WO2019031322A1 - 多層プリント配線板の製造方法及び多層プリント配線板 - Google Patents

多層プリント配線板の製造方法及び多層プリント配線板 Download PDF

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Publication number
WO2019031322A1
WO2019031322A1 PCT/JP2018/028770 JP2018028770W WO2019031322A1 WO 2019031322 A1 WO2019031322 A1 WO 2019031322A1 JP 2018028770 W JP2018028770 W JP 2018028770W WO 2019031322 A1 WO2019031322 A1 WO 2019031322A1
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WIPO (PCT)
Prior art keywords
resin composition
photosensitive resin
wiring board
printed wiring
cured film
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PCT/JP2018/028770
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English (en)
French (fr)
Japanese (ja)
Inventor
倫也 樋口
勇佐 藤原
田中　信也
文人 鈴木
橋本　壯一
貴 荒井
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互応化学工業株式会社
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Application filed by 互応化学工業株式会社 filed Critical 互応化学工業株式会社
Priority to KR1020207001703A priority Critical patent/KR102189000B1/ko
Priority to JP2019511789A priority patent/JP6705084B2/ja
Priority to CN201880051661.3A priority patent/CN110999554B/zh
Publication of WO2019031322A1 publication Critical patent/WO2019031322A1/ja

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    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/22—Secondary treatment of printed circuits
    • H05K3/28—Applying non-metallic protective coatings
    • H05K3/285—Permanent coating compositions
    • H05K3/287—Photosensitive compositions
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/22—Secondary treatment of printed circuits
    • H05K3/28—Applying non-metallic protective coatings
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/46—Manufacturing multilayer circuits

Definitions

  • the present invention relates to a method of manufacturing a multilayer printed wiring board and a multilayer printed wiring board.
  • an electrically insulating resin composition is used to produce an electrically insulating layer such as a solder resist layer, a plating resist layer, an etching resist layer, or an interlayer insulating layer of a printed wiring board.
  • a resin composition is, for example, a photosensitive resin composition (see Patent Document 1).
  • the interlayer insulating layer should be roughened in order to ensure adhesion between the interlayer insulating layer and a conductor layer produced thereon by a plating method or the like. Is performed (see Patent Document 1).
  • the interlayer insulating layer is roughened, the high frequency characteristics of the printed wiring board are degraded, and therefore, the transmission characteristics of high speed signals of the printed wiring board are degraded.
  • An object of the present invention is to provide a method for producing a multilayer printed wiring board capable of achieving high adhesion between an interlayer insulating layer and a conductor layer without roughening the interlayer insulating layer or reducing the degree of roughening. It is providing a wiring board.
  • a film is produced on a printed wiring board from a photosensitive resin composition.
  • the photosensitive resin composition comprises a carboxyl group-containing resin (A), an unsaturated compound (B) having at least one ethylenic unsaturated bond in one molecule, a photopolymerization initiator (C), and an epoxy compound (D) Containing).
  • a cured film is produced by photocuring the film. After treating the cured film with an alkaline solution, a conductor layer in contact with the cured film is produced.
  • the arithmetic average roughness Ra defined by JIS B0601-2001 of the surface of the cured film in contact with the conductor layer immediately before producing the conductor layer is less than 150 nm.
  • the multilayer printed wiring board according to an aspect of the present invention is manufactured by the above manufacturing method.
  • 1A to 1E are cross-sectional views showing steps of manufacturing a multilayer printed wiring board.
  • the following embodiment relates to a method of manufacturing a multilayer printed wiring board and a multilayer printed wiring board manufactured by this manufacturing method, in particular, manufacturing a multilayer printed wiring board for producing a cured film of a photosensitive resin composition on the printed wiring board.
  • the present invention relates to a method and a multilayer printed wiring board manufactured by this manufacturing method.
  • (meth) acrylic means at least one of "acrylic” and “methacrylic”.
  • (meth) acrylate means at least one of acrylate and methacrylate.
  • a film 4 is produced on a printed wiring board 1 from a photosensitive resin composition.
  • the photosensitive resin composition comprises a carboxyl group-containing resin (A), an unsaturated compound (B) having at least one ethylenic unsaturated bond in one molecule, a photopolymerization initiator (C), and an epoxy compound (D).
  • a photosensitive resin composition comprises a carboxyl group-containing resin (A), an unsaturated compound (B) having at least one ethylenic unsaturated bond in one molecule, a photopolymerization initiator (C), and an epoxy compound (D).
  • Contains The cured film 11 is produced by photocuring the film 4. After treating the cured film 11 with an alkaline solution, the conductor layer 8 in contact with the cured film 11 is produced.
  • the arithmetic average roughness Ra defined by JIS B0601-2001 of the surface of the cured film 11 in contact with the conductor layer 8 immediately before producing the conductor layer 8 is less than 150 n
  • the arithmetic average roughness Ra of the cured film 11 is less than 150 nm, the deterioration of the high frequency characteristics of the multilayer printed wiring board 20 is suppressed even if the conductor layer 8 in contact with the cured film 11 is produced.
  • the transmission characteristics of the high-speed signal of the multilayer printed wiring board 20 can be favorably maintained.
  • the adhesion between the interlayer insulating layer 7 formed of the cured film 11 and the conductor layer 8 can be improved.
  • the reason is not sufficiently clarified, when the cured film 11 is treated with an alkaline solution, the surface of the cured film 11 is not greatly roughened, but it is considered that fine irregularities are generated, and this is the interlayer insulating layer 7 and It is presumed that this is one of the factors contributing to the improvement of the adhesion with the conductor layer 8.
  • the photosensitive resin composition used in the present embodiment will be described in detail.
  • the photosensitive resin composition comprises a carboxyl group-containing resin (A), an unsaturated compound (B) having at least one ethylenically unsaturated bond in one molecule, a photopolymerization initiator (C), and an epoxy It contains the compound (D).
  • the carboxyl group-containing resin (A) preferably contains a carboxyl group-containing resin having an ethylenically unsaturated group.
  • the carboxyl group-containing resin (A) can have photoreactivity. Therefore, the carboxyl group-containing resin (A) can impart photosensitivity, specifically ultraviolet curability, to the photosensitive resin composition.
  • the carboxyl group-containing resin (A) preferably contains a carboxyl group-containing resin having an aromatic ring. In this case, high heat resistance and insulation reliability can be imparted to the cured product of the photosensitive resin composition.
  • the carboxyl group-containing resin (A) more preferably contains a carboxyl group-containing resin having a polycyclic aromatic ring of any one of a biphenyl skeleton, a naphthalene skeleton, a fluorene skeleton, and an anthracene skeleton. In this case, higher heat resistance and insulation reliability can be imparted to the cured product of the photosensitive resin composition.
  • the carboxyl group-containing resin (A) preferably contains a carboxyl group-containing resin (A1) having a bisphenol fluorene skeleton. In this case, higher heat resistance and insulation reliability can be imparted to the cured product of the photosensitive resin composition containing the carboxyl group-containing resin (A).
  • the carboxyl group-containing resin (A1) is, for example, an intermediate which is a reaction product of an epoxy compound (a1) and an unsaturated group-containing carboxylic acid (a2), an acid dianhydride (a3) and an acid monoanhydride (a4) And the reaction product of The epoxy compound (a1) has a bisphenol fluorene skeleton.
  • the bisphenol fluorene skeleton is represented by the following formula (1), and in the formula (1), R 1 to R 8 each independently represent hydrogen, an alkyl group having 1 to 5 carbon atoms, or a halogen.
  • Each of R 1 to R 8 in the formula (1) may be hydrogen, but may be an alkyl group of 1 to 5 carbon atoms or halogen. The reason is that even if the hydrogen in the aromatic ring is substituted with a low molecular weight alkyl group or halogen, there is no adverse effect on the physical properties of the carboxyl group-containing resin (A1), but rather a photosensitive resin composition containing the carboxyl group-containing resin (A1) It is because the heat resistance or the flame retardance of the cured product may be improved.
  • the carboxyl group-containing resin (A1) has a bisphenol fluorene skeleton derived from the epoxy compound (a1)
  • the cured product of the photosensitive resin composition containing the carboxyl group-containing resin (A1) has high heat resistance and insulation Confidence can be given.
  • the carboxyl group-containing resin (A1) will be more specifically described.
  • An intermediate is synthesized by reacting with a carboxylic acid (a2) containing 1).
  • the synthesis of the intermediate is defined as the first reaction.
  • the intermediate has a secondary hydroxyl group generated by the ring-opening addition reaction of an epoxy group and a carboxylic acid (a2) containing an unsaturated group-containing carboxylic acid (a2-1).
  • the reaction of the intermediate with the acid anhydride (a3) is defined as a second reaction.
  • the acid anhydride (a3) may include an acid monoanhydride and an acid dianhydride.
  • the acid monoanhydride is a compound having one acid anhydride group in which two carboxyl groups in one molecule are dehydrated and condensed.
  • the acid dianhydride is a compound having two acid anhydride groups, in which four carboxyl groups in one molecule are dehydrated and condensed.
  • the carboxyl group-containing resin (A1) may contain an unreacted component in the intermediate. Further, when the acid anhydride (a3) contains an acid monoanhydride and an acid dianhydride, the carboxyl group-containing resin (A1) is a component in an intermediate, a component in an acid monoanhydride and an acid dianhydride In addition to the reaction with the component in the intermediate, any one of the reaction between the component in the intermediate and the component in the acid monoanhydride, and the reaction of the component in the intermediate with the component in the acid dianhydride One or both may be contained. That is, the carboxyl group-containing resin (A1) may be a mixture containing a plurality of compounds having different structures such as these.
  • the carboxyl group-containing resin (A1) has photoreactivity by having an ethylenically unsaturated group derived from the unsaturated group-containing carboxylic acid (a2-1). Therefore, the carboxyl group-containing resin (A1) can impart photosensitivity, specifically ultraviolet curability, to the photosensitive resin composition.
  • the carboxyl group-containing resin (A1) contains a carboxyl group derived from the acid anhydride (a3), whereby the photosensitive resin composition contains at least one of an alkali metal salt and an alkali metal hydroxide. It is possible to impart developability with an alkaline aqueous solution.
  • the weight average molecular weight of the carboxyl group-containing resin (A1) is preferably in the range of 700 or more and 10000 or less. While being able to improve the insulation of the hardened
  • the weight average molecular weight is more preferably 900 or more, and particularly preferably 1000 or more. The weight average molecular weight is more preferably in the range of 8000 or less, and particularly preferably in the range of 5000 or less.
  • the polydispersity of the carboxyl group-containing resin (A1) is preferably in the range of 1.0 or more and 4.8 or less. In this case, excellent developability can be imparted to the photosensitive resin composition while securing good insulation of the cured product formed from the photosensitive resin composition.
  • the polydispersity of the carboxyl group-containing resin (A1) is more preferably 1.1 or more and 4.0 or less, and still more preferably 1.2 or more and 2.8 or less.
  • the carboxyl group-containing resin (A1) contains the unreacted components in the intermediate, the components in the intermediate and the acid anhydride.
  • Reactant of component with component in acid dianhydride, reactant of component in intermediate with component in acid monoanhydride, reactant of component in intermediate with component in acid dianhydride, etc. This can be achieved by a mixture containing various components appropriately. More specifically, this is achieved by controlling parameters such as the average molecular weight of the epoxy compound (a1), the amount of acid monoanhydride to the epoxy compound (a1), and the amount of acid dianhydride to the epoxy compound (a1) it can.
  • polydispersion degree is a value (Mw / Mn) of the ratio of the weight average molecular weight (Mw) with respect to the number average molecular weight (Mn) of carboxyl group-containing resin (A1).
  • the solid content acid value of the carboxyl group-containing resin (A1) is preferably in the range of 60 mg KOH / g to 140 mg KOH / g. In this case, the developability of the photosensitive resin composition is particularly improved.
  • the acid value is more preferably in the range of 80 mg KOH / g to 135 mg KOH / g, and the acid value is more preferably in the range of 90 mg KOH / g to 130 mg KOH / g.
  • the molecular weight of the carboxyl group-containing resin (A1) can be adjusted by crosslinking of acid dianhydride. In this case, a carboxyl group-containing resin (A1) in which the acid value and the molecular weight are adjusted is obtained. That is, the molecular weight and the acid value of the carboxyl group-containing resin (A1) can be easily adjusted by controlling the amount of the acid dianhydride contained in the acid anhydride (a3). In addition, the molecular weight of carboxyl group-containing resin (A1) is computed from the measurement result on the following conditions by gel permeation chromatography.
  • GPC apparatus Showa Denko SHODEX SYSTEM 11, Column: Four series of SHODEX KF-800P, KF-005, KF-003, KF-001, Mobile phase: THF, Flow rate: 1 ml / min, Column temperature: 45 ° C, Detector: RI, Conversion: polystyrene.
  • An epoxy compound (a1) has a structure shown, for example to following formula (2).
  • n is an integer in the range of 0 to 20, for example.
  • the average of n is particularly preferably in the range of 0 to 1.
  • the average of n is in the range of 0 to 1, even when the acid anhydride (a3) contains an acid dianhydride, an increase in excess molecular weight is likely to be suppressed.
  • the carboxylic acid (a2) includes unsaturated group-containing carboxylic acid (a2-1).
  • the carboxylic acid (a2) may contain only the unsaturated group-containing carboxylic acid (a2-1).
  • the carboxylic acid (a2) may contain an unsaturated group-containing carboxylic acid (a2-1) and a carboxylic acid other than the unsaturated group-containing carboxylic acid (a2-1).
  • the unsaturated group-containing carboxylic acid (a2-1) can contain, for example, a compound having only one ethylenically unsaturated group. More specifically, unsaturated group-containing carboxylic acid (a2-1) is, for example, acrylic acid, methacrylic acid, ⁇ -carboxy-polycaprolactone (n ⁇ 2) monoacrylate, crotonic acid, cinnamic acid, 2-acryloyloxy Ethylsuccinic acid, 2-methacryloyloxyethyl succinic acid, 2-acryloyloxyethyl phthalic acid, 2-methacryloyloxyethyl phthalic acid, 2-acryloyloxypropyl phthalic acid, 2-methacryloyloxypropyl phthalic acid, 2-acryloyloxyethylmaleic acid Acid, 2-methacryloyloxyethyl maleic acid, ⁇ -carboxyethyl acrylate, 2-acryloyloxyeth
  • the carboxylic acid (a2) may contain a polybasic acid (a2-2).
  • the polybasic acid (a2-2) is an acid in which two or more hydrogen atoms can be substituted for metal atoms in one molecule.
  • the polybasic acid (a2-2) preferably has two or more carboxyl groups.
  • the epoxy compound (a1) reacts with both the unsaturated group-containing carboxylic acid (a2-1) and the polybasic acid (a2-2).
  • the cross-linking of the epoxy group present in the two molecules of the epoxy compound (a1) with the polybasic acid (a2-1) results in an increase in molecular weight.
  • the insulation of the cured product of the photosensitive resin composition can be improved, and the dielectric loss tangent can be reduced.
  • the polybasic acid (a2-2) preferably contains a dicarboxylic acid.
  • polybasic acids (a2-2) include 4-cyclohexene-1,2-dicarboxylic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, It can contain one or more compounds selected from the group consisting of maleic acid, fumaric acid, phthalic acid, isophthalic acid and terephthalic acid.
  • the polybasic acid (a2-2) contains 4-cyclohexene-1,2-dicarboxylic acid.
  • a reactive solution is obtained by adding a carboxylic acid (a2) to a solvent solution of an epoxy compound (a1) and further adding a thermal polymerization inhibitor and a catalyst as needed, and stirring and mixing.
  • a temperature preferably 60 ° C. or more and 150 ° C. or less, particularly preferably 80 ° C. or more and 120 ° C. or less by a conventional method, an intermediate can be obtained.
  • Solvents include, for example, ketones such as methyl ethyl ketone and cyclohexanone, and aromatic hydrocarbons such as toluene and xylene, and ethyl acetate, butyl acetate, cellosolve acetate, butyl cellosolve acetate, carbitol acetate, butyl carbitol acetate, diethylene glycol monoethyl ether It can contain at least one component selected from the group consisting of acetate, acetates such as propylene glycol monomethyl ether acetate, and dialkyl glycol ethers.
  • the thermal polymerization inhibitor contains, for example, at least one of hydroquinone and hydroquinone monomethyl ether.
  • the catalyst is, for example, at least one selected from the group consisting of tertiary amines such as benzyldimethylamine and triethylamine, quaternary ammonium salts such as trimethylbenzylammonium chloride and methyltriethylammonium chloride, triphenylphosphine and triphenylstibin. It can contain one type of ingredient.
  • the catalyst comprises in particular triphenylphosphine. That is, it is preferable to react the epoxy compound (a1) with the carboxylic acid (a2) in the presence of triphenyl phosphine. In this case, the ring-opening addition reaction of the epoxy group in the epoxy compound (a1) and the carboxylic acid (a2) is particularly promoted, and a reaction rate (conversion rate) of 95% or more, 97% or more, or almost 100% is achieved. It is possible. In addition, the occurrence of ion migration in the layer containing the cured product of the photosensitive resin composition is suppressed, and the insulation of the layer containing the cured product is improved.
  • the amount of carboxylic acid (a2) relative to 1 mole of epoxy group of epoxy compound (a1) when reacting epoxy compound (a1) and carboxylic acid (a2) is within the range of 0.5 mole or more and 1.2 moles or less Is preferred. In this case, excellent photosensitivity 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 in the range of 0.5 mol or more and 1.2 mol or less with respect to 1 mol of the epoxy group of the epoxy compound (a1).
  • the carboxylic acid (a2) contains a carboxylic acid other than the unsaturated group-containing carboxylic acid (a2-1), the unsaturated group-containing carboxylic acid (a2-) relative to 1 mole of the epoxy group of the epoxy compound (a1)
  • the amount of 1) may be in the range of 0.5 mol or more and 0.95 mol or less.
  • the carboxylic acid (a2) contains a polybasic acid (a2-2)
  • the amount of the polybasic acid (a2-2) relative to 1 mole of the epoxy group of the epoxy compound (a1) is 0.025 mol or more. It is preferable that it is in the range of 25 mol or less. In this case, excellent photosensitivity and stability of the photosensitive resin composition can be obtained.
  • the epoxy compound (a1) it is also preferable to react the epoxy compound (a1) with the carboxylic acid (a2) under air bubbling.
  • the addition polymerization reaction of unsaturated groups can be suppressed to suppress the increase in molecular weight of the intermediate and the gelation of the solution of the intermediate.
  • excessive coloring of the carboxyl group-containing resin (A1), which is the final product, can be suppressed.
  • the intermediate thus obtained has a hydroxyl group formed by the reaction of the epoxy group in the epoxy compound (a1) and the carboxyl group in the carboxylic acid (a2).
  • the acid anhydride (a3) preferably contains an acid monoanhydride.
  • An acid monoanhydride is a compound which has one acid anhydride group.
  • the acid monoanhydride can contain the anhydride of a dicarboxylic acid.
  • Anhydrides such as 1,2,3,6-tetrahydrophthalic anhydride, phthalic anhydride, succinic anhydride, methylsuccinic anhydride, maleic anhydride, citraconic anhydride, glutaric anhydride, Itaconic anhydride, methyltetrahydrophthalic anhydride, methyl nadic anhydride, hexahydrophthalic anhydride, cyclohexane-1,2,4-tricarboxylic acid-1,2-anhydride, and methyl hexahydrophthalic anhydride And one or more compounds selected from the group consisting of In particular, it is preferable that the acid monoanhydride contains 1,2,3,6-tetrahydrophthalic anhydride.
  • the amount of 1,2,3,6-tetrahydrophthalic anhydride is preferably in the range of 20 mol% to 100 mol%, more preferably 40 mol% to 100 mol%, based on the whole acid anhydride. Is more preferable, but not limited thereto.
  • the acid anhydride (a3) preferably contains an acid dianhydride.
  • the acid dianhydride is a compound having two acid anhydride groups.
  • the acid dianhydride can contain an anhydride of tetracarboxylic acid.
  • Examples of the acid dianhydride are 1,2,4,5-benzenetetracarboxylic acid dianhydride, benzophenonetetracarboxylic acid dianhydride, methylcyclohexene tetracarboxylic acid dianhydride, tetracarboxylic acid dianhydride, naphthalene-1 1,4,5,8-tetracarboxylic acid dianhydride, ethylenetetracarboxylic acid dianhydride, 9,9'-bis (3,4-dicarboxyphenyl) fluorene dianhydride, glycerin bisan hydrotrimellitate mono Acetate, ethylene glycol bisanhydrotrimellitate, 3,3 ′, 4,4′-diphenyl
  • the acid dianhydride preferably contains an acid dianhydride having an aromatic ring.
  • the acid dianhydride preferably contains 3,3 ′, 4,4′-biphenyltetracarboxylic acid dianhydride.
  • the insulation of the cured product of the photosensitive resin composition can be improved while securing good developability of the photosensitive resin composition.
  • the transparency of the photosensitive resin composition is improved, and the resolution is improved accordingly.
  • the amount of 3,3 ′, 4,4′-biphenyltetracarboxylic acid dianhydride is preferably in the range of 20 mol% to 100 mol%, and preferably 40 mol% to 100 mol based on the total amount of the acid dianhydride. It is more preferable to be in the range of% or less, but it is not limited thereto.
  • an acid anhydride (a3) is added to a solvent solution of an intermediate, and if necessary, a thermal polymerization inhibitor and a catalyst are added and mixed by stirring to obtain a reactive solution.
  • a reactive solution By reacting this reactive solution at a temperature of preferably 60 ° C. or more and 150 ° C. or less, particularly preferably 80 ° C. or more and 120 ° C. or less, a carboxyl group-containing resin (A1) can be obtained.
  • the solvent, the catalyst and the polymerization inhibitor appropriate ones can be used, and the solvent, the catalyst and the polymerization inhibitor used in the synthesis of the intermediate can be used as they are.
  • the catalyst comprises in particular triphenylphosphine. That is, it is preferable to react the intermediate with the acid anhydride (a3) in the presence of triphenylphosphine. In this case, the reaction between the secondary hydroxyl group in the intermediate and the acid anhydride (a3) is particularly promoted, and a reaction rate (conversion rate) of 90% or more, 95% or more, 97% or more, or almost 100% is achieved. It is possible. In addition, the occurrence of ion migration in the layer containing the cured product of the photosensitive resin composition is suppressed, and the insulation of the layer containing the cured product is further improved.
  • the carboxyl group-containing resin (A) may contain a carboxyl group-containing resin having an aromatic ring and not having photopolymerization.
  • the carboxyl group-containing resin having an aromatic ring and not having photopolymerizability contains, for example, a polymer of an ethylenically unsaturated monomer containing an ethylenically unsaturated compound having a carboxyl group.
  • Ethylenically unsaturated compounds having a carboxyl group are acrylic acid, methacrylic acid, ⁇ -carboxy-polycaprolactone (n ⁇ 2) monoacrylate, 2- (meth) acryloyloxyethyl phthalate, 2- (meth) acryloyloxy Compounds such as ethyl-2-hydroxyethyl phthalate can be included.
  • the ethylenically unsaturated compound having a carboxyl group can also contain a reaction product of pentaerythritol triacrylate, pentaerythritol trimethacrylate or the like with a dibasic acid anhydride.
  • the ethylenically unsaturated monomer is a carboxyl group such as a linear or branched aliphatic or alicyclic (but may have a partially unsaturated bond in the ring) (meth) acrylic acid ester, etc. It may further contain an ethylenically unsaturated compound which does not have.
  • the carboxyl group-containing resin (A) contains a resin other than the carboxyl group-containing resin (A1), that is, a carboxyl group-containing resin not having a bisphenol fluorene skeleton (hereinafter, also referred to as a carboxyl group-containing resin (A2)) Good.
  • the carboxyl group-containing resin (A2) can contain, for example, a compound having a carboxyl group and not having photopolymerization (hereinafter, referred to as component (A2-1)).
  • component (A2-1) contains, for example, a polymer of an ethylenically unsaturated monomer containing an ethylenically unsaturated compound having a carboxyl group.
  • Ethylenically unsaturated compounds having a carboxyl group can contain compounds such as acrylic acid, methacrylic acid, ⁇ -carboxy-polycaprolactone (n ⁇ 2) monoacrylate and the like.
  • the ethylenically unsaturated compound having a carboxyl group can also contain a reaction product of pentaerythritol triacrylate, pentaerythritol trimethacrylate or the like with a dibasic acid anhydride.
  • Ethylenically unsaturated monomers are 2- (meth) acryloyloxyethyl phthalate, 2- (meth) acryloyloxyethyl-2-hydroxyethyl phthalate, linear or branched aliphatic or alicyclic (but with It may further contain an ethylenically unsaturated compound which does not have a carboxyl group, such as (meth) acrylic acid ester which may have a partial unsaturated bond in the ring.
  • the carboxyl group-containing resin (A2) may contain a compound having a carboxyl group and an ethylenically unsaturated group (hereinafter referred to as component (A2-2)).
  • the carboxyl group-containing resin (A2) may contain only the component (A2-2).
  • the component (A2-2) is, for example, an intermediate which is a reaction product of an epoxy compound (x1) having two or more epoxy groups in one molecule and an ethylenically unsaturated compound (x2), a polyvalent carboxylic acid and It contains a resin (referred to as a first resin (x)) which is a reaction product with at least one compound (x3) selected from the group of anhydrides.
  • the first resin (x) is obtained by, for example, adding a compound (x3) to an intermediate obtained by reacting an epoxy group in the epoxy compound (x1) with a carboxyl group in the ethylenically unsaturated compound (x2) It is obtained by
  • the epoxy compound (x1) can contain an appropriate epoxy compound such as a cresol novolac epoxy compound, a phenol novolac epoxy compound, and a biphenyl novolac epoxy compound.
  • the epoxy compound (x1) preferably contains at least one compound selected from the group consisting of biphenyl novolac epoxy compounds and cresol novolac epoxy compounds.
  • the epoxy compound (x1) may contain only a biphenyl novolac epoxy compound, or may contain only a cresol novolac epoxy compound.
  • the epoxy compound (x1) may contain a polymer of the ethylenically unsaturated compound (z).
  • the ethylenically unsaturated compound (z) contains, for example, a compound (z1) having an epoxy group such as glycidyl (meth) acrylate, or further does not have an epoxy group such as 2- (meth) acryloyloxyethyl phthalate Contains the compound (z2).
  • the ethylenically unsaturated compound (x2) preferably contains at least one of acrylic acid and methacrylic acid.
  • the compound (x3) contains one or more compounds selected from the group consisting of polyvalent carboxylic acids such as phthalic acid, tetrahydrophthalic acid and methyltetrahydrophthalic acid, and anhydrides of these polyvalent carboxylic acids, for example.
  • the compound (x3) preferably contains at least one polyvalent carboxylic acid selected from the group of phthalic acid, tetrahydrophthalic acid and methyltetrahydrophthalic acid.
  • the component (A2-2) is a resin which is a reaction product of a polymer of an ethylenically unsaturated monomer containing an ethylenically unsaturated compound having a carboxyl group and an ethylenically unsaturated compound having an epoxy group (second Resin (y)) may be contained.
  • the ethylenically unsaturated monomer may further contain an ethylenically unsaturated compound having no carboxyl group.
  • the second resin (y) is obtained by reacting an ethylenically unsaturated compound having an epoxy group with a part of the carboxyl group in the polymer.
  • the ethylenically unsaturated monomer may further contain an ethylenically unsaturated compound having no carboxyl group.
  • Ethylenically unsaturated compounds having a carboxyl group include, for example, compounds such as acrylic acid, methacrylic acid, ⁇ -carboxy-polycaprolactone (n ⁇ 2) monoacrylate, pentaerythritol triacrylate, and pentaerythritol trimethacrylate.
  • Ethylenically unsaturated compounds having no carboxyl group are, for example, 2- (meth) acryloyloxyethyl phthalate, 2- (meth) acryloyloxyethyl-2-hydroxyethyl phthalate, linear or branched aliphatic or fat It contains compounds such as (meth) acrylic acid esters of a cyclic group (however, some unsaturated bonds may be present in the ring).
  • the ethylenically unsaturated compound having an epoxy group preferably contains glycidyl (meth) acrylate.
  • the carboxyl group-containing resin (A) contains only the carboxyl group-containing resin (A1), only the carboxyl group-containing resin (A2), or the carboxyl group-containing resin (A1) and the carboxyl group-containing resin (A2).
  • the carboxyl group-containing resin (A) comprises 30 of the carboxyl group-containing resin (A1). It is preferable to contain mass% or more, 60 mass% or more is more preferable, 100 mass% is more preferable to be contained.
  • the content of the carboxyl group-containing resin (A) is preferably in the range of 5% by mass to 85% by mass with respect to the solid content of the photosensitive resin composition, and in the range of 10% by mass to 75% by mass.
  • the content is more preferably in the range of 26% by mass to 60% by mass, and particularly preferably in the range of 30% by mass to 45% by mass.
  • solid content amount is the total amount of all the components except volatile components, such as a solvent, from the photosensitive resin composition.
  • the solid content acid value of the carboxyl group-containing resin (A) is preferably in the range of 40 mg KOH / g to 160 mg KOH / g. In this case, the stability of the photosensitive resin composition is particularly improved.
  • the acid value is more preferably in the range of 60 mg KOH / g to 140 mg KOH / g, and more preferably in the range of 80 mg KOH / g to 135 mg KOH / g, and the acid value is 90 mg KOH / g to 130 mg KOH / g. It is particularly preferable if it is within the following range.
  • the unsaturated compound (B) can impart photocurability to the photosensitive resin composition.
  • Unsaturated compounds (B) are, for example, monofunctional (meth) acrylates such as 2-hydroxyethyl (meth) acrylate; and diethylene glycol di (meth) acrylate, trimethylolpropane di (meth) acrylate, trimethylolpropane tri (meth) Acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, ⁇ -caprolactone modified pentaerythritol hexaacrylate, tricyclodecanedihydrate It can contain at least one compound selected from the group consisting of polyfunctional (meth) acrylates such as methanol di (meth) acryl
  • the unsaturated compound (B) preferably contains a trifunctional compound, ie, a compound having three unsaturated bonds in one molecule.
  • a trifunctional compound ie, a compound having three unsaturated bonds in one molecule.
  • trifunctional compounds are, for example, trimethylolpropane tri (meth) acrylate, EO modified trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, ethoxylated isocyanurate tri (meth) acrylate and ⁇ -caprolactone modified It can contain at least one compound selected from the group consisting of tris- (2-acryloxyethyl) isocyanurate and ethoxylated glycerine tri (meth) acrylate.
  • the unsaturated compound (B) also preferably contains a phosphorus-containing compound (phosphorus-containing unsaturated compound).
  • a phosphorus-containing compound phosphorus-containing unsaturated compound
  • the phosphorus-containing unsaturated compound is, for example, 2-methacryloyloxyethyl acid phosphate (as a specific example, product number light ester P-1M and light ester P-2M manufactured by Kyoeisha Chemical Co., Ltd.), 2-acryloyloxyethyl acid phosphate (Specific example, product number light acrylate P-1A, manufactured by Kyoeisha Chemical Co., Ltd.), diphenyl-2-methacryloyloxyethyl phosphate (specific example, product number MR-260, manufactured by Daihachi Kogyo Co., Ltd.), and Showa Polymer Co., Ltd.
  • HFA-6003 which is an addition reaction product of HFA series (specifically, dipentaerythritol hexaacrylate and HCA (9,10-dihydro-9-oxa-10-phosphophenanthrene-10-oxide) as an example) HFA-6007, caprolactone Part number HFA-3003 and HFA-6127, etc., which are addition reaction products of modified dipentaerythritol hexaacrylate and HCA (9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide) It can contain at least one compound selected from the group.
  • the unsaturated compound (B) may contain a prepolymer.
  • the prepolymer is, for example, at least one selected from the group consisting of a prepolymer obtained by polymerizing a monomer having an ethylenically unsaturated bond and then adding an ethylenically unsaturated group, and an oligo (meth) acrylate prepolymer. Can be contained.
  • Oligo (meth) acrylate prepolymers are, for example, epoxy (meth) acrylate, polyester (meth) acrylate, urethane (meth) acrylate, alkyd resin (meth) acrylate, silicone resin (meth) acrylate, and pyran resin (meth) acrylate And at least one component selected from the group consisting of
  • the photopolymerization initiator (C) contains, for example, an acyl phosphine oxide photopolymerization initiator. That is, the photosensitive resin composition contains, for example, an acylphosphine oxide-based photopolymerization initiator. In this case, when the photosensitive resin composition is exposed to ultraviolet light, high sensitivity can be imparted to the photosensitive resin composition. In addition, the occurrence of ion migration in the layer containing the cured product of the photosensitive resin composition is suppressed, and the insulation reliability of the same layer is further improved.
  • the acyl phosphine oxide photopolymerization initiator is unlikely to inhibit the electrical insulation of the cured product. For this reason, a cured product having excellent electrical insulation can be obtained by exposing and curing the photosensitive resin composition, and the cured product is suitable as the interlayer insulating layer 7.
  • Acyl phosphine oxide photopolymerization initiators are, for example, monoacyl phosphine oxides such as 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide and 2,4,6-trimethylbenzoyl-ethyl-phenyl-phosphinate Photopolymerization initiators, as well as bis- (2,6-dichlorobenzoyl) phenyl phosphine oxide, bis- (2,6-dichlorobenzoyl) -2,5-dimethylphenyl phosphine oxide, bis- (2,6- Dichlorobenzoyl) -4-propylphenyl phosphine oxide, bis- (2,6-dichlorobenzoyl) -1-naphthyl phosphine oxide, bis- (2,6-dimethoxybenzoyl) phenyl phosphine oxide, bis- (2, 6-Dimethoxybenzoyl -2,4,
  • the acyl phosphine oxide photopolymerization initiator contains 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, and the acyl phosphine oxide photopolymerization initiator is 2,4,6-trimethylbenzoyl. It is also preferred to contain only diphenyl-phosphine oxide.
  • the photopolymerization initiator (C) preferably contains a hydroxyketone photopolymerization initiator in addition to the acyl phosphine oxide photopolymerization initiator. That is, the photosensitive resin composition preferably contains a hydroxyketone photopolymerization initiator. In this case, it is possible to impart higher photosensitivity to the photosensitive resin composition as compared with the case where the hydroxyketone photopolymerization initiator is not contained. Thus, when the coating film formed of the photosensitive resin composition is cured by irradiation with ultraviolet light, the coating film can be sufficiently cured from the surface to the deep portion.
  • hydroxyketone-based photopolymerization initiators examples include 1-hydroxy-cyclohexyl-phenyl-ketone, phenylglyoxyc acid methyl ester, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2- Methyl-1-propan-1-one, 2-hydroxy-1- ⁇ 4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] phenyl ⁇ -2-methyl-propan-1-one and 2 And -hydroxy-2-methyl-1-phenyl-propan-1-one.
  • the mass ratio of the acyl phosphine oxide type photopolymerization initiator to the hydroxy ketone type photopolymerization initiator is preferably in the range of 1: 0.01 to 1:10.
  • the curability in the vicinity of the surface of the coating film formed of the photosensitive resin composition and the curability in the deep portion can be improved in a well-balanced manner.
  • the organic filler (E) may cause light scattering in the photosensitive resin composition at the time of exposure. In this case, there is a possibility that the photosensitive resin composition may fail to obtain good developability.
  • the mass ratio of the acyl phosphine oxide type photopolymerization initiator to the hydroxy ketone type photopolymerization initiator is It is particularly preferable that the ratio is in the range of 1: 0.01 to 1: 1.
  • the photopolymerization initiator (C) also preferably contains a photopolymerization initiator having a benzophenone skeleton. That is, the photosensitive resin composition contains an acyl phosphine oxide type photo polymerization initiator and a photo polymerization initiator having a benzophenone skeleton, or an acyl phosphine oxide type photo polymerization initiator, a hydroxy ketone type photo polymerization initiator and a benzophenone It is also preferable to contain a photoinitiator having a skeleton. In this case, when the coating film formed of the photosensitive resin composition is partially exposed and then developed, the curing of the unexposed part is suppressed, and the resolution is particularly high.
  • cured material of the photosensitive resin composition of very fine pattern can be formed.
  • the interlayer insulating layer 7 of the multilayer printed wiring board 20 is produced from the photosensitive resin composition and the small diameter holes 6 for the vias 10 are provided in the interlayer insulating layer 7 by photolithography (FIG. 1C and FIG. 1D Reference)
  • the small diameter hole 6 can be formed precisely and easily.
  • the photopolymerization initiator having a benzophenone skeleton include bis (diethylamino) benzophenone.
  • the amount of the photopolymerization initiator having a benzophenone skeleton with respect to the acyl phosphine oxide photopolymerization initiator is preferably in the range of 0.5% by mass to 20% by mass.
  • the resolution is particularly high.
  • the amount of the photopolymerization initiator having a benzophenone skeleton with respect to the acyl phosphine oxide photopolymerization initiator is 20% by mass or less, the electrical insulating property of the cured product of the photosensitive resin composition and the light having a benzophenone skeleton It is hard to inhibit the polymerization initiator.
  • the amount of bis (diethylamino) benzophenone relative to the acyl phosphine oxide photopolymerization initiator is preferably in the range of 0.5% by mass to 20% by mass.
  • the organic filler (E) may cause light scattering in the photosensitive resin composition at the time of exposure.
  • the photosensitive resin composition may fail to obtain good developability.
  • the amount of the photopolymerization initiator having a benzophenone skeleton is 1% by mass or more with respect to the acyl phosphine oxide photopolymerization initiator It is particularly preferable to be in the range of 18% by mass or less.
  • the amount of bis (diethylamino) benzophenone is particularly preferably in the range of 1% by mass to 18% by mass with respect to the acyl phosphine oxide photopolymerization initiator.
  • the photopolymerization initiator (C) is not limited to the above preferred examples, and may contain at least one component appropriately selected from known compounds.
  • the photosensitive resin composition may further contain known photopolymerization accelerators, sensitizers and the like.
  • photosensitive resin compositions include benzoin and its alkyl ethers; acetophenones such as acetophenone and benzyl dimethyl ketal; anthraquinones such as 2-methylanthraquinone; 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2- Thioxanthones such as isopropyl thioxanthone, 4-isopropyl thioxanthone, 2,4-diisopropyl thioxanthone; benzophenones such as benzophenone, 4-benzoyl-4'-methyl diphenyl sulfide; xanthones such as 2,4-diisopropyl xanthone; ⁇ -hydroxy ketones such as hydroxy-2-methyl-1-phenyl-propan-1-one; 2-methyl-1- [
  • the photosensitive resin composition may optionally contain at least one of a photopolymerization initiator for visible light exposure and a photopolymerization initiator for near infrared light exposure.
  • the photosensitive resin composition contains, together with the photopolymerization initiator (C), a coumarin derivative such as 7-diethylamino-4-methylcoumarin which is a sensitizer for laser exposure method, a carbocyanine dye system, a xanthene dye system and the like. May be
  • An epoxy compound (D) can provide thermosetting property to the photosensitive resin composition.
  • the epoxy compound (D) preferably has at least two epoxy groups in one molecule.
  • the epoxy compound (D) may be a solvent-insoluble epoxy compound or a general-purpose solvent-soluble epoxy compound.
  • the epoxy compound (D) is a phenol novolac epoxy resin (specific example, product number EPICLON N-775 manufactured by DIC Corporation), cresol novolac epoxy resin (specific example, product number EPICLON N-695 manufactured by DIC Corporation), bisphenol A Novolak type epoxy resin (Specific example No. EPICLON N-865 manufactured by DIC Corporation), bisphenol A type epoxy resin (Specific example No.
  • Product number YDC-1312 Tertiary butyl catechol type epoxy resin (Specific example as product number EPICLON HP-820 manufactured by DIC Corporation), Dicyclopentadiene type epoxy resin (Specific example as DIC product number EPICLO) HP-7200), adamantane type epoxy resin (specific example, product number ADAMANTATE X-E-201 manufactured by Idemitsu Kosan Co., Ltd.), bisphenol type epoxy resin (specific example, product number YSLV-80XY manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.), biphenyl ether type Epoxy resin (as a specific example, product number YSLV-80DE manufactured by Nippon Steel Sumikin Chemical Co., Ltd.), tetrakisphenol ethane type epoxy resin (as a specific example, product number GTR-1800 manufactured by Nippon Kayaku Co., Ltd.) epoxy resin having a bisphenol fluorene skeleton
  • the epoxy compound (D) preferably contains a crystalline epoxy resin.
  • a crystalline epoxy resin is an epoxy resin which has melting
  • the crystalline epoxy resin is, for example, triglycidyl isocyanurate (1,3,5-tris (2,3-epoxypropyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H)- Trione), hydroquinone type crystalline epoxy resin (specific example: product name YDC-1312 manufactured by Nippon Steel Sumikin Chemical Co., Ltd.), biphenyl type crystalline epoxy resin (specific example: No.
  • YX-4000 manufactured by Mitsubishi Chemical Co., Ltd. diphenyl ether type Crystalline epoxy resin (as a specific example, product number YSLV-80DE manufactured by Nippon Steel Sumikin Chemical Co., Ltd.), bisphenol-type crystalline epoxy resin (as a specific example, product number YSLV-80XY, manufactured by Nippon Steel Sumikin Chemical Co., Ltd.), tetrakisphenol ethane type crystallinity Epoxy resin (as a specific example, product number GTR-1800 manufactured by Nippon Kayaku Co., Ltd. It may contain at least one component selected from the group consisting of bisphenol fluorene type crystalline epoxy resin (epoxy resin having a structure (S7) as a specific example).
  • S7 structure
  • the amount of the crystalline epoxy resin relative to the epoxy compound (D) is preferably in the range of 10% by mass to 100% by mass, and more preferably in the range of 30% by mass to 100% by mass, 35 It is more preferable that the content be in the range of not less than 100% by mass. In this case, the thermosetting reaction of the carboxyl group-containing resin and the epoxy resin is suppressed in the steps before the thermosetting of the photosensitive resin composition, and the developability can be improved.
  • the crystalline epoxy resin preferably contains a crystalline epoxy resin having a melting point of 110 ° C. or less. That is, the epoxy compound (D) preferably contains a crystalline epoxy resin having a melting point of 110 ° C. or less. In this case, the developability by the alkaline aqueous solution of the photosensitive resin composition is particularly improved. Crystalline epoxy resins having a melting point of 110 ° C.
  • biphenyl type epoxy resins specifically example, product number YX4000 manufactured by Mitsubishi Chemical Corporation
  • biphenyl ether type epoxy resins specifically example, product number YSLV-80DE manufactured by Nippon Steel Sumikin Chemical Co., Ltd.
  • at least one component selected from the group consisting of bisphenol-type epoxy resins specifically example, product number YSLV-80XY manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.
  • the epoxy compound (D) may contain triglycidyl isocyanurate.
  • the triglycidyl isocyanurate is preferably a ⁇ -form having a structure in which three epoxy groups are bonded in the same direction to the S-triazine ring skeleton surface, or this ⁇ -body and the S-triazine ring skeleton surface
  • the crystalline epoxy resin preferably also contains a crystalline epoxy resin having a melting point of less than 100 ° C. That is, the epoxy compound (D) also 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.
  • the crystalline epoxy resin having a melting point of less than 100 ° C. has high compatibility with components other than the epoxy resin (D) in the photosensitive resin composition, solvents, and the like, it is dispersed in the photosensitive resin composition , Easy to be uniformed. Furthermore, when the photosensitive resin composition contains a crystalline epoxy resin having a melting point of less than 100 ° C., crystallization hardly occurs even at a low temperature.
  • Crystalline epoxy resins having a melting point of less than 100 ° C. are, for example, biphenyl ether type epoxy resins (specific example, product number YSLV-80DE manufactured by Nippon Steel Sumikin Chemical Co., Ltd.), and bisphenol type epoxy resins (specific example, product number YSLV manufactured by Nippon Steel Sumikin Chemical) And at least one component selected from the group consisting of an epoxy resin having a bisphenol fluorene skeleton (an epoxy resin having a structure (S7) as a specific example).
  • the equivalent of the epoxy group contained in the crystalline epoxy resin having a melting point of less than 100 ° C. is the carboxyl group contained in the carboxyl group-containing resin (A) It is preferable if it is in the range of 0.2 or more and 2.0 or less to one equivalent, more preferably in the range of 0.25 or more and 1.7 or less, and in the range of 0.3 or more and 1.5 or less Is more preferable.
  • the epoxy compound (D) may contain a phosphorus-containing epoxy resin.
  • the phosphorus-containing epoxy resin is, for example, phosphoric acid-modified bisphenol F-type epoxy resin (specific example, product number EPICLON EXA-9726 and EPICLON EXA-9710 manufactured by DIC Corporation), product number Epotote FX-305 manufactured by Nippon Steel Sumikin Chemical Co., Ltd. Etc.
  • the photosensitive resin composition preferably further contains an organic filler (E).
  • an organic filler (E) In this case, the adhesion between the interlayer insulating layer 7 and the conductor layer 8 is further improved.
  • the organic filler (E) can also improve the thixotropy of the photosensitive resin composition and improve the stability (particularly storage stability).
  • the organic filler (E) preferably has a polar group.
  • the polar group preferably includes at least one group selected from the group consisting of a carboxyl group, an amino group and a hydroxyl group. In this case, the adhesion is particularly improved.
  • the developability of the cured product of the photosensitive resin composition is improved, and when the photosensitive resin composition contains a crystalline epoxy compound, the photosensitive resin of the crystalline epoxy compound
  • the solubility in the composition can be improved to prevent crystallization.
  • the dispersibility of the organic filler (E) in the photosensitive resin composition is improved.
  • the polar group particularly contains an amino group
  • the reactivity between the carboxyl group-containing resin (A) and the epoxy compound (D) can be enhanced, whereby the acid resistance and alkali resistance of the cured film can be improved.
  • the acid value of the organic filler (E) is preferably in the range of 1 mg KOH / g to 60 mg KOH / g. If the acid value is less than 1 mg KOH / g, the stability of the photosensitive resin composition and the developability of the cured product may be reduced. If the acid value is more than 60 mg KOH / g, the moisture resistance reliability of the cured product may be reduced.
  • the acid value of the organic filler (E) is more preferably 3 mg KOH / g or more, and even more preferably 40 mg KOH / g or less.
  • the organic filler (E) is, for example, a carboxylic acid monomer having a polymerizable unsaturated double bond such as acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, etc. It is obtained by polymerization or crosslinking.
  • an organic filler (E) is mix
  • the organic filler (E) preferably contains a rubber component having a polar group.
  • the polar group contains, for example, a carboxyl group, or contains a carboxyl group and a hydroxyl group.
  • the rubber component can impart flexibility to the cured product of the photosensitive resin composition.
  • the rubber component may be composed of a resin.
  • the rubber component preferably contains at least one polymer selected from the group consisting of crosslinked acrylic rubber, crosslinked NBR, crosslinked MBS and crosslinked SBR.
  • the photosensitive resin composition can have high transparency and can improve resolution.
  • flexibility can be imparted to the cured product of the photosensitive resin composition more effectively by the rubber component.
  • NBR is a copolymer of butadiene and acrylonitrile and is classified into nitrile rubber.
  • MBS is a copolymer composed of three components of methyl methacrylate, butadiene and styrene, and is classified into butadiene based rubbers.
  • SBR is a copolymer of styrene and butadiene and is classified into styrene rubber.
  • a specific example of the organic filler (E) provided as a dispersion is a product of JSR Corporation, product number XER-91-MEK (with a concentration of 15% by weight of a crosslinked rubber (NBR) having a carboxyl group with an average primary particle diameter of 0.07 ⁇ m) Methyl ethyl ketone dispersion, acid value 10.0 mg KOH / g), product number XER-32 and XER-92 manufactured by JSR Corporation, and product number XSK-500 manufactured by JSR Corporation (crosslinked rubber having carboxyl group and hydroxyl group (SBR)
  • NBR crosslinked rubber
  • SBR crosslinked rubber having carboxyl group and hydroxyl group
  • the organic filler (E) may contain components other than the rubber component.
  • the component 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 particles having a carboxyl group can contain at least one component selected from the group consisting of non-crosslinked styrene / acrylic resin particles and crosslinked styrene / acrylic resin particles.
  • Specific examples of the non-crosslinked styrene / acrylic resin fine particles include Part No. FS-201 (average primary particle diameter 0.5 ⁇ m) manufactured by Nippon Paint Industrial Coatings Co., Ltd.
  • crosslinked styrene / acrylic resin particles are manufactured by Nippon Paint Industrial Coatings Co., Ltd., part number MG-351 (average primary particle diameter 1.0 ⁇ m), and part number BGK-001 (average primary particle diameter 1.0 ⁇ m) including.
  • the organic filler (E) is, for example, melamine, dicyandiamide, imidazole compound, acetoguanamine, benzoguanamine, melamine-phenol-formalin resin, triazine compound, ethyl diamino-s-triazine, 2, It contains at least one component selected from the group consisting of triazine derivatives such as 4-diamino-S-triazine, 2,4-diamino-6-xylyl-S-triazine, thiazoles, and triazoles.
  • the organic filler (E) preferably contains melamine particles.
  • the adhesion between the interlayer insulating layer 7 and the conductor layer 8 is particularly improved.
  • the organic filler (E) can contain at least one component selected from the group consisting of the components described above. Moreover, the organic filler (E) can also contain the component which has a polar group other than the component demonstrated above.
  • the average primary particle size of the organic filler (E) is preferably 1 ⁇ m or less. In this case, the thixotropy of the photosensitive resin composition is efficiently enhanced. Therefore, the stability of the photosensitive resin composition is further improved.
  • the average primary particle diameter of the organic filler (E) is, for example, 0.001 ⁇ m or more.
  • the average primary particle size of the organic filler (E) is a median size (D50) measured by a laser diffraction type particle size distribution measuring apparatus.
  • the average primary particle size of the organic filler (E) is preferably 0.1 ⁇ m or less. In this case, the stability of the photosensitive resin composition is further improved, and the scattering during exposure is suppressed, whereby the resolution is further improved.
  • the particle diameter of the organic filler (E) in the photosensitive resin composition is preferably 10 ⁇ m or less.
  • the organic filler (E) may contain secondary particles formed by aggregation in the photosensitive resin composition.
  • the particle size of the organic filler (E) in the photosensitive resin composition means the particle size of particles including secondary particles.
  • the particle diameter of the organic filler (E) in the photosensitive resin composition can be measured using a laser diffraction / scattering type particle size distribution measuring device or an optical microscope.
  • the organic filler (E) in the photosensitive resin composition When the particle size of the organic filler (E) in the photosensitive resin composition is 10 ⁇ m or less, the organic filler (E) can be well dispersed in the photosensitive resin composition and in the interlayer insulating layer 7, whereby The adhesion between the interlayer insulating layer 7 and the conductor layer 8 is particularly improved. In addition, the stability of the photosensitive resin composition is further improved, and the scattering at the time of exposure is suppressed, whereby the resolution is further improved.
  • the particle diameter of the organic filler (E) in the photosensitive resin composition is more preferably 5 ⁇ m or less, still more preferably 1 ⁇ m or less, and particularly preferably 0.5 ⁇ m or less.
  • the particle size is, for example, 0.01 ⁇ m or more.
  • the photosensitive resin composition may contain an organic solvent.
  • the organic solvent is used for the purpose of liquefaction or varnishing of the photosensitive resin composition, adjustment of viscosity, adjustment of coating property, adjustment of film forming property, and the like.
  • organic solvent examples include straight-chain, branched, secondary or polyhydric alcohols such as ethanol, propyl alcohol, isopropyl alcohol, hexanol and ethylene glycol; ketones such as methyl ethyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene and xylene Kinds: Petroleum-based aromatic mixed solvents such as Swazole series (manufactured by Maruzen Petrochemical Co., Ltd.) and Solvesso series (manufactured by Exxon Chemical Co., Ltd.); Cellosolves such as cellosolve and butyl cellosolve; Carviles such as carbitol and butyl carbitol Propylene glycol alkyl ethers such as propylene glycol methyl ether; polypropylene glycol alkyl ethers such as dipropylene glycol methyl ether; ethyl acetate, butyl acetate, cellosolve acetate,
  • 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 in the range of 5% by mass to 85% by mass, and is preferably in the range of 10% by mass to 75% by mass. It is more preferable if it is in the range of 30% by mass to 60% by mass.
  • the amount of the carboxyl group-containing resin (A1) relative to the solid content of the photosensitive resin composition is preferably in the range of 5% by mass to 85% by mass, and preferably in the range of 10% by mass to 75% by mass. If there exist, it is more preferable if it exists in the range of 30 to 60 mass%.
  • the amount of the unsaturated compound (B) relative to the carboxyl group-containing resin (A) is preferably in the range of 1% by mass to 50% by mass, and more preferably in the range of 10% by mass to 45% by mass More preferably, it is in the range of 21% by mass to 40% by mass.
  • 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 to 30% by mass, and in the range of 1% by mass to 25% by mass Is more preferable.
  • the total of the equivalents of epoxy groups contained in the epoxy compound (D) is at least 0.7 or more per 2.5 equivalents of carboxyl groups contained in the carboxyl group-containing resin (A) It is preferably within the following range, more preferably within the range of 0.7 or more and 2.3 or less, and still more preferably within the range of 0.7 or more and 2.0 or less. Moreover, it is preferable that the sum total of the equivalent of the epoxy group contained in a crystalline epoxy resin exists in the range of 0.1 or more and 2.0 or less with respect to 1 equivalent of carboxyl groups contained in a carboxyl group-containing resin (A).
  • the total equivalent 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) is preferably in the range of 1 part by mass to 50 parts by mass with respect to 100 parts by mass of the carboxyl group-containing resin (A).
  • the amount of the organic filler (E) is 1 part by mass or more, the adhesion between the interlayer insulating layer 7 and the conductor layer 8 is particularly high, and good copper of the cured product of the photosensitive resin composition Plating adhesion is obtained.
  • the outstanding resolution of the photosensitive resin composition is obtained because the quantity of an organic filler (E) is 50 mass parts or less.
  • the content of the organic filler (E) falls within the above range, the thixotropy of the photosensitive resin composition is enhanced, and the stability is improved.
  • the amount of the organic filler (E) is more preferably 5 parts by mass or more, and further preferably 10 parts by mass or more.
  • the amount of the organic filler (E) is more preferably 30 parts by mass or less, and further preferably 20 parts by mass or less.
  • the amount of the organic solvent is such that when the coating film formed from the photosensitive resin composition is dried, the organic solvent is rapidly volatilized and eliminated, that is, the organic solvent It is preferable to adjust so that it does not remain in a dry film.
  • the amount of the organic solvent with respect to the entire photosensitive resin composition is preferably in the range of 0% by mass to 99.5% by mass, and more preferably in the range of 15% by mass to 60% by mass .
  • a ratio is suitably adjusted according to a coating method.
  • solid content amount is the total amount of all the components except volatile components, such as a solvent, from the photosensitive resin composition.
  • the photosensitive resin composition may further contain components other than the above components, as long as the effects of the present embodiment are not impaired.
  • the photosensitive resin composition may contain an inorganic filler.
  • the inorganic filler can contain, for example, one or more materials selected from the group consisting of barium sulfate, crystalline silica, nanosilica, carbon nanotubes, talc, bentonite, hydrotalcite, aluminum hydroxide, magnesium hydroxide, and titanium oxide .
  • the inorganic filler contains a white material such as titanium oxide or zinc oxide, the photosensitive resin composition and the cured product thereof can be whitened with the white material.
  • 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.
  • Photosensitive resin compositions include tolylene diisocyanate type, morpholine diisocyanate type, isophorone diisocyanate type and hexamethylene diisocyanate type blocked isocyanates blocked with caprolactam, oxime, malonic acid ester, etc .; melamine resin, n-butylated melamine resin Amino resins such as isobutylated melamine resin, butylated urea resin, butylated melamine urea cocondensing resin, benzoguanamine cocondensing resin; various thermosetting resins other than the above; UV curable epoxy (meth) acrylate; bisphenol A type Resins obtained by adding (meth) acrylic acid to epoxy resins such as phenol novolac type, cresol novolac type and alicyclic type; and diallyl phthalate resin, phenoxy resin, urethane resin, fluorine resin At least one resin selected from the group consisting of polymer compounds may be contained.
  • the photosensitive resin composition may contain a curing agent for curing the epoxy compound (D).
  • the curing agent include imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, 1- (2 Imidazole derivatives such as -cyanoethyl) -2-ethyl-4-methylimidazole; dicyandiamide, benzyldimethylamine, 4- (dimethylamino) -N, N-dimethylbenzylamine, 4-methoxy-N, N-dimethylbenzylamine, Amine compounds such as 4-methyl-N, N-dimethylbenzylamine; hydrazine compounds such as adipic acid hydrazide and sebacic acid hydrazide; phosphorus compounds such as triphenylphosphine; acid an
  • the photosensitive resin composition may contain an adhesion promoter.
  • adhesion promoters include guanamine, acetoguanamine, benzoguanamine, 2,4-diamino-6-methacryloyloxyethyl-S-triazine, 2-vinyl-4,6-diamino-S-triazine, 2-vinyl- S-triazine derivatives such as 4,6-diamino-S-triazine-isocyanuric acid adduct, 2,4-diamino-6-methacryloyloxyethyl-S-triazine-isocyanuric acid adduct and the like can be mentioned.
  • the photosensitive resin composition may contain a rheology control agent.
  • the rheology control agent facilitates optimization of the viscosity of the photosensitive resin composition.
  • a rheology control agent for example, urea modified medium polarity polyamide (product number BYK-430, BYK-431 manufactured by Big Chemie Japan Ltd.), polyhydroxycarboxylic acid amide (product number BYK manufactured by Big Chemie Japan Ltd.), Modified urea (product number BYK-410, BYK-411, BYK-420 manufactured by Big Chemie Japan Ltd.), high molecular weight urea derivative (product number BYK-415 manufactured by Big Chemie Japan Ltd.), urea modified urethane (Big Chemie Japan Ltd. stock Part No.
  • BYK made by company, BYK-425
  • polyurethane part No. BYK made by Big Chemie Japan KK
  • castor oil wax polyethylene wax, polyamide wax, bentonite, silica, silica gel, kaolin, clay And the like.
  • the photosensitive resin composition is a curing accelerator, a colorant, a copolymer such as silicone and acrylate, a leveling agent, an adhesion imparting agent such as a silane coupling agent, a thixotropy agent, a polymerization inhibitor, an antihalation agent, and a flame retardant.
  • Defoaming agent; Antioxidant; Surfactant; and Polymer dispersing agent may also contain at least one component selected from the group consisting of:
  • the photosensitive resin composition is, for example, liquid.
  • the photosensitive resin composition is liquid, for example, the raw materials of the photosensitive resin composition as described above are blended, and for example, the photosensitive resin composition is kneaded by a known kneading method using a triple roll, ball mill, sand mill or the like. Resin compositions may be prepared.
  • the raw material of the photosensitive resin composition contains a liquid component, a component having a low viscosity, etc., the portion excluding the liquid component, the component having a low viscosity, etc.
  • the photosensitive resin composition may be prepared by adding and mixing a liquid component, a component having a low viscosity, and the like.
  • the photosensitive resin composition can be prepared by stirring without mixing and kneading the raw materials.
  • the first agent may be prepared by mixing some of the components of the photosensitive resin composition
  • the second agent may be prepared by mixing the rest of the components.
  • the photosensitive resin composition may comprise a first agent and a second agent.
  • the unsaturated compound (B), a part of the organic solvent, and the thermosetting component are mixed in advance and dispersed to prepare the first agent, and the photosensitive resin is photosensitive.
  • the second agent may be prepared by mixing and dispersing the remainder of the components of the sexing resin composition. In this case, a necessary amount of the first agent and the second agent are mixed to prepare a mixture, and the mixture is cured to obtain a cured 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 liquid photosensitive resin composition described above onto a suitable support such as polyester, and then drying. Thus, a laminate (dry film with support) including the dry film and a support for supporting the dry film is obtained.
  • the photosensitive resin composition has a property such that it can be developed with an aqueous solution of sodium carbonate even if the film 4 has a thickness of 25 ⁇ m.
  • a 25 ⁇ m thick film 4 can be developed with an aqueous solution of sodium carbonate can be confirmed by the following method.
  • the photosensitive resin composition is applied onto a suitable substrate to form a wet coating, and the wet coating is heated at 80 ° C. for 40 minutes to form a coating 4 having a thickness of 25 ⁇ m.
  • Exposure is performed by irradiating the film 4 with ultraviolet light under the condition of 500 mJ / cm 2 in a state in which a negative mask having a transmitting portion for transmitting ultraviolet light and a shielding portion for shielding ultraviolet light is directly applied to the film 4. After the exposure, the film 4 is sprayed with a 1% Na 2 CO 3 aqueous solution at 30 ° C.
  • the photosensitive resin composition is disposed on the printed wiring board 1 and the photosensitive resin composition is photocured to produce the cured film 11. Subsequently, the cured film 11 is treated with an alkaline solution, and then the conductor layer 8 in contact with the cured film 11 is produced.
  • a printed wiring board 1 is prepared as shown in FIG. 1A.
  • the printed wiring board 1 at least includes, for example, the insulating layer 2 and the conductor wiring 3 thereon.
  • membrane 4 is produced by arrange
  • membrane 4 is produced by arrange
  • membrane 4 is produced by arrange
  • the photosensitive resin composition when the photosensitive resin composition is liquid, for example, the photosensitive resin composition is applied on the printed wiring board 1 to form a wet coating film.
  • the coating method of the photosensitive resin composition is a known method, such as a dipping method, a spray method, a spin coating method, a roll coating method, a curtain coating method or a screen printing method.
  • the wet coated film is dried, for example, at a temperature in the range of 60 ° C. or more and 120 ° C. or less.
  • the film 4 can be produced.
  • the film 4 when producing the film 4, when the photosensitive resin composition is a dry film, for example, the dry film is superimposed on the printed wiring board 1 in a state of 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, whereby the dry film is transferred onto the printed wiring board 1 from the support. Thereby, the film 4 made of a dry film is provided on the printed wiring board 1.
  • the film 4 is photocured to produce a cured film 11.
  • the film 4 is partially exposed to light so as to partially cure the film 4 as shown in FIG. 1C.
  • a negative mask is applied to the film 4 and then the film 4 is irradiated with ultraviolet light.
  • the negative mask includes a transmitting portion that transmits ultraviolet light and a shielding portion that shields ultraviolet light, and the shielding portion is provided at a position that matches the position of the via 10.
  • the negative mask is, for example, a phototool such as a mask film or a plate.
  • Light sources of ultraviolet light include, for example, chemical lamps, low pressure mercury lamps, medium pressure mercury lamps, high pressure mercury lamps, ultra high pressure mercury lamps, xenon lamps, metal halide lamps, LEDs, g-rays (436 nm), h rays (405 nm), i rays (365 nm), and It is selected from the group consisting of two or more of g-line, h-line and i-line in combination.
  • the exposure method may be a method other than the method using a negative mask.
  • the film 4 may be exposed by a direct writing method in which only the portion of the film 4 to be exposed is irradiated with ultraviolet light emitted from a light source.
  • the light source applied to the direct writing method is, for example, a high pressure mercury lamp, an ultra high pressure mercury lamp, a metal halide lamp, an LED, g-ray (436 nm), h-ray (405 nm), i-ray (365 nm), g-ray, h-ray and i-ray Are selected from the group consisting of two or more of the above.
  • the photosensitive resin composition is a dry film
  • ultraviolet rays are irradiated to the film 4 made of the dry film through the support without peeling the support.
  • the coating 4 may be exposed to light and subsequently the support may be peeled off from the coating 4 before development processing.
  • the entire film 4 may be photocured to produce the cured film 11, instead of partially photocuring the film 4.
  • the cured film 11 is treated with an alkaline solution.
  • the alkaline solution is, for example, an alkaline aqueous solution containing one or both of an alkali metal salt and an alkali metal hydroxide. More specifically, the alkaline aqueous solution is, for example, sodium carbonate, potassium carbonate, ammonium carbonate, sodium hydrogencarbonate, potassium hydrogencarbonate, ammonium hydrogencarbonate, sodium hydrogencarbonate, sodium hydroxide, potassium hydroxide, ammonium hydroxide, tetramethylammonium hydroxide and water. It contains at least one component selected from the group consisting of lithium oxide.
  • the solvent in the alkaline aqueous solution may be water alone, or may be a mixture of water and a hydrophilic organic solvent such as lower alcohols.
  • the pH of the alkaline solution is preferably 8.5 or more and 14 or less.
  • the pH of the alkaline solution is more preferably 9 or more, further preferably 9.5 or more, and particularly preferably 10 or more.
  • the pH of the alkaline solution is more preferably 13.5 or less, still more preferably 13 or less, and particularly preferably 12.5 or less.
  • the cured film 11 can be treated with an alkaline solution, and at the same time the non-exposed portion 5 of the film 4 can be removed from the printed wiring board 1 with the alkaline solution. That is, simultaneously with processing the cured film 11 with an alkaline solution, development processing can be performed with this alkaline solution. Thereby, the holes 6 can be provided at the positions where the vias 10 are to be formed as shown in FIG. 1D.
  • the treatment with 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 group in the film 4 before exposure.
  • the treatment with an alkaline solution is more preferably performed in the state where the reaction rate of the epoxy group is 40% or less, still more preferably 30% or less, and particularly preferably 20% or less .
  • the reaction rate of the epoxy group is calculated from the intensity of the peak derived from the epoxy group at 910 cm ⁇ 1 in an IR spectrum obtained by performing infrared spectral analysis of the film 4 and the cured film 11.
  • the reaction rate of the epoxy group is the normalized value (S 0 ) of the area of the peak at 910 cm -1 in the IR spectrum obtained by infrared spectroscopy of the film 4, and the infrared ray of the cured film 11 after treatment with an alkaline solution. From the normalized value (S 1 ) of the area of the peak at 910 cm ⁇ 1 in the IR spectrum obtained by the spectral analysis, it is calculated by the formula of (S 0 ⁇ S 1 ) ⁇ S 0 ⁇ 100 (%).
  • the normalized value (S 0 ) and the normalized value (S 1 ) are relative to the area of the peak in the IR spectrum that does not change even when the film 4 is exposed, for example, the peak at 750 cm -1. It is a value.
  • the cured film 11 may be subjected to a cleaner treatment using a known chemical solution before producing the conductor layer 8.
  • the cleaner treatment is preferably a treatment that does not roughen the cured film 11.
  • a cleaner liquid a liquid containing a cleaner security gant 902 manufactured by Atotech Japan KK at a concentration of 40 ml / L, a cleaner additive 902 at a concentration of 3 ml / L, and a NaOH at a concentration of 20 g / L
  • the cured product 11 is cleaned.
  • the cured film 11 is immersed in an aqueous solution containing sodium persulfate at a concentration of 100 g / L and sulfuric acid at a concentration of 10 ml / L, and then washed with water.
  • the conductor layer 8 in contact with the cured film 11 is produced.
  • the conductor layer 8 is a conductor wiring made of metal such as copper, for example.
  • the arithmetic average roughness Ra defined by JIS B0601-2001 of the surface of the cured film 11 in contact with the conductor layer 8 immediately before producing the conductor layer 8 is less than 150 nm. This can be easily achieved if the cured film 11 is produced from the photosensitive resin composition by a conventional method, for example, the method described above.
  • Multilayer printed wiring board 20 can have good high frequency characteristics as arithmetic mean roughness Ra is less than 150 nm.
  • the arithmetic mean roughness Ra is preferably less than 100 nm, more preferably less than 80 nm, and particularly preferably less than 30 nm. Moreover, this arithmetic mean roughness Ra is 5 nm or more, for example.
  • hole plating 9 has a cylindrical shape covering the inner surface of hole 6 in FIG. 1E, hole plating 9 may be filled in the entire inside of hole 6.
  • the conductor layer 8 and the hole plating 9 can be produced by a known method such as an additive method.
  • the adhesion between the interlayer insulating layer 7 formed of the cured film 11 and the conductor layer 8 can be further improved.
  • the conditions of the heat treatment are, for example, in a range of heating temperature of 120 ° C. or more and 200 ° C. or less, and in a range of heating time of 30 minutes to 120 minutes.
  • the conductor layer 8 can also be produced by subjecting the cured film 11 to electroless plating and electrolytic plating in this order. In this case, it is preferable to carry out heat treatment between the electroless plating treatment and the electrolytic plating treatment, and further heat treatment after the electrolytic plating treatment. Also in this case, the adhesion between the interlayer insulating layer 7 formed of the cured film 11 and the conductor layer 8 can be further improved.
  • the heat treatment is not performed on the cured film 11 until the conductive layer 8 is produced after the cured film 11 is produced, or the heating temperature is 200 ° C. or less and the heating time is 150 minutes or less It is preferable to perform heat treatment which satisfies either or both of the above. That is, it is preferable that the cured film 11 be not subjected to heat treatment after the cured film 11 is produced until the conductive layer 8 is produced, and even if the heat treatment is performed, the condition is that the heating temperature is It is preferable to satisfy one or both of being 200 ° C. or less and heating time being 150 minutes or less.
  • the heating temperature is more preferably 180 ° C. or less, still more preferably 160 ° C. or less, and particularly preferably 140 ° C. or less.
  • the heating time is more preferably 120 minutes or less, still more preferably 90 minutes or less, and particularly preferably 60 minutes or less.
  • membrane 4 in the cured film 11 after heat processing may become less than 95%.
  • the reaction rate of this epoxy group is based on the amount of epoxy group in the film 4 before exposure.
  • the heat treatment is more preferably performed so that the reaction rate of the epoxy group is less than 90%, still more preferably less than 85%, and particularly preferably less than 80%.
  • the reaction rate of the epoxy group is calculated from the intensity of the peak derived from the epoxy group at 910 cm ⁇ 1 in the IR spectrum obtained by performing infrared spectroscopy of the film 4 and the cured film 11 after the heat treatment.
  • the reaction rate of the epoxy group is the normalized value (S 0 ) of the area of the peak at 910 cm -1 in the IR spectrum obtained by infrared spectroscopy of the film 4, and the infrared spectrum of the cured film 11 after heat treatment From the normalized value (S 2 ) of the area of the peak of 910 cm ⁇ 1 in the IR spectrum obtained in the above, it is calculated by the formula of (S 0 ⁇ S 2 ) ⁇ S 0 ⁇ 100 (%).
  • the values of normalized value (S 0 ) and normalized value (S 2 ) are relative to the area of a peak that does not change even when the film 4 is exposed in the IR spectrum, for example, a peak of 750 cm -1.
  • the adhesion between the interlayer insulating layer 7 and the conductor layer 8 can be particularly improved.
  • the heat treatment is not performed, and even when the heat treatment is performed, the photosensitive resin is applied to the surface of the cured film 11 as long as the conditions are within the above-described range. It is inferred that many functional groups derived from the components in the composition are present, and the interaction between the functional groups and the conductor layer 8 contributes to the improvement of the adhesion.
  • the treatment with the oxidizing agent is not performed on the cured film 11 until the conductor layer 8 is produced after the cured film 11 is produced. In this case, it is easy to achieve that the arithmetic average roughness Ra of the cured film 11 is less than 150 nm by preventing the cured film 11 from being roughened by the oxidizing agent. Even when the treatment with an oxidizing agent is performed, the treatment is preferably such a treatment that the arithmetic average roughness Ra of the cured film 11 can be achieved to be less than 150 nm.
  • the hole 6 When the hole 6 is provided in the cured film 11, it is useful to remove the smear in the hole 6 by subjecting the cured film 11 to a desmearing process using an oxidizing agent before producing the conductor layer 8.
  • the photosensitive resin composition can have excellent developability and resolution, even when the holes 6 are provided in the cured film 11, smear is unlikely to remain. Therefore, even when the treatment with the oxidizing agent is not performed or when the light treatment with the oxidizing agent is performed, the trouble caused by the smear hardly occurs.
  • the multilayer printed wiring board 20 including the interlayer insulating layer 7 formed of the cured film 11 and the conductor layer 8 in contact with the interlayer insulating layer 7 can be manufactured.
  • the thickness of the interlayer insulating layer 7 is, for example, in the range of 3 ⁇ m to 50 ⁇ m.
  • high adhesion between the interlayer insulating layer 7 and the conductor layer 8 can be achieved even if the interlayer insulating layer 7 is not roughened or the degree of roughening is small.
  • Synthesis Example A-1 A bisphenol fluorene type epoxy represented by the formula (2) in a four-necked flask equipped with a reflux condenser, a thermometer, an air blowing tube and a stirrer and all R 1 to R 7 in the formula (2) are hydrogen 250 parts by mass of resin (epoxy equivalent 250 g / eq) 60 parts by mass of propylene glycol monomethyl ether acetate 140 parts by mass of diethylene glycol monoethyl ether acetate 0.2 parts by mass of methyl hydroquinone 72 parts by mass of acrylic acid .5 parts by weight were added to prepare a mixture. The mixture was heated in a flask at a temperature of 115 ° C. for 12 hours with stirring under air bubbling. This prepared a solution of the intermediate.
  • resin epoxy equivalent 250 g / eq
  • Synthesis Example A-2 The carboxyl group-containing resin having an aromatic ring of Synthesis Example A-2 was prepared as follows. Biphenyl novolak epoxy resin (manufactured by Nippon Kayaku Co., Ltd., part number NC-3000-H, epoxy equivalent 288 g / eq) 288 mass in a four-necked flask equipped with a reflux condenser, a thermometer, an air blowing tube and a stirrer A mixture was prepared by adding 1 part, 155 parts by mass of diethylene glycol monoethyl ether acetate, 0.2 parts by mass of methyl hydroquinone, 72 parts by mass of acrylic acid, and 3 parts by mass of triphenylphosphine. The mixture was heated in a flask at a temperature of 115 ° C. for 12 hours with stirring under air bubbling. This prepared a solution of the intermediate.
  • Biphenyl novolak epoxy resin manufactured by Nippon Kayaku Co., Ltd., part number NC-3000-H,
  • the compounding quantity in Table 1 shows the mass part of solid amount of a description component.
  • methyl ethyl ketone is blended in the photosensitive resin composition as a diluent.
  • -Organic filler A having a polar group (dispersion liquid): methyl ethyl ketone dispersion containing crosslinked rubber (NBR) having a carboxyl group with an average primary particle diameter of 0.07 ⁇ m in a proportion of 15% by weight, manufactured by JSR Corporation, product number XER- 91-MEK, acid value 10.0 mg KOH / g.
  • Organic filler B having a polar group (dispersion liquid): methyl ethyl ketone dispersion containing crosslinked rubber (SBR) having carboxyl group and hydroxyl group having an average primary particle diameter of 0.07 ⁇ m at a concentration of 15% by weight, manufactured by JSR Corporation Product number XSK-500.
  • a dispersion varnish of finely divided melamine prepared by dispersing 1.5 parts by mass of finely divided melamine in 3.5 parts by mass of tricyclodecane dimethanol diacrylate with a bead mill. Maximum particle size of fine powder melamine 5 ⁇ m or less.
  • Organic filler having no polar group (dispersion liquid): 1.5 parts by mass of glycidyl-modified acrylonitrile butadiene rubber in powder form and having an average primary particle diameter of 0.3 ⁇ m in 2.5 parts by mass of tricyclodecane dimethanol diacrylate Dispersion varnish of glycidyl-modified acrylonitrile butadiene rubber, prepared by dispersing in a bead mill.
  • Coupling agent 3-glycidoxypropyl trimethoxysilane.
  • Silica manufactured by Nissan Chemical Industries, Ltd., Model No.
  • MEK-EC-2130Y methyl ethyl ketone dispersed silica sol, grade improved in compatibility with epoxy resin, solid content concentration 30 mass%, average primary particle diameter 10 nm or more and 15 nm or less.
  • -Unsaturated compound A tricyclodecane dimethanol diacrylate (including tricyclodecane dimethanol diacrylate derived from a dispersion of an organic filler).
  • -Unsaturated compound B trimethylolpropane triacrylate.
  • Photopolymerization initiator A 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, manufactured by BASF, product number Irgacure TPO.
  • Photopolymerization initiator B 1-hydroxy-cyclohexyl-phenyl-ketone, manufactured by BASF, product number Irgacure 184.
  • Photopolymerization initiator C 4,4′-bis (diethylamino) benzophenone.
  • Epoxy compound biphenyl type crystalline epoxy resin, manufactured by Mitsubishi Chemical Corporation, part number YX4000, epoxy equivalent weight 186 g / eq.
  • Antioxidant Hindered phenolic antioxidant, manufactured by BASF, product number IRGANOX 1010.
  • -Surface conditioner manufactured by DIC Corporation, part number Megafuck F-477.
  • 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, test pieces were produced as follows. The outline of each example, comparative example and reference example is shown in Tables 2-10.
  • a glass epoxy copper clad laminate (FR-4 type) provided with a 17.5 ⁇ m thick copper foil was prepared.
  • a comb-shaped electrode having a line width / space width of 50 ⁇ m / 50 ⁇ m was formed on the glass epoxy copper clad laminate as a conductor wiring by a subtractive method, to obtain a printed wiring board.
  • the conductor wiring was roughened by dissolving and removing the surface layer portion of a thickness of about 1 ⁇ m in the conductor wiring of the printed wiring board with an etching agent (organic acid based micro-etching agent manufactured by MEC Corporation, product number CZ-8101).
  • an etching agent organic acid based micro-etching agent manufactured by MEC Corporation, product number CZ-8101.
  • the dry film was heat-laminated on the entire surface of the printed wiring board with a vacuum laminator.
  • the conditions for the heat lamination are 0.5 MPa, 80 ° C., and 1 minute.
  • a 30 ⁇ m thick film made of a dry film was formed on the printed wiring board so as to cover the conductor wiring.
  • a negative mask having circular shaped shielding portions of 30 ⁇ m, 45 ⁇ m and 60 ⁇ m in diameter, and stripe-shaped shielding portions having a line width / space width of 40 ⁇ m / 40 ⁇ m from the polyethylene terephthalate film.
  • the film was irradiated with ultraviolet light under the condition of 300 mJ / cm 2 through a negative mask to cure the exposed portion of the film, thereby producing a cured film.
  • the film made of polyethylene terephthalate was peeled off from the cured film.
  • the cured film was treated with an alkaline solution, and at the same time the non-exposed part of the film was removed with this alkaline solution.
  • the cured film was sprayed with a 1% Na 2 CO 3 aqueous solution (pH 11) at 30 ° C. for 90 seconds at a spray pressure of 0.2 MPa.
  • pure water was sprayed onto the cured film at a spraying pressure of 0.2 MPa for 90 seconds for cleaning.
  • an opening was formed in the portion of the cured film from which the unexposed portion was removed.
  • the cured film was not treated with the alkaline solution.
  • the cured film was subjected to infrared spectral analysis to obtain an IR spectrum.
  • reaction rate of the epoxy group was classified as follows.
  • the cured film was irradiated with ultraviolet light of 1000 mJ / cm 2 using a high pressure mercury lamp.
  • 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 at 25 ° C. for 1 minute, and then washed with water.
  • the surface roughness (arithmetic mean roughness (Ra)) of the cured film in the test piece after surface treatment was measured by a laser microscope. The results were classified as follows. The results are shown in the table.
  • D Arithmetic mean roughness (Ra) is 150 nm or more.
  • the cured film is subjected to electroless copper plating treatment (MV plus treatment by Atotech Japan Co., Ltd.), and then heated at 150 ° C. for 1 hour, and subsequently under a current density of 2 A / dm 2 A copper film was formed to a thickness of 33 ⁇ m by electrolytic copper plating treatment, and then the test piece was heated at 180 ° C. for 30 minutes. Thus, a copper plating layer was formed on the cured film.
  • the peel strength of the copper plating layer with respect to the cured film is in accordance with JIS C6481 except when blistering occurs in at least one of heating after electroless copper plating and heating after electrolytic copper plating. It was measured.
  • the adhesion of the copper plating layer was evaluated as follows.
  • C The electrical resistance was maintained at 10 6 ⁇ or more until 70 hours from the start of the test, but the electrical resistance became less than 10 6 ⁇ before 85 hours from the start of the test.
  • D The electrical resistance value was less than 10 6 ⁇ before 70 hours from the start of the test.
  • Opening Property The circular opening corresponding to the circular shielding part of the negative mask of the cured film in the test piece of each example, comparative example and reference example was observed and evaluated as follows.
  • C Openings corresponding to shields of 30 ⁇ m and 45 ⁇ m in diameter are not formed, but openings corresponding to shields of 60 ⁇ m in diameter are formed.
  • a stripe-shaped opening corresponding to the stripe-shaped shielding portion of the cured film in the test piece of each example, comparative example and reference example was observed and evaluated as follows.
  • D The outline of the opening has a large rattling and the resolution is poor.
  • the film (4) is formed of a photosensitive resin composition on the printed wiring board (1).
  • the photosensitive resin composition comprises a carboxyl group-containing resin (A), an unsaturated compound (B) having at least one ethylenic unsaturated bond in one molecule, a photopolymerization initiator (C), and an epoxy compound (D).
  • a cured film (11) is produced by photocuring the film (4). After treating the cured film (11) with an alkaline solution, a conductor layer (8) in contact with the cured film (11) is produced.
  • the arithmetic average roughness Ra defined by JIS B0601-2001 of the surface of the cured film (11) in contact with the conductor layer (8) immediately before producing the conductor layer (8) is less than 150 nm.
  • the interlayer insulating layer (7) made of the cured film (11) is not roughened or the degree of roughening is small, the interlayer insulating layer (7) and the conductor layer (8) A multilayer printed wiring board (20) can be obtained which can achieve high adhesion between the two.
  • the arithmetic average roughness Ra is less than 80 nm.
  • the multilayer printed wiring board (20) can have good high frequency characteristics.
  • the cured film (11) is manufactured, and then the conductive layer (8) is manufactured. In the meantime, the cured film (11) is not subjected to the heat treatment or subjected to the heat treatment so that the reaction rate of the epoxy group based on the film (4) is less than 95%.
  • the adhesion between the interlayer insulating layer (7) made of the cured film (11) and the conductor layer (8) can be improved.
  • the photosensitive resin composition is a dry film.
  • the interlayer insulating layer (7) made of the cured film (11) is not roughened or the degree of roughening is small, the interlayer insulating layer (7) and the conductor layer (8) A multilayer printed wiring board (20) can be obtained which can achieve high adhesion between the two.
  • the photosensitive resin composition further contains an organic filler (E). .
  • the adhesion between the interlayer insulating layer (7) made of the cured film (11) and the conductor layer (8) is improved.
  • the organic filler (E) has a polar group.
  • the adhesion between the interlayer insulating layer (7) made of the cured film (11) and the conductor layer (8) is further improved.
  • the polar group is at least one group selected from the group consisting of a carboxyl group, an amino group and a hydroxyl group. Including.
  • the adhesion between the interlayer insulating layer (7) made of the cured film (11) and the conductor layer (8) is particularly improved.
  • particles of the organic filler (E) in the photosensitive resin composition The diameter is 10 ⁇ m or less.
  • the adhesion between the interlayer insulating layer (7) made of the cured film (11) and the conductor layer (8) is particularly improved.
  • the adhesion between the interlayer insulating layer (7) made of the cured film (11) and the conductor layer (8) is particularly improved.
  • the conductor layer (11) is produced after the cured film (11) is produced.
  • the cured film (11) is not treated with an oxidizing agent until it is produced.
  • the arithmetic average roughness Ra of the cured film (11) is less than 150 nm by preventing the cured film (11) from being roughened by the oxidizing agent.
  • the multilayer printed wiring board (20) of the tenth aspect according to the present invention is manufactured by the manufacturing method according to any one of the first to ninth aspects.

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