WO2017125966A1 - 感光性樹脂組成物、ドライフィルム、及びプリント配線板 - Google Patents
感光性樹脂組成物、ドライフィルム、及びプリント配線板 Download PDFInfo
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- WO2017125966A1 WO2017125966A1 PCT/JP2016/002474 JP2016002474W WO2017125966A1 WO 2017125966 A1 WO2017125966 A1 WO 2017125966A1 JP 2016002474 W JP2016002474 W JP 2016002474W WO 2017125966 A1 WO2017125966 A1 WO 2017125966A1
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- resin composition
- photosensitive resin
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- carboxyl group
- acid
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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
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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
- 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
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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
- 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
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/02—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding
- H05K3/06—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding the conductive material being removed chemically or electrolytically, e.g. by photo-etch process
- H05K3/061—Etching masks
- H05K3/064—Photoresists
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 an interlayer insulating layer containing a cured product of the photosensitive resin composition, and the photosensitive resin composition.
- the present invention relates to a printed wiring board including a solder resist 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.
- Patent Document 1 discloses a photosensitive resin composition containing an organic filler.
- Patent Document 1 discloses using an organic filler whose surface is coated with silica in a resin composition containing a carboxyl group-containing resin, a photopolymerization initiator, and an organic filler.
- the surface of the organic filler is coated with silica to improve the electrical characteristics of the layer obtained from the resin composition and increase the strength of the layer.
- Patent Document 1 an organic filler whose surface is coated with silica must be used. It is not easy to obtain a photosensitive resin composition containing an organic filler and having excellent developability, thixotropy, plating resistance, insulation reliability, and adhesion.
- An object of the present invention is to develop a photosensitive resin composition excellent in developability, thixotropy, plating resistance, insulation reliability, and adhesion, a dry film that is a dried product of the photosensitive resin composition, and the photosensitive resin. It is providing a printed wiring board provided with the interlayer insulation 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), an organic filler (E) containing an organic filler (E1) having a carboxyl group, at least one melamine compound (F) selected from the group of melamine and melamine derivatives, Containing.
- 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.
- 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), an organic filler (E) containing an organic filler (E1) having a carboxyl group, and at least one melamine compound (F) selected from the group of melamine and melamine derivatives. .
- the carboxyl group-containing resin (A) preferably contains a carboxyl group-containing resin having an ethylenically unsaturated group. Since the carboxyl group-containing resin (A) has an ethylenically unsaturated group, it has photoreactivity. For this reason, the carboxyl group-containing resin (A) can impart photosensitivity, specifically, ultraviolet curability, to the photosensitive resin composition.
- the carboxyl group-containing resin (A) preferably contains a carboxyl group-containing resin having an aromatic ring.
- the carboxyl group-containing resin (A) contains an aromatic ring, high heat resistance and insulation reliability can be imparted to the cured product of the photosensitive resin composition containing the carboxyl group-containing resin (A).
- the carboxyl group-containing resin (A) includes a carboxyl group-containing resin having any polycyclic aromatic ring among a biphenyl skeleton, a naphthalene skeleton, a fluorene skeleton, and an anthracene skeleton.
- the photosensitive resin composition containing carboxyl group-containing resin (A) because carboxyl group-containing resin (A) contains any polycyclic aromatic ring among biphenyl skeleton, naphthalene skeleton, fluorene skeleton, and anthracene skeleton. Higher heat resistance and insulation reliability can be imparted to the cured product. More preferably, the carboxyl group-containing resin (A) includes a carboxyl group-containing resin having a bisphenolfluorene skeleton. When the carboxyl group-containing resin (A) includes a bisphenolfluorene skeleton, higher heat resistance and insulation reliability can be imparted to the cured product of the photosensitive resin composition containing the carboxyl group-containing resin (A).
- the carboxyl group-containing resin (A) preferably contains a carboxyl group-containing resin (A1) having a bisphenol fluorene skeleton as described below.
- the carboxyl group-containing resin (A1) includes, for example, an epoxy compound (a1) having a bisphenolfluorene skeleton represented by the following formula (1), a carboxylic acid (a2) containing an unsaturated group-containing carboxylic acid (a2-1), It is a reaction product of an intermediate that is a reaction product of (1) and an acid anhydride (a3).
- R 1 to R 8 are each independently hydrogen, an alkyl group having 1 to 5 carbon atoms, or halogen.
- the carboxyl group-containing resin (A1) includes an epoxy compound (a1) having a bisphenolfluorene skeleton (S1) represented by the following formula (1) and a carboxylic acid (a2) containing an unsaturated group-containing carboxylic acid (a2-1) And the intermediate obtained thereby and the acid anhydride (a3) are reacted.
- R 1 to R 8 are each independently hydrogen, an alkyl group having 1 to 5 carbon atoms, or halogen. That is, each of R 1 to R 8 in Formula (1) may be hydrogen, but may be an alkyl group having 1 to 5 carbon atoms or 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.
- the carboxyl group-containing resin (A1) has a bisphenolfluorene skeleton represented by the formula (1) derived from the epoxy compound (a1), high heat resistance and insulation reliability can be imparted to the cured product of the photosensitive resin composition. . Moreover, the developability excellent in the photosensitive resin composition can be provided because carboxyl group-containing resin (A1) has a carboxyl group derived from an acid anhydride (a3). Furthermore, thermosetting property can be provided to the photosensitive resin composition because the photosensitive resin composition contains an epoxy resin.
- the carboxyl group-containing resin (A1) can be synthesized, for example, as described below.
- An intermediate is synthesized by reacting with the acid (a2).
- the synthesis of the intermediate is defined as the first reaction.
- the intermediate has a structure (S3) represented by the following formula (3) generated by the ring-opening addition reaction between the epoxy group and the carboxylic acid (a2).
- the intermediate has a secondary hydroxyl group generated by the ring-opening addition reaction between the epoxy group and the carboxylic acid (a2) in the structure (S3).
- A is a carboxylic acid residue. This A contains an unsaturated group-containing carboxylic acid residue.
- the reaction between the intermediate and the acid anhydride (a3) is defined as the second reaction.
- the acid anhydride (a3) may include acid monoanhydride and acid dianhydride.
- the acid monoanhydride is a compound having one acid anhydride group in which two carboxyl groups in one molecule are dehydrated and condensed.
- An acid dianhydride is a compound having two acid anhydride groups obtained by dehydration condensation of four carboxyl groups in one molecule.
- the acid anhydride (a3) may contain at least one of acid dianhydride (a3-2) and acid monoanhydride (a3-1).
- acid anhydride (a3) contains acid monoanhydride (a3-1)
- the carboxyl group-containing resin (A1) is represented by the bisphenolfluorene skeleton (S1) represented by the formula (1) and the following formula (4): Structure (S4).
- 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 (a3-1).
- A is a carboxylic acid residue
- B is an acid monoanhydride residue. This A contains an unsaturated group-containing carboxylic acid residue.
- the carboxyl group-containing resin (A1) is represented by the bisphenolfluorene skeleton (S1) represented by the formula (1) and the following formula (5): Structure (S5).
- the structure (S5) is generated by the reaction between two acid anhydride groups in the acid dianhydride (a3-2) and two secondary hydroxyl groups in the intermediate. That is, the structure (S5) is formed by crosslinking two secondary hydroxyl groups with the acid dianhydride (a3-2).
- 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 a carboxylic acid residue and D is an acid dianhydride residue. This A contains an unsaturated group-containing carboxylic acid residue.
- the carboxyl group-containing resin (A1) can be obtained by reacting the secondary hydroxyl group in the intermediate with the acid anhydride (a3).
- the acid anhydride (a3) contains an acid dianhydride (a3-2) and an acid monoanhydride (a3-1)
- a part of the secondary hydroxyl groups in the intermediate and the acid dianhydride ( a3-2) and another part of the secondary hydroxyl groups in the intermediate are reacted with acid monoanhydride (a3-1).
- 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 (a3-2) reacts with the secondary hydroxyl group in the intermediate.
- A is a carboxylic acid residue and D is an acid dianhydride residue. This A contains an unsaturated group-containing carboxylic acid 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 acid anhydride (a3) contains the acid dianhydride (a3-2)
- the carboxyl group-containing resin (A1) contains the acid dianhydride (a3-2)
- the number of structures (S2) and structures (S6) is reduced, or the structure (S2) and structure (S6) are almost eliminated from the carboxyl group-containing resin (A1).
- the carboxyl group-containing resin (A1) has a bisphenolfluorene skeleton (S1), and when the acid anhydride (a3) contains acid monoanhydride (a3-1), the structure (S4) And the acid anhydride contains the acid dianhydride (a3-2), it can have the structure (S5). Further, when the acid anhydride (a3) contains acid monoanhydride (a3-1), the carboxyl group-containing resin (A1) may have at least one of the structure (S2) and the structure (S3). is there. When the acid anhydride (a3) contains the acid dianhydride (a3-2), the carboxyl group-containing resin (A1) has at least one of the structure (S2) and the structure (S6). There is.
- the carboxyl group-containing resin (A1) has the structure (S2), There may be at least one of the structure (S3) and the structure (S6).
- the carboxyl group-containing resin (A1) is an epoxy compound (a1).
- the secondary secondary hydroxyl group and the acid anhydride (a3) may react with each other.
- 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 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.
- 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 (a2-1), 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 the acid anhydride (a3), at least one of an alkali metal salt and an alkali metal hydroxide is added to the photosensitive resin composition. The developability by the alkaline aqueous solution to contain can be provided.
- the molecular weight of the carboxyl group-containing resin (A1) depends on the number of crosslinks by the acid dianhydride (a3-2). . 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 (a3) contains an acid dianhydride (a3-2) and an acid monoanhydride (a3-1), the acid dianhydride (a3-2) and the acid monoanhydride (a3-1) And the amount of acid monoanhydride (a3-1) relative to acid dianhydride (a3-2) can be easily obtained to obtain a carboxyl group-containing resin (A1) having a desired molecular weight and acid value. .
- 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, tackiness of a film formed from the photosensitive resin composition is further suppressed, and 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 polydispersity of the carboxyl group-containing resin (A1) is preferably in the range of 1.0 to 4.8. In this case, it was excellent in the photosensitive resin composition while ensuring good insulation reliability and plating resistance (for example, resistance to whitening during electroless nickel / gold plating) of the cured product formed from the photosensitive resin composition. Developability can be imparted.
- the polydispersity of the carboxyl group-containing resin (A1) is more preferably in the range of 1.1 to 4.0, and still more preferably in the range of 1.2 to 2.8.
- the polydispersity is a value (Mw / Mn) of the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) of the carboxyl group-containing resin (A1).
- the 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 (a3) contains acid dianhydride (a3-2), an excess due to the addition of acid dianhydride (a3-2) will occur. Increase in molecular weight tends to be suppressed.
- the carboxylic acid (a2) includes an unsaturated group-containing carboxylic acid (a2-1).
- the carboxylic acid (a2) may contain only the unsaturated group-containing carboxylic acid (a2-1).
- the carboxylic acid (a2) may contain a carboxylic acid other than the unsaturated group-containing carboxylic acid (a2-1) and the unsaturated group-containing carboxylic acid (a2-1).
- the unsaturated group-containing carboxylic acid (a2-1) can contain, for example, a compound having only one ethylenically unsaturated group in one molecule. More specifically, the unsaturated group-containing carboxylic acid (a2-1) is, for example, acrylic acid, methacrylic acid, ⁇ -carboxy-polycaprolactone (n ⁇ 2) monoacrylate, crotonic acid, cinnamic acid, 2-acryloyloxy Ethyl succinic acid, 2-methacryloyloxyethyl succinic acid, 2-acryloyloxyethyl phthalic acid, 2-methacryloyloxyethyl phthalic acid, 2-acryloyloxypropyl phthalic acid, 2-methacryloyloxypropyl phthalic acid, 2-acryloyloxyethyl malein Acid, 2-methacryloyloxyethyl maleic acid, ⁇ -carboxyethyl acrylate, 2-acryloyloxy
- the carboxylic acid (a2) may contain a polybasic acid (a2-2).
- the polybasic acid (a2-2) is an acid capable of substituting two or more hydrogen atoms with metal atoms in one molecule.
- the polybasic acid (a2-2) preferably has two or more carboxyl groups.
- the epoxy compound (a1) reacts with both the unsaturated group-containing carboxylic acid (a2-1) and the polybasic acid (a2-2).
- the polybasic acid (a2-1) cross-links the epoxy groups present in the two molecules of the epoxy compound (a1), thereby increasing the molecular weight.
- the tackiness of the film formed from the photosensitive resin composition can be further controlled, and the insulation reliability and plating resistance of the cured product can be further improved.
- the polybasic acid (a2-2) preferably contains a dicarboxylic acid.
- a dicarboxylic acid For example, 4-cyclohexene-1,2-dicarboxylic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, maleic acid, fumaric acid, phthalic acid, isophthalic acid
- One or more compounds selected from the group consisting of acid and terephthalic acid can be contained.
- the polybasic acid (a2-2) contains 4-cyclohexene-1,2-dicarboxylic acid.
- the reactive solution is obtained by adding the 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) and the carboxylic acid (a2) in the presence of triphenylphosphine. In this case, the ring-opening addition reaction between the epoxy group and the carboxylic acid (a2) in the epoxy compound (a1) is particularly accelerated, and a reaction rate (conversion rate) of 95% or more, 97% or more, or almost 100% is achieved. it can. For this reason, the intermediate body which has a structure (S3) is obtained with a high yield. Moreover, generation
- the amount of the carboxylic acid (a2) relative to 1 mol of the epoxy group of the epoxy compound (a1) is in the range of 0.5 to 1.2 mol. Is preferred. In this case, a photosensitive resin composition having excellent photosensitivity and stability can be obtained. From the same viewpoint, the amount of the unsaturated group-containing carboxylic acid (a2-1) relative to 1 mol of the epoxy group of the epoxy compound (a1) is preferably in the range of 0.5 to 1.2 mol, 0.8 More preferably in the range of -1.2 mol.
- the carboxylic acid (a2) contains a carboxylic acid other than the unsaturated group-containing carboxylic acid (a2-1), the unsaturated group-containing carboxylic acid (a2-) with respect to 1 mol of the epoxy group of the epoxy compound (a1).
- the amount of 1) may be in the range of 0.5 to 0.95 mol.
- the carboxylic acid (a2) contains a polybasic acid (a2-2)
- the amount of the polybasic acid (a2-2) relative to 1 mol of the epoxy group of the epoxy compound (a1) is 0.025-0. It is preferably within the range of 25 mol. In this case, a photosensitive resin composition having excellent photosensitivity and stability can be obtained.
- the intermediate thus obtained comprises a hydroxyl group produced by a reaction between the epoxy group of the epoxy compound (a1) and the carboxyl group of the carboxylic acid (a2).
- Acid monoanhydride (s3-1) is a compound having one acid anhydride group.
- the acid monoanhydride (a3-1) can contain an anhydride of a dicarboxylic acid.
- Acid monoanhydride (a3-1) is, for example, phthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylnadic acid anhydride, hexahydrophthalic anhydride, Methyl hexahydrophthalic anhydride, succinic anhydride, methyl succinic anhydride, maleic anhydride, citraconic anhydride, glutaric anhydride, cyclohexane-1,2,4-tricarboxylic acid-1,2-anhydride And at least one compound selected from the group consisting of itaconic anhydride.
- the acid monoanhydride (a3-1) contains 1,2,3,6-tetrahydrophthalic anhydride. That is, the acid anhydride (a3) 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.
- S4 structure
- 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 (a3-1) is preferably in the range of 20 to 100 mol%, and in the range of 40 to 100 mol%. Although it is more preferable, it is not limited to these ranges.
- Acid dianhydride (a3-2) is a compound having two acid anhydride groups.
- the acid dianhydride (a3-2) can contain an anhydride of tetracarboxylic acid.
- Examples of the acid dianhydride (a3-2) include 1,2,4,5-benzenetetracarboxylic dianhydride, benzophenone tetracarboxylic dianhydride, methylcyclohexene tetracarboxylic dianhydride, and tetracarboxylic dianhydride.
- the acid dianhydride (a3-2) 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 with respect to the total amount of acid dianhydride (a3-2) is preferably in the range of 20 to 100 mol%, preferably 40 to 100 mol%. Although it is more preferable to be within the range, it is not limited to these ranges.
- a known method can be employed.
- a reactive solution is obtained by adding an acid anhydride (a3) to a solvent solution of an intermediate, further adding a thermal polymerization inhibitor and a catalyst as necessary, and stirring and mixing.
- 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.
- the solvent, catalyst and polymerization inhibitor appropriate ones can be used, and the solvent, catalyst and polymerization inhibitor used in the synthesis of the intermediate can also be used as they are.
- the catalyst contains triphenylphosphine. That is, it is preferable to react the intermediate and the acid anhydride (a3) in the presence of triphenylphosphine. In this case, the reaction between the secondary hydroxyl group and the acid anhydride (a3) in the intermediate is particularly accelerated, and a reaction rate (conversion rate) of 90% or more, 95% or more, 97% or more, or almost 100% is achieved. it can. 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 acid anhydride (a3) contains an acid dianhydride (a3-2) and an acid monoanhydride (a3-1), the acid dianhydride with respect to 1 mol of the epoxy group of the epoxy compound (a1)
- the amount of (a3-2) is preferably in the range of 0.05 to 0.24 mol.
- the amount of acid monoanhydride (a3-1) 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).
- the carboxyl group-containing resin (A1) in which the acid value and the molecular weight are appropriately adjusted can be easily obtained.
- the intermediate and the acid anhydride (a3) are also preferable to react the intermediate and the acid anhydride (a3) under air bubbling.
- the developability by the alkaline aqueous solution of the photosensitive resin composition improves especially by suppressing the excessive molecular weight increase of the produced
- the carboxyl group-containing resin (A) may contain only the carboxyl group-containing resin (A1) or only a carboxyl group-containing resin other than the carboxyl group-containing resin (A1), and the carboxyl group-containing resin (A1) and the carboxyl group-containing resin. You may contain carboxyl group-containing resin other than resin (A1).
- the carboxyl group-containing resin other than the carboxyl group-containing resin (A1) includes a carboxyl group-containing resin having no bisphenolfluorene skeleton (hereinafter also referred to as a carboxyl group-containing resin (A2)).
- the carboxyl group-containing resin (A2) can contain, for example, a compound having a carboxyl group and not having photopolymerizability (hereinafter referred to as component (A2-1)).
- component (A2-1) contains, for example, a polymer of an ethylenically unsaturated monomer including an ethylenically unsaturated compound having a carboxyl group.
- the ethylenically unsaturated compound having a carboxyl group can contain 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 (A2) may contain a compound having a carboxyl group and an ethylenically unsaturated group (hereinafter referred to as “component (A2-2)”).
- the carboxyl group-containing resin (A2) may contain only the component (A2-2).
- the component (A2-2) includes, for example, an intermediate that is a reaction product of an epoxy compound (x1) having two or more epoxy groups in one molecule and an ethylenically unsaturated compound (x2), a polyvalent carboxylic acid, and It contains a resin (referred to as first resin (x)) that is a reaction product with at least one compound (x3) selected from the group of anhydrides.
- the compound (x3) is added to an intermediate obtained by reacting the epoxy group in the epoxy compound (x1) with the carboxyl group in the ethylenically unsaturated compound (x2).
- the epoxy compound (x1) 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 (x1) preferably contains at least one compound selected from the group of biphenyl novolac type epoxy compounds and cresol novolac type epoxy compounds.
- the epoxy compound (x1) may contain only a biphenyl novolac type epoxy compound or may contain only a cresol novolac type epoxy compound.
- the epoxy compound (x1) may contain a polymer of the ethylenically unsaturated compound (z).
- the ethylenically unsaturated compound (z) contains, for example, a compound (z1) having an epoxy group such as glycidyl (meth) acrylate, or further has no epoxy group such as 2- (meth) acryloyloxyethyl phthalate. Contains compound (z2).
- the ethylenically unsaturated compound (x2) preferably contains at least one of acrylic acid and methacrylic acid.
- Compound (x3) contains, for example, 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 (x3) preferably contains at least one polycarboxylic acid selected from the group of phthalic acid, tetrahydrophthalic acid, and methyltetrahydrophthalic acid.
- the component (A2-2) is a resin (second resin) which is a reaction product of a polymer of an ethylenically unsaturated monomer containing an ethylenically unsaturated compound having a carboxyl group and an ethylenically unsaturated compound having an epoxy group.
- the ethylenically unsaturated monomer may further contain an ethylenically unsaturated compound having no carboxyl group.
- the second resin (y) is obtained by reacting an ethylenically unsaturated compound having an epoxy group with a part of the carboxyl group in the polymer.
- the ethylenically unsaturated monomer may further contain an ethylenically unsaturated compound having no carboxyl group.
- 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), only the carboxyl group-containing resin (A2), or the carboxyl group-containing resin (A1) and the carboxyl group-containing resin (A2).
- the carboxyl group-containing resin (A) preferably contains 30% by mass or more of the carboxyl group-containing resin (A1), more preferably contains 50% by mass or more, and further preferably contains 60% by mass or more. It is still more preferable to contain 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 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, for example, an acyl phosphine oxide photopolymerization initiator (C1).
- 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.
- 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 organic filler (E) may cause light scattering in the photosensitive resin composition during exposure. In this case, there may be a problem that good developability cannot be obtained with the photosensitive resin composition.
- the acylphosphine oxide photopolymerization initiator (C1) and the hydroxyketone photopolymerization initiator (C2 ) Is particularly preferably within the range of 1: 0.01 to 1: 1.
- the photopolymerization initiator (C) preferably contains a photopolymerization initiator (C3) having a benzophenone skeleton. That is, the photosensitive resin composition contains an acyl phosphine oxide photopolymerization initiator (C1) and a photopolymerization initiator (C3) having a benzophenone skeleton, or an acyl phosphine oxide photopolymerization initiator (C1), It is also preferable to contain a hydroxyketone photopolymerization initiator (C2) and a photopolymerization initiator (C3) having a benzophenone skeleton.
- the photopolymerization initiator (C3) having a benzophenone skeleton include bis (diethylamino) benzophenone.
- the amount of the photopolymerization initiator (C3) having a benzophenone skeleton with respect to the acylphosphine oxide photopolymerization initiator (C1) is preferably in the range of 0.5 to 20% by mass.
- the amount of the photopolymerization initiator (C3) having a benzophenone skeleton with respect to the acylphosphine oxide photopolymerization initiator (C1) is 0.5% by mass or more, the resolution is particularly high.
- the amount of the photopolymerization initiator (C3) having a benzophenone skeleton with respect to the acylphosphine oxide photopolymerization initiator (C1) is 20% by mass or less, the electrical insulation of the cured product of the photosensitive resin composition is improved.
- the photopolymerization initiator (C3) having a benzophenone skeleton is difficult to inhibit.
- the amount of bis (diethylamino) benzophenone relative to the acylphosphine oxide photopolymerization initiator (C1) is preferably in the range of 0.5 to 20% by mass.
- the organic filler (E) may cause light scattering in the photosensitive resin composition during exposure. In this case, there may be a problem that good developability cannot be obtained with the photosensitive resin composition.
- the amount of the photopolymerization initiator (C3) having a benzophenone skeleton is the same as that of the acylphosphine oxide photopolymerization initiator (C1). It is particularly preferably in the range of 1 to 18% by mass. From the same viewpoint, the amount of bis (diethylamino) benzophenone is particularly preferably in the range of 1 to 18% by mass relative to the acylphosphine oxide photopolymerization initiator (C1).
- 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 (D1).
- the developability of the photosensitive resin composition can be improved.
- the organic filler (E1) has a carboxyl group, the compatibility of the crystalline epoxy resin (D1) is improved with the organic filler (E1), and the crystalline epoxy resin (D1) in the photosensitive resin composition is recrystallized. Can be prevented.
- the epoxy compound (D) may further contain an amorphous epoxy resin (D2).
- the “crystalline epoxy resin” is an epoxy resin having a melting point
- the “amorphous epoxy resin” is an epoxy resin having no melting point.
- the crystalline epoxy resin (D1) is, for example, 1,3,5-tris (2,3-epoxypropyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, Hydroquinone type crystalline 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 (part number YSLV-80DE manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.), bisphenol type crystalline epoxy resin (particularly product name YSLV-80XY manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.), tetrakisphenol ethane type crystalline epoxy resin (specific example As specific examples, Nippon Kayaku Co., Ltd. product number GTR-1800), bisphenol fluoro Preferably it contains one or more components selected
- the crystalline epoxy resin (D1) preferably has two epoxy groups in one molecule. In this case, it is possible to further prevent cracks in the cured product while the temperature change is repeated.
- the crystalline epoxy resin (D1) preferably has an epoxy equivalent of 150 to 300 g / eq. This epoxy equivalent is the gram weight of the crystalline epoxy resin (D1) containing 1 gram equivalent of epoxy groups.
- the crystalline epoxy resin (D1) has a melting point. Examples of the melting point of the crystalline epoxy resin (D1) include 70 to 180 ° C.
- the epoxy compound (D) preferably contains a crystalline epoxy resin (D1-1) having a melting point of 110 ° C. or lower.
- a crystalline epoxy resin (D1-1) having a melting point of 110 ° C. or lower In this case, the developability of the photosensitive resin composition with an alkaline aqueous solution is particularly improved. Crystalline epoxy resin (D1-1) having a melting point of 110 ° C.
- biphenyl type epoxy resin specifically, product number YX-4000 manufactured by Mitsubishi Chemical Corporation
- biphenyl ether type epoxy resin specifically, Nippon Steel & Sumikin Chemical Co., Ltd.
- Company-made part number YSLV-80DE specifically, Nippon Steel & Sumikin Chemical Co., Ltd.
- bisphenol type epoxy resin particularly Nippon Steel & Sumikin Chemicals part number YSLV-80XY
- bisphenolfluorene type crystalline epoxy resin particularly epoxy resin having structure (S7)
- the amorphous epoxy resin (D2) is, for example, a phenol novolac type epoxy resin (specifically, product number EPICLON N-775 manufactured by DIC Corporation), or a cresol novolac type epoxy resin (specific example, product number EPICLON N manufactured by DIC Corporation).
- YSLV-120TE manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., rubber core-shell polymer modified bisphenol A type epoxy resin Kaneka product number MX-156), rubber-like core-shell polymer modified bisphenol F type epoxy resin (as a specific example, product number MX-13 manufactured by Kaneka Corporation) 6) and at least one component selected from the group consisting of rubber particle-containing bisphenol F type epoxy resin (specifically, product number Kane Ace MX-130 manufactured by Kaneka Corporation) is preferable.
- the epoxy compound (D) may contain a phosphorus-containing epoxy resin.
- the phosphorus-containing epoxy resin may be contained in the crystalline epoxy resin (D1) or may be contained in the amorphous epoxy resin (D2).
- 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.
- Organic filler (E) can impart thixotropy to the photosensitive resin composition.
- the organic filler (E) includes an organic filler (E1).
- the organic filler (E1) has a carboxyl group. Among the carboxyl groups, some of the carboxyl groups are preferably exposed on the surface of the organic filler (E1).
- the organic filler (E1) has high compatibility in the photosensitive resin composition and can impart stronger thixotropy to the photosensitive resin composition.
- the photosensitive resin composition contains the organic filler (E1) having a carboxyl group, the developability of the photosensitive resin composition can be improved.
- the carboxyl group of an organic filler (E1) can react with the epoxy compound (for example, epoxy compound (D)) in the photosensitive resin composition at the time of thermosetting. Thereby, the hardened
- the organic filler (E1) contained in the cured product is easily deteriorated at the stage of roughening the surface of the cured product.
- the organic filler (E1) thus altered is easily removed from the cured product when a rough surface is imparted to the cured product. Thereby, a rough surface can be provided to the surface of the cured product to improve the adhesion between the cured product and the plating layer.
- the photosensitive resin composition contains the organic filler (E1), the non-uniformity of the coating film due to the fluidity of the photosensitive resin composition can be reduced. Thereby, the film thickness of the layer formed with the photosensitive resin composition can be easily made uniform.
- the photosensitive resin composition may not contain a rheology control agent.
- the carboxyl group of the organic filler (E1) is formed as a side chain in the product by polymerizing or crosslinking a carboxylic acid monomer such as acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, etc. Is done.
- the carboxylic acid monomer has a carboxyl group and a polymerizable unsaturated double bond.
- the organic filler (E1) improves the stability (particularly storage stability) of the photosensitive resin composition in order to enhance the thixotropy of the photosensitive resin composition.
- the organic filler (E1) has a carboxyl group, it improves the developability of the cured product and improves the compatibility of the crystalline epoxy resin to prevent crystallization in the photosensitive resin composition. it can.
- the carboxyl group content of the organic filler (E1) is not particularly limited, but the acid value of the organic filler (E1) is preferably 1 to 60 mgKOH / g by acid-base titration. If the acid value is less than 1 mgKOH / g, the stability of the photosensitive resin composition and the developability of the cured product may be reduced. If the acid value is larger than 60 mgKOH / g, the moisture resistance reliability of the cured product may be lowered.
- the acid value of the organic filler (E1) is more preferably 3 to 40 mgKOH / g.
- the organic filler (E1) has a hydroxyl group. Of these hydroxyl groups, some hydroxyl groups are preferably exposed on the surface of the organic filler (E1). Thus, the dispersibility of the organic filler (E1) in the photosensitive resin composition further improves because the organic filler (E1) has a hydroxyl group.
- the organic filler (E1) preferably has an average primary particle size of 1 ⁇ m or less.
- the average primary particle diameter of the organic filler (E1) is 1 ⁇ m or less, the thixotropy of the photosensitive resin composition is efficiently increased. Therefore, the stability of the photosensitive resin composition is further improved.
- cured material can be made fine because the average primary particle diameter of an organic filler (E1) will be 1 micrometer or less. Thereby, as the surface area of the cured product increases, the anchor effect increases and the adhesion between the rough surface and the plating layer can be improved.
- the lower limit of the average primary particle diameter of the organic filler (E1) is not particularly limited, but is preferably 0.001 ⁇ m or more, for example.
- the average primary particle size by a laser diffraction particle size distribution measuring device, is measured as D 50.
- the average primary particle diameter of the organic filler (E1) is more preferably 0.4 ⁇ m or less, and further preferably 0.1 ⁇ m or less.
- the roughness of the rough surface formed in the cured product can be made particularly fine.
- scattering during exposure can be suppressed in the photosensitive resin composition, whereby the resolution of the photosensitive resin composition can be further improved.
- the organic filler (E1) is preferably dispersed with a maximum particle size of less than 1.0 ⁇ m, more preferably less than 0.5 ⁇ m, in the photosensitive resin composition.
- Maximum particle diameter by laser diffraction type particle size distribution measuring device, is measured as D 50. Alternatively, the maximum particle size is measured by observing the cured product with a transmission electron microscope (TEM).
- the organic filler (E1) may aggregate in the photosensitive resin composition (for example, can form secondary particles). In this case, the maximum particle diameter means the size of the particles after aggregation.
- the average primary particle diameter of the organic filler (E1) is 0.1 ⁇ m or less and the organic filler (E1) is dispersed with a particle diameter of 0.5 ⁇ m or less.
- the maximum particle size is usually larger than the average primary particle size.
- the organic filler (E1) preferably contains a rubber component. Moreover, it is preferable that an organic filler (E1) contains only a rubber component.
- the rubber component can impart flexibility to the cured product of the photosensitive resin composition.
- the rubber component can be composed of a resin.
- the rubber component preferably contains at least one polymer selected from crosslinked acrylic rubber, crosslinked NBR, crosslinked MBS, and crosslinked SBR. In this case, the rubber component can impart excellent flexibility to the cured product of the photosensitive resin composition. Furthermore, a more appropriate rough surface can be imparted to the surface of the cured product.
- the rubber component includes a crosslinked structure formed when the monomers constituting the polymer are copolymerized.
- NBR is generally a copolymer of butadiene and acrylonitrile, and is classified as a nitrile rubber.
- MBS is generally a copolymer composed of three components of methyl methacrylate, butadiene, and styrene, and is classified as a butadiene rubber.
- SBR is generally a copolymer of styrene and butadiene, and is classified as styrene rubber.
- Specific examples of the organic filler (E1) include product number XER-91-MEK manufactured by JSR Corporation, product number XER-32-MEK manufactured by JSR Corporation, product number XSK-500 manufactured by JSR Corporation, and the like.
- XER-91-MEK is a crosslinked rubber (NBR) having a carboxyl group having an average primary particle size of 0.07 ⁇ m, and a methyl ethyl ketone dispersion having a content of 15% by weight of the crosslinked rubber. With an acid value of 10.0 mg KOH / g.
- XER-32-MEK is a dispersion in which a carboxyl group-modified hydrogenated nitrile rubber polymer (linear particles) is dispersed in methyl ethyl ketone at a content of 17% by weight with respect to the total amount of the dispersion.
- XSK-500 is a crosslinked rubber (SBR) having an average primary particle size of 0.07 ⁇ m and having a carboxyl group and a hydroxyl group, and is provided as a methyl ethyl ketone dispersion having a content of the crosslinked rubber of 15% by weight.
- an organic filler (E1) may be mix
- product number XER-92 manufactured by JSR Corporation may be mentioned.
- Organic filler (E1) may contain particle components other than rubber components.
- the organic filler (E1) can contain at least one particle component selected from the group consisting of acrylic resin fine particles having a carboxyl group and cellulose fine particles having a carboxyl group.
- the acrylic resin fine particles having a carboxyl group can contain at least one particle component selected from the group consisting of non-crosslinked styrene / acrylic resin fine particles and crosslinked styrene / acrylic resin fine particles.
- product number FS-201 average primary particle size 0.5 ⁇ m
- Nippon Paint Industrial Coatings Co., Ltd. may be mentioned.
- the organic filler (E1) may contain a particle component other than the particle component selected from the rubber component, the acrylic resin fine particles, and the cellulose fine particles.
- the organic filler (E1) can contain a particle component having a carboxyl group. That is, the particle component having a carboxyl group may be different from the particle component selected from the rubber component, the acrylic resin fine particles, and the cellulose fine particles.
- the organic filler (E) may further contain an organic filler other than the organic filler (E1).
- Organic fillers other than the said organic filler (E1) do not need to have a carboxyl group.
- the organic filler other than the organic filler (E1) may have an average primary particle size larger than 1 ⁇ m.
- the photosensitive resin composition is other than the organic filler (E1).
- the organic filler may not be included.
- Organic filler (E) may contain only organic filler (E1) or organic filler (E1) and organic filler other than organic filler (E1).
- the organic filler (E) preferably contains 30% by mass or more, more preferably 50% by mass or more, and still more preferably 100% by mass of the organic filler (E1).
- the stability of the photosensitive resin composition is further improved.
- cured material and a plating layer can further be improved.
- the melamine compound (F) is at least one compound selected from the group of melamine and melamine derivatives.
- the photosensitive resin composition contains melamine, the adhesion between the cured product of the photosensitive resin composition and a metal such as copper is increased. For this reason, the photosensitive resin composition especially suitable as an insulating material for printed wiring boards is obtained.
- the plating resistance of the cured product of the photosensitive resin composition that is, the whitening resistance during the electroless nickel / gold plating process is improved. Thereby, the grade which remarkably corrodes the hardened
- the photosensitive resin composition contains the melamine compound (F)
- the surface of the cured product of the photosensitive resin composition is roughened in the previous step of the plating treatment, the thickness of the layer containing the cured product is increased. Can be made difficult to thin.
- adhesion between the cured product of the photosensitive resin composition and a plating layer made of copper, gold, or the like can be improved.
- the surface of the cured layer of the photosensitive resin composition is treated with, for example, potassium permanganate in the pre-process of the plating treatment.
- the oxidant contained sometimes roughened.
- the layer of the cured product was treated with the oxidizing agent, the surface of the cured product layer was excessively corroded, and the thickness of this layer might be reduced.
- the carboxyl group-containing resin has a relatively high resistance to the oxidizing agent, but even if the photosensitive resin composition contains the carboxyl group-containing resin, the thickness of the cured product layer becomes excessively thin with the oxidizing agent. It turns out that there is something.
- the carboxyl group-containing resin sometimes deteriorates the developability of the photosensitive resin composition. If the molecular weight of the carboxyl group-containing resin is reduced in order to improve developability, the resistance of the cured product layer to the oxidizing agent is reduced, and the thickness of the cured product layer is further reduced with the oxidizing agent. I understood. For this reason, conventionally, in order to improve the adhesion between the cured product and the plating layer, it has been difficult to appropriately roughen the surface of the cured product layer of the photosensitive resin composition with the oxidizing agent. Therefore, in the present embodiment, in view of these problems, the organic filler (E) and the melamine compound (F) are contained.
- the photosensitive resin composition contains both the melamine compound (F) and the organic filler (E), it was excellent in developability, thixotropy, plating resistance, insulation reliability, and adhesion.
- a photosensitive resin composition is obtained. Specifically, for example, an appropriate rough surface can be imparted to the cured product of the photosensitive resin composition, and adhesion between the cured product and the plating layer can be improved. Moreover, when giving a rough surface to hardened
- a melamine compound (F) 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 melamine compound (F) may be soluble in the photosensitive resin composition.
- the melamine compound (F) when the melamine compound (F) is hardly soluble in the photosensitive resin composition, the melamine compound (F) having an average particle diameter of 20 ⁇ m or less, preferably 15 ⁇ m or less is dispersed in the photosensitive resin composition. It is preferable.
- the melamine compound (F) is uniformly dispersed in the photosensitive resin composition, the melamine compound (F) is more easily coordinated with the metal element. Thereby, the adhesiveness of the photosensitive resin composition can further be improved.
- a melamine compound (F) may be used as a melamine dispersion varnish which the melamine or the melamine derivative disperse
- the minimum of the average particle diameter of a melamine compound (F) is not specifically limited, It can be 0.01 micrometer or more.
- the coupling agent (G) includes a coupling agent (G1).
- the coupling agent (G1) contains an atom selected from a silicon atom, an aluminum atom, a titanium atom, and a zirconia atom.
- the coupling agent (G1) further contains two or more functional groups selected from alkoxy groups, acyloxy groups and alkoxides.
- the coupling agent (G1) may contain two or more alkoxy groups, may contain two or more acyloxy groups, and may contain two or more alkoxides.
- the coupling agent (G1) may contain two or more different functional groups selected from an alkoxy group, an acyloxy group, and an alkoxide.
- the coupling agent (G1) has the dispersibility of the organic filler (E1) in the photosensitive resin composition by reaction or interaction with the carboxyl group contained in the carboxyl group-containing resin (A) and the organic filler (E1). In order to enhance, the thixotropy and stability (especially storage stability) of the photosensitive resin composition are improved.
- the functional group selected from an alkoxy group, an acyloxy group, and an alkoxide is preferably directly bonded to an atom selected from a silicon atom, an aluminum atom, a titanium atom, and a zirconia atom.
- examples of the coupling agent (G1) include tetraethoxysilane, tetramethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinylmethyldiethoxysilane, and vinylmethyl.
- examples of the coupling agent (G1) include acetoalkoxy aluminum diisopropylate, aluminum diisopropoxy monoethyl acetoacetate, aluminum trisethyl acetoacetate and the like. .
- examples of the coupling agent (G1) include isopropyl tristearoyl titanate, isopropyl tris (dioctyl pyrophosphate) titanate, tetraoctyl bis (ditridecyl phosphate titanate), tetra (2-2-diallyloxymethyl-1-butyl) bis (ditridecyl) phosphate titanate, bis (dioctylpyrophosphate) oxyacetate titanate, bis (dioctylpyrophosphate) ethylene titanate and the like.
- the coupling agent (G1) contains a zirconia atom
- examples of the coupling agent (G1) include zirconium tetranormal propoxide, zirconium tetranormal butoxide and the like.
- the coupling agent (G1) preferably contains a silicon atom.
- the coupling agent (G1) may be a silane coupling agent.
- the coupling agent (G1) preferably contains a functional group selected from a methoxy group, an ethoxy group, and an acetoxy group.
- a methoxy group and an ethoxy group are classified into alkoxy groups.
- the acetoxy group is classified as an acyloxy group.
- the coupling agent (G1) may contain only a methoxy group, may contain only an ethoxy group, or may contain only an acetoxy group. Further, the coupling agent (G1) may contain a different functional group selected from a methoxy group, an ethoxy group, and an acetoxy group.
- the coupling agent (G1) contains a functional group selected from a methoxy group, an ethoxy group, and an acetoxy group, the reactivity between the organic filler (E1) and the coupling agent (G1) is improved, and the photosensitive resin Aggregation of the organic filler (E1) in the composition is less likely to occur. Therefore, the thixotropy and stability of the photosensitive resin composition are further improved. Moreover, the favorable resolution of the photosensitive resin composition is obtained.
- the coupling agent (G1) preferably contains two to four functional groups selected from an alkoxy group, an acyloxy group, and an alkoxide.
- the coupling agent (G1) may contain 2 to 4 alkoxy groups, may contain 2 to 4 acyloxy groups, and may contain 2 to 4 alkoxides.
- the coupling agent (G1) may contain 2 to 4 methoxy groups, 2 to 4 ethoxy groups, or 2 to 4 acetoxy groups. Good.
- the coupling agent (G1) may contain two to four different functional groups selected from an alkoxy group, an acyloxy group, and an alkoxide.
- the coupling agent (G1) contains two to four functional groups selected from an alkoxy group, an acyloxy group and an alkoxide, so that excessive crosslinking is caused by a reaction between the organic filler (E1) and the coupling agent (G1). Reaction can be suppressed and the dispersibility of the organic filler (E1) in the photosensitive resin composition can be improved, and at the same time, gelation can be suppressed.
- the coupling agent (G1) preferably contains at least one functional group selected from an amino group, an epoxy group, a vinyl group, a methacryl group, a mercapto group, an isocyanate group, and a sulfide group.
- the coupling agent (G1) contains at least one functional group selected from an amino group, an epoxy group, a vinyl group, a methacryl group, a mercapto group, an isocyanate group, and a sulfide group, and thus included in the organic filler (E1).
- the dispersibility of the organic filler (E1) in the photosensitive resin composition can be further efficiently increased. Therefore, the thixotropy, stability and resolution of the photosensitive resin composition are further improved.
- the coupling agent (G1) contains an amino group
- the amino group is introduced by, for example, an aminoalkyl group.
- a coupling agent (G1) contains an epoxy group
- an epoxy group is introduce
- the coupling agent (G1) contains a vinyl group
- the vinyl group is directly bonded to, for example, a silicon atom.
- the coupling agent (G1) contains an amino group, an epoxy group, or a vinyl group
- the reactivity with the organic filler (E1) increases, and the dispersibility of the organic filler (E1) in the photosensitive resin composition further increases. Increases efficiently.
- the coupling agent (G1) has an epoxy group or a vinyl group.
- the coupling agent (G1) has an epoxy group or a vinyl group, the insulating property between lines of the photosensitive resin composition is increased, and the stability is further improved.
- the coupling agent (G) may further contain a coupling agent other than the coupling agent (G1).
- the coupling agent other than the coupling agent (G1) may not contain an atom selected from a silicon atom, an aluminum atom, a titanium atom, and a zirconia atom.
- the coupling agent other than the coupling agent (G1) may not contain two or more functional groups selected from an alkoxy group, an acyloxy group, and an alkoxide.
- the photosensitive resin composition is other than the coupling agent (G1).
- a coupling agent may not be included.
- the coupling agent (G) contains only the coupling agent (G1) or a coupling agent other than the coupling agent (G1) and the coupling agent (G1).
- the coupling agent (G) preferably contains 30% by mass or more, more preferably 50% by mass or more, and still more preferably 100% by mass of the coupling agent (G1). In this case, the dispersibility of the organic filler (E) in the photosensitive resin composition can be particularly improved.
- the photosensitive resin composition may contain an organic solvent.
- the organic solvent is used for the purpose of liquefaction or varnishing of the photosensitive resin composition, viscosity adjustment, application property adjustment, film formation property adjustment, and the like.
- Organic solvents include, for example, linear, branched, secondary or polyhydric alcohols such as ethanol, propyl alcohol, isopropyl alcohol, hexanol and ethylene glycol; ketones such as methyl ethyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene and xylene Petroleum aromatic mixed solvents such as Swazol series (manufactured by Maruzen Petrochemical Co., Ltd.), Solvesso series (manufactured by Exxon Chemical Co., Ltd.), cellosolves such as cellosolve and butylcellosolve, and carbitols such as carbitol and butylcarbitol 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
- 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 carboxyl group-containing resin (A1) relative to the solid content of the photosensitive resin composition is preferably in the range of 5 to 85% by mass, more preferably in the range of 10 to 75% by mass, 30 More preferably, it is in the range of ⁇ 60% by mass.
- 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 (D1) is within 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). Is more preferable, and is more preferably in the range of 0.2 to 1.9, and still more preferably in the range of 0.3 to 1.5. Alternatively, the total of equivalents of epoxy groups contained in the crystalline epoxy resin (D1) is within a range of 0.7 to 2.5 with respect to 1 equivalent of carboxyl groups contained in the carboxyl group-containing resin (A). Also good.
- the content of the organic filler (E) is preferably in the range of 1 to 40 parts by mass when the content of the carboxyl group-containing resin (A) is 100 parts by mass.
- the content of the organic filler (E) is within this range, the thixotropy of the photosensitive resin composition is increased and the stability is improved.
- cured material of the photosensitive resin composition can be moderately roughened, and, thereby, the adhesiveness of the rough surface of hardened
- the content of the organic filler (E) is more preferably in the range of 5 to 20 parts by mass, with the content of the carboxyl group-containing resin (A) being 100 parts by mass, preferably 10 to 17 parts by mass.
- the content of the organic filler (E1) is preferably in the range of 1 to 40 parts by mass when the content of the carboxyl group-containing resin (A) is 100 parts by mass.
- the content of the organic filler (E1) is within this range, the thixotropy of the photosensitive resin composition is increased, and the stability is effectively improved.
- cured material of the photosensitive resin composition can be roughened more appropriately.
- the content of the organic filler (E1) is more preferably in the range of 5 to 20 parts by mass, when the content of the carboxyl group-containing resin (A) is 100 parts by mass, and 10 to 17 parts by mass. More preferably it is.
- the content of the rubber component is preferably in the range of 1 to 40 parts by mass, preferably in the range of 5 to 20 parts by mass, when the content of the carboxyl group-containing resin (A) is 100 parts by mass. More preferred is 10 to 17 parts by mass.
- the amount of the melamine compound (F) relative to the carboxyl group-containing resin (A) is preferably in the range of 0.1 to 10% by mass, and more preferably in the range of 0.5 to 5% by mass.
- the content of the coupling agent (G) is 0.01 to 7 when the content of the organic filler (E) is 100 parts by mass. It is preferably within the range of parts by mass. When the content of the coupling agent (G) falls within this range, aggregation of the organic filler (E) in the photosensitive resin composition is prevented, and dispersibility is improved.
- the content of the coupling agent (G) is more preferably in the range of 0.05 to 5 parts by mass when the content of the organic filler (E) is 100 parts by mass.
- the content of the coupling agent (G1) is preferably in the range of 0.01 to 7 parts by mass when the content of the organic filler (E1) is 100 parts by mass.
- the content of the coupling agent (G1) falls within this range, aggregation of the organic filler (E1) in the photosensitive resin composition is efficiently prevented, and dispersibility is effectively improved.
- the content of the coupling agent (G1) is more preferably in the range of 0.05 to 5 parts by mass when the content of the organic filler (E1) is 100 parts 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.
- the photosensitive resin composition may contain an inorganic filler.
- the inorganic filler can contain, for example, one or more materials selected from the group consisting of barium sulfate, crystalline silica, nanosilica, carbon nanotubes, talc, bentonite, hydrotalcite, aluminum hydroxide, magnesium hydroxide, and titanium oxide.
- the inorganic filler contains a white material such as titanium oxide or zinc oxide, the photosensitive resin composition and its cured product can be whitened with the white material.
- the proportion of the inorganic filler in the photosensitive resin composition is appropriately set, but is preferably in the range of 0 to 300% by mass with respect to the carboxyl group-containing resin (A).
- the photosensitive resin composition may not contain fine powder silica as an inorganic filler. Although finely divided silica imparts thixotropy, it tends to reduce insulation reliability.
- the photosensitive resin composition is imparted with excellent thixotropy by the organic filler (E1). Further, particularly excellent insulation reliability is imparted by the acylphosphine oxide photopolymerization initiator (C1).
- 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
- the photosensitive resin composition may contain an adhesion-imparting agent other than the melamine compound (F).
- adhesion-imparting agent include guanamine, acetoguanamine, benzoguanamine, 2,4-diamino-6-methacryloyloxyethyl-S-triazine, 2-vinyl-4,6-diamino-S-triazine, 2-vinyl- Examples thereof include S-triazine derivatives such as 4,6-diamino-S-triazine / isocyanuric acid adduct and 2,4-diamino-6-methacryloyloxyethyl-S-triazine / isocyanuric acid adduct.
- the photosensitive resin composition may contain a rheology control agent.
- the viscosity of the photosensitive resin composition is easily optimized by the rheology control agent.
- the rheology control agent include urea-modified medium polarity polyamides (product numbers BYK-430 and BYK-431 manufactured by Big Chemie Japan Co., Ltd.), polyhydroxycarboxylic acid amides (product numbers BYK-405 manufactured by Big Chemie Japan Co., Ltd.), Modified urea (product numbers BYK-410, BYK-411, BYK-420 manufactured by Big Chemie Japan Co., Ltd.), polymer urea derivative (product number BYK-415 manufactured by Big Chemie Japan Co., Ltd.), urea modified urethane (Big Chemie Japan stock) Company product number BYK-425), polyurethane (product number BYK-428 manufactured by Big Chemie Japan Co., Ltd.), castor oil wax, polyethylene wax, polyamide wax, bentonite, silica, si
- Photosensitive resin composition includes curing accelerator; colorant; copolymer of silicone, acrylate, etc .; leveling agent; thixotropic agent; polymerization inhibitor; antihalation agent; flame retardant; It may contain at least one component selected from the group consisting of agents; pigments; and 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 40 minutes to form a film having a thickness of 25 ⁇ m.
- the film is exposed by irradiating the film with ultraviolet light under the condition of 500 mJ / cm 2 with a negative mask having an exposed part that transmits ultraviolet light and a non-exposed part that blocks ultraviolet light directly applied. After the exposure, a 1% Na 2 CO 3 aqueous solution at 30 ° C.
- 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.
- the laminated body dry film with a support body
- the support body which supports a dry film is obtained.
- pressure is applied to the dry film and the core material 1
- the support is peeled from the dry film, so that the dry film is placed on the core material 1 from the support.
- 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.
- ultraviolet light sources include chemical lamps, low-pressure mercury lamps, medium-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, xenon lamps, metal halide lamps, LEDs, g-line (436 nm), h-line (405 nm), i-line (365 nm), and It is selected from the group consisting of a combination of two or more of g-line, h-line and i-line.
- the exposure method may be a method other than a method using a negative mask.
- 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.
- Light sources applied to the direct drawing method include, for example, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a metal halide lamp, LED, g-line (436 nm), h-line (405 nm), i-line (365 nm), and g-line, h-line, and i-line. Selected from the group consisting of two or more of the 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 thickness of the interlayer insulating layer 7 is not particularly limited, but may be in the range of 10 to 50 ⁇ m.
- 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 same procedure as a general desmear process using an oxidizing agent can be performed.
- an oxidizing agent is brought into contact with the outer surface of the interlayer insulating layer 7 to give a rough surface to the interlayer insulating layer 7.
- 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.
- the oxidizing agent may be an oxidizing agent available as a desmear liquid.
- the oxidizing agent can be constituted by a commercially available desmear swelling liquid and desmear liquid.
- Such an oxidizing agent can contain, for example, at least one permanganate selected from the group of sodium permanganate and potassium permanganate.
- 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.
- the thickness of the solder resist layer is not particularly limited, but may be in the range of 10 to 50 ⁇ m.
- 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.
- the solder resist layer may be provided with a rough surface in the same manner as the interlayer insulating layer. Thereby, the adhesiveness of a soldering resist layer and the metal material which comprises conductor wiring, solder, etc. can be improved.
- an electrically insulating layer such as a solder resist layer or an interlayer insulating layer is particularly well formed from a dry film containing a dried product of the photosensitive resin composition or from a coating film of the photosensitive resin composition. be able to. By providing a rough surface to this electrically insulating layer, the adhesion between the electrically insulating layer and the metal material can be improved.
- the weight average molecular weight and acid value of the carboxyl group-containing resin are as shown in Table 1.
- the polydispersity (Mw / Mn) of the carboxyl group-containing resin and the molar ratio between the components are also shown in Table 1.
- 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 3 biphenyl novolac type epoxy resin (product name NC-3000-H manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent 288 g / eq).
- Epoxy compound 4 Cresol novolak type epoxy resin (product name YDC-700-5, manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., epoxy equivalent 203 g / eq).
- Epoxy compound 5 bisphenol A type epoxy resin (manufactured by Mitsubishi Chemical Corporation, product number jER1001, epoxy equivalent 472 g / eq).
- ⁇ -carboxy-polycaprolactone (n ⁇ 2) monoacrylate manufactured by Toagosei Co., Ltd., trade name Aronix M-5300 (number average molecular weight 290).
- photosensitive resin compositions of Examples 1 to 12 and Comparative Examples 1 to 3 were prepared as follows. A part of the components shown in the “Composition” column of Tables 2 to 4 below were kneaded with three rolls. Next, the kneaded product was transferred into a flask, and all components shown in Tables 2 to 4 below were stirred and mixed to obtain a photosensitive resin composition.
- the melamine compound (F) was uniformly dispersed in the photosensitive resin composition.
- the photosensitive resin compositions of Examples 13 to 32 and Comparative Examples 4 to 8 were prepared as follows.
- a photosensitive resin composition was obtained by stirring and mixing the components shown in the column of “Composition” in Table 5, Table 6 and Table 7 below in a flask.
- the photosensitive resin composition was subjected to pressure filtration with a filter having a hole diameter of 30 ⁇ m.
- the photosensitive resin composition of Comparative Example 9 was prepared as follows. While stirring a 65% solution of a carboxyl group-containing resin and a coupling agent shown in the column of “Composition” in Table 7 below in the flask, a part of the other components are kneaded with a three-roll roll and then the flask. Next, all the remaining components were added and stirred and mixed in the flask to obtain a photosensitive resin composition.
- the photosensitive resin composition was filtered under pressure with a filter having a hole diameter of 30 ⁇ m.
- the photosensitive resin compositions of Examples 33 to 46 and Comparative Examples 10 to 14 were prepared as follows. The components shown in the column of “Composition” in Table 8 and Table 9 below were mixed, kneaded with a three-roller, and then stirred and mixed in a flask to obtain a photosensitive resin composition. The photosensitive resin composition was filtered under pressure with a filter having a hole diameter of 5 ⁇ m.
- Unsaturated compound (TMPTA) trimethylolpropane triacrylate.
- Unsaturated compound (DPCA) ⁇ -caprolactone-modified dipentaerystol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd., product number KAYARAD DPCA-20).
- 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 (IC184) 1-hydroxy-cyclohexyl-phenyl-ketone (product number Irgacure 184, manufactured by BASF).
- Photopolymerization initiator (IC1173) 2-hydroxy-2-methyl-1-phenyl-propan-1-one (manufactured by BASF, product number Irgacure 1173).
- Photopolymerization initiator (IC907) 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one (manufactured by BASF, product number Irgacure 907).
- Crystalline epoxy resin (YX4000) Biphenyl type crystalline epoxy resin (product name YX-4000 manufactured by Mitsubishi Chemical Corporation, melting point 105 ° C., epoxy equivalent 187 g / eq).
- Crystalline epoxy resin (YSLV80XY) Bisphenol type crystalline epoxy resin (product name YSLV-80XY, manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., melting point 75 to 85 ° C., 192 g / eq).
- Amorphous epoxy resin (EXA4816): 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) in solid content A solution dissolved in diethylene glycol monoethyl ether acetate at 90% (epoxy equivalent in terms of solid content of 90% is 455.56 g / eq).
- Amorphous epoxy resin (NC3000): solution of amorphous epoxy resin; biphenyl novolac type epoxy resin (manufactured by Nippon Kayaku Co., Ltd., product number NC-3000, softening point 53-63 ° C., epoxy equivalent 280 g / eq)
- Organic filler (XER-91): Dispersion of organic filler having carboxyl group; Cross-linked rubber (NBR) having an average primary particle size of 0.07 ⁇ m in methyl ethyl ketone at a content of 15% by weight with respect to the total amount of the dispersion Dispersed dispersion (manufactured by JSR Corporation, product number XER-91-MEK, acid value 10.0 mgKOH / g).
- Organic filler (XER-32): Dispersion of organic filler having carboxyl group; Polymer (linear particles) of carboxyl group-modified hydrogenated nitrile rubber (NBR) at a content of 17% by weight with respect to the total amount of the dispersion A dispersion (manufactured by JSR Corporation, product number XER-32-MEK) dispersed in methyl ethyl ketone.
- Organic filler (XSK-500) dispersion of organic filler having carboxyl group and hydroxyl group; methyl ethyl ketone containing 15% by weight of crosslinked rubber (SBR) having an average primary particle size of 0.07 ⁇ m with respect to the total amount of the dispersion Dispersed liquid (product number XSK-500, manufactured by JSR Corporation).
- Fine silica Product number MT-10, manufactured by Tokuyama Corporation.
- 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.
- Melamine dispersed varnish A fine melamine dispersed varnish manufactured by Nissan Chemical Industries, Ltd. Disperse 1.5 parts fine melamine and 3.5 parts unsaturated compound trimethylolpropane triacrylate in a bead mill.
- Coupling agent (GP-TMS) 3-glycidoxypropyltrimethoxysilane.
- Coupling agent (TEOS) tetraethoxysilane.
- Coupling agent (MTMS) methyltrimethoxysilane.
- Coupling agent (AEAP-MDMS) N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane.
- Coupling agent (VL-TMS) Vinyltrimethoxysilane.
- Antioxidant A hindered phenol antioxidant, manufactured by BASF, product number IRGANOX 1010. Surfactant: manufactured by DIC, product number MegaFuck F-477.
- -Rheology control agent manufactured by Big Chemy Japan, product number BYK-430.
- Colorant (BY-mix) Color pigment dispersion varnish containing a color index Pigment Blue 15: 3 and a color index Pigment Yellow 147 in a weight ratio of 1: 2.5 in total.
- Colorant (Blue) phthalocyanine blue.
- Antifoaming agent Product number KS-66 manufactured by Shin-Etsu Silicone Co., Ltd.
- Solvent (EDGAC) Diethylene glycol monoethyl ether acetate.
- Solvent (MEK) methyl ethyl ketone.
- the dry film was produced with the following method.
- the photosensitive resin composition was applied on a polyethylene terephthalate film with an applicator, and then dried by heating at 95 ° C. for 25 minutes to form a dry film on the film.
- Two types of dry films having a thickness of 25 ⁇ m and a thickness of 30 ⁇ m were produced.
- test pieces were prepared by the dry film method using a dry film as follows.
- a glass epoxy copper clad laminate (FR-4 type) provided with a copper foil having a thickness of 17.5 ⁇ m was prepared.
- a comb-shaped electrode having a line width / space width of 50 ⁇ m / 50 ⁇ m was formed as a conductor wiring by this subtractive method on this glass epoxy copper clad laminate, thereby obtaining a printed wiring board (core material).
- the conductive wiring of the printed wiring board was roughened by dissolving and removing the surface portion of the conductive wiring having a thickness of about 1 ⁇ m with an etching agent (organic acid-based microetching agent, product number CZ-8100 manufactured by MEC Co., Ltd.).
- the dry film was heat laminated on the entire surface of the printed wiring board with a vacuum laminator.
- the heating lamination conditions were 0.5 MPa, 80 ° C., and 1 minute.
- coat which consists of a dry film was formed on the printed wiring board.
- This film in a state of applying a negative mask having a non-exposed portion having a pattern including a circular shape with a diameter of 50 ⁇ m or 60 ⁇ m directly, 250 mJ / cm 2 (except Example 44) in the film, or 500 mJ / cm 2 (Example 44) exposure was performed by irradiating with ultraviolet rays.
- the diameter of the circular shape was 50 ⁇ m
- the diameter of the circular shape was 60 ⁇ m.
- the polyethylene terephthalate film was peeled from the dry film (coating). After the film was peeled off, the exposed film was developed. In the development process, a 1% Na 2 CO 3 aqueous solution at 30 ° C. was sprayed onto the film for 90 seconds at a spray pressure of 0.2 MPa. Subsequently, the coating film was washed by spraying pure water at a spray pressure of 0.2 MPa for 90 seconds. Thereby, the part which was not exposed in a film
- Example 1 to 12 and Comparative Examples 1 to 3 the film was irradiated with ultraviolet rays under the condition of 1000 mJ / cm 2 , and then the film was heated at 160 ° C. for 60 minutes.
- Examples 13 to 32 and Comparative Examples 4 to 9 after the film was irradiated with ultraviolet rays under the condition of 1000 mJ / cm 2 , the film was heated at 180 ° C. for 60 minutes.
- Example 44 the film was heated at 160 ° C. for 60 minutes, and then the film was irradiated with ultraviolet rays under the condition of 1000 mJ / cm 2 .
- cured material (it can also be said to be hardened
- Examples 33 to 43, 45, 46, and Comparative Examples 10 to 14 For Examples 33 to 43, 45, and 46 and Comparative Examples 10 to 14, test pieces were prepared by the coating method using the photosensitive resin composition as follows.
- a glass epoxy copper clad laminate (FR-4 type) provided with a copper foil having a thickness of 17.5 ⁇ m was prepared.
- a comb-shaped electrode having a line width / space width of 50 ⁇ m / 50 ⁇ m was formed as a conductor wiring by this subtractive method on this glass epoxy copper clad laminate, thereby obtaining a printed wiring board (core material).
- the conductive wiring of the printed wiring board was roughened by dissolving and removing the surface portion of the conductive wiring having a thickness of about 1 ⁇ m with an etching agent (organic acid-based microetching agent, 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 spin coating.
- This wet coating film was heated at 80 ° C. for 40 minutes and preliminarily dried to form a film having a thickness of 25 ⁇ m.
- the film was exposed by irradiating it 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 to the film.
- the exposed film was developed. In the development process, a 1% Na 2 CO 3 aqueous solution at 30 ° C. was sprayed onto the film for 90 seconds at a spray pressure of 0.2 MPa. Subsequently, the coating film was washed by spraying pure water at a spray pressure of 0.2 MPa for 90 seconds.
- Test 1 The test pieces of Examples 1 to 12 and Comparative Examples 1 to 3 were evaluated by the following procedure. The results are shown in Tables 2 and 3 below. The following (1-1) to (1-6) were evaluated using test pieces having a film formed from a dry film having a thickness of 25 ⁇ m. The following (1-7) and (1-8) were evaluated with test pieces having a film formed from a dry film having a thickness of 30 ⁇ m.
- (1-3) Plating resistance After a nickel plating layer is formed using a commercially available electroless nickel plating bath on a portion of the conductor wiring of the test piece of each example and comparative example that is exposed to the outside, a commercially available product is available. A gold plating layer was formed using an electroless gold plating bath. This formed the metal layer which consists of a nickel plating layer and a gold plating layer. The layer and metal layer which consisted of hardened
- A No abnormality was observed in the appearance of the layer made of the cured product and the metal layer, and peeling of the layer made of the cured product by the cellophane adhesive tape peeling test did not occur.
- B Although discoloration was recognized in the layer which consists of hardened
- C Lifting of the layer made of the cured product was observed, and peeling of the layer made of the cured product by the cellophane adhesive tape peeling test occurred.
- B The electric resistance value was always maintained at 10 8 ⁇ or more until 1000 hours passed from the start of the test, but the electric resistance value became less than 10 8 ⁇ before 2000 hours passed from the start of the test.
- C The electric resistance value was less than 10 8 ⁇ before 1000 hours passed from the start of the test.
- membrane layer which consists of hardened
- cured material with respect to a desmear liquid was evaluated by the following evaluation criteria.
- 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. A: Blister was not confirmed at the time of heating after the electroless copper plating treatment, and no blister was confirmed at the time of heating after the electrolytic copper plating treatment.
- the adhesive strength of copper was 0.4 kN / m or more.
- B Blister was not confirmed at the time of heating after electroless copper plating treatment, and blister was not confirmed at the time of heating after electrolytic copper plating treatment. Moreover, the adhesive strength of copper was less than 0.4 kN / m.
- C Blisters were confirmed during heating after the electroless copper plating treatment or during heating after the electrolytic copper plating treatment.
- the particle size distribution of the photosensitive resin composition was measured with MT3300EXII manufactured by Microtrack Bell Co., Ltd., and the results were evaluated as follows.
- D The maximum particle size was larger than 20 ⁇ m by particle size distribution measurement.
- Examples 13 to 32 are affected by the colorant and melamine, a composition containing no colorant and melamine dispersion varnish in the composition of Examples 13 to 32 shown in Tables 5 to 7 was prepared. As an evaluation of Examples 13 to 32, a particle size distribution was measured.
- a wet paint film was formed by applying the photosensitive resin composition to the entire surface of the printed wiring board by the spin coat method. This wet coating film was heated at 80 ° C. for 40 minutes or 60 minutes to form a film having a thickness of 25 ⁇ m. This film was developed without exposure. In the development process, a 1% Na 2 CO 3 aqueous solution at 30 ° C. was jetted for 90 seconds at a jet pressure of 0.2 MPa, and then pure water was jetted for 90 seconds at a jet pressure of 0.2 MPa. The printed wiring board after the treatment was observed, and the result was evaluated as follows. A: The film was completely removed regardless of whether the heating time of the wet coating film was 40 minutes or 60 minutes.
- the diameter of the bottom of the hole is 50 ⁇ m or more.
- B The diameter of the bottom of the hole is 50 ⁇ m or more and less than 53 ⁇ m.
- C The diameter of the bottom of the hole is 40 ⁇ m or more and less than 50 ⁇ m.
- D The diameter of the bottom of the hole is less than 40 ⁇ m, or no clear hole is formed.
- a nickel plating layer is formed on a portion of the conductor wiring of the test piece of each example and comparative example exposed to the outside using a commercially available electroless nickel plating bath, and then commercially available.
- a gold plating layer was formed using an electroless gold plating bath. This formed the metal layer which consists of a nickel plating layer and a gold plating layer. The layer and metal layer which consisted of hardened
- A No abnormality was observed in the appearance of the layer made of the cured product and the metal layer, and peeling of the layer made of the cured product by the cellophane adhesive tape peeling test did not occur.
- B Although discoloration was recognized in the layer which consists of hardened
- C Lifting of the layer made of the cured product was observed, and peeling of the layer made of the cured product by the cellophane adhesive tape peeling test occurred.
- B The electric resistance value was always maintained at 10 6 ⁇ or more until 45 hours passed from the start of the test, but the electric resistance value became less than 10 6 ⁇ before 60 hours passed from the start of the test.
- C The electrical resistance value was less than 10 6 ⁇ before 45 hours passed from the start of the test.
- Example 44 evaluated with the test piece which has a membrane
- Example 44 since the membrane
- a wet paint film was formed by applying the photosensitive resin composition to the entire surface of the printed wiring board by spin coating. This wet coating film was heated at 80 ° C. for 40 minutes or 60 minutes to form a film having a thickness of 25 ⁇ m. This film was developed without exposure. In the development process, a 1% Na 2 CO 3 aqueous solution at 30 ° C. was jetted for 90 seconds at a jet pressure of 0.2 MPa, and then pure water was jetted for 90 seconds at a jet pressure of 0.2 MPa. The printed wiring board after the treatment was observed, and the result was evaluated as follows. A: The film was completely removed regardless of whether the heating time of the wet coating film was 40 minutes or 60 minutes.
- Example 44 The developability of Example 44 was determined by development during test piece preparation. In Example 44, development was possible without problems in the development step after exposure for test piece production.
- a nickel plating layer is formed using a commercially available electroless nickel plating bath on a portion of the conductor wiring of the test piece of each example and comparative example exposed to the outside, and then commercially available.
- a gold plating layer was formed using an electroless gold plating bath. This formed the metal layer which consists of a nickel plating layer and a gold plating layer. The layer and metal layer which consisted of hardened
- A No abnormality was observed in the appearance of the layer made of the cured product and the metal layer, and peeling of the layer made of the cured product by the cellophane adhesive tape peeling test did not occur.
- B Although discoloration was recognized in the layer which consists of hardened
- C Lifting of the layer made of the cured product was observed, and peeling of the layer made of the cured product by the cellophane adhesive tape peeling test occurred.
- B The electric resistance value was constantly maintained at 10 6 ⁇ or more until 55 hours passed from the start of the test, but the electric resistance value became less than 10 6 ⁇ before 70 hours passed from the start of the test.
- C 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 55 hours passed from the start of the test.
- D The electric resistance value was less than 10 6 ⁇ before 35 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. It is selected from the group consisting of a saturated compound (B), a photopolymerization initiator (C), an epoxy compound (D), an organic filler (E) containing an organic filler (E1) having a carboxyl group, and melamine and melamine derivatives. And at least one melamine compound (F).
- the average primary particle diameter of the organic filler (E1) is 1 ⁇ m or less in the first aspect.
- the organic filler (E1) contains a rubber component.
- the photosensitive resin composition according to the fourth aspect of the present invention is the photosensitive resin composition according to the third aspect, wherein the rubber component is at least one heavy selected from the group consisting of crosslinked acrylic rubber, crosslinked NBR, crosslinked MBS, and crosslinked SBR. Contains coalescence.
- the photopolymerization initiator (C) is an acylphosphine oxide photopolymerization initiator (C1). Containing In the photosensitive resin composition according to the sixth aspect of the present invention, in the fifth aspect, the photopolymerization initiator (C) further contains a photopolymerization initiator having a benzophenone skeleton.
- the carboxyl group-containing resin (A) is a carboxyl group-containing resin having an ethylenically unsaturated group. contains.
- the carboxyl group-containing resin (A) contains a carboxyl group-containing resin having a bisphenolfluorene skeleton.
- the epoxy compound (D) contains a crystalline epoxy resin (D1).
- the photosensitive resin composition according to the tenth aspect of the present invention in any one of the first to ninth aspects, further contains a coupling agent (G), and the coupling agent (G) contains a silicon atom.
- a coupling agent (G1) containing an atom selected from an aluminum atom, a titanium atom and a zirconia atom, and further containing two or more functional groups selected from an alkoxy group, an acyloxy group and an alkoxide.
- the coupling agent (G1) contains a silicon atom.
- the coupling agent (G1) further includes an amino group, an epoxy group, a vinyl group, a methacryl group, a mercapto group, an isocyanate group, And at least one functional group selected from sulfide groups.
- the dry film according to the thirteenth aspect of the present invention is a dried product of the photosensitive resin composition according to any one of the first to twelfth aspects.
- a printed wiring board according to a fourteenth aspect of the present invention includes an interlayer insulating layer containing a cured product of the photosensitive resin composition according to any one of the first to twelfth aspects.
- the printed wiring board according to the fifteenth aspect of the present invention includes a solder resist layer containing a cured product of the photosensitive resin composition according to any one of the first to twelfth aspects.
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Abstract
Description
カラム:SHODEX KF-800P,KF-005,KF-003,KF-001の4本直列、
移動相:THF、
流量:1ml/分、
カラム温度:45℃、
検出器:RI、
換算:ポリスチレン。
合成例A-1~合成例A-4、及び合成例B-1~合成例B-3
還流冷却器、温度計、空気吹き込み管及び攪拌機を取付けた四つ口フラスコ内に、表1中の「第一反応」欄に示す原料成分を加えて、これらをエアバブリング下で攪拌することで混合物を調製した。この混合物を四つ口フラスコ内でエアバブリング下で攪拌しながら、「第一反応」欄の「反応条件」欄に示す反応温度及び反応時間で加熱した。これにより、中間体の溶液を調製した。
・エポキシ化合物1:式(7)で示され、式(7)中のR1~R8がすべて水素であるエポキシ当量250g/eqのビスフェノールフルオレン型エポキシ化合物。
・エポキシ化合物2:式(7)で示され、式(7)中のR1及びR5がいずれもメチル基、R2~R4及びR6~R8がいずれも水素であるエポキシ当量279g/eqのビスフェノールフルオレン型エポキシ化合物。
・エポキシ化合物3:ビフェニルノボラック型エポキシ樹脂(日本化薬株式会社製の品名NC-3000-H、エポキシ当量288g/eq)。
・エポキシ化合物4:クレゾールノボラック型エポキシ樹脂(新日鉄住金化学株式会社製の品名YDC-700-5、エポキシ当量203g/eq)。
・エポキシ化合物5:ビスフェノールA型エポキシ樹脂(三菱化学株式会社製、品番jER1001、エポキシ当量472g/eq)。
・ω-カルボキシ-ポリカプロラクトン(n≒2)モノアクリレート:東亞合成株式会社製、商品名アロニックスM-5300(数平均分子量290)。
実施例1~12、比較例1~3の感光性樹脂組成物については、次のように調製した。後掲の表2~表4の「組成」の欄に示す成分の一部を3本ロールで混練した。次にこの混練物をフラスコ内に移して後掲の表2~表4に示す全成分を撹拌混合することで、感光性樹脂組成物を得た。感光性樹脂組成物を作製する際、メラミン化合物(F)を感光性樹脂組成物中で均一に分散させた。
・不飽和化合物(TMPTA):トリメチロールプロパントリアクリレート。
・不飽和化合物(DPCA):ε-カプロラクトン変性ジペンタエリストールヘキサアクリレート(日本化薬株式会社製、品番KAYARAD DPCA-20)。
・光重合開始剤(TPO):2,4,6-トリメチルベンゾイル-ジフェニル-フォスフィンオキサイド(BASF社製、品番Irgacure TPO)。
・光重合開始剤(IC819):ビス-(2,4,6-トリメチルベンゾイル)フェニルフォスフィンオキサイド(BASF社製、品番Irgacure 819)。
・光重合開始剤(IC184):1-ヒドロキシ-シクロヘキシル-フェニル-ケトン(BASF社製、品番Irgacure 184)。
・光重合開始剤(IC1173):2-ヒドロキシ-2-メチル-1-フェニル-プロパン-1-オン(BASF社製、品番Irgacure 1173)。
・光重合開始剤(EAB):4,4’-ビス(ジエチルアミノ)ベンゾフェノン。
・光重合開始剤(IC907):2-メチル-1-(4-メチルチオフェニル)-2-モルフォリノプロパン-1-オン(BASF社製、品番Irgacure 907)。
・結晶性エポキシ樹脂(YX4000):ビフェニル型結晶性エポキシ樹脂(三菱化学株式会社製の品名YX-4000、融点105℃、エポキシ当量187g/eq)。
・結晶性エポキシ樹脂(YSLV80XY):ビスフェノール型結晶性エポキシ樹脂(新日鉄住金化学株式会社製の品名YSLV-80XY、融点75~85℃、192g/eq)。
・非晶性エポキシ樹脂(EXA4816):非晶性エポキシ樹脂の溶液;長鎖炭素鎖含有ビスフェノールA型エポキシ樹脂(DIC製、品番EPICLON EXA-4816、液状樹脂、エポキシ当量410g/eq)を固形分90%でジエチレングリコールモノエチルエーテルアセテートに溶解した溶液(固形分90%換算のエポキシ当量は、455.56g/eq)。
・非晶性エポキシ樹脂(NC3000):非晶性エポキシ樹脂の溶液;ビフェニルノボラック型エポキシ樹脂(日本化薬株式会社製、品番NC-3000、軟化点53~63℃、エポキシ当量280g/eq)を固形分80%でジエチレングリコールモノエチルエーテルアセテートに溶解した溶液(固形分80%換算のエポキシ当量は、350g/eq)。
・有機フィラー(XER-91):カルボキシル基を有する有機フィラーの分散液;平均一次粒子径0.07μmの架橋ゴム(NBR)を、分散液全量に対して含有量15重量%で、メチルエチルケトン中で分散させた分散液(JSR株式会社製、品番XER-91-MEK、酸価10.0mgKOH/g)。
・有機フィラー(XER-32):カルボキシル基を有する有機フィラーの分散液;カルボキシル基変性水素化ニトリルゴム(NBR)のポリマー(線状粒子)を、分散液全量に対して含有量17重量%で、メチルエチルケトン中で分散させた分散液(JSR株式会社製、品番XER-32-MEK)。
・有機フィラー(XSK-500):カルボキシル基及び水酸基を有する有機フィラーの分散液;平均一次粒子径0.07μmの架橋ゴム(SBR)を、分散液全量に対して含有量15重量%で、メチルエチルケトン中で分散させた分散液(JSR株式会社製、品番XSK-500)。
・有機フィラー(NBR-powder):エポキシ基を有する有機フィラー;パウダー状で、平均一次粒子径0.3μmのグリシジル変性アクリロニトリルブタジエンゴム。
・微粉シリカ:株式会社トクヤマ製、品番MT-10。
・メラミン:日産化学工業株式会社製、微粉メラミン;感光性樹脂組成物中において平均粒子径8μmで分散。
・メラミン誘導体:メラミンと1,2,3,6-テトラヒドロ無水フタル酸との反応物であるメラミン-テトラヒドロフタル酸塩;感光性樹脂組成物中において平均粒子径6μmで分散。
・メラミン分散ワニス:日産化学工業株式会社製、微粉メラミンの分散ワニス。微粉メラミン1.5部、及び不飽和化合物トリメチロールプロパントリアクリレート3.5部をビーズミルにて分散。
・カップリング剤(GP-TMS):3-グリシドキシプロピルトリメトキシシラン。
・カップリング剤(TEOS):テトラエトキシシラン。
・カップリング剤(MTMS):メチルトリメトキシシラン。
・カップリング剤(AEAP-MDMS):N-(2-アミノエチル)-3-アミノプロピルメチルジメトキシシラン。
・カップリング剤(VL-TMS):ビニルトリメトキシシラン。
・酸化防止剤:ヒンダードフェノール系酸化防止剤、BASF社製、品番IRGANOX 1010。
・界面活性剤:DIC製、品番メガファックF-477。
・レオロジーコントロール剤:ビッグケミー・ジャパン株式会社製、品番BYK-430。
・着色剤(BY-mix): カラーインデックスPigment Blue 15:3と、カラーインデックスPigment Yellow 147とを、重量比で1:2.5の割合で合計15重量%含有する色顔料分散ワニス。
・着色剤(Blue):フタロシアニンブルー。
・消泡剤:信越シリコーン株式会社製、品番KS-66。
・溶剤(EDGAC):ジエチレングリコールモノエチルエーテルアセテート。
・溶剤(MEK):メチルエチルケトン。
実施例及び比較例について、次の方法によりドライフィルムを作製した。感光性樹脂組成物を、ポリエチレンテレフタレート製のフィルム上にアプリケータで塗布してから、95℃で25分加熱することで乾燥させることにより、フィルム上にドライフィルムを形成した。厚み25μmと、厚み30μmとの2種類のドライフィルムを作製した。
<実施例1~32、44、及び比較例1~9>
実施例1~32、44、及び比較例1~9については、以下のようにドライフィルムを用いて、ドライフィルム法によりテストピースを作製した。
実施例33~43、45、46、及び比較例10~14については、以下のように感光性樹脂組成物を用いて、塗布法によりテストピースを作製した。
実施例1~12及び比較例1~3の各々のテストピースを、下記手順で評価した。その結果を下記表2及び表3に示す。なお、下記(1-1)~(1-6)は、厚み25μmのドライフィルムから形成された皮膜を有するテストピースで評価した。下記(1-7)及び(1-8)は、厚み30μmのドライフィルムから形成された皮膜を有するテストピースで評価した。
各実施例及び比較例のテストピースについて、前記現像処理後のプリント配線板の非露光部を観察し、その結果を次のように評価した。
良好:露光されていない皮膜が全て除去されている。
不適:露光されていない皮膜の一部がプリント配線板上に残存した。
各実施例及び比較例のテストピースにおける硬化物からなる層に形成された穴を観察し、その結果を次のように評価した。
A:穴の底の直径が40μm以上である。
B:穴の底の直径が25μm以上40μm未満である。
C:穴の底の直径が25μm未満である。
D:明確な穴が形成されない。
各実施例及び比較例のテストピースの導体配線における外部に露出する部分の上に、市販の無電解ニッケルメッキ浴を用いてニッケルメッキ層を形成してから、市販の無電解金メッキ浴を用いて金メッキ層を形成した。これにより、ニッケルメッキ層及び金メッキ層からなる金属層を形成した。硬化物からなる層及び金属層を目視で観察した。また、硬化物からなる層に対してセロハン粘着テープ剥離試験をおこなった。その結果を次のように評価した。
A:硬化物からなる層及び金属層の外観に異常は認められず、セロハン粘着テープ剥離試験による硬化物からなる層の剥離は生じなかった。
B:硬化物からなる層に変色が認められるが、セロハン粘着テープ剥離試験による硬化物からなる層の剥離は生じなかった。
C:硬化物からなる層の浮き上がりが認められ、セロハン粘着テープ剥離試験による硬化物からなる層の剥離が生じた。
各実施例及び比較例のテストピースにおける導体配線(くし型電極)にDC30Vのバイアス電圧を印加しながら、テストピースを121℃、97%R.H.の試験環境下に100時間曝露した。この試験環境下における硬化物からなる層のくし型電極間の電気抵抗値を常時測定し、その結果を次の評価基準により評価した。
A:試験開始時から100時間経過するまでの間、電気抵抗値が常に106Ω以上を維持した。
B:試験開始時から80時間経過するまでは電気抵抗値が常に106Ω以上を維持したが、試験開始時から100時間経過する前に電気抵抗値が106Ω未満となった。
C:試験開始時から80時間経過する前に電気抵抗値が106Ω未満となった。
各実施例及び比較例のテストピースにおける硬化物からなる層の上に導電テープを貼り付けた。この導電テープにDC100Vのバイアス電圧を印加しながら、テストピースを85℃、85%R.H.の試験環境下に2000時間曝露した。この試験環境下における硬化物からなる層の導体配線と導電テープとの間の電気抵抗値を常時測定し、その結果を次の評価基準により評価した。
A:試験開始時から2000時間経過するまでの間、電気抵抗値が常に108Ω以上を維持した。
B:試験開始時から1000時間経過するまでは電気抵抗値が常に108Ω以上を維持したが、試験開始時から2000時間経過する前に電気抵抗値が108Ω未満となった。
C:試験開始時から1000時間経過する前に電気抵抗値が108Ω未満となった。
各実施例及び比較例のテストピースを121℃、100%R.H.の環境下で100時間放置した後、硬化物からなる層の外観を次の評価基準により評価した。
A:硬化物からなる層に異常は見られなかった。
B:硬化物からなる層に変色が見られた。
C:硬化物からなる層に大きな変色が見られ、一部膨れが発生していた。
各実施例及び比較例のテストピースにおける硬化物からなる層の外表面を、メッキ処理前の前工程において一般的なデスミア処理に基いた下記手順で粗化させた。デスミア用膨潤液として市販されている膨潤液(アトテックジャパン(株)製のスウェリング・ディップ・セキュリガンスP)を用いて膨潤処理を60℃で5分間行い、硬化物の表面を膨潤させた。そして、この膨潤された表面に対して湯洗を行った。続いて過マンガン酸カリウムを含有し、デスミア液として市販されている酸化剤(アトテックジャパン(株)製のコンセントレート・コンパクトCP)を用いて粗化処理を80℃で10分間行い、湯洗後の表面を粗化した。このように粗化された表面に対して湯洗を行い、更に、この硬化物表面におけるデスミア液の残渣を中和液(アトテックジャパン(株)製のリダクションソリューション・セキュリガントP)を用いて40℃で5分間除去した。そして、中和後の硬化物表面を水洗した。このようにして粗面が付与された皮膜(感光性樹脂組成物の硬化物からなる層)の膜厚を測定し、デスミア液に対する硬化物の粗化耐性を次の評価基準により評価した。
A:粗化による膜厚の減少が5μm未満である。
B:粗化による膜厚の減少が5μm以上、10μm未満である。
C:粗化による膜厚の減少が10μm以上である。
各実施例及び比較例のテストピースについて、硬化物からなる層に、上記(1-7)の方法で粗面を付与した後、市販の薬液を用いてテストピースの粗面に無電解銅メッキ処理で初期配線を形成した。この初期配線が設けられたテストピースを150℃で1時間加熱した。更に電解銅メッキ処理により、2A/dm2の電流密度の下で市販の薬液から初期配線に厚さ33μmの銅を直接析出させた。続いて銅を析出させたテストピースを180℃で30分間加熱して銅メッキ層を形成した。このようにして形成された銅メッキ層と、テストピースにおける硬化物との密着性を次の評価基準により評価した。ここで、無電解銅メッキ処理後及び電解銅メッキ処理後の両方の加熱時にテストピースにブリスターが確認されない場合、銅メッキ層と硬化物との密着強度を下記の手順で評価した。この密着強度はJIS-C6481に準拠して測定された。
A:無電解銅メッキ処理後の加熱時にブリスターが確認されず、電解銅メッキ処理後の加熱時でもブリスターが確認されなかった。また、銅の密着強度は0.4kN/m以上であった。
B:無電解銅メッキ処理後の加熱時にブリスターが確認されず、電解銅メッキ処理後の加熱時でもブリスターが確認されなかった。また、銅の密着強度は0.4kN/m未満であった。
C:無電解銅メッキ処理後の加熱時、あるいは電解銅メッキ処理後の加熱時にブリスターが確認された。
実施例13~32及び比較例4~9の各々の感光性樹脂組成物、ドライフィルム及びテストピースを、下記手順で評価した。その結果を下記の表5、表6及び表7に示す。なお、(2-5)~(2-12)は、厚み30μmのドライフィルムから形成された皮膜を有するテストピースで評価した。
各実施例及び比較例について、感光性樹脂組成物の粒度分布をマイクロトラック・ベル株式会社製のMT3300EXIIで計測し、その結果を次のように評価した。
A:粒度分布測定により、最大粒子径が0.5μm以下であった。
B:粒度分布測定により、最大粒子径が0.5μmより大きく、1.0μm以下であった。
C:粒度分布測定により、最大粒子径が1.0μmより大きく、20μm以下であった。
D:粒度分布測定により、最大粒子径が20μmより大きかった。
各実施例及び比較例について、感光性樹脂組成物を冷蔵庫(4℃)に1週間保存した後、感光性樹脂組成物を観察し、その結果を次のように評価した。
A:感光性樹脂組成物中の成分の分離は生じておらず、均一な状態を保っていた。
B:感光性樹脂組成物に若干の濁りが見られたが、沈殿物は見られなかった。
C:感光性樹脂組成物中の成分に分離が生じ、沈殿物が見られた。
各実施例及び比較例について、フィルム上に形成した厚み30μmのドライフィルムを観察し、その結果を次のように評価した。
A:凝集物及びボイド(泡)は観察されず、表面状態は均一であった。
B:凝集物及び/又はボイド(泡)が若干観察された。
C:凝集物及び/又はボイド(泡)が多く観察され、表面状態は均一でなかった、あるいは、均一な膜厚が得られなかった。
各実施例及び比較例について、プリント配線板の一面全面に感光性樹脂組成物をスピンコート法で塗布することで、湿潤塗膜を形成した。この湿潤塗膜を80℃で40分又は60分加熱することで、厚み25μmの皮膜を形成した。この皮膜に、露光することなく現像処理を施した。現像処理に当たっては、皮膜に30℃の1%Na2CO3水溶液を0.2MPaの噴射圧で90秒間噴射してから、純水を0.2MPaの噴射圧で90秒間噴射した。処理後のプリント配線板を観察し、その結果を次のように評価した。
A:湿潤塗膜の加熱時間が40分、60分のいずれの場合でも、皮膜が全て除去されている。
B:湿潤塗膜の加熱時間が40分である場合には皮膜が全て除去されたが、60分では皮膜の一部がプリント配線板上に残存した。
C:湿潤塗膜の加熱時間が40分、60分のいずれの場合でも、皮膜の一部がプリント配線板上に残存した。
各実施例及び比較例のテストピースについて、硬化物からなる層に形成された穴を観察し、その結果を次のように評価した。
A:穴の底の直径が50μm以上である。
B:穴の底の直径が50μm以上53μm未満である。
C:穴の底の直径が40μm以上50μm未満である。
D:穴の底の直径が40μm未満であり、或いは明確な穴が形成されない。
各実施例及び比較例のテストピースの導体配線における外部に露出する部分の上に、市販の無電解ニッケルメッキ浴を用いてニッケルメッキ層を形成してから、市販の無電解金メッキ浴を用いて金メッキ層を形成した。これにより、ニッケルメッキ層及び金メッキ層からなる金属層を形成した。硬化物からなる層及び金属層を目視で観察した。また、硬化物からなる層に対してセロハン粘着テープ剥離試験をおこなった。その結果を次のように評価した。
A:硬化物からなる層及び金属層の外観に異常は認められず、セロハン粘着テープ剥離試験による硬化物からなる層の剥離は生じなかった。
B:硬化物からなる層に変色が認められるが、セロハン粘着テープ剥離試験による硬化物からなる層の剥離は生じなかった。
C:硬化物からなる層の浮き上がりが認められ、セロハン粘着テープ剥離試験による硬化物からなる層の剥離が生じた。
各実施例及び比較例のテストピースにおける導体配線(くし型電極)にDC30Vのバイアス電圧を印加しながら、テストピースを121℃、97%R.H.の試験環境下に120時間曝露した。この試験環境下における硬化物からなる層のくし型電極間の電気抵抗値を常時測定し、その結果を次の評価基準により評価した。
A:試験開始時から120時間経過するまでの間、電気抵抗値が常に106Ω以上を維持した。
B:試験開始時から100時間経過するまでは電気抵抗値が常に106Ω以上を維持したが、試験開始時から120時間経過する前に電気抵抗値が106Ω未満となった。
C:試験開始時から80時間経過するまでは電気抵抗値が常に106Ω以上を維持したが、試験開始時から100時間経過する前に電気抵抗値が106Ω未満となった。
D:試験開始時から80時間経過する前に電気抵抗値が106Ω未満となった。
各実施例及び比較例のテストピースにおける硬化物からなる層の上に導電テープを貼り付けた。この導電テープにDC100Vのバイアス電圧を印加しながら、テストピースを121℃、97%R.H.の試験環境下に60時間曝露した。この試験環境下における硬化物からなる層の導体配線と導電テープとの間の電気抵抗値を常時測定し、その結果を次の評価基準により評価した。
A:試験開始時から60時間経過するまでの間、電気抵抗値が常に106Ω以上を維持した。
B:試験開始時から45時間経過するまでは電気抵抗値が常に106Ω以上を維持したが、試験開始時から60時間経過する前に電気抵抗値が106Ω未満となった。
C:試験開始時から45時間経過する前に電気抵抗値が106Ω未満となった。
各実施例及び比較例のテストピースを121℃、100%R.H.の環境下で100時間放置した後、硬化物からなる層の外観を次の評価基準により評価した。
A:硬化物からなる層に異常は見られなかった。
B:硬化物からなる層に変色が見られた。
C:硬化物からなる層に大きな変色が見られ、一部膨れが発生していた。
各実施例及び比較例のテストピースを温度変化させ、-65℃で10分(低温条件)と、150℃で10分(高温条件)とを経たもの1サイクルとして、750サイクル及び1000サイクルの温度サイクル試験を行った。その後、硬化物からなる層の外観を次の評価基準により評価した。
A:1000サイクルでクラックが見られなかった。
B:750サイクルでクラックが見られないが、1000サイクルでクラックが見られた。
C:750サイクルでクラックが見られた。
各実施例及び比較例のテストピースについて、上記「評価試験1」の(1-7)と同様の試験、及び評価を行った。
各実施例及び比較例のテストピースについて、上記「評価試験1」の(1-8)と同様の試験、及び評価を行った。
実施例33~46及び比較例10~14の各々の感光性樹脂組成物及びテストピースを、下記手順で評価した。その結果を下記の表8及び表9に示す。なお、実施例44は、厚み25μmのドライフィルムから形成された皮膜を有するテストピースで評価した。
各実施例及び比較例の感光性樹脂組成物を、ポリエチレンテレフタレート製のフィルム上にアプリケータを用いて膜厚50μmに塗布してから、60℃で20分加熱した後、80℃で40分加熱することで乾燥させることにより、フィルム上に乾燥塗膜を形成した。塗膜を観察し、外観を次の評価基準により評価した。
良 :塗膜にムラが見られず、均一である。
不適:塗膜にムラが見られる。
各実施例及び比較例のテストピースの作製時に、被膜の露光後に被膜からネガマスクを取り外す際の被膜のタック性の程度を、次に示すように評価した。
A:被膜からネガマスクを取り外す際に抵抗が感じられず、ネガマスクを取り外した後の被膜には貼付痕が認められない。
B:被膜からネガマスクを取り外す際に抵抗が感じられ、ネガマスクを取り外した後の被膜には貼付痕が認められた。
C:被膜からネガマスクを取り外すことが困難であり、無理にネガマスクを取り外すと被膜が破損した。
各実施例及び比較例について、プリント配線板の一面全面に感光性樹脂組成物をスピンコート法で塗布することで、湿潤塗膜を形成した。この湿潤塗膜を80℃で40分又は60分加熱することで、厚み25μmの皮膜を形成した。この皮膜に、露光することなく現像処理を施した。現像処理に当たっては、皮膜に30℃の1%Na2CO3水溶液を0.2MPaの噴射圧で90秒間噴射してから、純水を0.2MPaの噴射圧で90秒間噴射した。処理後のプリント配線板を観察し、その結果を次のように評価した。
A:湿潤塗膜の加熱時間が40分、60分のいずれの場合でも、皮膜が全て除去されている。
B:湿潤塗膜の加熱時間が40分である場合には皮膜が全て除去されたが、60分では皮膜の一部がプリント配線板上に残存した。
C:湿潤塗膜の加熱時間が40分、60分のいずれの場合でも、皮膜の一部がプリント配線板上に残存した。
各実施例及び比較例のテストピースにおける硬化物からなる層に形成された穴を観察し、その結果を次のように評価した。
A:穴の底の直径が40μm以上である。
B:穴の底の直径が25μm以上40μm未満である。
C:穴の底の直径が25μm未満である。
D:明確な穴が形成されない。
各実施例及び比較例のテストピースの導体配線における外部に露出する部分の上に、市販の無電解ニッケルメッキ浴を用いてニッケルメッキ層を形成してから、市販の無電解金メッキ浴を用いて金メッキ層を形成した。これにより、ニッケルメッキ層及び金メッキ層からなる金属層を形成した。硬化物からなる層及び金属層を目視で観察した。また、硬化物からなる層に対してセロハン粘着テープ剥離試験をおこなった。その結果を次のように評価した。
A:硬化物からなる層及び金属層の外観に異常は認められず、セロハン粘着テープ剥離試験による硬化物からなる層の剥離は生じなかった。
B:硬化物からなる層に変色が認められるが、セロハン粘着テープ剥離試験による硬化物からなる層の剥離は生じなかった。
C:硬化物からなる層の浮き上がりが認められ、セロハン粘着テープ剥離試験による硬化物からなる層の剥離が生じた。
各実施例及び比較例のテストピースにおける導体配線(くし型電極)にDC30Vのバイアス電圧を印加しながら、テストピースを121℃、97%R.H.の試験環境下に150時間曝露した。この試験環境下における硬化物からなる層のくし型電極間の電気抵抗値を常時測定し、その結果を次の評価基準により評価した。
A:試験開始時から150時間経過するまでの間、電気抵抗値が常に106Ω以上を維持した。
B:試験開始時から120時間経過するまでは電気抵抗値が常に106Ω以上を維持したが、試験開始時から150時間経過する前に電気抵抗値が106Ω未満となった。
C:試験開始から60時間経過するまでは電気抵抗値が常に106Ω以上を維持したが、試験開始時から120時間経過する前に電気抵抗値が106Ω未満となった。
D:試験開始時から60時間経過する前に電気抵抗値が106Ω未満となった。
各実施例及び比較例のテストピースにおける硬化物からなる層の上に導電テープを貼り付けた。この導電テープにDC100Vのバイアス電圧を印加しながら、テストピースを121℃、97%R.H.の試験環境下に70時間曝露した。この試験環境下における硬化物からなる層の導体配線と導電テープとの間の電気抵抗値を常時測定し、その結果を次の評価基準により評価した。
A:試験開始時から70時間経過するまでの間、電気抵抗値が常に106Ω以上を維持した。
B:試験開始時から55時間経過するまでは電気抵抗値が常に106Ω以上を維持したが、試験開始時から70時間経過する前に電気抵抗値が106Ω未満となった。
C:試験開始時から35時間経過するまでは電気抵抗値が常に106Ω以上を維持したが、試験開始時から55時間経過する前に電気抵抗値が106Ω未満となった。
D:試験開始時から35時間経過する前に電気抵抗値が106Ω未満となった。
各実施例及び比較例のテストピースを121℃、100%R.H.の環境下で100時間放置した後、硬化物からなる層の外観を次の評価基準により評価した。
A:硬化物からなる層に異常は見られなかった。
B:硬化物からなる層に変色が見られた。
C:硬化物からなる層に大きな変色が見られ、一部膨れが発生していた。
各実施例及び比較例のテストピースを温度変化させ、-65℃で10分(低温条件)と、150℃で10分(高温条件)とを経たもの1サイクルとして、500サイクル及び1000サイクルの温度サイクル試験を行った。その後、硬化物からなる層の外観を次の評価基準により評価した。
A:1000サイクルでクラックが見られなかった。
B:500サイクルでクラックが見られないが、1000サイクルでクラックが見られた。
C:500サイクルでクラックが見られた。
各実施例及び比較例のテストピースについて、上記「評価試験1」の(1-7)と同様の試験、及び評価を行った。
各実施例及び比較例のテストピースについて、上記「評価試験1」の(1-8)と同様の試験、及び評価を行った。
本発明の第6の態様に係る感光性樹脂組成物は、第5の態様において、光重合開始剤(C)は、さらにベンゾフェノン骨格を有する光重合開始剤を含有する。
本発明の第10の態様に係る感光性樹脂組成物は、第1乃至第9のいずれか一の態様において、カップリング剤(G)をさらに含有し、カップリング剤(G)は、ケイ素原子、アルミニウム原子、チタン原子、及びジルコニア原子から選ばれる原子を含有し、さらにアルコキシ基、アシルオキシ基及びアルコキシドから選ばれる官能基を二つ以上含有するカップリング剤(G1)を含有する。
Claims (15)
- カルボキシル基含有樹脂(A)と、
エチレン性不飽和結合を一分子中に少なくとも一つ有する不飽和化合物(B)と、
光重合開始剤(C)と、
エポキシ化合物(D)と、
カルボキシル基を有する有機フィラー(E1)を含む有機フィラー(E)と、
メラミン及びメラミン誘導体の群から選択される少なくとも1種のメラミン化合物(F)と、を含有する、
感光性樹脂組成物。 - 前記有機フィラー(E1)の平均一次粒子径が1μm以下である、
請求項1に記載の感光性樹脂組成物。 - 前記有機フィラー(E1)は、ゴム成分を含有する、
請求項1又は2に記載の感光性樹脂組成物。 - 前記ゴム成分は、架橋アクリルゴム、架橋NBR、架橋MBS、及び架橋SBRの群から選択される少なくとも1種の重合体を含有する、
請求項3に記載の感光性樹脂組成物。 - 前記光重合開始剤(C)は、アシルフォスフィンオキサイド系光重合開始剤(C1)を含有する、
請求項1乃至4のいずれか一項に記載の感光性樹脂組成物。 - 前記光重合開始剤(C)は、さらにベンゾフェノン骨格を有する光重合開始剤を含有する、
請求項5に記載の感光性樹脂組成物。 - 前記カルボキシル基含有樹脂(A)は、エチレン性不飽和基を有するカルボキシル基含有樹脂を含有する、
請求項1乃至6のいずれか一項に記載の感光性樹脂組成物。 - 前記カルボキシル基含有樹脂(A)は、ビスフェノールフルオレン骨格を有するカルボキシル基含有樹脂を含有する、
請求項1乃至7のいずれか一項に記載の感光性樹脂組成物。 - 前記エポキシ化合物(D)は、結晶性エポキシ樹脂(D1)を含有する、
請求項1乃至8のいずれか一項に記載の感光性樹脂組成物。 - カップリング剤(G)をさらに含有し、
前記カップリング剤(G)は、ケイ素原子、アルミニウム原子、チタン原子、及びジルコニア原子から選ばれる原子を含有し、さらにアルコキシ基、アシルオキシ基及びアルコキシドから選ばれる官能基を二つ以上含有するカップリング剤(G1)を含有する、
請求項1乃至9のいずれか一項に記載の感光性樹脂組成物。 - 前記カップリング剤(G1)は、ケイ素原子を含有する、
請求項10に記載の感光性樹脂組成物。 - 前記カップリング剤(G1)は、さらに、アミノ基、エポキシ基、ビニル基、メタクリル基、メルカプト基、イソシアネート基、及びスルフィド基から選ばれる少なくとも一つの官能基を含有する、
請求項11に記載の感光性樹脂組成物。 - 請求項1乃至12のいずれか一項に記載の感光性樹脂組成物の乾燥物である、ドライフィルム。
- 請求項1乃至12のいずれか一項に記載の感光性樹脂組成物の硬化物を含む層間絶縁層を備える、プリント配線板。
- 請求項1乃至12のいずれか一項に記載の感光性樹脂組成物の硬化物を含むソルダーレジスト層を備える、プリント配線板。
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KR101956661B1 (ko) | 2019-03-11 |
TW201727373A (zh) | 2017-08-01 |
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CN108475015B (zh) | 2022-03-18 |
TWI653506B (zh) | 2019-03-11 |
CN108475015A (zh) | 2018-08-31 |
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