WO2016121395A1 - Composition de résine sensible à la lumière, film sec, et carte de circuits imprimés - Google Patents

Composition de résine sensible à la lumière, film sec, et carte de circuits imprimés Download PDF

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Publication number
WO2016121395A1
WO2016121395A1 PCT/JP2016/000428 JP2016000428W WO2016121395A1 WO 2016121395 A1 WO2016121395 A1 WO 2016121395A1 JP 2016000428 W JP2016000428 W JP 2016000428W WO 2016121395 A1 WO2016121395 A1 WO 2016121395A1
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Prior art keywords
resin composition
photosensitive resin
carboxyl group
group
acid
Prior art date
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PCT/JP2016/000428
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English (en)
Japanese (ja)
Inventor
倫也 樋口
橋本　壯一
尚 丸澤
田中　信也
貴 荒井
浩信 川里
真司 稲葉
Original Assignee
互応化学工業株式会社
新日鉄住金化学株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
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Priority claimed from JP2015014500A external-priority patent/JP6767090B2/ja
Priority claimed from JP2016008984A external-priority patent/JP6391121B2/ja
Application filed by 互応化学工業株式会社, 新日鉄住金化学株式会社 filed Critical 互応化学工業株式会社
Priority to KR1020177021274A priority Critical patent/KR20170102307A/ko
Priority to CN201680007349.5A priority patent/CN107209457B/zh
Priority to KR1020187033307A priority patent/KR20180125634A/ko
Publication of WO2016121395A1 publication Critical patent/WO2016121395A1/fr

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    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/14—Polycondensates modified by chemical after-treatment
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/42—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof
    • 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
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • 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
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G03F7/029—Inorganic compounds; Onium compounds; Organic compounds having hetero atoms other than oxygen, nitrogen or sulfur
    • 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
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G03F7/031—Organic compounds not covered by group G03F7/029
    • 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
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • 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 photosensitive resin composition, a dry film that is a dried product of the photosensitive resin composition, a printed wiring board including a solder resist layer that includes a cured product of the photosensitive resin composition, and the photosensitive resin composition.
  • the present invention relates to a printed wiring board including an interlayer insulating layer containing a cured product.
  • an electrically insulating resin composition has been used to form electrically insulating layers such as a solder resist layer, a plating resist layer, an etching resist layer, and an interlayer insulating layer of a printed wiring board.
  • a resin composition is, for example, a photosensitive resin composition.
  • Japanese Patent No. 4508929 discloses the use of a carboxyl group-containing resin having a fluorene skeleton obtained by reacting fluorene epoxy (meth) acrylate with a polyvalent carboxylic acid or an anhydride thereof.
  • a plating layer may be formed on a layer made of a cured product of a photosensitive resin composition containing a carboxyl group-containing resin having a bisphenolfluorene skeleton.
  • the surface of the cured product layer is roughened with an oxidizing agent containing, for example, potassium permanganate, so that the cured product layer and the plating layer are obtained. May improve the adhesion.
  • the cured product layer is treated with the oxidizing agent, the surface of the cured product layer may be corroded, and the thickness of the layer may be reduced.
  • a carboxyl group-containing resin having a bisphenolfluorene skeleton has a relatively high resistance to the oxidizing agent, but even if the photosensitive resin composition contains this carboxyl group-containing resin, the thickness of the cured product layer is not oxidized. May become thinner with the agent.
  • a carboxyl group-containing resin having a bisphenolfluorene skeleton may reduce the developability of the photosensitive resin composition. If the molecular weight of the carboxyl group-containing resin is decreased in order to improve developability, the resistance of the cured layer to the oxidizing agent is reduced, and the thickness of the cured product layer is further reduced with the oxidizing agent. May end up. For this reason, in order to improve the adhesiveness of hardened
  • the object of the present invention is to obtain an excellent developability even when the photosensitive resin composition contains a carboxyl group-containing resin having a bisphenolfluorene skeleton, and in the preceding step of the plating treatment,
  • a photosensitive resin composition capable of making it difficult to reduce the thickness of the cured product with an oxidizing agent and roughening the surface of the cured product with an oxidizing agent, a dry film that is a dried product of the photosensitive resin composition, It is providing a printed wiring board provided with the soldering resist layer containing the hardened
  • a photosensitive resin composition includes a carboxyl group-containing resin (A), an unsaturated compound (B) having at least one ethylenically unsaturated bond in one molecule, a photopolymerization initiator ( C), an epoxy compound (D), and a component (E) containing at least one compound selected from the group of melamine and melamine derivatives, wherein the carboxyl group-containing resin (A) is a bisphenolfluorene skeleton. Containing a carboxyl group-containing resin (A1).
  • the dry film according to one embodiment of the present invention is a dried product of the photosensitive resin composition.
  • a printed wiring board according to an aspect of the present invention includes an interlayer insulating layer containing a cured product of the photosensitive resin composition.
  • a printed wiring board according to an aspect of the present invention includes a solder resist layer containing a cured product of the photosensitive resin composition.
  • the photosensitive resin composition contains a carboxyl group-containing resin having a bisphenolfluorene skeleton, excellent developability can be obtained, and curing can be performed in the previous step of the plating treatment.
  • the thickness of the product layer can be made difficult to reduce with an oxidizing agent, and the surface of the cured product can be roughened with an oxidizing agent.
  • FIGS. 1A to 1E are cross-sectional views illustrating steps of manufacturing a multilayer printed wiring board according to an embodiment of the present invention.
  • (meth) acryl means at least one of “acryl” and “methacryl”.
  • (meth) acrylate means at least one of acrylate and methacrylate.
  • the photosensitive resin composition according to this embodiment includes a carboxyl group-containing resin (A), an unsaturated compound (B) having at least one ethylenically unsaturated bond in one molecule, and a photopolymerization initiator (C). And an epoxy compound (D) and a component (E).
  • the carboxyl group-containing resin (A) contains a carboxyl group-containing resin (A1) having a bisphenolfluorene skeleton.
  • the carboxyl group-containing resin (A1) is, for example, a reaction product of an intermediate that is a reaction product of the epoxy compound (a1) and the unsaturated group-containing carboxylic acid (a2) and an acid anhydride.
  • the epoxy compound (a1) is represented by the following formula (1), and in the formula (1), R 1 to R 8 are each independently hydrogen, an alkyl group having 1 to 5 carbon atoms, or halogen, and a bisphenolfluorene skeleton. Have.
  • the carboxyl group-containing resin (A1) is synthesized by reacting the epoxy compound (a1) with the unsaturated group-containing carboxylic acid (a2), and reacting the resulting intermediate with an acid anhydride.
  • Each of R 1 to R 8 in Formula (1) may be hydrogen, but may be an alkyl group having 1 to 5 carbon atoms or halogen. This is because even if hydrogen in the aromatic ring is substituted with a low molecular weight alkyl group or halogen, the physical properties of the carboxyl group-containing resin (A1) are not adversely affected, but rather the photosensitive resin composition containing the carboxyl group-containing resin (A1). This is because the heat resistance or flame retardancy of the cured product may be improved.
  • Component (E) contains at least one compound from the group of melamine and melamine derivatives.
  • a component (E) may contain only a melamine, may contain only a melamine derivative, and may contain a melamine and a melamine derivative.
  • Melamine is 2,4,6-triamino-1,3,5-triazine and is generally available from commercially available compounds.
  • the melamine derivative may be a compound having one triazine ring and an amino group in one molecule. Examples of melamine derivatives include guanamine; acetoguanamine; benzoguanamine; 2,4-diamino-6-methacryloyloxyethyl-S-triazine, 2-vinyl-4,6-diamino-S-triazine, 2-vinyl-4,6.
  • -S-triazine derivatives such as diamino-S-triazine isocyanuric acid adduct, 2,4-diamino-6-methacryloyloxyethyl-S-triazine isocyanuric acid adduct; and melamine such as melamine-tetrahydrophthalate
  • melamine derivatives include Shikoku Kasei Kogyo Co., Ltd. product name VD-1, product name VD-2, and product name VD-3.
  • the melamine derivative is preferably a compound having one triazine ring and two or more amino groups in one molecule.
  • the melamine derivative does not contain melamine.
  • the melamine derivative dispersed in the photosensitive resin composition is included in, for example, the conductive wiring of the plating layer or the core material and arranged with the metal element located on the contact surface with the photosensitive resin composition. Join. For this reason, the adhesiveness of the photosensitive resin composition can be improved.
  • the metal element include gold, silver, copper, and nickel.
  • the component (E) When the component (E) is soluble or hardly soluble in the photosensitive resin composition, the component (E) having an average particle size of 20 ⁇ m or less, preferably 15 ⁇ m or less is dispersed in the photosensitive resin composition. Good. In this case, since the component (E) is uniformly dispersed in the photosensitive resin composition, the component (E) is more easily coordinated with the metal element. Thereby, the adhesiveness of the photosensitive resin composition can further be improved. Although the minimum of the average particle diameter of a component (E) is not specifically limited, It can be 0.01 micrometer or more. The average particle diameter of Component (E), by a laser diffraction particle size distribution measuring apparatus in a state of being dispersed component (E) in the photosensitive resin composition of the uncured, measured as D 50.
  • the carboxyl group-containing resin (A1) will be described more specifically.
  • the carboxyl group-containing resin (A1) first, at least a part of the epoxy group (see formula (2)) of the epoxy compound (a1) is reacted with the unsaturated group-containing carboxylic acid (a2).
  • the intermediate is then synthesized.
  • the intermediate has a structure (S3) represented by the following formula (3) generated by a ring-opening addition reaction between an epoxy group and an unsaturated group-containing carboxylic acid (a2). That is, the intermediate has a secondary hydroxyl group generated by a ring-opening addition reaction between an epoxy group and an unsaturated group-containing carboxylic acid (a2) in the structure (S3).
  • A is an unsaturated group-containing carboxylic acid residue.
  • carboxyl group-containing resin (A1) can be synthesized.
  • the acid anhydride may contain at least one of acid dianhydride (a3) and acid monoanhydride (a4).
  • the carboxyl group-containing resin (A1) has a bisphenolfluorene skeleton (S1) represented by the formula (1) and a structure (S4) represented by the following formula (4). And have.
  • the structure (S4) is generated by the reaction between the secondary hydroxyl group in the intermediate structure (S3) and the acid anhydride group in the acid monoanhydride (a4).
  • A is an unsaturated group-containing carboxylic acid residue
  • B is an acid monoanhydride residue.
  • the carboxyl group-containing resin (A1) has a bisphenolfluorene skeleton (S1) and a structure (S5) represented by the following formula (5).
  • Structure (S5) is generated by the reaction between two acid anhydride groups in acid dianhydride (a3) and two secondary hydroxyl groups in the intermediate. That is, the structure (S5) is generated by crosslinking the two secondary hydroxyl groups with the acid dianhydride (a3).
  • the case where two secondary hydroxyl groups present in one molecule of the intermediate are crosslinked and the case where two secondary hydroxyl groups present in each of the two molecules of the intermediate are crosslinked It is possible.
  • the two secondary hydroxyl groups present in the two molecules of the intermediate are cross-linked, the molecular weight increases.
  • A is an unsaturated group-containing carboxylic acid residue
  • D is an acid dianhydride residue.
  • a secondary hydroxyl group in the intermediate and an acid anhydride can be reacted to obtain a carboxyl group-containing resin (A1).
  • the acid anhydride contains an acid dianhydride (a3) and an acid monoanhydride (a4)
  • a part of the secondary hydroxyl group in the intermediate is reacted with the acid dianhydride (a3)
  • Another part of the secondary hydroxyl groups in the intermediate is reacted with acid monoanhydride (a4).
  • carboxyl group-containing resin (A1) can be synthesized.
  • the carboxyl group-containing resin (A1) has a bisphenolfluorene skeleton (S1), a structure (S4), and a structure (S5).
  • the carboxyl group-containing resin (A1) may further have a structure (S6) represented by the following formula (6).
  • the structure (S6) occurs when only one of the two acid anhydride groups in the acid dianhydride (a3) reacts with the secondary hydroxyl group in the intermediate.
  • A is an unsaturated group-containing carboxylic acid residue
  • D is an acid dianhydride residue.
  • the carboxyl group-containing resin (A1) has a structure (S2) represented by the formula (2), that is, an epoxy group It is possible. Further, when a part of the structure (S3) in the intermediate remains unreacted, the carboxyl group-containing resin (A1) may have the structure (S3).
  • the structure (S2) in the carboxyl group-containing resin (A1) is optimized by optimizing the reaction conditions during the synthesis of the carboxyl group-containing resin (A1).
  • the number of structures (S6) is reduced, or the structure (S2) and the structure (S6) are almost eliminated from the carboxyl group-containing resin (A1).
  • the carboxyl group-containing resin (A1) has a bisphenolfluorene skeleton (S1), and has a structure (S4) when the acid anhydride contains acid monoanhydride (a4).
  • S1 bisphenolfluorene skeleton
  • S4 structure when the acid anhydride contains acid monoanhydride (a4).
  • the carboxyl group-containing resin (A1) may have at least one of the structure (S2) and the structure (S3).
  • carboxyl group-containing resin (A1) may have at least 1 type in a structure (S2) and a structure (S6).
  • the carboxyl group-containing resin (A1) has a structure (S2), a structure (S3), a structure ( And at least one of S6).
  • the carboxyl group-containing resin (A1) is an epoxy compound (a1). It may have a structure produced by the reaction between the secondary secondary hydroxyl group and the acid anhydride.
  • the structure of the above-mentioned carboxyl group-containing resin (A1) is reasonably inferred based on the common general technical knowledge, and the structure of the carboxyl group-containing resin (A1) cannot be specified by analysis.
  • the reason is as follows.
  • the epoxy compound (a1) itself has a secondary hydroxyl group for example, when n is 1 or more in the formula (7)
  • the carboxyl group-containing resin depends on the number of secondary hydroxyl groups in the epoxy compound (a1).
  • the structure of (A1) changes greatly.
  • the intermediate and the acid dianhydride (a3) react, as described above, two secondary hydroxyl groups present in one molecule of the intermediate are acid dianhydrides (a3).
  • the carboxyl group-containing resin (A1) finally obtained contains a plurality of molecules having different structures, and even when the carboxyl group-containing resin (A1) is analyzed, the structure cannot be specified.
  • the carboxyl group-containing resin (A1) Since the carboxyl group-containing resin (A1) has an ethylenically unsaturated group derived from the unsaturated group-containing carboxylic acid (a2), it has photoreactivity. For this reason, carboxyl group-containing resin (A1) can impart photosensitivity (specifically, ultraviolet curable) to the photosensitive resin composition. Moreover, since the carboxyl group-containing resin (A1) has a carboxyl group derived from an acid anhydride, 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 aqueous solution.
  • the acid anhydride contains an acid dianhydride (a3)
  • the molecular weight of the carboxyl group-containing resin (A1) depends on the number of crosslinks by the acid dianhydride (a3). For this reason, the carboxyl group-containing resin (A1) in which the acid value and the molecular weight are appropriately adjusted is obtained.
  • the acid anhydride contains acid dianhydride (a3) and acid dianhydride (a4)
  • a carboxyl group-containing resin (A1) having a desired molecular weight and acid value can be easily obtained.
  • the weight average molecular weight of the carboxyl group-containing resin (A1) is preferably in the range of 700 to 10,000.
  • the weight average molecular weight is 700 or more, the tackiness of the film formed from the photosensitive resin composition is further suppressed, and the insulation reliability and plating resistance of the cured product are further improved.
  • the developability by the alkaline aqueous solution of the photosensitive resin composition improves especially that a weight average molecular weight is 10,000 or less.
  • the weight average molecular weight is more preferably in the range of 900 to 8000, and particularly preferably in the range of 1000 to 5000.
  • the solid content acid value of the carboxyl group-containing resin (A1) is preferably in the range of 60 to 140 mgKOH / g. In this case, the developability of the photosensitive resin composition is particularly improved.
  • the solid content acid value is more preferably in the range of 80 to 135 mgKOH / g, and still more preferably in the range of 90 to 130 mgKOH / g.
  • the weight average molecular weight (Mw) of the carboxyl group-containing resin (A1) is calculated from the molecular weight measurement result by gel permeation chromatography.
  • the molecular weight measurement by gel permeation chromatography can be performed, for example, under the following conditions.
  • GPC device SHODEX SYSTEM 11, manufactured by Showa Denko KK
  • the epoxy compound (a1) has a structure (S7) represented by the following formula (7), for example.
  • N in the formula (7) is a number in the range of 0 to 20, for example.
  • the average of n is particularly preferably in the range of 0-1. If the average of n is in the range of 0 to 1, particularly when the acid anhydride contains acid dianhydride (a3), an excessive increase in molecular weight due to addition of acid dianhydride (a3) is likely to be suppressed. Become.
  • the unsaturated group-containing carboxylic acid (a2) can contain, for example, a compound having only one ethylenically unsaturated group in one molecule. More specifically, unsaturated group-containing carboxylic acid (a2) is, for example, acrylic acid, methacrylic acid, ⁇ -carboxy-polycaprolactone (n ⁇ 2) monoacrylate, crotonic acid, cinnamic acid, 2-acryloyloxyethyl succinate.
  • the reactive solution is obtained by adding the unsaturated group-containing carboxylic acid (a2) to the solvent solution of the epoxy compound (a1), further adding a thermal polymerization inhibitor and a catalyst as necessary, and stirring and mixing.
  • An intermediate can be obtained by reacting this reactive solution at a temperature of preferably 60 to 150 ° C., particularly preferably 80 to 120 ° C., by a conventional method.
  • Solvents include, for example, ketones such as methyl ethyl ketone and cyclohexanone, and aromatic hydrocarbons such as toluene and xylene, and ethyl acetate, butyl acetate, cellosolve acetate, butyl cellosolve acetate, carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether It can contain at least one component selected from the group consisting of acetates such as acetate and dialkyl glycol ethers.
  • the thermal polymerization inhibitor contains, for example, at least one of hydroquinone and hydroquinone monomethyl ether.
  • the catalyst is at least selected from the group consisting of tertiary amines such as benzyldimethylamine and triethylamine, quaternary ammonium salts such as trimethylbenzylammonium chloride and methyltriethylammonium chloride, triphenylphosphine, and triphenylstibine.
  • tertiary amines such as benzyldimethylamine and triethylamine
  • quaternary ammonium salts such as trimethylbenzylammonium chloride and methyltriethylammonium chloride
  • triphenylphosphine triphenylstibine.
  • a kind of component can be contained.
  • the catalyst contains triphenylphosphine. That is, it is preferable to react the epoxy compound (a1) with the unsaturated group-containing carboxylic acid (a2) in the presence of triphenylphosphine. In this case, the ring-opening addition reaction between the epoxy group and the unsaturated group-containing carboxylic acid (a2) in the epoxy compound (a1) is particularly accelerated, and the reaction rate (conversion) is 95% or more, 97% or more, or almost 100%. Rate). For this reason, the intermediate body which has a structure (S3) is obtained with a high yield. Moreover, generation
  • the amount of the unsaturated group-containing carboxylic acid (a2) relative to 1 mol of the epoxy group of the epoxy compound (a1) is 0.8 to 1. It is preferably within a range of 2 moles. In this case, a photosensitive resin composition having excellent photosensitivity and storage stability can be obtained.
  • the intermediate thus obtained comprises a hydroxyl group generated by a reaction between the epoxy group of the epoxy compound (a1) and the carboxyl group of the unsaturated group-containing carboxylic acid (a2).
  • Acid dianhydride (a3) is a compound having two acid anhydride groups.
  • the acid dianhydride (a3) can contain an anhydride of tetracarboxylic acid.
  • Acid dianhydride (a3) is, for example, 1,2,4,5-benzenetetracarboxylic dianhydride, benzophenone tetracarboxylic dianhydride, methylcyclohexene tetracarboxylic dianhydride, tetracarboxylic dianhydride, Naphthalene-1,4,5,8-tetracarboxylic dianhydride, ethylenetetracarboxylic dianhydride, 9,9'-bis (3,4-dicarboxyphenyl) fluorene dianhydride, glycerin bisanhydrotri Melitate monoacetate, ethylene glycol bisanhydro trimellitate, 3,3 ', 4,4'-diphenylsulfone tetracarboxylic dianhydride, 1,3,
  • the acid dianhydride (a3) preferably contains 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride. That is, it is preferable that D in Formula (5) and Formula (6) includes a 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride residue. In this case, while ensuring good developability of the photosensitive resin composition, it is possible to further suppress the tackiness of a film formed from the photosensitive resin composition and further improve the insulation reliability and plating resistance of the cured product. .
  • the amount of 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride relative to the total amount of acid dianhydride (a3) is preferably in the range of 20 to 100 mol%, and in the range of 40 to 100 mol%. Although it is more preferable to be within, it is not restricted to these ranges.
  • Acid monoanhydride (a4) is a compound having one acid anhydride group.
  • the acid monoanhydride (a4) can contain an anhydride of a dicarboxylic acid.
  • Examples of the acid monoanhydride (a4) include phthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylnadic acid anhydride, hexahydrophthalic anhydride, methylhexa Hydrophthalic anhydride, succinic anhydride, methyl succinic anhydride, maleic anhydride, citraconic anhydride, glutaric anhydride, cyclohexane-1,2,4-tricarboxylic acid-1,2-anhydride, and It can contain at least one compound selected from the group consisting of itaconic anhydride.
  • the acid monoanhydride (a4) contains 1,2,3,6-tetrahydrophthalic anhydride. That is, the acid anhydride preferably contains 1,2,3,6-tetrahydrophthalic anhydride. That is, it is preferable that the carboxyl group-containing resin (A1) has the structure (S4), and B in the formula (4) includes a 1,2,3,6-tetrahydrophthalic anhydride residue.
  • the acid monoanhydride (a4) contains 1,2,3,6-tetrahydrophthalic anhydride. That is, the acid anhydride preferably contains 1,2,3,6-tetrahydrophthalic anhydride. That is, it is preferable that the carboxyl group-containing resin (A1) has the structure (S4), and B in the formula (4) includes a 1,2,3,6-tetrahydrophthalic anhydride residue.
  • the amount of 1,2,3,6-tetrahydrophthalic anhydride relative to the total amount of acid monoanhydride (a4) is preferably in the range of 20 to 100 mol%, and preferably in the range of 40 to 100 mol%. Although more preferable, it is not limited to these ranges.
  • a known method can be employed. For example, an acid anhydride is added to the solvent solution of the intermediate, and a thermal polymerization inhibitor and a catalyst are further added as necessary, followed by stirring and mixing to obtain a reactive solution. By reacting this reactive solution at a temperature of preferably 60 to 150 ° C., particularly preferably 80 to 120 ° C., a carboxyl group-containing resin (A1) can be obtained by a conventional method.
  • a solvent, catalyst and polymerization inhibitor appropriate ones can be used, and the solvent, catalyst and polymerization inhibitor used in the synthesis of the intermediate can also be used as they are.
  • the catalyst contains triphenylphosphine. That is, it is preferable to react an intermediate with an acid anhydride in the presence of triphenylphosphine. In this case, the reaction between the secondary hydroxyl group and the acid anhydride in the intermediate is particularly accelerated, and a reaction rate (conversion rate) of 90%, 95%, 97%, or almost 100% can be achieved. For this reason, the carboxyl group-containing resin (A1) having at least one of the structure (S4) and the structure (S5) is obtained in a high yield. Moreover, generation
  • the amount of the acid dianhydride (a3) is 1 mol of the epoxy group of the epoxy compound (a1), A range of 0.05 to 0.24 mol is preferred.
  • the amount of acid monoanhydride (a4) is preferably in the range of 0.3 to 0.7 mol with respect to 1 mol of the epoxy group of the epoxy compound (a1). In this case, the carboxyl group-containing resin (A1) in which the acid value and the molecular weight are appropriately adjusted can be easily obtained.
  • the carboxyl group-containing resin (A) may contain only the carboxyl group-containing resin (A1), or a carboxyl group-containing resin other than the carboxyl group-containing resin (A1) (hereinafter also referred to as carboxyl group-containing resin (F)). May further be contained.
  • the carboxyl group-containing resin (F) can contain, for example, a compound having a carboxyl group and not having photopolymerizability (hereinafter referred to as (F1) component).
  • (F1) A component contains the polymer of the ethylenically unsaturated monomer containing the ethylenically unsaturated compound which has a carboxyl group, for example.
  • the ethylenically unsaturated compound having a carboxyl group can contain compounds such as acrylic acid, methacrylic acid, and ⁇ -carboxy-polycaprolactone (n ⁇ 2) monoacrylate.
  • the ethylenically unsaturated compound having a carboxyl group can also contain a reaction product of pentaerythritol triacrylate, pentaerythritol trimethacrylate and the like with a dibasic acid anhydride.
  • Ethylenically unsaturated monomers include 2- (meth) acryloyloxyethyl phthalate, 2- (meth) acryloyloxyethyl-2-hydroxyethyl phthalate, linear or branched aliphatic or alicyclic (provided that It may further contain an ethylenically unsaturated compound having no carboxyl group, such as (meth) acrylic acid ester (which may partially have an unsaturated bond in the ring).
  • the carboxyl group-containing resin (F) may contain a compound having a carboxyl group and an ethylenically unsaturated group (hereinafter referred to as (F2) component). Moreover, carboxyl group-containing resin (F) may contain only the (F2) component.
  • the component (F2) includes, for example, an intermediate that is a reaction product of an epoxy compound (g1) having two or more epoxy groups in one molecule and an ethylenically unsaturated compound (g2), a polyvalent carboxylic acid and its anhydride.
  • a resin (referred to as a first resin (g)) that is a reaction product with at least one compound (g3) selected from the group of substances.
  • the first resin (g) is obtained by adding the compound (g3) to an intermediate obtained by reacting the epoxy group in the epoxy compound (g1) with the carboxyl group in the ethylenically unsaturated compound (g2).
  • the epoxy compound (g1) can contain an appropriate epoxy compound such as a cresol novolac epoxy compound, a phenol novolac epoxy compound, or a biphenyl novolac epoxy compound.
  • the epoxy compound (g1) preferably contains at least one compound selected from the group of biphenyl novolac type epoxy compounds and cresol novolac type epoxy compounds.
  • the epoxy compound (g1) may contain only a biphenyl novolac type epoxy compound or may contain only a cresol novolac type epoxy compound.
  • the epoxy compound (g1) may contain a polymer of the ethylenically unsaturated compound (h).
  • the ethylenically unsaturated compound (h) contains a compound (h1) having an epoxy group such as glycidyl (meth) acrylate, or further has no epoxy group such as 2- (meth) acryloyloxyethyl phthalate.
  • the ethylenically unsaturated compound (g2) preferably contains at least one of acrylic acid and methacrylic acid.
  • the compound (g3) contains one or more compounds selected from the group consisting of polyvalent carboxylic acids such as phthalic acid, tetrahydrophthalic acid, and methyltetrahydrophthalic acid, and anhydrides of these polyvalent carboxylic acids.
  • the compound (g3) preferably contains at least one polycarboxylic acid selected from the group of phthalic acid, tetrahydrophthalic acid, and methyltetrahydrophthalic acid.
  • the component (F2) is a resin (second resin) that is a reaction product of a polymer of an ethylenically unsaturated monomer containing an ethylenically unsaturated compound having a carboxyl group and an ethylenically unsaturated compound having an epoxy group. (I)) may be contained.
  • the ethylenically unsaturated monomer may further contain an ethylenically unsaturated compound having no carboxyl group.
  • the second resin (i) can be obtained by reacting an ethylenically unsaturated compound having an epoxy group with a part of the carboxyl group in the polymer.
  • the ethylenically unsaturated monomer may further contain an ethylenically unsaturated compound having no carboxyl group.
  • the ethylenically unsaturated compound having a carboxyl group include compounds such as acrylic acid, methacrylic acid, ⁇ -carboxy-polycaprolactone (n ⁇ 2) monoacrylate, pentaerythritol triacrylate, and pentaerythritol trimethacrylate.
  • Examples of the ethylenically unsaturated compound having no carboxyl group include 2- (meth) acryloyloxyethyl phthalate, 2- (meth) acryloyloxyethyl-2-hydroxyethyl phthalate, linear or branched aliphatic or fatty acid It contains a compound such as a (meth) acrylic acid ester of a cyclic group (however, it may have a partially unsaturated bond in the ring).
  • the ethylenically unsaturated compound having an epoxy group preferably contains glycidyl (meth) acrylate.
  • the carboxyl group-containing resin (A) contains only the carboxyl group-containing resin (A1) or the carboxyl group-containing resin (A1) and the carboxyl group-containing resin (F).
  • the carboxyl group-containing resin (A) preferably contains 30% by mass or more of the carboxyl group-containing resin (A1), more preferably 50% by mass or more, and still more preferably 100% by mass.
  • the heat resistance and insulation reliability of the cured product of the photosensitive resin composition can be particularly improved.
  • membrane formed from the photosensitive resin composition can fully be reduced.
  • the developability of the photosensitive resin composition with an alkaline aqueous solution can be secured.
  • the photosensitive resin composition includes a carboxyl group-containing resin (A), an unsaturated compound (B) having at least one ethylenically unsaturated bond in one molecule, and a photopolymerization initiator (C). And an epoxy compound (D) and a component (E).
  • the unsaturated compound (B) can impart photocurability to the photosensitive resin composition.
  • the unsaturated compound (B) is, for example, a monofunctional (meth) acrylate such as 2-hydroxyethyl (meth) acrylate; and diethylene glycol di (meth) acrylate, trimethylolpropane di (meth) acrylate, trimethylolpropane tri (meth) Acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, ⁇ -caprolactone modified pentaerythritol hexaacrylate, tricyclodecandi
  • At least one compound selected from the group consisting of polyfunctional (meth) acrylates such as methanol di (meth) acrylate
  • the unsaturated compound (B) preferably contains a trifunctional compound, that is, a compound having three unsaturated bonds in one molecule.
  • a trifunctional compound that is, a compound having three unsaturated bonds in one molecule.
  • Trifunctional compounds include, for example, trimethylolpropane tri (meth) acrylate, EO modified trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, ethoxylated isocyanuric acid tri (meth) acrylate and ⁇ -caprolactone modified It can contain at least one compound selected from the group consisting of tris- (2-acryloxyethyl) isocyanurate and ethoxylated glycerin tri (meth) acrylate.
  • the unsaturated compound (B) contains a phosphorus-containing compound (phosphorus-containing unsaturated compound).
  • Phosphorus-containing unsaturated compounds include, for example, 2-methacryloyloxyethyl acid phosphate (specific examples: product number light ester P-1M and light ester P-2M manufactured by Kyoeisha Chemical Co., Ltd.), 2-acryloyloxyethyl acid phosphate (Specific examples are product number light acrylate P-1A manufactured by Kyoeisha Chemical Co., Ltd.), diphenyl-2-methacryloyloxyethyl phosphate (specific examples are product number MR-260 manufactured by Daihachi Industry Co., Ltd.), and Showa Polymer Co., Ltd.
  • HFA series (part number HFA-6003, which is an addition reaction product of dipentaerystol hexaacrylate and HCA (9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide) as a specific example, and HFA-6007, caprolactone Product No. HFA-3003, HFA-6127, etc., which are addition reaction products of modified dipentaerystol 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 at least one selected from the group consisting of, for example, a prepolymer obtained by polymerizing a monomer having an ethylenically unsaturated bond and then adding an ethylenically unsaturated group, and oligo (meth) acrylate prepolymers These compounds can be contained.
  • Oligo (meth) acrylate prepolymers include, for example, epoxy (meth) acrylate, polyester (meth) acrylate, urethane (meth) acrylate, alkyd resin (meth) acrylate, silicone resin (meth) acrylate, and spirane resin (meth) acrylate At least one component selected from the group consisting of:
  • the photopolymerization initiator (C) contains, for example, an acyl phosphine oxide photopolymerization initiator (C1). That is, the photosensitive resin composition contains, for example, an acyl phosphine oxide photopolymerization initiator (C1).
  • the photosensitive resin composition contains the carboxyl group-containing resin (A1), high sensitivity to ultraviolet rays can be imparted to the photosensitive resin composition.
  • cured material of the photosensitive resin composition is suppressed, and the insulation reliability of the same layer improves further.
  • the acylphosphine oxide photopolymerization initiator (C1) is unlikely to hinder the electrical insulation of the cured product. For this reason, by curing the photosensitive resin composition by exposure, a cured product having excellent electrical insulation can be obtained.
  • This cured product can be used as, for example, a solder resist layer, a plating resist layer, an etching resist layer, or an interlayer insulating layer. Is preferred.
  • Acylphosphine oxide photopolymerization initiators (C1) include monoacyl such as 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, 2,4,6-trimethylbenzoyl-ethyl-phenyl-phosphinate, etc.
  • Phosphine oxide photopolymerization initiator and bis- (2,6-dichlorobenzoyl) phenylphosphine oxide, bis- (2,6-dichlorobenzoyl) -2,5-dimethylphenylphosphine oxide, bis- (2 , 6-Dichlorobenzoyl) -4-propylphenylphosphine oxide, bis- (2,6-dichlorobenzoyl) -1-naphthylphosphine oxide, bis- (2,6-dimethoxybenzoyl) phenylphosphine oxide, bis- (2,6-dimethoxybe Zoyl) -2,4,4-trimethylpentylphosphine oxide, bis- (2,6-dimethoxybenzoyl) -2,5-dimethylphenylphosphine oxide, bis- (2,4,6-trimethylbenzoyl) phenylphosphine Contains at least one component selected from the group consist
  • the acylphosphine oxide photopolymerization initiator (C1) preferably contains 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, and the acylphosphine oxide photopolymerization initiator (C1) contains 2, It is also preferred to contain only 4,6-trimethylbenzoyl-diphenyl-phosphine oxide.
  • the photopolymerization initiator (C) preferably contains a hydroxyketone photopolymerization initiator (C2) in addition to the acylphosphine oxide photopolymerization initiator (C1). That is, the photosensitive resin composition preferably contains a hydroxyketone photopolymerization initiator (C2). In this case, higher photosensitivity can be imparted to the photosensitive resin composition as compared with the case where the hydroxyketone photopolymerization initiator (C2) is not contained. Thereby, when irradiating and hardening an ultraviolet-ray to the coating film formed from the photosensitive resin composition, it becomes possible to fully harden a coating film over the deep part from the surface.
  • Examples of the hydroxyketone photopolymerization initiator (C2) include 1-hydroxy-cyclohexyl-phenyl-ketone, phenylglyoxyc acid methyl ester, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy -2-Methyl-1-propan-1-one, 2-hydroxy-1- ⁇ 4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] phenyl ⁇ -2-methyl-propane-1- On and 2-hydroxy-2-methyl-1-phenyl-propan-1-one.
  • the mass ratio of the acylphosphine oxide photopolymerization initiator (C1) and the hydroxyketone photopolymerization initiator (C2) is preferably in the range of 1: 0.01 to 1:10. In this case, the curability in the vicinity of the surface of the coating film formed from the photosensitive resin composition and the curability in the deep portion can be improved in a well-balanced manner.
  • the photopolymerization initiator (C) preferably contains bis (diethylamino) benzophenone (C3). That is, the photosensitive resin composition contains an acyl phosphine oxide photopolymerization initiator (C1) and bis (diethylamino) benzophenone (C3), or an acyl phosphine oxide photopolymerization initiator (C1), a hydroxyketone type. It is also preferable to contain a photopolymerization initiator (C2) and bis (diethylamino) benzophenone (C3). In this case, when developing after partially exposing the coating film formed from the photosensitive resin composition, since the hardening of the part which is not exposed is suppressed, resolution becomes especially high.
  • cured material of the photosensitive resin composition of a very fine pattern can be formed.
  • an interlayer insulating layer of a multilayer printed wiring board is prepared from a photosensitive resin composition and a small-diameter hole for a through hole is provided in the interlayer insulating layer by a photolithography method (see FIG. 1), the small-diameter hole is formed. Precise and easy to form.
  • the amount of bis (diethylamino) benzophenone (C3) relative to the acylphosphine oxide photopolymerization initiator (C1) is preferably in the range of 0.5 to 20% by mass.
  • the amount of bis (diethylamino) benzophenone (C3) with respect to the acylphosphine oxide photopolymerization initiator (C1) is 0.5% by mass or more, the resolution is particularly high.
  • the amount of bis (diethylamino) benzophenone (C3) relative to the acylphosphine oxide-based photopolymerization initiator (C1) is 20% by mass or less, the electrical insulation of the cured product of the photosensitive resin composition is increased to bis (diethylamino). ) Benzophenone (C3) is difficult to inhibit.
  • the photosensitive resin composition may further contain a known photopolymerization accelerator, sensitizer and the like.
  • the photosensitive resin composition includes benzoin and its alkyl ethers; acetophenones such as acetophenone and benzyldimethyl ketal; anthraquinones such as 2-methylanthraquinone; 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2- Thioxanthones such as isopropylthioxanthone, 4-isopropylthioxanthone and 2,4-diisopropylthioxanthone; benzophenones such as benzophenone and 4-benzoyl-4′-methyldiphenyl sulfide; xanthones such as 2,4-diisopropylxanthone; ⁇ -hydroxyketones such as hydroxy-2-methyl-1-phenyl-propan-1-one; 2-methyl-1- [4-
  • the photosensitive resin composition includes known photopolymerization initiators (C) and tertiary amines such as p-dimethylbenzoic acid ethyl ester, p-dimethylaminobenzoic acid isoamyl ester, and 2-dimethylaminoethylbenzoate. You may contain a photoinitiator, a sensitizer, etc.
  • the photosensitive resin composition may contain at least one of a photopolymerization initiator for visible light exposure and a photopolymerization initiator for near infrared exposure, if necessary.
  • the photosensitive resin composition contains a photopolymerization initiator (C) and a coumarin derivative such as 7-diethylamino-4-methylcoumarin, which is a sensitizer for laser exposure, a carbocyanine dye system, a xanthene dye system, and the like. May be.
  • the epoxy compound (D) can impart thermosetting properties to the photosensitive resin composition.
  • the epoxy compound (D) preferably contains a crystalline epoxy resin. In this case, the developability of the photosensitive resin composition can be improved.
  • the epoxy compound (D) may further contain an amorphous epoxy resin.
  • the “crystalline epoxy resin” is an epoxy resin having a melting point
  • the “amorphous epoxy resin” is an epoxy resin having no melting point.
  • Examples of crystalline epoxy resins include 1,3,5-tris (2,3-epoxypropyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, hydroquinone type crystals Epoxy resin (specifically, product name YDC-1312 manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.), biphenyl type crystalline epoxy resin (specifically, product name YX-4000 manufactured by Mitsubishi Chemical Corporation), diphenyl ether type crystalline epoxy resin (specifically For example, Nippon Steel & Sumikin Chemical Co., Ltd., product number YSLV-80DE), bisphenol type crystalline epoxy resin (specifically, Nippon Steel & Sumikin Chemical Co., Ltd.
  • product name YSLV-80XY tetrakisphenol ethane type crystalline epoxy resin (specific example) Nippon Kayaku Co., Ltd. product number GTR-1800), bisphenolfluorene type
  • the crystalline epoxy resin preferably has two epoxy groups in one molecule.
  • the crystalline epoxy resin preferably has an epoxy equivalent of 150 to 300 g / eq. This epoxy equivalent is the gram weight of a crystalline epoxy resin containing 1 gram equivalent of epoxy groups.
  • the crystalline epoxy resin has a melting point. Examples of the melting point of the crystalline epoxy resin include 70 to 180 ° C.
  • the epoxy compound (D) preferably contains a crystalline epoxy resin having a melting point of 110 ° C. or lower.
  • the developability of the photosensitive resin composition with an alkaline aqueous solution is particularly improved.
  • biphenyl type epoxy resins specifically, product number YX-4000 manufactured by Mitsubishi Chemical Corporation
  • biphenyl ether type epoxy resins specifically, product number YSLV manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.
  • a bisphenol-type epoxy resin specifically, product number YSLV-80XY manufactured by Nippon Steel & Sumikin Chemical
  • a bisphenolfluorene-type crystalline epoxy resin specifically, an epoxy resin having the structure (S7). At least one component.
  • Amorphous epoxy resins include, for example, phenol novolac type epoxy resins (specifically, product number EPICLON N-775 manufactured by DIC Corporation) and cresol novolac type epoxy resins (specific examples, product number EPICLON N-695 manufactured by DIC Corporation).
  • Bisphenol A novolac type epoxy resin (specific example, product number EPICLON N-865 manufactured by DIC Corporation), bisphenol A type epoxy resin (specific example, product number jER1001 manufactured by Mitsubishi Chemical Corporation), bisphenol F type epoxy resin (specific example As product number jER4004P manufactured by Mitsubishi Chemical Co., Ltd.), bisphenol S type epoxy resin (specifically, product number EPICLON EXA-1514 manufactured by DIC Corporation), bisphenol AD type epoxy resin, biphenyl novolac Type epoxy resin (part number NC-3000 manufactured by Nippon Kayaku Co., Ltd.), hydrogenated bisphenol A type epoxy resin (part number ST-4000D manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.), naphthalene type epoxy resin (particular Examples include DIC Corporation part numbers EPICLON HP-4032, EPICLON HP-4700, EPICLON HP-4770), tertiary butyl catechol type epoxy resin (specific examples DIC Corporation part number EPICLON HP-820), dicyclopentad
  • Type epoxy resin (specifically, product number EPICLON HP-7200 manufactured by DIC), adamantane type epoxy resin (specific example, product number ADAMANTATE X-E-201 manufactured by Idemitsu Kosan Co., Ltd.), special bifunctional epoxy resin (tool)
  • product numbers YL7175-500 and YL7175-1000 manufactured by Mitsubishi Chemical Corporation product numbers EPICLON TSR-960, EPICLON TER-601, EPICLON TSR-250-80BX, EPICLON 1650-75MPX, EPICLON EXA- manufactured by DIC Corporation 4850, EPICLON EXA-4816, EPICLON EXA-4822, and EPICLON EXA-9726
  • product number YSLV-120TE manufactured by Nippon Steel & Sumikin Chemical Co., Ltd. rubber core-shell polymer modified bisphenol A type epoxy resin (specifically, manufactured by Kaneka Corporation) Product number MX-156), rubber-like core-shell polymer modified
  • the epoxy compound (D) may contain a phosphorus-containing epoxy resin.
  • the phosphorus-containing epoxy resin may be contained in the crystalline epoxy resin or may be contained in the amorphous epoxy resin.
  • Examples of the phosphorus-containing epoxy resin include phosphoric acid-modified bisphenol F type epoxy resin (specific examples, product numbers EPICLON EXA-9726 and EPICLON EXA-9710 manufactured by DIC Corporation), and product number Epototo FX-305 manufactured by Nippon Steel & Sumikin Chemical Co., Ltd. Etc.
  • the photosensitive resin composition according to this embodiment may contain an organic solvent.
  • the organic solvent is used for the purpose of liquefaction or varnishing of the photosensitive resin composition, viscosity adjustment, application property adjustment, film formation property adjustment, and the like.
  • Organic solvents include, for example, linear, branched, secondary or polyhydric alcohols such as ethanol, propyl alcohol, isopropyl alcohol, hexanol and ethylene glycol; ketones such as methyl ethyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene and xylene Petroleum aromatic mixed solvents such as Swazol series (manufactured by Maruzen Petrochemical Co., Ltd.) and Solvesso series (manufactured by Exxon Chemical Co.); cellosolves such as cellosolve and butylcellosolve; Tolls; propylene glycol alkyl ethers such as propylene glycol methyl ether; polypropylene glycol alkyl ethers such as dipropylene glycol methyl ether; ethyl acetate, butyl acetate, cellosolve acetate, cal Acetic acid esters such as tall acetate; as well as containing at least
  • the photosensitive resin composition contains an inorganic filler (K).
  • the inorganic filler (K) tends to be less corroded by the oxidizing agent than the cured product of the photosensitive resin composition. That is, the cured product of the photosensitive resin composition has a portion that is easily corroded by the oxidizing agent and a portion that is not easily corroded on the outer surface thereof. For this reason, when roughening the outer surface of the hardened
  • the inorganic filler (K) is, 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. Can be contained.
  • the inorganic filler (K) contains a white material such as titanium oxide or zinc oxide, the photosensitive resin composition and its cured product can be whitened with the white material.
  • the amount of the inorganic filler (K) in the photosensitive resin composition is appropriately set, but the amount of the inorganic filler (K) with respect to the carboxyl group-containing resin (A) is in the range of 1 to 300% by mass. Preferably, it is in the range of 3 to 200% by mass, more preferably in the range of 5 to 100% by mass.
  • the inorganic filler (K) preferably contains silica (k).
  • Silica (k) has a hydroxyl group. This hydroxyl group is considered to be modified with the oxidizing agent. For this reason, a rough surface can be imparted to the surface of silica (k) with the oxidizing agent.
  • the cured product of the photosensitive resin composition is corroded with the oxidizing agent, even if it is a difficult corrosion site where silica (k) is located on the surface of the cured product, the difficult corrosion site is appropriately corroded with the oxidizing agent. be able to.
  • the rough surface more suitable for a plating process can be provided to hardened
  • Silica (k) preferably has an average particle size of 1 ⁇ m or less.
  • the lower limit of the average particle diameter of silica (k) is not particularly limited, but is preferably 0.001 ⁇ m or more, for example.
  • the average particle size by a laser diffraction particle size distribution measuring device, is measured as D 50.
  • the average particle size of silica (k) is more preferably 0.1 ⁇ m or less. In this case, the roughness of the rough surface formed in the cured product can be made particularly fine. In addition, scattering during exposure can be suppressed in the photosensitive resin composition, whereby the resolution of the photosensitive resin composition can be further improved.
  • the inorganic filler (K) contains only silica (k) or silica (k) and an inorganic filler other than silica (k).
  • the inorganic filler (K) preferably contains 30% by mass or more of silica (k), more preferably 50% by mass or more, and still more preferably 100% by mass. In this case, the adhesion between the cured product and the plating layer can be particularly improved.
  • the photosensitive resin composition preferably contains a silane coupling agent.
  • the dispersibility of the inorganic filler (K) can be improved.
  • the resolution of the photosensitive resin composition can also be improved.
  • the silane coupling agent is a compound containing a silicon atom and 2 to 4 hydrolyzable groups selected from the group of —OCH 3 group, —OC 2 H 5 group, and —OCOCH 3 group.
  • Silane coupling agents may contain reactive groups such as amino groups, epoxy groups, vinyl (allyl) groups, methacryl groups, mercapto groups, isocyanate groups, sulfide groups, or methyl groups in addition to hydrolyzable groups. Good.
  • silane coupling agents include 3- (2-aminoethylamino) propyldimethoxymethylsilane, 3- (2-aminoethylamino) propyltriethoxysilane, and 3- (2-aminoethylamino) propyltrimethoxysilane.
  • Amino compounds such as 3-aminopropyldiethoxymethylsilane, 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, Epoxys such as 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidyloxypropyl (dimethoxy) methylsilane, diethoxy (3-glycidyloxypropyl) methylsilane, 3-acryloxypropyltrimethoxysila (Meth) acrylates such as 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, vinyltrimethoxysilane
  • the oxidizing agent may be an oxidizing agent available as a desmear liquid.
  • Such an oxidizing agent can contain, for example, at least one permanganate selected from the group of sodium permanganate and potassium permanganate.
  • the amount of the component in the photosensitive resin composition is appropriately adjusted so that the photosensitive resin composition has photocurability and can be developed with an alkaline solution.
  • the amount of the carboxyl group-containing resin (A) relative to the solid content of the photosensitive resin composition is preferably within the range of 5 to 85% by mass, more preferably within the range of 10 to 75% by mass, and 30 to 60%. If it is in the range of mass%, it is still more preferable.
  • the amount of the unsaturated compound (B) relative to the carboxyl group-containing resin (A) is preferably in the range of 1 to 50% by mass, more preferably in the range of 10 to 45% by mass, and 21 to 40% by mass. If it is in the range, it is more preferable.
  • the amount of the photopolymerization initiator (C) relative to the carboxyl group-containing resin (A) is preferably in the range of 0.1 to 30% by mass, and more preferably in the range of 1 to 25% by mass.
  • the total of the equivalents of epoxy groups contained in the epoxy compound (D) is 0.7 to 2.5 with respect to 1 equivalent of carboxyl groups contained in the carboxyl group-containing resin (A). Is preferably in the range of 0.7 to 2.3, more preferably in the range of 0.7 to 2.0. Further, the total of the equivalents of the epoxy groups contained in the crystalline epoxy resin is preferably in the range of 0.1 to 2.0 with respect to 1 equivalent of the carboxyl groups contained in the carboxyl group-containing resin (A), A range of 0.2 to 1.9 is more preferable, and a range of 0.3 to 1.5 is more preferable.
  • the amount of the component (E) relative to the carboxyl group-containing resin (A) is preferably in the range of 0.1 to 10% by mass, more preferably in the range of 0.5 to 5% by mass.
  • 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 quickly volatilized and eliminated, that is, the organic solvent. Is preferably adjusted so as not to remain in the dry film.
  • the amount of the organic solvent relative to the entire photosensitive resin composition is preferably in the range of 0 to 99.5% by mass, and more preferably in the range of 15 to 60% by mass.
  • a ratio is suitably adjusted according to the application method.
  • solid content is a total amount of all the components remove
  • the photosensitive resin composition may further contain components other than the above components.
  • Photosensitive resin composition comprising tolylene diisocyanate, morpholine diisocyanate, isophorone diisocyanate and hexamethylene diisocyanate blocked isocyanates blocked with caprolactam, oxime, malonic acid ester, etc .; melamine resin, n-butylated melamine resin , Amino resins such as isobutylated melamine resin, butylated urea resin, butylated melamine urea cocondensation resin, benzoguanamine cocondensation resin; various other thermosetting resins; ultraviolet curable epoxy (meth) acrylate; bisphenol A type , Phenol novolak type, cresol novolak type, alicyclic type and other epoxy resins obtained by adding (meth) acrylic acid; 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 hydrazide and sebacic acid hydrazide; phosphorus compounds such as triphenylphosphine; acid anhydr
  • Photosensitive resin composition includes curing accelerator; colorant; copolymer such as silicone and acrylate; leveling agent; adhesion imparting agent such as silane coupling agent; thixotropic agent; polymerization inhibitor; antihalation agent; An antifoaming agent; an antioxidant; a surfactant; and at least one component selected from the group consisting of polymer dispersants.
  • the content of the amine compound in the photosensitive resin composition is preferably as small as possible. If it does in this way, the electrical insulation of the layer which consists of hardened
  • the amount of the amine compound relative to the carboxyl group-containing resin (A) is preferably 6% by mass or less, and more preferably 4% by mass or less.
  • the photosensitive resin composition can be prepared by blending the raw materials of the photosensitive resin composition as described above and kneading by a known kneading method using, for example, a three-roll, ball mill, sand mill or the like.
  • the raw material of the photosensitive resin composition contains a liquid component, a low viscosity component, etc.
  • the part of the raw material excluding the liquid component, the low viscosity component, etc. is first kneaded, and the resulting mixture is
  • the photosensitive resin composition may be prepared by adding and mixing a liquid component, a component having a low viscosity, and the like.
  • the first agent may be prepared by mixing a part 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 include 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.
  • the second agent may be prepared by mixing and dispersing the remainder of the components of the conductive resin composition. In this case, it is possible to prepare a mixed solution by mixing the necessary amount of the first agent and the second agent in a timely manner and curing the mixed solution to obtain a cured product.
  • the photosensitive resin composition according to this embodiment is suitable for an electrically insulating material for a printed wiring board.
  • the photosensitive resin composition is suitable for materials for electrically insulating layers such as a solder resist layer, a plating resist layer, an etching resist layer, and an interlayer insulating layer.
  • the photosensitive resin composition according to the present embodiment preferably has such a property that even a 25 ⁇ m thick film can be developed with an aqueous sodium carbonate solution.
  • the photosensitive resin composition since it is possible to produce a sufficiently thick electrically insulating layer from the photosensitive resin composition by a photolithography method, the photosensitive resin composition is used as an interlayer insulating layer, a solder resist layer, etc. in a printed wiring board. It can be widely applied to fabricate. Of course, it is also possible to produce an electrically insulating layer having a thickness of less than 25 ⁇ m from the photosensitive resin composition.
  • a wet paint film is formed by applying the photosensitive resin composition on a suitable substrate, and this wet paint film is heated at 80 ° C. for 30 minutes to form a film having a thickness of 25 ⁇ m.
  • the film is exposed by irradiating the film with ultraviolet rays under a condition of 500 mJ / cm 2 with a negative mask having an exposed part that transmits ultraviolet rays and a non-exposed part that blocks ultraviolet rays directly applied. After the exposure, a 1% Na 2 CO 3 aqueous solution at 30 ° C.
  • the film having a thickness of 25 ⁇ m can be developed with an aqueous sodium carbonate solution when a portion corresponding to the non-exposed portion of the film is removed and no residue is observed.
  • FIGS. 1A to 1E an example of a method for producing a printed wiring board including an interlayer insulating layer formed from the photosensitive resin composition according to the present embodiment will be described with reference to FIGS. 1A to 1E.
  • a through hole is formed in the interlayer insulating layer by photolithography.
  • a core material 1 is prepared as shown in FIG. 1A.
  • the core material 1 includes, for example, at least one insulating layer 2 and at least one conductor wiring 3.
  • the conductor wiring 3 provided on one surface of the core material 1 is hereinafter referred to as a first conductor wiring 3.
  • a film 4 is formed on one surface of the core material 1 from a photosensitive resin composition. Examples of the method for forming the film 4 include a coating method and a dry film method.
  • a photosensitive resin composition is applied on the core material 1 to form a wet paint film.
  • the method for applying the photosensitive resin composition is selected from the group consisting of known methods such as dipping, spraying, spin coating, roll coating, curtain coating, and screen printing.
  • the wet coating film is dried at a temperature in the range of 60 to 120 ° C., for example, whereby the coating film 4 can be obtained.
  • a photosensitive resin composition is first applied on an appropriate support made of polyester or the like and then dried to form a dry film that is a dried product of the photosensitive resin composition on the support. To do. Thereby, a laminated body provided with a dry film and the support body which supports a dry film is obtained. After the dry film in this laminate is overlaid on the core material 1, pressure is applied to the dry film and the core material 1, and then the support is peeled from the dry film, so that the dry film is placed on the core material 1 from the support. Transfer to Thereby, the coating 4 made of a dry film is provided on the core material 1.
  • the coating 4 is partially cured by exposing the coating 4 as shown in FIG. 1C.
  • a negative mask is applied to the film 4 and then the film 4 is irradiated with ultraviolet rays.
  • the negative mask includes an exposure part that transmits ultraviolet light and a non-exposure part that blocks ultraviolet light, and the non-exposure part is provided at a position that matches the position of the through hole 10.
  • the negative mask is a photo tool such as a mask film or a dry plate.
  • the ultraviolet light source is selected from the group consisting of chemical lamps, low-pressure mercury lamps, medium-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, xenon lamps, and metal halide lamps, for example.
  • the exposure method may be a method other than a method using a negative mask.
  • the film 4 may be exposed by a direct drawing method in which only the portion of the film 4 to be exposed is irradiated with ultraviolet rays emitted from a light source.
  • the light source applied to the direct drawing method is, for example, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a metal halide lamp, g-line (436 nm), h-line (405 nm), i-line (365 nm), and g-line, h-line, and i-line. It is selected from the group consisting of two or more kinds of combinations.
  • the film 4 is exposed by irradiating the film 4 made of the dry film with ultraviolet rays through the support without peeling the support after the dry film in the laminate is stacked on the core material 1. Subsequently, the support may be peeled off from the film 4 before development processing.
  • the coating 4 is developed to remove the unexposed portion 5 of the coating 4 shown in FIG. 1C, whereby the hole 6 is formed at the position where the through hole 10 is formed as shown in FIG. 1D.
  • an appropriate developer according to the composition of the photosensitive resin composition can be used.
  • the developer is, for example, an alkaline aqueous solution containing at least one of an alkali metal salt and an alkali metal hydroxide, or an organic amine.
  • the alkaline aqueous solution is, for example, sodium carbonate, potassium carbonate, ammonium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, ammonium hydrogen carbonate, sodium hydroxide, potassium hydroxide, ammonium hydroxide, tetramethyl ammonium hydroxide and water. It contains at least one component selected from the group consisting of lithium oxide.
  • the solvent in the alkaline aqueous solution may be water alone or a mixture of water and a hydrophilic organic solvent such as lower alcohols.
  • the organic amine contains, for example, at least one component selected from the group consisting of monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine and triisopropanolamine.
  • the developer is preferably an alkaline aqueous solution containing at least one of an alkali metal salt and an alkali metal hydroxide, and particularly preferably an aqueous sodium carbonate solution. In this case, it is possible to improve the work environment and reduce the burden of waste disposal.
  • the coating 4 is cured by heating.
  • the heating conditions are, for example, a heating temperature range of 120 to 200 ° C. and a heating time range of 30 to 120 minutes.
  • the coating film 4 may be further irradiated with ultraviolet rays before or after heating. In this case, photocuring of the film 4 can be further advanced.
  • the interlayer insulating layer 7 made of a cured product of the photosensitive resin composition is provided on the core material 1.
  • the second conductor wiring 8 and the hole plating 9 can be provided on the interlayer insulating layer 7 by a known method such as an additive method.
  • a printed wiring board 11 having a through hole 10 for electrically connecting the first conductor wiring 3 and the second conductor wiring 8 is obtained.
  • the hole plating 9 has a cylindrical shape that covers the inner surface of the hole 6, but the entire inner side of the hole 6 may be filled with the hole plating 9.
  • the entire inner surface of the hole 6 and a part of the outer surface of the interlayer insulating layer 7 can be roughened. In this manner, the adhesion between the core material 1 and the hole plating 9 can be improved by roughening a part of the outer surface of the interlayer insulating layer 7 and the inner side surface of the hole 6.
  • the present invention is not limited to this, and a method of imparting a rough surface to a cured product such as plasma treatment, UV treatment, or ozone treatment can be appropriately employed.
  • an initial wiring can be formed by subjecting a part of the roughened outer surface and the inner side surface of the hole 6 to electroless metal plating. Thereafter, the hole plating 9 can be formed by depositing a metal in the electrolyte plating solution on the initial wiring by electrolytic metal plating.
  • the core material includes, for example, at least one insulating layer and at least one conductor wiring.
  • a film is formed from the photosensitive resin composition on the surface of the core material where the conductor wiring is provided.
  • Examples of the method for forming the film include a coating method and a dry film method.
  • the coating method and the dry film method the same method as that for forming the interlayer insulating layer can be employed.
  • the film is partially cured by exposure. The exposure method can be the same as the method for forming the interlayer insulating layer.
  • the film is subjected to a development process to remove the unexposed part of the film, whereby the exposed part of the film remains on the core material.
  • the coating on the core material is heated and cured.
  • the developing method and the heating method can be the same as the method for forming the interlayer insulating layer.
  • the film may be further irradiated with ultraviolet rays before or after heating. In this case, photocuring of the film can be further advanced.
  • a solderless resist layer made of a cured product of the photosensitive resin composition is provided on the core material.
  • a printed wiring board provided with the core material provided with an insulating layer and the conductor wiring on it, and the soldering resist layer which partially covers the surface in which the conductor wiring in a core material is provided is obtained.
  • Epoxy compound 1 a bisphenolfluorene type epoxy compound represented by the formula (7) and having an epoxy equivalent of 250 g / eq, wherein R 1 to R 8 in the formula (7) are all hydrogen.
  • Epoxy compound 2 epoxy equivalent 279 g represented by the formula (7), wherein R 1 and R 5 in the formula (7) are all methyl groups, and R 2 to R 4 and R 6 to R 8 are all hydrogen / Eq bisphenolfluorene type epoxy compound.
  • Epoxy compound A biphenyl novolac type epoxy resin (product name NC-3000-H manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent 288 g / eq).
  • Epoxy compound B Cresol novolac type epoxy resin (product name YDC-700-5, manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., epoxy equivalent 203 g / eq).
  • ⁇ -carboxy-polycaprolactone (n ⁇ 2) monoacrylate manufactured by Toagosei Co., Ltd., trade name Aronix M-5300 (number average molecular weight 290).
  • Photopolymerization initiator (TPO) 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide (product number Irgacure TPO manufactured by BASF).
  • Photopolymerization initiator (IC819) bis- (2,4,6-trimethylbenzoyl) phenylphosphine oxide (manufactured by BASF, product number Irgacure 819).
  • Photopolymerization initiator (IC1173) 2-hydroxy-2-methyl-1-phenyl-propan-1-one (manufactured by BASF, product number Irgacure 1173).
  • Photopolymerization initiator (EAB) 4,4′-bis (diethylamino) benzophenone.
  • Photopolymerization initiator (IC907) 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one (manufactured by BASF, product number Irgacure 907).
  • Photopolymerization initiator (DETX) 2,4-diethylthioxanthen-9-one.
  • Amorphous epoxy resin (EXA-4816): solution of amorphous epoxy resin; long-chain carbon chain-containing bisphenol A type epoxy resin (manufactured by DIC, product number EPICLON EXA-4816, liquid resin, epoxy equivalent 410 g / eq) A solution having a solid content of 90% and dissolved in diethylene glycol monoethyl ether acetate (epoxy equivalent in terms of solid content of 90% is 455.56 g / eq).
  • Melamine manufactured by Nissan Chemical Industries, Ltd., fine melamine; dispersed in the photosensitive resin composition with an average particle size of 8 ⁇ m.
  • Melamine derivative Melamine-tetrahydrophthalate which is a reaction product of melamine and 1,2,3,6-tetrahydrophthalic anhydride; dispersed in the photosensitive resin composition with an average particle size of 6 ⁇ m.
  • Antioxidant A hindered phenol antioxidant, manufactured by BASF, product number IRGANOX 1010.
  • Inorganic filler (A-8) crystalline silica (manufactured by Unimin, IMSIL A-8, average particle size of 2 to 3 ⁇ m).
  • Antifoaming agent manufactured by Shin-Etsu Silicone, product number KS-66.
  • Silane coupling agent 3-glycidoxypropyltrimethoxysilane.
  • Example 1 to 9 and Comparative Examples 1 and 2 [Production of test pieces] Each test piece of Examples 1 to 9 and Comparative Examples 1 and 2 was produced by the following procedure.
  • Examples 1 to 7, 9 and Comparative Examples 1 and 2 A glass epoxy copper clad laminate (FR-4 type) provided with a 35 ⁇ m thick copper foil was prepared.
  • a comb-type electrode having a line width / space width of 50 ⁇ m / 50 ⁇ m was formed as a conductor wiring on the glass epoxy copper clad laminate by a subtractive method, thereby obtaining a printed wiring board.
  • the conductor wiring was roughened by dissolving and removing the surface portion of the printed wiring board having a thickness of about 1 ⁇ m with a product number CZ-8100 manufactured by MEC Co., Ltd.
  • a wet paint film was formed by applying the photosensitive resin composition to the entire surface of the printed wiring board by screen printing.
  • This wet coating film was heated at 80 ° C. for 30 minutes and preliminarily dried to form a film having a thickness of 25 ⁇ m.
  • the film was exposed by irradiating the film with ultraviolet rays under the condition of 500 mJ / cm 2 in a state where a negative mask having a non-exposed portion having a pattern including a circular shape with a diameter of 50 ⁇ m was directly applied.
  • the exposed film was developed.
  • a 1% Na 2 CO 3 aqueous solution at 30 ° C. was sprayed onto the film for 90 seconds at a spray pressure of 0.2 MPa.
  • the coating film was washed by spraying pure water at a spray pressure of 0.2 MPa for 90 seconds.
  • the film was irradiated with ultraviolet rays under the condition of 1000 mJ / cm 2 .
  • the film was then heated at 150 ° C. for 60 minutes. This formed the layer which consists of hardened
  • Example 8 A photosensitive resin composition was obtained by kneading the components shown in the “Composition” column of Table 4 below with three rolls. When producing this photosensitive resin composition, melamine was uniformly dispersed in the photosensitive resin composition.
  • the photosensitive resin composition was applied on a polyethylene terephthalate film with an applicator and then dried by heating at 80 to 110 ° C. to form a dry film having a thickness of 25 ⁇ m on the film.
  • a dry film was heat-laminated on the same printed wiring board as in Examples 1 to 7 and 9 and Comparative Examples 1 and 2.
  • the heat lamination was performed with a vacuum laminator under conditions of 0.5 MPa, 80 ° C., and 1 minute. Thereby, a film having a thickness of 25 ⁇ m was formed on the printed wiring board.
  • a cured product of the photosensitive resin composition cured product of a dry film
  • the printed wiring board core material
  • Tackiness When the test pieces of each Example and Comparative Example were prepared, the degree of tackiness of the coating when the negative mask was removed from the coating after exposure of the coating was evaluated as follows. A: Resistance is not felt when removing the negative mask from the film, and no sticking marks are observed on the film after the negative mask is removed. B: Resistance was felt when the negative mask was removed from the coating, and sticking marks were observed on the coating after the negative mask was removed. C: It was difficult to remove the negative mask from the coating, and the coating was damaged when the negative mask was forcibly removed.
  • A No abnormality was observed in the appearance of the layer made of the cured product and the metal layer, and the metal layer was not peeled by the cellophane adhesive tape peel test.
  • B Although discoloration was recognized in the layer which consists of hardened
  • C Lifting of the layer made of the cured product was observed, and the metal layer was peeled off by the cellophane adhesive tape peeling test.
  • the conductive tape was affixed on the layer which consists of hardened
  • B The electric resistance value was always maintained at 10 6 ⁇ or more until 35 hours passed from the start of the test, but the electric resistance value became less than 10 6 ⁇ before 50 hours passed from the start of the test.
  • C The electric resistance value was always maintained at 10 6 ⁇ or more until 20 hours passed from the start of the test, but the electric resistance value became less than 10 6 ⁇ before 35 hours passed from the start of the test.
  • D The electric resistance value was less than 10 6 ⁇ before 20 hours passed from the start of the test.
  • Copper plating adhesion test (7-1) Roughening resistance The outer surface of the cured layer in the test pieces of each Example and Comparative Example was roughened by the following procedure based on a general desmear treatment. It was. Swelling treatment (Swelling Dip Securigans P manufactured by Atotech Japan Co., Ltd.) commercially available as a swelling liquid for desmear was performed at 60 ° C. for 5 minutes to swell the surface of the cured product. Then, the swollen surface was washed with hot water.
  • Swelling treatment Silicon Dip Securigans P manufactured by Atotech Japan Co., Ltd.
  • membrane layer which consists of hardened
  • cured material with respect to a desmear liquid was evaluated by the following evaluation criteria.
  • C The reduction in film thickness due to roughening is 10 ⁇ m or more.
  • the adhesion between the copper plating layer thus formed and the cured product in the test piece was evaluated according to the following evaluation criteria.
  • the adhesion strength between the copper plating layer and the cured product was evaluated by the following procedure. This adhesion strength was measured according to JIS-C6481. S: Blisters were not confirmed during heating after the electroless copper plating treatment, and no blisters were confirmed during heating after the electrolytic copper plating treatment.
  • the adhesive strength of copper was 0.4 kN / m or more.
  • Example 10 to 21 and Comparative Examples 3 to 6 [Production of test pieces] Each of the photosensitive resin compositions of Examples 10 to 21 and Comparative Examples 3 to 6 was coated on a polyethylene terephthalate film with an applicator and then dried by heating at 95 ° C. for 25 minutes. A dry film having a thickness of 25 ⁇ m was formed on the film.
  • Test pieces of Examples 10 to 21 and Comparative Examples 3 to 6 were produced in the same manner as in Example 8. However, the intensity of ultraviolet rays at the time of the first exposure immediately after laminating the dry film on the printed wiring board was set to 250 mJ / cm 2 . And the temperature which heats the membrane
  • the test environment is 85 ° C., 85% R.D. H.
  • the conductor wiring and the conductive tape in the test pieces of each Example and Comparative Example were The electrical resistance value of was constantly measured. The results were evaluated according to the following evaluation criteria.
  • C The electric resistance value was less than 10 8 ⁇ before 1000 hours passed from the start of the test.
  • the photosensitive resin composition of the first aspect according to the present invention is a non-polymer having a carboxyl group-containing resin (A) and at least one ethylenically unsaturated bond in one molecule.
  • the carboxyl group-containing resin (A) contains a carboxyl group-containing resin (A1) having a bisphenolfluorene skeleton.
  • the photosensitive resin composition contains a carboxyl group-containing resin having a bisphenolfluorene skeleton, excellent developability can be obtained, and in the previous step of the plating treatment, The thickness of the layer containing the cured product of the resin composition can be made difficult to reduce with an oxidizing agent, and the surface of the cured product can be roughened with an oxidizing agent.
  • the carboxyl group-containing resin (A1) is an epoxy compound (a1) having a bisphenolfluorene skeleton and an unsaturated group-containing carboxylic acid (a2). It may be a reaction product of an intermediate that is a reactant and an acid anhydride.
  • the epoxy compound (D) may contain a crystalline epoxy resin.
  • the developability of the photosensitive resin composition can be improved.
  • the photosensitive resin composition of the fourth aspect may further contain an inorganic filler (K) in any one of the first to third aspects.
  • the rough surface suitable for a plating process can be provided to the hardened
  • the inorganic filler (K) may contain silica (k).
  • the difficult corrosion location can be appropriately corroded.
  • the rough surface more suitable for a plating process can be provided to hardened
  • the average particle diameter of the silica (k) may be 1 ⁇ m or less.
  • cured material of the photosensitive resin composition can be made fine.
  • the anchor effect increases as the surface area of the cured product increases, and the adhesion between the rough surface and the plating layer can be improved.
  • the photopolymerization initiator (C) contains an acylphosphine oxide photopolymerization initiator (C1). May be.
  • the photosensitive resin composition contains the carboxyl group-containing resin (A1)
  • the photosensitive resin composition has high photosensitivity when the photosensitive resin composition is exposed to ultraviolet rays. Can be granted.
  • cured material excellent in electrical insulation is obtained.
  • the photopolymerization initiator (C) may contain a hydroxyketone photopolymerization initiator (C2). Good.
  • higher photosensitivity can be imparted to the photosensitive resin composition as compared with the case where no hydroxyketone photopolymerization initiator (C2) is contained.
  • the photopolymerization initiator (C) may contain bis (diethylamino) benzophenone (C3).
  • the ninth aspect when the coating film formed from the photosensitive resin composition is partially exposed and then developed, the resolution is particularly improved by suppressing the curing of the unexposed part. . For this reason, it becomes possible to form a very fine pattern with the hardened
  • the dry film of the tenth aspect is a dried product of the photosensitive resin composition of any one of the first to ninth aspects.
  • the photosensitive resin composition contains a carboxyl group-containing resin having a bisphenolfluorene skeleton, excellent developability can be obtained, and in the previous step of the plating treatment, a dry film can be obtained.
  • the thickness of the layer containing the cured product can be made difficult to reduce with an oxidizing agent, and the surface of the cured product can be roughened with an oxidizing agent.
  • the printed wiring board according to the eleventh aspect includes an interlayer insulating layer containing a cured product of the photosensitive resin composition according to any one of the first to ninth aspects.
  • a printed wiring board having an excellent interlayer insulating layer can be obtained.
  • the printed wiring board according to the twelfth aspect includes a solder resist layer containing a cured product of the photosensitive resin composition according to any one of the first to ninth aspects.
  • a printed wiring board having an excellent solder resist layer can be obtained.
  • the method for producing a photosensitive resin composition comprises reacting an epoxy compound (a1) having a bisphenolfluorene skeleton with an unsaturated group-containing carboxylic acid (a2) to obtain an intermediate, An intermediate and an acid anhydride are reacted to synthesize a carboxyl group-containing resin (A1), a carboxyl group-containing resin (A) containing the carboxyl group-containing resin (A1), and an ethylenically unsaturated bond An unsaturated compound (B) having at least one per molecule, a photopolymerization initiator (C), an epoxy compound (D), and a component (E) are mixed to obtain a photosensitive resin composition.
  • the component (E) contains at least one compound selected from the group of melamine and melamine derivatives.
  • a photosensitive resin composition having excellent developability can be obtained even when a carboxyl group-containing resin having a bisphenolfluorene skeleton is contained. And when giving a rough surface to the hardened

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Abstract

L'invention concerne une composition de résine sensible à la lumière qui contient une résine contenant un groupe carboxyle (A), un composé insaturé (B), un initiateur de photopolymérisation (C), un composé époxy (D), et un composé (E) contenant au moins un composé choisi dans le groupe comprenant la mélamine et des dérivés de la mélamine. La résine contenant un groupe carboxyle (A) contient une résine contenant un groupe carboxyle (A1) comportant un squelette de bisphénol fluorène.
PCT/JP2016/000428 2015-01-28 2016-01-28 Composition de résine sensible à la lumière, film sec, et carte de circuits imprimés WO2016121395A1 (fr)

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CN201680007349.5A CN107209457B (zh) 2015-01-28 2016-01-28 感光性树脂组合物、干膜和印刷布线板
KR1020187033307A KR20180125634A (ko) 2015-01-28 2016-01-28 감광성 수지 조성물, 드라이 필름, 및 프린트 배선판

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018117214A1 (fr) * 2016-12-21 2018-06-28 三菱ケミカル株式会社 Composition de résine pouvant durcir et film, article moulé, pré-impregné et plastique renforcé par des fibres utilisant ladite composition de résine pouvant durcir
CN108610456A (zh) * 2018-05-15 2018-10-02 南京驭新光电技术有限公司 一种光敏环氧树脂组合物及其制备方法和应用
JP2019077856A (ja) * 2017-10-19 2019-05-23 サムソン エレクトロ−メカニックス カンパニーリミテッド． 光硬化性及び熱硬化性樹脂組成物、並びにその硬化物

Families Citing this family (1)

* Cited by examiner, † Cited by third party
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JP6720910B2 (ja) * 2017-03-28 2020-07-08 味の素株式会社 感光性樹脂組成物

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001131242A (ja) * 1999-11-02 2001-05-15 Nippon Kayaku Co Ltd 樹脂組成物及びこれらの硬化物
JP2001131241A (ja) * 1999-11-02 2001-05-15 Nippon Kayaku Co Ltd 樹脂組成物及びこれらの硬化物
JP2005189841A (ja) * 2003-12-01 2005-07-14 Showa Denko Kk レジスト用硬化性難燃組成物、その硬化方法及び用途
JP2006096962A (ja) * 2004-09-28 2006-04-13 Sanei Kagaku Kk 感光性熱硬化性樹脂組成物、並びにレジスト被覆プリント配線板及びその製造法
WO2013021734A1 (fr) * 2011-08-11 2013-02-14 互応化学工業株式会社 Composition de résine pour résists
WO2013172009A1 (fr) * 2012-05-15 2013-11-21 日本化薬株式会社 Composé de type polyester réactif et composition de résine durcissable sous l'effet d'un rayonnement d'énergie active
JP2015011256A (ja) * 2013-07-01 2015-01-19 互応化学工業株式会社 ソルダーレジスト用組成物及びプリント配線版

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5651735A (en) * 1979-10-03 1981-05-09 Asahi Chem Ind Co Ltd Photoreactive composition
WO2000058788A1 (fr) * 1999-03-26 2000-10-05 Nippon Steel Chemical Co., Ltd. Article multicouche photopolymerisable haute definition et dispositif semiconducteur fabrique avec cet article
JP3912405B2 (ja) * 2003-11-11 2007-05-09 三菱化学株式会社 硬化性組成物、硬化物、カラーフィルタ及び液晶表示装置

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001131242A (ja) * 1999-11-02 2001-05-15 Nippon Kayaku Co Ltd 樹脂組成物及びこれらの硬化物
JP2001131241A (ja) * 1999-11-02 2001-05-15 Nippon Kayaku Co Ltd 樹脂組成物及びこれらの硬化物
JP2005189841A (ja) * 2003-12-01 2005-07-14 Showa Denko Kk レジスト用硬化性難燃組成物、その硬化方法及び用途
JP2006096962A (ja) * 2004-09-28 2006-04-13 Sanei Kagaku Kk 感光性熱硬化性樹脂組成物、並びにレジスト被覆プリント配線板及びその製造法
WO2013021734A1 (fr) * 2011-08-11 2013-02-14 互応化学工業株式会社 Composition de résine pour résists
WO2013172009A1 (fr) * 2012-05-15 2013-11-21 日本化薬株式会社 Composé de type polyester réactif et composition de résine durcissable sous l'effet d'un rayonnement d'énergie active
JP2015011256A (ja) * 2013-07-01 2015-01-19 互応化学工業株式会社 ソルダーレジスト用組成物及びプリント配線版

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018117214A1 (fr) * 2016-12-21 2018-06-28 三菱ケミカル株式会社 Composition de résine pouvant durcir et film, article moulé, pré-impregné et plastique renforcé par des fibres utilisant ladite composition de résine pouvant durcir
JPWO2018117214A1 (ja) * 2016-12-21 2018-12-20 三菱ケミカル株式会社 硬化性樹脂組成物、並びにこれを用いたフィルム、成形品、プリプレグ及び繊維強化プラスチック
TWI655239B (zh) * 2016-12-21 2019-04-01 日商三菱化學股份有限公司 硬化性樹脂組成物，以及使用該組成物的膜、成形品、預浸體及纖維強化塑膠
US11161975B2 (en) 2016-12-21 2021-11-02 Mitsubishi Chemical Corporation Curable resin composition, and film, molded article, prepreg, and fiber-reinforced plastic using said curable resin composition
JP2019077856A (ja) * 2017-10-19 2019-05-23 サムソン エレクトロ−メカニックス カンパニーリミテッド． 光硬化性及び熱硬化性樹脂組成物、並びにその硬化物
JP7193074B2 (ja) 2017-10-19 2022-12-20 サムソン エレクトロ－メカニックス カンパニーリミテッド． 光硬化性及び熱硬化性樹脂組成物、並びにその硬化物
CN108610456A (zh) * 2018-05-15 2018-10-02 南京驭新光电技术有限公司 一种光敏环氧树脂组合物及其制备方法和应用
CN108610456B (zh) * 2018-05-15 2020-06-12 南京驭新光电技术有限公司 一种光敏环氧树脂组合物及其制备方法和应用

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