resin composition can have high transparency and can improve the 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 nitrile rubber. MBS is a copolymer composed of three components of methyl methacrylate, butadiene and styrene, and is classified as butadiene rubber. SBR is a copolymer of styrene and butadiene, and is classified as styrene rubber.

Specific examples of the organic filler (E) provided as a dispersion liquid include: JSR Co., Ltd. product model XER-91-MEK (crosslinked rubber (NBR) with an average primary particle diameter of 0.07 μm and a carboxyl group) Methyl ethyl ketone dispersion with a concentration of 15% by weight, acid value is 10.0 mgKOH / g), product models XER-32-MEK and XER-92 manufactured by JSR Corporation, and product model XSK manufactured by JSR Corporation -500 (dispersion of crosslinked rubber (SBR) with carboxyl and hydroxyl groups).

The organic filler (E) may contain components other than rubber components. The components other than the rubber component can 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 can 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 the commercial model FS-201 (average primary particle size 0.5 μm) manufactured by Nippon Paint Industrial Coatings Co., Ltd. Specific examples of the cross-linked styrene / acrylic resin fine particles include: product model MG-351 (average primary particle diameter 1.0 μm) manufactured by Nippon Paint Industrial Coatings Co., Ltd., and product model BGK-001 (average primary particle) The particle size is 1.0 μm).

When the polar group contains an amine group, the organic filler (E) contains, for example, at least one component selected from the group consisting of melamine, dicyandiamide, imidazole-based compounds, methylguanamine, benzene Guanidine, melamine-phenol-formaldehyde resin; triazine compound, ethyldiamino-s-triazine, 2,4-diamino-s-triazine, 2,4-diamino-6-xylene Tris derivatives such as s-triazine; thiazole compounds; and, triazole compounds. When the polar group contains an amine group, the organic filler (E) preferably contains melamine particles. If the organic filler (E) contains melamine particles, the adhesion between the interlayer insulating layer 7 and the conductor layer 8 can be particularly improved.

The organic filler (E) can contain at least one component selected from the group consisting of the components described above. In addition, the organic filler (E) can also contain a component having a polar group other than the components described above.

The average primary particle size of the organic filler (E) is preferably 1 μm or less. In this case, the shakeability of the photosensitive resin composition can be improved efficiently. Therefore, the stability of the photosensitive resin composition can be further improved. The average primary particle size of the organic filler (E) is, for example, 0.001 μm or more. The average primary particle size of the organic filler (E) is the median particle size (D50) measured by a laser diffraction particle size distribution measuring device. The average primary particle size of the organic filler (E) is preferably 0.1 μm or less. In this case, the stability of the photosensitive resin composition can be further improved, and scattering during exposure can be suppressed, so the resolution can be further improved.

The particle size of the organic filler (E) in the photosensitive resin composition is preferably 10 μm or less. In the photosensitive resin composition, the organic filler (E) may contain secondary particles formed by aggregation. At this time, the particle size of the organic filler (E) in the photosensitive resin composition means the particle size 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 particle size distribution measuring device or an optical microscope. If the particle size of the organic filler (E) in the photosensitive resin composition is 10 μm or less, the organic filler (E) can be well dispersed in the photosensitive resin composition and the interlayer insulating layer 7, whereby the interlayer can be particularly improved Adhesion between the insulating layer 7 and the conductor layer 8. In addition, the stability of the photosensitive resin composition can be further improved, and scattering during exposure can be suppressed, so the resolution can be further improved. The particle size of the organic filler (E) in the photosensitive resin composition is more preferably 5 μm or less, still more preferably 1 μm or less, and particularly preferably 0.5 μm or less. In addition, the particle size is, for example, 0.01 μm or more.

The photosensitive resin composition may contain an organic solvent. The organic solvent is used for the following purposes: liquidification or varnishing of the photosensitive resin composition, adjustment of viscosity, adjustment of coating properties, adjustment of film-forming properties, and the like.

The organic solvent can contain, for example, at least one compound selected from the group consisting of ethanol, propanol, isopropanol, hexanol, ethylene glycol, and other straight-chain, branched-chain, secondary, or polyhydric alcohols; Ketones such as methyl ethyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene and xylene; Swasol series (manufactured by Maruzen Petrochemical Company), Solvesso series (manufactured by ExxonMobil Chemical Company), etc. Petroleum-based aromatic mixed solvents; celluloids such as celluloid and butyl cellulose; carbitols such as carbitol and butyl carbitol; propylene glycol alkyl ethers such as propylene glycol methyl ether; two Polypropylene glycol alkyl ethers such as propylene glycol methyl ether; acetates such as ethyl acetate, butyl acetate, cellulose acetate, and carbitol acetate; and, dioxane glycol ethers.

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

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

The amount of the photopolymerization initiator (C) relative to the carboxyl group-containing resin (A) is preferably in the range of 0.1% by mass or more and 30% by mass or less, and if it is in the range of 1% by mass or more and 25% by mass or less Inside is even better.

Regarding the amount of the epoxy compound (D), it is preferable that the total amount of equivalents of epoxy groups contained in the epoxy compound (D) is 0.7 or more with respect to 1 equivalent of carboxyl groups contained in the carboxyl group-containing resin (A). The range of 2.5 or less is more preferably 0.7 or more and 2.3 or less, and if it is 0.7 or more and 2.0 or less, it is even more preferably. In addition, it is preferable that the total amount of equivalents of epoxy groups contained in the crystalline epoxy resin is in the range of 0.1 or more and 2.0 or less, and if 0.2 It is more preferably within the range of above and below 1.9, and further more preferably within the range of above 0.3 and below 1.5. Alternatively, the total amount of equivalents of 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 carboxyl groups contained in the carboxyl group-containing resin (A).

The amount of the organic filler (E) relative to 100 parts by mass of the carboxyl group-containing resin (A) is preferably within a range of 1 part by mass or more and 50 parts by mass or less. 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 becomes particularly high, and a good copper plating density of the cured product of the photosensitive resin composition can be obtained Togetherness. In addition, when the amount of the organic filler (E) is 50 parts by mass or less, excellent resolution of the photosensitive resin composition can be obtained. In addition, by setting the content of the organic filler (E) within the above range, the shakeability of the photosensitive resin composition can be improved and the stability can be 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. In addition, the amount of the organic filler (E) is more preferably 30 parts by mass or less, and even more preferably 20 parts by mass or less.

When the photosensitive resin composition contains an organic solvent, the amount of the organic solvent is preferably such that when the coating film formed of the photosensitive resin composition is dried, the organic solvent can quickly volatilize and disappear, that is Adjust so that the organic solvent does not remain in the dried film. In particular, the amount of the organic solvent is preferably in the range of 0% by mass or more and 99.5% by mass or less with respect to the entire photosensitive resin composition, and even more in the range of 15% by mass or more and 60% by mass or less. good. In addition, the suitable ratio of the organic solvent differs depending on the coating method and the like. Therefore, it is preferable to adjust the ratio appropriately according to the coating method.

The solid content refers to the total amount of all components remaining after removing volatile components such as solvents from the photosensitive resin composition.

The photosensitive resin composition may further contain components other than the above components as long as the effect of the present embodiment is not hindered.

The photosensitive resin composition may contain an inorganic filler. In this case, it is possible to reduce the curing shrinkage of the film formed of the photosensitive resin composition. The inorganic filler can contain, for example, one or more materials selected from the group consisting of: barium sulfate, crystalline silica, nano silica, carbon nanotube, talc, bentonite, Hydrotalcite, aluminum hydroxide, magnesium hydroxide, and titanium dioxide. When the inorganic filler contains white materials such as titanium dioxide and zinc oxide, the photosensitive resin composition and its hardened product can be whitened by the aforementioned white materials. When the photosensitive resin composition contains an inorganic filler, the amount of the inorganic filler relative to the carboxyl group-containing resin (A) is preferably in the range of more than 0% by mass and 300% by mass or less.

The photosensitive resin composition may contain at least one resin selected from the group consisting of toluene diisocyanate and morpholine diisocyanate which are blocked with caprolactam, oxime, malonate, etc. , Isophorone diisocyanate and hexamethylene diisocyanate blocked isocyanate; melamine resin, n-butylated melamine resin, isobutylated melamine resin, butylated urea resin, butylated melamine urea co-condensation resin, Amino-based resins such as benzoguanamine co-condensation resins; various thermosetting resins other than the foregoing; ultraviolet-curable epoxy (meth) acrylates; p-bisphenol A type, phenol novolak type, cresol Resins obtained by adding (meth) acrylic acid to epoxy resins such as novolac type and alicyclic type; and, diallyl phthalate resin, phenoxy resin, urethane resin, fluorine resin, etc. Polymer compound.

The photosensitive resin composition may contain a curing agent for curing the epoxy compound (D). The hardener can contain, for example, at least one component selected from the group consisting of imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenyl Imidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, 1- (2-cyanoethyl) -2-ethyl-4-methylimidazole and other imidazole derivatives; dicyandiamide, benzene Methyldimethylamine, 4- (dimethylamino) -N, N-dimethylbenzylamine, 4-methoxy-N, N-dimethylbenzylamine, 4-methyl -N, N-dimethylbenzylamine and other amine compounds; hexamethylene dihydrazine, deca dihydrazide and other hydrazine compounds; triphenylphosphine and other phosphorus compounds; acid anhydride; phenol; thiol; Lewis acid amine complex Thing; and, onium salt. Commercial products of these components are, for example: 2MZ-A, 2MZ-OK, 2PHZ, 2P4BHZ, 2P4MHZ (all are trade names of imidazole compounds) manufactured by Shikoku Chemicals Co., Ltd .; manufactured by San-Apro Co., Ltd. U-CAT3503N, U-CAT3502T (all are the trade names of blocked isocyanate compounds of dimethylamine); DBU, DBN, U-CATSA102, U-CAT5002 (all are bicyclic amidine compounds and their salts).

The photosensitive resin composition may contain an adhesion-imparting agent. Examples of the adhesion-imparting agent include the following s-triazine derivatives: guanamine, methylguanamine, benzoguanamine, and 2,4-diamino-6-methacryloyloxyethyl -s-triazine, 2-vinyl-4,6-diamino-s-triazine, 2-vinyl-4,6-diamino-s-triazine / isocyanuric acid adduct , 2,4-Diamino-6-methacryloyloxyethyl-s-triazine / isocyanuric acid adducts, etc.

The photosensitive resin composition may contain a rheology modifier. With the rheology modifier, the viscosity of the photosensitive resin composition can be easily optimized. Examples of rheology modifiers include urea-modified mid-polar polyamide (product models BYK-430, BYK-431 manufactured by BYK Japan Co., Ltd.) and polyhydroxycarboxamide (manufactured by BYK Japan Co., Ltd.). Product model BYK-405), modified urea (product models BYK-410, BYK-411, BYK-420 made by BYK Japan Co., Ltd.), polymer urea derivatives (product model BYK-made by BYK Japan Co., Ltd.) 415), urea-modified amine ester (product model BYK-425 manufactured by BYK Japan Co., Ltd.), polyurethane ester (product model BYK-428 manufactured by BYK Japan Co., Ltd.), castor oil wax, polyethylene wax, polyamide Wax, bentonite, silica, silica gel, kaolin, clay.

The photosensitive resin composition may contain at least one component selected from the group consisting of: hardening accelerator; colorant; copolymer of polysiloxane, acrylate, etc .; leveling agent; silane Adhesiveness-imparting agents such as coupling agents; thixotropic agents; polymerization inhibitors; antihalation agents; flame retardants; defoamers; antioxidants; surfactants; and, polymer dispersants.

The photosensitive resin composition is, for example, liquid. When the photosensitive resin composition is liquid, the photosensitive resin composition can be prepared by, for example, blending the raw materials of the photosensitive resin composition as described above, and using, for example, a three-roll mill (three) -kneading by a well-known kneading method such as roll mill, ball mill, sand mill, etc. When the raw material of the photosensitive resin composition contains a liquid component, a component with a low viscosity, etc., the photosensitive resin composition can be prepared in the following manner: first, except for the liquid component and the component with a low viscosity, The other parts are kneaded, and then liquid components, components with low viscosity, etc. are added to the obtained mixture and mixed. Also, for example, when all the raw materials have been dispersed in the solvent, the photosensitive resin composition can be prepared by mixing the raw materials and stirring them without kneading.

In consideration of storage stability and the like, a first agent may be prepared by mixing a part of the components of the photosensitive resin composition, and a second agent may be prepared by mixing the remaining components. That is, the photosensitive resin composition may include the first agent and the second agent. At this time, for example, the first agent may be prepared by mixing and dispersing the unsaturated compound (B), a part of the organic solvent, and the thermosetting component in the components of the photosensitive resin composition in advance, and then by The remaining components of the resin composition are mixed and dispersed to prepare a second agent. At this time, a required amount of the first agent and the second agent are mixed in a timely manner to prepare a mixed liquid, and the mixed liquid is hardened to obtain a hardened product.

The photosensitive resin composition may be a dry film. The dry film can be produced, for example, by applying the same liquid composition as the above-mentioned liquid photosensitive resin composition to a suitable support made of polyester or the like, and then drying. Thereby, a laminate (dry film with a support) can be obtained, which includes a dry film and a support for supporting the dry film.

The photosensitive resin composition preferably has the property that even the film 4 with a thickness of 25 μm can be developed with an aqueous sodium carbonate solution. At this time, it is possible to produce a sufficiently thick interlayer insulating layer 7 from the photosensitive resin composition by photolithography. Of course, the interlayer insulating layer 7 having a thickness thinner than 25 μm can also be produced from the photosensitive resin composition.

It can be confirmed by the following method whether the film 4 having a thickness of 25 μm can be developed with a sodium carbonate aqueous solution. By coating a photosensitive resin composition on an appropriate substrate to form a wet coating film, the wet coating film is heated at 80 ° C. for 40 minutes, thereby forming a film 4 having a thickness of 25 μm. In a state where the negative mask is directly attached to the film 4, the film 4 is irradiated with ultraviolet light at a condition of 500 mJ / cm ² to perform exposure, and the negative mask has a penetrating portion through which ultraviolet rays penetrate , And a shielding part for shielding ultraviolet rays. After the exposure, the following treatment is carried out: first, spray a 30% 1% sodium carbonate (Na ₂ CO ₃ ) aqueous solution to the film 4 with a spray pressure of 0.2 MPa for 90 seconds, and then spray pure water with a spray pressure of 0.2 MPa for 90 seconds . After the treatment, the film 4 was observed. As a result, when the portion of the film 4 corresponding to the shielding portion was removed and no residue could be confirmed, it can be judged that the film 4 having a thickness of 25 μm can be developed with a sodium carbonate aqueous solution.

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

In this method, the cured film 11 is produced by disposing the photosensitive resin composition on the printed wiring board 1 and photo-curing the photosensitive resin composition. Next, the cured film 11 is first treated with an alkaline solution, and then 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 has, for example, at least an insulating layer 2 and a conductor line 3 on which the conductor line 3 is located.

As shown in FIG. 1B, the photosensitive resin composition is arranged on the printed wiring board 1 so as to cover the conductor wiring 3, thereby producing the coating film 4.

When the film 4 is produced, when the photosensitive resin composition is liquid, for example, the photosensitive resin composition is applied to the printed wiring board 1 to form a wet film. The coating method of the photosensitive resin composition is a well-known method, for example, a dipping method, a spray method, a spin coating method, a roll coating method, a curtain coating method, or a screen printing method. Next, in order to volatilize the organic solvent in the photosensitive resin composition, for example, the wet coating film is dried at a temperature in the range of 60 ° C or more and 120 ° C or less. With this, the film 4 can be produced.

When the film 4 is produced, when the photosensitive resin composition is a dry film, for example, the dry film is laminated on the printed wiring board 1 while being supported by a support. In this state, pressure is applied to the dry film and the printed wiring board 1, and then the support is peeled from the dry film, thereby transferring the dry film from the support to the printed wiring board 1. By this, the film 4 made of a dry film is provided on the printed wiring board 1.

Then, the film 4 is photocured to produce a cured film 11. For this reason, for example, as shown in FIG. 1C, the film 4 is partially cured by exposing the film 4. For this purpose, for example, the negative mask is attached to the film 4 first, and then the film 4 is irradiated with ultraviolet rays. The negative mask includes a penetration portion that penetrates ultraviolet rays and a shielding portion that shields ultraviolet rays, and the shielding portion is provided at a position that matches the position of the through hole 10. The negative mask is, for example, a photo tool such as a mask film or a dry plate. The ultraviolet light source can be selected from the group consisting of, for example, chemical lamps, low-pressure mercury lamps, medium-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, xenon lamps, metal halogen lamps, and light-emitting diodes (LEDs) ), G-line (436nm), h-line (405nm), i-line (365nm); and a combination of two or more of g-line, h-line and i-line.

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

When the photosensitive resin composition is a dry film, the dry film of the laminate can be laminated on the printed wiring board 1, and then the dry film can be formed through the support without peeling off the support. The film 4 is irradiated with ultraviolet rays, thereby exposing the film 4 and then peeling off the support from the film 4 before the development process.

Furthermore, in the case where the through-hole 10 is not provided in the multilayer printed wiring board 20, the entire film 4 may be photocured to produce the cured film 11 instead of partially photocuring the film 4.

Then, the cured film 11 is treated with an alkaline solution. When the cured film 11 is subjected to a heat treatment before the conductor layer 8 is formed, it is preferable to treat the cured film 11 with an alkaline solution before the heat treatment.

The alkaline solution is, for example, an alkaline aqueous solution containing either or both of an alkali metal salt and an alkali metal hydroxide. The alkaline aqueous solution, more specifically, contains, for example, at least one component selected from the group consisting of: sodium carbonate, potassium carbonate, ammonium carbonate, sodium bicarbonate, potassium bicarbonate, ammonium bicarbonate, sodium hydroxide , Potassium hydroxide, ammonium hydroxide, tetramethylammonium hydroxide, and lithium hydroxide. The solvent in the alkaline aqueous solution may be only water, or may be a mixture of hydrophilic organic solvents such as water and lower alcohols. The pH of the alkaline solution is preferably 8.5 or more and 14 or less. The pH value of the alkaline solution is more preferably 9 or more, even more preferably 9.5 or more, and particularly preferably 10 or more. In addition, the pH value of the alkaline aqueous solution is more preferably 13.5 or less, more preferably 13 or less, and particularly preferably 12.5 or less.

When the film 4 is partially photocured, the cured film 11 can be treated with an alkaline solution, and the unexposed portion 5 of the film 4 can be removed from the printed wiring board 1 using this alkaline solution. That is, the cured solution 11 can be processed with an alkaline solution, and a development process can be performed with this alkaline solution. With this, as shown in FIG. 1D, the hole 6 can be provided at the position where the through hole 10 is to be formed.

The treatment performed by the alkaline solution is preferably performed in a state where the reaction rate of the epoxy group based on the film 4 is 50% or less. The reaction rate of this epoxy group is based on the amount of epoxy groups in the film 4 before exposure. The treatment carried out by the alkaline solution is more preferably carried out in a state where the reaction rate of epoxy groups is 40% or less, and still more preferably carried out in a state where the reaction rate of epoxy groups is 30% or less. Preferably, the reaction rate is 20% or less. Furthermore, the reaction of epoxy groups, based on infrared (IR) spectrum 910cm ^- calculating the peak intensity derived from the epoxy group at ^1, the infrared spectrum is implemented by an infrared film 4 and the film 11 is cured Obtained by spectral analysis. In detail, the reaction of epoxy groups, based on the film 4 by the infrared spectroscopic analysis of the obtained IR spectrum 910cm ^- standardized value of the area of the peak at ¹ (S _0), and the alkaline solution by implementation of a cured film to infrared spectroscopic analysis after treatment 11 IR spectrum of the obtained 910cm ^{- 1} at the area of the peak of the normalized value (S _1), and is calculated using the following formula: (S ₀ -S ₁₎ ÷ S ₀ × 100 (%). Furthermore, the normalized value (S ₀ ) and the normalized value (S ₁ ) are relative values obtained by using the area of the following peak in the IR spectrum as a reference: a peak that does not change even if the film 4 is exposed, For example, the peak at 750cm ^{- 1} . I.e., normalized value (S _0), IR spectra obtained in 910cm 4 by the infrared spectroscopic analysis of the film ^- measured value of a peak area of ^a (P _0), and 750cm ^- peak area at ¹ The measured value (R ₀ ) has a relationship of S ₀ = P ₀ / R ₀ . Further, the normalized value (S _1), IR spectrum of the obtained cured film 910cm by the infrared spectroscopic analysis of 11 ^- at the area of the peak ^measured value (P _1), and 750cm ^{- a} peak areas of The measured value (R ₁ ) has a relationship of S ₁ = P ₁ / R ₁ .

After the treatment with an alkaline solution is performed, and before the conductor layer 8 is formed, the cured film 11 may be cleaned using a known chemical solution. The cleaning process is preferably a process that does not roughen the cured film 11. Cleaning treatment, for example, with a cleaning solution (containing Cleaner Securiganth 902 manufactured by Ato Technology Co., Ltd. of 40ml / L concentration, Cleaner Additive 902 of 3ml / L concentration, and NaOH solution of 20g / L concentration) to the cured film 11 Perform cleaning. Next, the cured film 11 was 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, and then washed with water.

Then, the conductor layer 8 in contact with the cured film 11 is produced. The conductor layer 8 is, for example, a conductor line made of metal such as copper. As described above, immediately before the production of the conductor layer (8), the arithmetic mean roughness Ra of the surface of the cured film (11) in contact with the conductor layer (8) specified by JIS B0601-2001 is less than 150 nm. This can be easily achieved by producing the cured film 11 from the photosensitive resin composition by a usual method, for example, the method already described.

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

When the holes 6 are formed in the cured film 11, the through holes 10 are formed by forming the perforated plating layer 9 inside the holes 6. In addition, in FIG. 1E, the perforated plating layer 9 has a cylindrical shape covering the inner surface of the hole 6, but the entire inner side of the hole 6 may be filled with the perforated plating layer 9.

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

Preferably, the conductor layer 8 is formed first, and then the cured film 11 is subjected to a heat treatment. At this time, the adhesion between the interlayer insulating layer 7 composed of the cured film 11 and the conductor layer 8 can be further improved. The conditions of the heat treatment are, for example, a heating temperature in the range of 120 ° C or more and 200 ° C or less, and a heating time in the range of 30 minutes or more and 120 minutes or less.

The conductor layer 8 can also be produced by sequentially performing an electroless plating process and an electroplating process on the cured film 11. In this case, it is preferable that the heat treatment is performed between the electroless plating treatment and the plating treatment, and the heat treatment is further performed after the plating treatment. At this time, the adhesion between the interlayer insulating layer 7 composed of the cured film 11 and the conductor layer 8 can be further improved.

From the production of the cured film 11 to the production of the conductor layer 8, it is preferable that the cured film 11 is not subjected to heat treatment or the cured film 11 is subjected to one or both of the following conditions: the heating temperature is 200 ℃ or less, and heating time is 150 minutes or less. That is, from the production of the cured film 11 to the formation of the conductor layer 8, it is preferred that the cured film 11 is not subjected to heat treatment, and even in the case of performing the heat treatment, the conditions are preferably such that One or both: 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 lower, further more preferably 160 ° C or lower, and particularly preferably 140 ° C or lower. The heating time is more preferably 120 minutes or less, further preferably 90 minutes or less, and particularly preferably 60 minutes or less.

In addition, the heat treatment is preferably performed in such a manner that the reaction rate of the epoxy group based on the coating film 4 in the cured film 11 after the heat treatment is less than 95%. The reaction rate of this epoxy group is based on the amount of epoxy groups in the film 4 before exposure. The heat treatment is more preferably carried out in such a way that the reaction rate of the epoxy group is less than 90%, further preferably carried out in such a way that the reaction rate of the epoxy group is less than 85%, and particularly preferably in the form of making the epoxy group The reaction rate is less than 80%. Furthermore, the reaction of epoxy groups, based on the IR spectrum of 910 cm ^- calculating the peak intensity derived from ^an epoxy group, which is an IR spectrum of a cured film by the film 4 and the heat treatment implement 11 Obtained by infrared spectroscopy. In detail, the reaction of epoxy groups, based on 910cm film 4 by the infrared spectroscopic analysis of the obtained IR spectrum ^- normalized value of the peak area at ¹ (S _0), and processed by heat hardening after 910cm IR spectrum of the infrared spectroscopic analysis of the film 11 obtained in the ^- area of the peak at ^a normalized value (S _2), and is calculated using the following _{formula: (S 0 -S 2) ÷} S 0 × 100 (% ). Furthermore, the normalized value (S ₀ ) and the normalized value (S ₂ ) are relative values obtained by using the area of the following peak in the IR spectrum as a reference: a peak that does not change even if the film 4 is exposed For example, the peak at 750cm ^{- 1} . I.e., normalized value (S _0), IR spectra obtained in 910cm 4 by the infrared spectroscopic analysis of the film ^- measured value of a peak area of ^a (P _0), and 750cm ^- peak area at ¹ The measured value (R ₀ ) has a relationship of S ₀ = P ₀ / R ₀ . Further, normalized value (S _2), 910cm IR spectrum obtained by the infrared spectroscopic analysis of cured film 11 ^- of the peak area found at ¹ (P _2), and 750cm ^{- a} peak areas of The measured value (R ₂ ) has a 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 sufficiently clear, it is presumed that if the heat treatment is not performed, and the condition is still within the above range even when the heat treatment is performed, there is a relatively large amount of surface on the surface of the cured film 11 compared to the case where this method is not used. There are many functional groups derived from components in the photosensitive resin composition, and the interaction between this functional group and the conductor layer 8 contributes to the improvement of adhesion.

After the cured film 11 is produced until the conductor layer 8 is produced, it is preferable that the cured film 11 is not treated with an oxidizing agent. At this time, it is possible to prevent the cured film 11 from becoming rough due to the oxidizing agent, and it becomes easy to achieve that the arithmetic average roughness Ra of the cured film 11 is less than 150 nm. It is preferable that the treatment is such that even when the treatment with an oxidizing agent is performed, the arithmetic average roughness Ra of the cured film 11 can be achieved to be less than 150 nm.

Furthermore, when the holes 6 are provided in the cured film 11, the cured film 11 is subjected to desmear treatment using an oxidant before the conductor layer 8 is formed. For removing the smear in the holes 6, useful. However, in this embodiment, the photosensitive resin composition can have excellent developability and resolution. Therefore, even if the holes 6 are provided in the cured film 11, it is difficult for residue to remain. Therefore, even when the treatment with the oxidizing agent is not performed or when the slight treatment with the oxidizing agent is performed, it is not easy to cause a defect caused by the rubber slag.

According to the above, it is possible to produce a multilayer printed wiring board 20 including: an interlayer insulating layer 7 composed of the cured film 11; and a conductor layer 8 in contact with the interlayer insulating layer 7. The thickness of the interlayer insulating layer 7 is, for example, in the range of 3 μm or more and 50 μm or less. As described above, the multilayer printed wiring board 20 can achieve high adhesion between the interlayer insulating layer 7 and the conductor layer 8 even if the interlayer insulating layer 7 is not roughened or the degree of roughening is small. [Example]

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

[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, a thermometer, an air blowing tube, and a stirrer, 250 parts by mass of Represented by formula (2) and all of R ¹ to R ⁷ in formula (2) are hydrogen bisphenol fusiform epoxy resins (epoxy equivalent of 250 g / eq), 60 parts by mass of propylene glycol monomethyl ether acetic acid An ester, 140 parts by mass of diethylene glycol monoethyl ether acetate, 0.2 parts by mass of methylhydroquinone, 72 parts by mass of acrylic acid, and 1.5 parts by mass of triphenylphosphine were used to prepare a mixture. In the flask, the mixture was stirred with air bubbling and heated at 115 ° C for 12 hours. By this, a solution of the intermediate is prepared.

Then, 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 were added to the intermediate solution in the flask Propylene glycol monomethyl ether acetate, and the solution was stirred while the air was bubbling, while heating at 115 ° C for 6 hours, and further heating at 80 ° C for 1 hour. With this, a 65% by mass solution of the carboxyl group-containing resin A-1 was obtained. The weight average molecular weight of the carboxyl group-containing resin A-1 is 3096, and the acid value is 105 mgKOH / g.

[Synthesis Example A-2] The carboxyl group-containing resin having an aromatic ring in Synthesis Example A-2 was prepared in the following manner. In a four-necked flask equipped with a reflux cooler, a thermometer, an air blowing tube and a stirrer, add 288 parts by mass of biphenol novolac epoxy resin (manufactured by Nippon Kayaku Co., Ltd., product model NC-3000-H, Epoxy equivalent of 288g / eq), 155 parts by mass of diethylene glycol monoethyl ether acetate, 0.2 parts by mass of methylhydroquinone, 72 parts by mass of acrylic acid, and 3 parts by mass of triphenylphosphine, To prepare the mixture. In the flask, the mixture was stirred with air bubbling and heated at 115 ° C for 12 hours. By this, a solution of the intermediate is prepared.

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

(2) Preparation of photosensitive resin composition (Composition Examples 1 to 9) In the flask, the components shown in Table 1 were blended, and stirred and mixed at a temperature of 35 ° C for 2 hours, thereby obtaining Composition Example 1 The photosensitive resin composition of -9 (refer to Table 1). The photosensitive resin compositions of Composition Examples 1 to 9 were filtered with a 300-mesh filter, and further filtered with a filter with a pore size of 10 μm. The particle size of the organic filler contained in the photosensitive resin compositions of Composition Examples 1 to 9 was confirmed by a laser diffraction scattering particle size distribution measuring device, and as a result, the maximum particle size was all 10 μm or less.

In addition, the blending amount in Table 1 shows the mass part of the solid content amount of the component described in the table. Although not described in the table, methyl ethyl ketone as a diluent is blended into the photosensitive resin composition.

The details of the components shown in Table 1 are as follows.・ Organic filler A (dispersion) with polar groups: A methyl ethyl ketone dispersion containing a cross-linked rubber (NBR) with an average primary particle size of 0.07 μm and a proportion of 15% by weight, JSR Limited Manufactured by the company, product model XER-91-MEK, acid value is 10.0mgKOH / g.・ Organic filler B (dispersion) with polar groups: a methyl ethyl ketone dispersion containing a cross-linked rubber (SBR) having a carboxyl group and a hydroxyl group and an average primary particle diameter of 0.07 μm at a concentration of 15% by weight , Manufactured by JSR Co., Ltd., product model XSK-500.・ Organic filler C (dispersion) with polar group: manufactured by Nissan Chemical Industry Co., Ltd. The fine powder melamine dispersion varnish is prepared by dispersing 1.5 parts by mass of melamine fine powder in 3.5 parts by mass of tricyclodecane dimethanol diacrylate using a bead mill. The maximum particle size of the fine powder melamine is 5 μm or less.・ Organic filler (dispersion liquid) without polar group: a glycidyl modified acrylonitrile butadiene rubber dispersion varnish, using a bead mill, 1.5 parts by mass of powder with an average primary particle size of 0.3 μm The glycidyl modified acrylonitrile butadiene rubber is prepared by dispersing 2.5 parts by mass of tricyclodecane dimethanol diacrylate.・ Coupling agent: 3-glycidoxypropyltrimethoxysilane.・ Silicon dioxide: manufactured by Nissan Chemical Industry Co., Ltd., product model MEK-EC-2130Y, methyl ethyl ketone-dispersed silica sol, grade with improved compatibility with epoxy resin, solid content concentration of 30% by mass , The average primary particle size is 10 nm or more and 15 nm or less.・ Unsaturated compound A: Tricyclodecane dimethanol diacrylate (containing tricyclodecane dimethanol diacrylate in a dispersion liquid derived from an organic filler).・ Unsaturated compound B: Trimethylolpropane triacrylate.・ Unsaturated compound C: a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate, manufactured by Nippon Kayaku Co., Ltd., product type KAYARAD DPHA.・ Photopolymerization initiator A: 2,4,6-trimethylbenzyl-diphenyl-phosphine oxide, manufactured by BASF, Irgacure TPO.・ Photopolymerization initiator B: 1-hydroxy-cyclohexyl-phenyl-ketone, manufactured by BASF, Irgacure 184.・ Photopolymerization initiator C: 4,4’-bis (diethylamino) diphenyl ketone.・ Epoxy compound: Biphenyl crystalline epoxy resin, manufactured by Mitsubishi Chemical Corporation, product model YX4000, epoxy equivalent is 186g / eq.・ Antioxidants: hindered phenolic antioxidants, manufactured by BASF, product model IRGANOX 1010.・ Surface conditioner: DIC Corporation, product model MEGAFACE F-477.

[Table 1]

(3) Preparation of test pieces (Examples 1 to 29, Comparative examples 1 to 27, Reference examples 1 to 18) Using the photosensitive resin compositions of Composition Examples 1 to 9, the test pieces 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 First, apply the photosensitive resin composition of Composition Examples 1 to 9 to a film made of polyethylene terephthalate with an applicator, and then use 95 It was heated at ℃ for 25 minutes to dry it, thereby forming a dry film with a thickness of 30 μm on the film.

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

Using an etchant (organic acid-based micro-etching agent manufactured by MEC Co., Ltd., product model CZ-8101) to dissolve and remove the surface layer part of the conductor line of the printed wiring board with a thickness of about 1 μm, thereby roughening the conductor line .

Using a vacuum laminator, the dry film is heated and laminated on the entire surface of one side of the printed wiring board. The conditions for heat lamination are 0.5 MPa, 80 ° C, and 1 minute. With this, a film composed of a dry film and having a film thickness of 30 μm is formed on the printed wiring board so as to cover the conductor line.

The infrared spectrum analysis of this film was carried out to obtain an IR spectrum.

Then, from the film made of polyethylene terephthalate, with the negative mask directly in contact with the film, the coating film was irradiated with ultraviolet rays at a condition of 300 mJ / cm ² via the negative mask, thereby The exposed portion of the film was cured to produce a cured film. The negative mask had circular shielding portions with diameters of 30 μm, 45 μm, and 60 μm, and striped shielding portions with line width / pitch of 40 μm / 40 μm. The self-hardening film peels off a film made of polyethylene terephthalate.

Then, in each of Examples and Reference Examples 1 to 9, the cured film was treated with an alkaline solution, and at the same time, the unexposed portion of the film was removed with this alkaline solution. When the treatment was carried out, a 1% sodium carbonate (Na ₂ CO ₃ ) aqueous solution (pH 11) at 30 ° C. was sprayed on the cured film at a spray pressure of 0.2 MPa for 90 seconds. Then, pure water was sprayed on the cured film at a spray pressure of 0.2 MPa for 90 seconds to perform cleaning. With this, an opening is formed where the unexposed portion of the cured film is removed. On the other hand, in each Comparative Example and Reference Examples 10 to 18, the cured film was not treated with an alkaline solution.

(3-2) Heat treatment of cured film In each of Examples 1 to 27, Comparative Examples, and Reference Examples, the cured film was heated at 150 ° C 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.

Then, infrared spectrum analysis of the cured film was carried out to obtain an IR spectrum.

The IR spectrum of the film in 910cm ^- standardized value of the area of the peak at ¹ (S _0), and IR spectrum of the cured film 11 of 910cm ^- the area of the peak at ^a normalized value (S _2), and using The following formula is used to calculate the reaction rate (percentage) of epoxy groups: (S ₀ -S ₂ ) ÷ S ₀ × 100 (%). Further, normalized value (S _0), the IR spectrum of the film is based on the 910 cm ^- the measured values of the peak area at ¹ (P _0), and 750cm ^- Found (R ₀₎ of the peak area at ¹ and the use of S ₀ = P ₀ / R ₀ is calculated from the equation obtained value; normalized value (S _2), according to the IR spectrum of the cured film 910cm ^- Found area of the peak at ¹ (P _2), and 750cm ^- Found (R & lt _2), using equation S ₂ = P ₂ / R ₂ of the area of the peak at ^a calculated value obtained. In addition, the decimal point of the calculation result of the reaction rate of the epoxy group is rounded off.

Based on this result, the reaction rate of epoxy groups is classified in the following manner. A: The reaction rate of epoxy groups is less than 85%. B: The reaction rate of epoxy groups is 85% or more but less than 90%. C: The reaction rate of epoxy groups is 90% or more but less than 95%. D: The reaction rate of epoxy groups is 95% or more.

Then, in each example, each comparative example, and each reference example, a high-pressure mercury lamp was used to irradiate 1000 mJ / cm ² of ultraviolet light to the cured film.

(3-3) Surface treatment of cured film (3-3-1) Cases of Examples 1 to 9, 28 to 29 and Comparative Examples 1 to 9 (no roughening) The cured film was cleaned by the following method deal with. Immerse the cured film in a cleaning solution (manufactured by Ato Technology Co., Ltd., Japan, containing 40ml / L of Cleaner Securiganth 902, 3ml / L of Cleaner Additive 902, 20g / L of NaOH) 5 minute. Then, the cured film was immersed in an aqueous solution of SnCl ₂ at a concentration of 0.1 g / L for 3 minutes, and then washed with water. Next, 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., and then washed with water.

(3-3-2) Cases of Examples 10 to 18 and Comparative Examples 10 to 18 (low-level roughening) First, a swelling solution for degumming slag (Japanese Atotech Co., Ltd.) Manufactured by the company, containing 500mL / L concentration of Swelling Dip Securiganth P, 3g / L concentration of NaOH solution) for 15 minutes to swell, and then the hardened film was washed with hot water. Then, by immersing the hardened film in a degumming slag solution containing potassium permanganate (manufactured by ATO Technology Co., Ltd., Japan, containing a concentration of 580mL / L Concentrate Compact CP and a concentration of 40g / L NaOH) Liquid) for 10 minutes to roughen the surface of the cured film, and then wash with hot water. Then, by immersing the hardened film in a neutralizing solution at 40 ° C (manufactured by Ato Technology Co., Ltd., Japan, containing 70mL / L concentration of Reduction solution Securiganth P500, 50mL / L concentration of sulfuric acid (98%)) In 5 minutes, remove the residue of the glue removal liquid on the surface of the cured film, and then wash with water. Then, the cured film was subjected to cleaning treatment by the same method as in the case of (4-1) above.

(3-3-3) Cases of Examples 19 to 27 and Comparative Examples 19 to 27 (moderate roughening) First, by immersing the surface of the cured film in a swelling solution for degumming residue at 80 ° C (Japan Atto Technology) It is manufactured by Co., Ltd. and contains 500 mL / L concentration of Swelling Dip Securiganth P and 3 g / L concentration of NaOH solution for 5 minutes to swell it, and then the cured film is washed with hot water. Then, by immersing the hardened film in a descumming solution containing potassium permanganate (manufactured by Ato Technology Co., Ltd., Japan, containing a concentration of 580mL / L Concentrate Compact CP and a concentration of 40g / L NaOH) Liquid) for 5 minutes to roughen the surface of the cured film, and then wash with hot water. Then, by immersing the hardened film in a neutralizing solution at 40 ° C (manufactured by Ato Technology Co., Ltd., Japan, containing 70mL / L concentration of Reduction solution Securiganth P500, 50mL / L concentration of sulfuric acid (98%)) In 5 minutes, remove the residue of the glue removal liquid on the surface of the cured film, and then wash with water. Then, the cured film was subjected to cleaning treatment by the same method as in the case of (4-1) above.

(3-3-4) Cases of Reference Examples 1 to 18 (Highly Roughened) First, by immersing the surface of the cured film in a swelling solution for degumming slag (manufactured by Ato Technology Co., Ltd., Japan, including 500 mL / L concentration of Swelling Dip Securiganth P, 3g / L concentration of NaOH solution) for 7.5 minutes to swell it, and then wash the cured film with hot water. Then, by immersing the hardened film in a degumming slag solution containing potassium permanganate (manufactured by Ato Technology Co., Ltd., Japan, containing a concentration of 580mL / L Concentrate Compact CP and a concentration of 40g / L NaOH) Liquid) for 7.5 minutes to roughen the surface of the cured film, and then wash with hot water. Then, by immersing the hardened film in a neutralizing solution at 40 ° C (manufactured by Ato Technology Co., Ltd., Japan, containing 70mL / L concentration of Reduction solution Securiganth P500, 50mL / L concentration of sulfuric acid (98%)) In 5 minutes, remove the residue of the glue removal liquid on the surface of the cured film, and then wash with water. Then, the cured film was subjected to cleaning treatment by the same method as in the case of (4-1) above.

The surface roughness (arithmetic mean roughness (Ra)) of the cured film of the surface-treated test piece was measured with a laser microscope. Use the following methods to classify the results. The results are shown in the table below. A: The arithmetic average roughness (Ra) is less than 30 nm. B: The arithmetic average roughness (Ra) is 30 nm or more but less than 80 nm. C: The arithmetic average roughness (Ra) is 80 nm or more but less than 150 nm. D: The arithmetic average roughness (Ra) is 150 nm or more.

(4) Evaluation test For the test pieces of each example, comparative example and reference example, the following test was carried out. The results are shown in Tables 2 to 10.

(4-1) Adhesion of copper plating The hardened film was first subjected to electroless copper treatment (MV-Plus treatment by Japan Atto Technology Co., Ltd.), and then heated at 150 ° C for 1 hour, and then, at 2A / dm A copper plating process was performed at a current density of ² to form a copper film having a thickness of 33 μm, and then the test piece was heated at 180 ° C. for 30 minutes. With this, a copper plating layer is formed on the cured film. Except when at least one of heating after electroless copper plating and heating after copper electroplating produces blister, the peel strength of the copper plating layer to the cured film is measured in accordance with JIS C6481. Based on this result, the adhesion of the copper plating layer was evaluated in the following manner. A: The peel strength of the copper plating layer is 0.2 kN / m or more. B: The peel strength of the copper plating layer is 0.1 kN / m or more but less than 0.2 kN / m. C: The peel strength of the copper plating layer is less than 0.1 kN / m. D: Bubbles are generated in at least one of heating time after electroless copper plating treatment and heating time after copper electroplating treatment.

(4-2) Electrical insulation: After heating the test piece at 150 ° C for 1 hour and further at 180 ° C for 30 minutes, apply a direct current (DC) of 30V between the comb electrodes in the conductor line in the test piece Bias voltage, the test piece is exposed to a test environment at 130 ° C and 85% relative humidity (RH) for 100 hours. In this test environment, the resistance value of the cured film between the comb electrodes was continuously measured, and the results were evaluated in the following manner. A: From the beginning of the test to the lapse of 100 hours, the resistance value has been maintained at 10 ⁶ Ω or more. B: From the beginning of the test to 85 hours elapsed, the resistance value has been maintained at 10 ⁶ Ω or more, but from the beginning of the test to 100 hours before the resistance value has been less than 10 ⁶ Ω. C: From the beginning of the test to the lapse of 70 hours, the resistance value has been maintained at 10 ⁶ Ω or more, but from the beginning of the test to 85 hours before the lapse of resistance value has been less than 10 ⁶ Ω. D: From the beginning of the test until 70 hours have passed, the resistance value has been less than 10 ⁶ Ω.

(4-3) Opening property Observe the circular opening of the cured film of the test piece of each example, comparative example and reference example, and evaluate the result in the following manner. The opening corresponds to the circle of the negative mask Shaped shield. A: The openings corresponding to the shielding portions with diameters of 30 μm, 45 μm, and 60 μm are all formed. B: No openings corresponding to the shielding portions with a diameter of 30 μm were formed, but there were openings corresponding to the shielding portions with a diameter of 45 μm and 60 μm. C: No openings corresponding to shielding portions with a diameter of 30 μm and 45 μm were formed, but there were openings corresponding to shielding portions with a diameter of 60 μm. D: No openings corresponding to the shielding portions with diameters of 30 μm, 45 μm, and 60 μm were formed.

(4-4) Resolution Observe the stripe-shaped openings of the cured film in the test pieces of each example, comparative example and reference example, and evaluate the results in the following manner. The openings correspond to the stripe-shaped shielding portions . A: There is no unevenness in the outline of the opening, and the resolution is clear and sharp. B: A slight unevenness was observed in the outline of the opening, but the resolution was clear. C: Unevenness of the outline of the opening is observed, and the resolution is slightly poor. D: The unevenness 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 can be seen from the above-mentioned embodiments, the method for manufacturing a multilayer printed wiring board (20) of the first aspect of the present invention is to form a film (4) on the printed wiring board (1) from 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 photo-hardening of the coating film (4) produces a cured film (11). First, the cured film (11) is treated with an alkaline solution, and then a conductor layer (8) in contact with the cured film (11) is formed. Immediately before the production of the conductor layer (8), the arithmetic average roughness Ra of the surface of the cured film (11) in contact with the conductor layer (8) specified by JIS B0601-2001 is less than 150 nm.

According to the first aspect, it is possible to obtain a multilayer printed wiring board (20) that can achieve interlayer insulation even if the interlayer insulating layer (7) composed of the cured film (11) is not roughened or has a small degree of roughening High adhesion between layer (7) and conductor layer (8).

The method for manufacturing the multilayer printed wiring board (20) of the second aspect of the present invention is that 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.

The method for manufacturing a multilayer printed wiring board (20) according to the third aspect of the present invention is that in the first or second aspect, after the cured film (11) is produced until the conductor layer (8) is produced, it is not correct. The cured film (11) is subjected to heat treatment, or the cured film (11) is subjected to heat treatment so that the reaction rate of the epoxy group based on the film (4) is less than 95%.

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

In the manufacturing method of the multilayer printed wiring board (20) of the fourth aspect of the present invention, in any of the first to third aspects, the photosensitive resin composition is a dry film.

According to the fourth aspect, it is possible to obtain a multilayer printed wiring board (20) that can achieve interlayer insulation even if the interlayer insulating layer (7) composed of the cured film (11) is not roughened or the roughness is small High adhesion between layer (7) and conductor layer (8).

In the manufacturing method of the multilayer printed wiring board (20) of the fifth aspect of the present invention, in any of the first to fourth aspects, the photosensitive resin composition further contains an organic filler (E).

According to the fifth aspect, the adhesion between the interlayer insulating layer (7) composed of the cured film (11) and the conductor layer (8) can be improved.

In the sixth aspect of the present invention, the method for manufacturing a multilayer printed wiring board (20) is that in the fifth aspect, the organic filler (E) has a polar group.

According to the sixth aspect, the adhesion between the interlayer insulating layer (7) composed of the cured film (11) and the conductor layer (8) can be further improved.

According to the seventh aspect of the present invention, in the method for manufacturing a multilayer printed wiring board (20), in the sixth aspect, the polar group includes at least one group selected from the group consisting of a carboxyl group, an amine group, and a hydroxyl group.

According to the seventh aspect, the adhesion between the interlayer insulating layer (7) composed of the cured film (11) and the conductor layer (8) can be particularly improved.

The method for manufacturing a multilayer printed wiring board (20) of the eighth aspect of the present invention is that in any of the fifth to seventh aspects, the particles of the organic filler (E) in the photosensitive resin composition The diameter is 10 μm or less. The adhesion between the interlayer insulating layer (7) composed of the cured film (11) and the conductor layer (8) can be particularly improved.

According to the eighth aspect, the adhesion between the interlayer insulating layer (7) composed of the cured film (11) and the conductor layer (8) can be particularly improved.

The manufacturing method of the multilayer printed wiring board (20) of the ninth aspect of the present invention is in any of the first to eighth aspects, from the production of the cured film (11) to the production of the conductor layer (11) ) Until then, the cured film (11) is not treated with an oxidizing agent.

According to the ninth aspect, it is possible to prevent the cured film (11) from being roughened by the oxidizing agent, and it becomes 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 the manufacturing method of any one of the first to ninth aspects.

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 circuit board

2‧‧‧Insulation

3‧‧‧Conductor line

4‧‧‧film

5‧‧‧ unexposed part

6‧‧‧ hole

7‧‧‧Interlayer insulation

8‧‧‧Conductor layer

9‧‧‧Perforated plating

10‧‧‧Through hole

11‧‧‧hardened film

20‧‧‧ multilayer printed circuit board

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

Domestic storage information (please note in order of storage institution, date, number) No

Overseas hosting information (please note in order of hosting country, institution, date, number) No

Claims (10)

A method for manufacturing a multilayer printed wiring board, in which a film is made from a photosensitive resin composition on the printed wiring board; the photosensitive resin composition contains: a carboxyl group-containing resin (A), having at least one ethylenic unsaturation in one molecule Bonded unsaturated compound (B), photopolymerization initiator (C), and epoxy compound (D); then photoharden the aforementioned film to produce a cured film; then first harden the aforementioned film with an alkaline solution The film is processed to produce a conductive layer in contact with the cured film; and immediately before the conductive layer is produced, the arithmetic mean roughness of the surface of the cured film in contact with the conductive layer specified by Japanese Industrial Standard B0601-2001 Ra is less than 150nm. The method for manufacturing a multilayer printed wiring board according to claim 1, wherein the arithmetic average roughness Ra is less than 80 nm. The method for manufacturing a multilayer printed wiring board according to claim 1 or 2, wherein the cured film is not subjected to a heat treatment from the production of the cured film to the production of the conductor layer, or the film is used as the The above-mentioned cured film is subjected to heat treatment so that the reaction rate of the base epoxy group is less than 95%. The method for manufacturing a multilayer printed wiring board according to claim 1 or 2, wherein the photosensitive resin composition is a dry film. The method for manufacturing a multilayer printed wiring board according to claim 1 or 2, wherein the photosensitive resin composition further contains an organic filler (E). The method for manufacturing a multilayer printed wiring board according to claim 5, wherein the organic filler (E) has a polar group. The method for manufacturing a multilayer printed wiring board according to claim 6, wherein the polar group includes at least one group selected from the group consisting of a carboxyl group, an amine group, and a hydroxyl group. The method of manufacturing a multilayer printed wiring board according to claim 5, wherein the particle diameter of the organic filler (E) in the photosensitive resin composition is 10 μm or less. The method for manufacturing a multilayer printed wiring board according to claim 1 or 2, wherein the cured film is not treated with an oxidizing agent after the cured film is produced until the conductive layer is produced. A multilayer printed wiring board is manufactured by the method for manufacturing a multilayer printed wiring board according to any one of claims 1 to 9.