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WO2016117509A1 - Composition de résine photosensible, élément photosensible, procédé de formation de motif de résine photosensible, et procédé de production de structure - Google Patents

Composition de résine photosensible, élément photosensible, procédé de formation de motif de résine photosensible, et procédé de production de structure Download PDF

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Publication number
WO2016117509A1
WO2016117509A1 PCT/JP2016/051294 JP2016051294W WO2016117509A1 WO 2016117509 A1 WO2016117509 A1 WO 2016117509A1 JP 2016051294 W JP2016051294 W JP 2016051294W WO 2016117509 A1 WO2016117509 A1 WO 2016117509A1
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WIPO (PCT)
Prior art keywords
photosensitive resin
group
resin layer
resin composition
mass
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2016/051294
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English (en)
Japanese (ja)
Inventor
有紀子 村松
沢辺　賢
絵美子 太田
翔太 岡出
相哲 李
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Resonac Corp
Original Assignee
Hitachi Chemical Co Ltd
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Application filed by Hitachi Chemical Co Ltd filed Critical Hitachi Chemical Co Ltd
Priority to JP2016570627A priority Critical patent/JP6733553B2/ja
Publication of WO2016117509A1 publication Critical patent/WO2016117509A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G03F7/029—Inorganic compounds; Onium compounds; Organic compounds having hetero atoms other than oxygen, nitrogen or sulfur
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G03F7/031—Organic compounds not covered by group G03F7/029
    • 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
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • G03F7/033—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
    • 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
    • G03F7/26—Processing photosensitive materials; Apparatus therefor
    • G03F7/40—Treatment after imagewise removal, e.g. baking
    • 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
    • H05K3/10—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern
    • H05K3/18—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using precipitation techniques to apply the conductive material
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/46—Manufacturing multilayer circuits

Definitions

  • the present disclosure relates to a photosensitive resin composition, a photosensitive element, a resist pattern forming method, and a structure manufacturing method.
  • a photosensitive resin composition is widely known as a resist material used for etching treatment or plating treatment.
  • a printed wiring board is, for example, a structure in which a plurality of wiring layers are formed on a core board, a copper clad laminate as a core board, an interlayer insulating material provided between each wiring layer, and a solder provided on the outermost surface. And a resist.
  • a semiconductor element is usually mounted on the printed wiring board via a die bonding material or an underfill material.
  • the entire surface may be sealed with a transfer sealing material, and a metal cap (lid) for the purpose of improving heat dissipation may be attached.
  • semiconductor devices have become lighter and thinner, and the density of semiconductor elements and multilayer printed wiring boards has been increasing. Further, packaging forms such as a package-on-package in which a semiconductor device is stacked on a semiconductor device are actively performed, and it is expected that the mounting density of the semiconductor device will be further increased in the future.
  • FIG. 1 is a schematic diagram showing a conventional method for producing a multilayer printed wiring board.
  • the multilayer printed wiring board 100 shown in FIG. 1F has a wiring pattern on the surface and inside.
  • the multilayer printed wiring board 100 is obtained by laminating a copper clad laminate, an interlayer insulating material, a metal foil, and the like and appropriately forming a wiring pattern by an etching method or a semi-additive method.
  • the multilayer printed wiring board is manufactured as follows, for example. First, an interlayer insulating layer 103 is formed on both surfaces of a copper clad laminate 101 having a wiring pattern 102 on the surface (see FIG. 1A). As a method of forming the interlayer insulating layer 103, a thermosetting resin composition may be printed using a screen printer or a roll coater, or a film made of the thermosetting resin composition is prepared in advance, and a laminator is used. This film can also be attached to the surface of a printed wiring board.
  • an opening 104 is formed using a YAG laser or a carbon dioxide gas laser in a place that needs to be electrically connected to the outside, and smear (residue) around the opening 104 is removed by a desmear process (FIG. 1B). reference).
  • the seed layer 105 is formed by an electroless plating method (see FIG. 1C).
  • a photosensitive resin composition is laminated on the seed layer 105 to form a photosensitive resin composition layer (photosensitive resin composition layer forming step). Then, a predetermined portion of the photosensitive resin composition layer is irradiated with an actinic ray to cure the exposed portion (exposure step).
  • cured material of the photosensitive resin composition is formed by removing (developing) an unexposed part (development process, refer FIG.1 (d)).
  • a wiring pattern (circuit) 107 is formed by an electrolytic plating method (circuit formation step).
  • cured material (pattern of the photosensitive resin layer) 106 of the photosensitive resin composition is peeled and removed with a peeling liquid (peeling process process). Further, the seed layer 105 is removed by etching (see FIG. 1E).
  • the multilayer printed wiring board 100 can be manufactured by repeating the above and forming the solder resist 108 on the outermost surface (see FIG. 1F). In the multilayer printed wiring board 100 obtained in this way, semiconductor elements are mounted at corresponding locations, and electrical connection can be ensured.
  • a large opening having a via diameter of 100 ⁇ m or more for example, a cylindrical opening
  • the throughput decreases as the number of laser shots increases, and in the case of a minute opening (for example, a cylindrical opening) having a via diameter of 60 ⁇ m or less, a laser to be used in accordance with the opening diameter is selected.
  • a laser to be used in accordance with the opening diameter is selected.
  • problems such as the necessity of proper use and the difficulty of providing a special shape.
  • each opening when forming an opening using a laser, each opening must be formed one by one. Therefore, it takes time when it is necessary to provide a large number of fine openings, and a resin around the opening. Therefore, there is also a problem that the reliability of the obtained multilayer printed wiring board is lowered unless the residue is removed.
  • Japanese Patent Laid-Open No. 08-279678 Japanese Patent Laid-Open No. 11-054913 JP 2001-217543 A Japanese Patent Laid-Open No. 2003-017848 International Publication No. 2013/054790 Japanese Patent Laid-Open No. 11-274727
  • the photosensitive resin composition for obtaining the resin layer in which the opening is formed has excellent opening property even when a fine opening (for example, an opening having a diameter of 30 ⁇ m or less) is formed. Is required.
  • the present disclosure has been made in view of the above problems, and an object of the present disclosure is to provide a photosensitive resin composition having excellent openability even when a fine opening is formed. Moreover, this indication aims at providing the formation method of the photosensitive element using the said photosensitive resin composition, the resist pattern, and the structure.
  • the present inventors have used a binder polymer, a specific photopolymerizable compound, and a photopolymerization initiator in combination, thereby providing a photosensitive resin having excellent opening properties. It was found that a composition was obtained.
  • the photosensitive resin composition according to the first embodiment of the present disclosure includes a binder polymer, a photopolymerizable compound, and a photopolymerization initiator, and the photopolymerizable compound is represented by the following general formula (1). And a compound having one ethylenically unsaturated bond in the molecule.
  • R 11 represents an alkylene group having 1 to 20 carbon atoms, a cycloalkylene group having 1 to 10 carbon atoms, or a phenylene group
  • R 12 and R 13 are each independently a hydrogen atom or Represents a methyl group
  • X 11 and X 12 each independently represent an oxyalkylene group or a polyoxyalkylene group containing at least one selected from the group consisting of an oxyethylene group and an oxypropylene group
  • X 11 and X 12 The total number of oxyethylene groups and oxypropylene groups contained in is from 12 to 80.
  • the photosensitive resin composition according to the second embodiment of the present disclosure contains a binder polymer, a photopolymerizable compound, and a photopolymerization initiator, and the photopolymerizable compound has the following general formula (2). And a compound having one ethylenically unsaturated bond in the molecule.
  • R 21 , R 22 and R 23 each independently represents an alkylene group having 1 to 20 carbon atoms
  • R 24 , R 25 and R 26 each independently represents a hydrogen atom or a methyl group.
  • X 21 , X 22 and X 23 each independently represent an oxyalkylene group or a polyoxyalkylene group containing at least one selected from the group consisting of an oxyethylene group and an oxypropylene group, and X 21 , X 22 the total number of oxyethylene groups and oxypropylene groups contained in and X 23 is 15-120.
  • the photosensitive resin composition according to the present disclosure is excellent in openability (removability) even when a fine opening (for example, a cylindrical opening having a diameter of 30 ⁇ m or less) is formed.
  • a fine opening for example, a cylindrical opening having a diameter of 30 ⁇ m or less
  • the photosensitive resin composition according to the present disclosure can form an opening while suppressing generation of a residue derived from the photosensitive resin composition.
  • the photosensitive resin composition according to the present disclosure it is possible to obtain a resist pattern having excellent opening properties, and to obtain a structure having fine openings and excellent reliability sufficiently efficiently. be able to.
  • a cylindrical opening be suitably formed, but also openings having other shapes (for example, lines) while suppressing generation of residues derived from the photosensitive resin composition.
  • a line-shaped opening for obtaining a conductor pattern having a shape can also be formed.
  • the compound having one ethylenically unsaturated bond in the molecule may include a compound represented by the following general formula (3).
  • R 31 represents an alkyl group having 1 to 5 carbon atoms, a halogen atom or a hydroxyl group
  • R 32 represents a hydrogen atom or a methyl group
  • R 33 represents a hydrogen atom, a methyl group or a halogen atom.
  • A represents a methyl group
  • A represents an alkylene group having 2 to 4 carbon atoms
  • m represents an integer of 1 to 4
  • n represents an integer of 0 to 4.
  • n is 2 or more, a plurality of R 31 may be the same or different.
  • the binder polymer may have a structural unit derived from (meth) acrylic acid alkyl ester.
  • the acid value of the binder polymer may be 60 to 250 mgKOH / g.
  • the binder polymer may have a weight average molecular weight of 10,000 to 100,000.
  • the photopolymerization initiator may contain a 2,4,5-triarylimidazole dimer.
  • the photosensitive resin composition according to the present disclosure may further contain a sensitizing dye.
  • the photosensitive resin composition according to the present disclosure may further contain a hydrogen donor.
  • the photosensitive element according to the present disclosure includes a support and a photosensitive resin layer formed on the support using the photosensitive resin composition according to the present disclosure.
  • a method of forming a resist pattern according to the present disclosure includes a step of forming a photosensitive resin layer on a substrate using the photosensitive resin composition according to the present disclosure or the photosensitive element according to the present disclosure, and the photosensitive resin An exposure step of irradiating a predetermined portion of the layer with actinic rays to cure the predetermined portion, and removing a portion other than the predetermined portion of the photosensitive resin layer from the substrate, And a developing step of forming a resist pattern made of a cured product on the substrate.
  • the wavelength of the actinic ray may be in the range of 340 to 430 nm.
  • an opening is provided in an insulating layer formed on a surface of a substrate having a conductor circuit, and a wiring portion connected to the conductor circuit is formed in the opening.
  • a first photosensitive resin layer is formed on the substrate so as to cover a conductor circuit using the photosensitive resin composition according to the present disclosure or the photosensitive element according to the present disclosure.
  • the structure manufacturing method according to the present disclosure may further include a thermosetting step of thermosetting the thermosetting resin layer as a step between the thermosetting resin layer forming step and the pattern exposing step.
  • a seed layer serving as a base of the wiring portion is formed by an electroless plating method so as to cover at least a part of the thermosetting resin layer after the opening is formed.
  • Seed layer forming step and second patterning step of forming a second photosensitive resin layer so as to cover the seed layer, and then subjecting the second photosensitive resin layer to exposure processing and development processing to pattern the second photosensitive resin layer
  • a wiring part patterning step of patterning the wiring part by peeling the pattern of the second photosensitive resin layer after forming the wiring part by electrolytic plating so as to cover at least a part of the seed layer
  • a seed layer removing step of removing a seed layer in a region where the wiring portion is not formed.
  • the photosensitive resin composition having excellent opening properties even when a fine opening is formed. Moreover, according to this indication, the photosensitive element using the said photosensitive resin composition, the formation method of a resist pattern, and the manufacturing method of a structure can be provided.
  • (meth) acrylic acid means at least one of acrylic acid and methacrylic acid
  • “(meth) acrylate” means at least one of acrylate and methacrylate.
  • the “(poly) oxyalkylene group” means at least one of an oxyalkylene group and a polyoxyalkylene group in which two or more alkylene groups are linked by an ether bond.
  • the “(poly) oxyethylene group” means at least one of an oxyethylene group and a polyoxyethylene group in which two or more ethylene groups are connected by an ether bond.
  • the “(poly) oxypropylene group” means at least one of an oxypropylene group and a polyoxypropylene group in which two or more propylene groups are connected by an ether bond.
  • EO-modified means a compound having a (poly) oxyethylene group
  • PO-modified means a compound having a (poly) oxypropylene group
  • EO ⁇ PO “Modified” means a compound having both a (poly) oxyethylene group and a (poly) oxypropylene group.
  • the “oxyalkylene group” is a group represented by (—C p H 2p —O—) (p: an integer of 1 or more), and the “oxyethylene group” is (—C 2 H 4 And —oxypropylene group ”is a group represented by (—C 3 H 6 —O—).
  • process is not limited to an independent process, and is included in this term if the intended purpose of the process is achieved even when it cannot be clearly distinguished from other processes. It is.
  • the numerical range indicated by using “ ⁇ ” indicates a range including the numerical values described before and after “ ⁇ ” as the minimum value and the maximum value, respectively.
  • the content of each component in the composition means the total amount of the plurality of substances present in the composition unless there is a specific notice when there are a plurality of substances corresponding to each component in the composition.
  • layer includes not only a structure formed on the entire surface but also a structure formed on a part when observed as a plan view.
  • laminated indicates that the layers are stacked, and two or more layers may be combined, or two or more layers may be detachable.
  • the photosensitive resin composition according to the present embodiment includes (A) a binder polymer (hereinafter also referred to as “component (A)”), and (B) photopolymerizability.
  • component (B) a binder polymer
  • component (C) a photopolymerization initiator
  • the component (B) includes a compound represented by the following general formula (1) and a compound having one ethylenically unsaturated bond in the molecule. .
  • the component (B) includes a compound represented by the following general formula (2) and a compound having one ethylenically unsaturated bond in the molecule.
  • the component (B) may include both a compound represented by the following general formula (1) and a compound represented by the following general formula (2). That is, in the photosensitive resin composition according to this embodiment, the component (B) is selected from the group consisting of a compound represented by the following general formula (1) and a compound represented by the following general formula (2). And at least one compound having one ethylenically unsaturated bond in the molecule may be included.
  • the photosensitive resin composition according to the present embodiment may further contain other components as necessary.
  • R 11 represents an alkylene group having 1 to 20 carbon atoms, a cycloalkylene group having 1 to 10 carbon atoms, or a phenylene group
  • R 12 and R 13 are each independently a hydrogen atom or A methyl group
  • X 11 and X 12 each independently comprise at least one selected from the group consisting of an oxyethylene group and an oxypropylene group (poly) oxyalkylene group (oxyalkylene group or polyoxyalkylene group)
  • the total number of oxyethylene groups and oxypropylene groups contained in X 11 and X 12 (total number in the molecule) is 12-80.
  • the oxyethylene group and the oxypropylene group may be present randomly or may form a block.
  • R 21 , R 22 and R 23 each independently represents an alkylene group having 1 to 20 carbon atoms, and R 24 , R 25 and R 26 each independently represents a hydrogen atom or a methyl group.
  • X 21 , X 22 and X 23 are each independently a (poly) oxyalkylene group (oxyalkylene group or polyoxyalkylene group) containing at least one selected from the group consisting of an oxyethylene group and an oxypropylene group
  • the total number of oxyethylene groups and oxypropylene groups contained in X 21 , X 22 and X 23 (total number in the molecule) is 15 to 120. When both an oxyethylene group and an oxypropylene group are present, the oxyethylene group and the oxypropylene group may be present randomly or may form a block.
  • binder polymer ((A): Binder polymer) First, the binder polymer will be described.
  • the binder polymer is not particularly limited, but may be soluble in an alkaline aqueous solution from the viewpoint of further improving developability.
  • the component (A) may have a structural unit derived from a polymerizable monomer described later, and can be produced, for example, by radical polymerization of a polymerizable monomer described later.
  • polymerizable monomer examples include (meth) acrylic acid; (meth) acrylic acid alkyl ester, (meth) acrylic acid cycloalkyl ester, (meth) acrylic acid benzyl, and (meth) acrylic acid benzyl derivatives.
  • the component (A) has a structural unit derived from a (meth) acrylic acid alkyl ester from the viewpoint of further improving the opening of the photosensitive resin layer with an alkaline aqueous solution when the conductor circuit is exposed and the opening is formed. Also good.
  • the component (A) may be obtained by radical polymerization of an alkyl (meth) acrylate.
  • Examples of the (meth) acrylic acid alkyl ester include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, (meth) Hexyl acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, undecyl (meth) acrylate and (meth) ) Dodecyl acrylate.
  • the (meth) acrylic acid alkyl ester can be used alone or in combination of two or more.
  • the content of the structural unit is that of the structural unit constituting the component (A) from the viewpoint of further excellent adhesion and openability. It may be 30 to 85% by mass, 40 to 80% by mass, or 50 to 75% by mass based on the total solid content. This content may be 30% by mass or more, 40% by mass or more, or 50% by mass or more from the viewpoint of further improving the adhesion. Moreover, this content may be 85 mass% or less, 80 mass% or less, or 75 mass% or less from the viewpoint of further improving the openability.
  • the content of the structural unit is the solid content of the structural unit constituting the component (A) from the viewpoint of further improving adhesion and openability. It may be 5 to 80% by mass, 10 to 70% by mass, or 15 to 60% by mass based on the total mass. This content may be 5% by mass or more, 10% by mass or more, or 15% by mass or more from the viewpoint of further improving developability and openability. Moreover, this content may be 80 mass% or less, 70 mass% or less, and 60 mass% or less from a viewpoint which is further excellent in adhesiveness.
  • the component (A) may have a structural unit derived from benzyl (meth) acrylate or a derivative thereof from the viewpoint of further improving the opening and adhesion.
  • the content of the structural unit is 5 based on the total solid mass of the structural unit constituting the component (A). It may be ⁇ 60% by mass, 10 to 55% by mass, or 20 to 50% by mass. This content may be 5% by mass or more, 10% by mass or more, or 20% by mass or more from the viewpoint of further excellent adhesion. Moreover, this content may be 60 mass% or less, 55 mass% or less, and 50 mass% or less from a viewpoint which is further excellent in opening property.
  • the acid value of the component (A) may be 60 to 250 mgKOH / g, 100 to 250 mgKOH / g, or 100 to 230 mgKOH / g from the viewpoint of further improving developability and developer resistance. It may be 130 to 230 mg KOH / g.
  • the acid value of a component can be measured with reference to the measuring method of the Example mentioned later.
  • the weight average molecular weight (Mw) of the component (A) is measured by gel permeation chromatography (GPC) (converted by a calibration curve using standard polystyrene), from the viewpoint of further improving developability and developer resistance, It may be 10,000 to 100,000, may be 20,000 to 80,000, and may be 25,000 to 70,000.
  • the weight average molecular weight of the component (A) may be 100,000 or less, 80000 or less, or 70000 or less from the viewpoint of further improving developability.
  • the weight average molecular weight of the component (A) may be 10,000 or more, 20000 or more, or 25000 or more from the viewpoint of further improving the developer resistance.
  • a weight average molecular weight can be measured with reference to the measuring method of the Example mentioned later.
  • one type of binder polymer may be used alone, or two or more types of binder polymers may be used in any combination.
  • a binder polymer in the case of using two or more types in combination, for example, two or more types of binder polymers comprising different copolymer components (binder polymers containing different monomer units as copolymer components), two types having different weight average molecular weights
  • binder polymers and two or more types of binder polymers having different dispersities can be mentioned.
  • a polymer having a multimode molecular weight distribution described in JP-A No. 11-327137 can also be used.
  • the content of the component (A) may be in the following range with respect to 100 parts by mass of the total amount of the component (A) and the component (B), from the viewpoint of further excellent film formability, sensitivity, and adhesion.
  • the content of the component (A) may be 30 parts by mass or more, 40 parts by mass or more, or 50 parts by mass or more.
  • (A) 70 mass parts or less may be sufficient as content of a component, and 65 mass parts or less may be sufficient as it. From these viewpoints, the content of the component (A) may be 30 to 70 parts by mass, 40 to 70 parts by mass, or 50 to 65 parts by mass.
  • component (B) urethane di (meth) acrylate having a total number of structural units of oxyethylene groups and oxypropylene groups per functional group of 6 to 40, and Contains compounds with one (only one) ethylenically unsaturated bond in the molecule.
  • the functional group means a (meth) acryloyl group.
  • Urethane di (meth) acrylate contains a compound represented by the above general formula (1).
  • the photosensitive resin composition according to the first embodiment contains a compound represented by the general formula (1) and a compound having one ethylenically unsaturated bond in the molecule, thereby exposing the conductor circuit.
  • the opening property can be improved when forming an opening (for example, an opening formed in the photosensitive resin layer with an alkaline aqueous solution).
  • X 11 and X 12 may be independently composed of an oxyethylene group and an oxypropylene group, and include an oxyalkylene group other than the oxyethylene group and the oxypropylene group. There may be. Examples of oxyalkylene groups other than oxyethylene groups and oxypropylene groups include oxybutylene groups. When an oxyalkylene group other than an oxyethylene group and an oxypropylene group is present, the oxyalkylene group and the oxyethylene group and / or oxypropylene group may be present randomly or may form a block. .
  • the compound represented by the general formula (1) may be, for example, a compound represented by the following general formula (1a).
  • R 11 represents an alkylene group having 1 to 20 carbon atoms, a cycloalkylene group having 1 to 10 carbon atoms, or a phenylene group, as in Formula (1)
  • R 12 and R 13 Are each independently a hydrogen atom or a methyl group
  • a 1 O and B 1 O are each independently an oxyethylene group or an oxypropylene group
  • (A 1 O) a1 , (B 1 O) b1 , (A 1 O) c1 and (B 1 O) d1 each represent a (poly) oxyethylene group or a (poly) oxypropylene group.
  • a1, b1, c1 and d1 represent the number of structural units of the corresponding structural unit
  • a1, b1, c1 and d1 represent an integer value in a single molecule, and averaged as an aggregate of a plurality of types of molecules. Indicates a rational number that is a value.
  • a1 + b1 + c1 + d1 is 12 to 80.
  • a1, b1, c1 and d1 can each independently take a numerical value of 0 to 80. ]
  • R 11 represents an alkylene group having 2 to 18 carbon atoms, a cycloalkylene group having 3 to 8 carbon atoms, or a phenylene group from the viewpoint of further improving the adhesion. It may be an alkylene group having 1 to 15 carbon atoms, a cycloalkylene group having 1 to 7 carbon atoms, or a phenylene group, an alkylene group having 2 to 10 carbon atoms, or 3 to 6 carbon atoms. It may be a cycloalkylene group or a phenylene group.
  • R 12 and R 13 may be a methyl group from the viewpoint of further improving the adhesion.
  • a1 + b1 + c1 + d1 may be 12 to 70 or 12 to 60 from the viewpoint of further improving developability, openability and flexibility.
  • the flexibility will be described.
  • a resist pattern is formed on a thin substrate having a thickness of 0.5 mm or less, if the resist pattern is peeled off from the substrate due to substrate deflection or the like, a short circuit of a circuit (copper wiring or the like) pattern occurs in the subsequent process. Therefore, it is desirable that the resist pattern to be formed has excellent flexibility. If these characteristics are poor, the resist pattern is likely to be chipped, which causes a short circuit of a circuit (copper wiring, etc.) pattern in the subsequent process.
  • Examples of the compound represented by the general formula (1) or (1a) include a compound represented by the following formula (A) (UA-13 (trade name, manufactured by Shin-Nakamura Chemical Co., Ltd.): (EO ) (PO) -modified urethane dimethacrylate (ethylene oxide average 2 mol, propylene oxide average 18 mol adduct)) is commercially available.
  • the compound represented by General formula (1) or General formula (1a) can be used individually or in combination of 2 or more types.
  • the photosensitive resin composition according to the second embodiment includes an isocyanurate-derived tri (meth) acrylate having 5 to 40 total structural units of oxyethylene groups and oxypropylene groups per functional group as the component (B). And a compound having one (only one) ethylenically unsaturated bond in the molecule.
  • the functional group means a (meth) acryloyl group.
  • Isocyanurate-derived tri (meth) acrylate contains a compound represented by the above general formula (2).
  • the isocyanurate-derived tri (meth) acrylate can be said to be a tri (meth) acrylate having a skeleton derived from isocyanurate.
  • the photosensitive resin composition according to the second embodiment contains a compound represented by the general formula (2) and a compound having one ethylenically unsaturated bond in the molecule, thereby exposing the conductor circuit.
  • the opening property can be improved when forming an opening (for example, an opening formed in the photosensitive resin layer with an alkaline aqueous solution).
  • X 21 , X 22 and X 23 may each independently be an oxyethylene group and an oxypropylene group, and may represent an oxyalkylene group other than the oxyethylene group and the oxypropylene group. It may be an aspect including. Examples of oxyalkylene groups other than oxyethylene groups and oxypropylene groups include oxybutylene groups. When an oxyalkylene group other than an oxyethylene group and an oxypropylene group is present, the oxyalkylene group and the oxyethylene group and / or oxypropylene group may be present randomly or may form a block. .
  • the compound represented by the general formula (2) may be, for example, a compound represented by the following general formula (2a).
  • R 21 , R 22 and R 23 each independently represents an alkylene group having 1 to 20 carbon atoms, and R 21 , R 22 and R 23 may be unsubstituted or substituted.
  • the substituents may be the same as or different from each other, and R 24 , R 25 and R 26 each independently represent a hydrogen atom or a methyl group, and A 2 O and B 2 O each independently represent an oxyethylene group or an oxypropylene group, (a 2 O) a2, (B 2 O) b2, (a 2 O) c2, (B 2 O) d2, (a 2 O) e2 And (B 2 O) f2 each represents a (poly) oxyethylene group or a (poly) oxypropylene group.
  • the oxyethylene group and the oxypropylene group may be present randomly or may form a block.
  • a2, b2, c2, d2, e2 and f2 represent the number of structural units of the corresponding structural unit
  • a2, b2, c2, d2, e2 and f2 represent integer values in a single molecule
  • a rational number that is an average value is shown as an assembly of molecules.
  • a2 + b2 + c2 + d2 + e2 + f2 is 15 to 120.
  • a2, b2, c2, d2, e2, and f2 can each independently take a value of 0 to 120. ]
  • R 21 , R 22 and R 23 may be an alkylene group having 2 to 18 carbon atoms from the viewpoint of further improving the adhesiveness. It may be an alkylene group having 15 to 15 or an alkylene group having 2 to 10 carbon atoms.
  • R 24 , R 25 and R 26 may be a methyl group from the viewpoint of further improving the adhesion.
  • a2 + b2 + c2 + d2 + e2 + f2 may be 15 to 100 or 15 to 90 from the viewpoint of further improving developability, openability and flexibility.
  • Examples of the compound represented by the general formula (2) or the general formula (2a) include a compound represented by the following formula (B) (UA-7100 (trade name, manufactured by Shin-Nakamura Chemical Co., Ltd.): (EO ) Modified isocyanurate-derived trimethacrylate (ethylene oxide average 27 mol adduct)) is commercially available.
  • the compounds represented by general formula (2) or general formula (2a) can be used alone or in combination of two or more.
  • the content may be 10 parts by mass or more, 20 parts by mass or more, 30 parts by mass or more, or 50 parts by mass or more.
  • the content is less than 100 parts by mass, may be 95 parts by mass or less, may be 90 parts by mass or less, and may be 85 parts by mass or less.
  • the content may be 10 parts by mass or more and less than 100 parts by mass, may be 20 parts by mass or more and less than 100 parts by mass, or may be 30 parts by mass or more and less than 100 parts by mass. It may be 20 to 95 parts by mass, 30 to 90 parts by mass, or 50 to 85 parts by mass.
  • content of the compound represented by General formula (1) is the following from a viewpoint which is further excellent in opening property with respect to 100 mass parts of (B) component. It may be a range.
  • the content of the compound represented by the general formula (1) may be 10 parts by mass or more, 20 parts by mass or more, 30 parts by mass or more, and 50 parts by mass or more. There may be.
  • the content of the compound represented by the general formula (1) is less than 100 parts by mass, may be 95 parts by mass or less, may be 90 parts by mass or less, or may be 85 parts by mass or less. Good.
  • the content of the compound represented by the general formula (1) may be 10 parts by mass or more and less than 100 parts by mass, 20 parts by mass or more and less than 100 parts by mass, or 30 parts by mass. Or more, less than 100 parts by weight, 20 to 95 parts by weight, 30 to 90 parts by weight, or 50 to 85 parts by weight.
  • content of the compound represented by General formula (2) is the following from a viewpoint which is further excellent in opening property with respect to 100 mass parts of (B) component. It may be a range.
  • the content of the compound represented by the general formula (2) may be 10 parts by mass or more, 20 parts by mass or more, 30 parts by mass or more, and 50 parts by mass or more. There may be.
  • the content of the compound represented by the general formula (2) is less than 100 parts by mass, may be 95 parts by mass or less, may be 90 parts by mass or less, and may be 85 parts by mass or less. Good.
  • the content of the compound represented by the general formula (2) may be 10 parts by mass or more and less than 100 parts by mass, or 20 parts by mass or more and less than 100 parts by mass, or 30 parts by mass. Or more, less than 100 parts by weight, 20 to 95 parts by weight, 30 to 90 parts by weight, or 50 to 85 parts by weight.
  • Examples of the compound having one ethylenically unsaturated bond in the molecule include fumaric acid compounds.
  • the compounds having one ethylenically unsaturated bond in the molecule can be used alone or in combination of two or more.
  • the compound having one ethylenically unsaturated bond in the molecule may contain a compound represented by the following general formula (3) from the viewpoint of further excellent adhesion.
  • R 31 represents an alkyl group having 1 to 5 carbon atoms, a halogen atom or a hydroxyl group
  • R 32 represents a hydrogen atom or a methyl group
  • R 33 represents a hydrogen atom, a methyl group or a halogen atom.
  • A represents a methyl group
  • A represents an alkylene group having 2 to 4 carbon atoms
  • m represents an integer of 1 to 4
  • n represents an integer of 0 to 4.
  • n is 2 or more, a plurality of R 31 may be the same or different.
  • R 32 may be a methyl group from the viewpoint of further improving the adhesion.
  • R 33 may be a methyl halide group from the viewpoint of availability.
  • A may be a propylene group from the viewpoint of further improving adhesion, and may be an ethylene group from the viewpoint of further improving developability.
  • m may be 1 from the viewpoint of further improving the adhesion.
  • n may be 0, 1 or 0 from the viewpoint of further improving developability.
  • the content of the compound having one ethylenically unsaturated bond in the molecule may be in the following range with respect to 100 parts by mass of the component (B) from the viewpoint of further improving the opening property.
  • the content of the compound having one ethylenically unsaturated bond in the molecule is larger than 0 part by mass, 5 parts by mass or more, 10 parts by mass or more, and 15 parts by mass or more. May be.
  • the content of the compound having one ethylenically unsaturated bond in the molecule may be 90 parts by mass or less, 80 parts by mass or less, 70 parts by mass or less, and 50 parts by mass. Or less.
  • the content of the compound having one ethylenically unsaturated bond in the molecule may be more than 0 parts by mass and 90 parts by mass or less, or 5 to 80 parts by mass. It may be up to 70 parts by mass, or 15 to 50 parts by mass.
  • Component (B) is a photopolymerizable compound other than the compound represented by the general formula (1), the compound represented by the general formula (2), and a compound having one ethylenically unsaturated bond in the molecule. If it can contain a compound and can be photocrosslinked, it can be used without any particular limitation.
  • Component (B) is a compound having an ethylenically unsaturated bond (a compound represented by general formula (1), a compound represented by general formula (2), and one ethylenically unsaturated bond in the molecule. Excluding compounds having).
  • the compound which has an ethylenically unsaturated bond As a compound which has an ethylenically unsaturated bond, the compound which has two ethylenically unsaturated bonds in a molecule
  • the photopolymerizable compound other than the compound represented by the general formula (1), the compound represented by the general formula (2), and the compound having one ethylenically unsaturated bond in the molecule may be used alone or Two or more types can be used in combination.
  • Examples of the compound having two ethylenically unsaturated bonds in the molecule include EO-modified urethane di (meth) acrylate other than the compound represented by the general formula (1), bisphenol type di (meth) acrylate, polyethylene glycol di ( (Meth) acrylate, polypropylene glycol di (meth) acrylate, polybutylene glycol di (meth) acrylate, 2,2-bis (4- (methacryloxypolyethoxy) phenyl) propane, and 2,2-bis (4- ( Methacryloxypolyethoxypolypropoxy) phenyl) propane.
  • the compounds having two ethylenically unsaturated bonds in the molecule can be used alone or in combination of two or more.
  • Examples of the compound having three ethylenically unsaturated bonds in the molecule include EO-modified isocyanurate-derived tri (meth) acrylate other than the compound represented by the general formula (2), and the general formula (2).
  • the content of the component (B) may be in the following range with respect to 100 parts by mass of the total amount of the component (A) and the component (B).
  • the content of the component (B) may be 30 parts by mass or more, 35 parts by mass or more, or 40 parts by mass or more from the viewpoint that the sensitivity and adhesion tend to be further improved. It may be.
  • the content of the component (B) may be 70 parts by mass or less, 60 parts by mass or less, and 50 parts by mass or less from the viewpoint that the developability tends to be further improved. May be. From these viewpoints, the content of the component (B) may be 30 to 70 parts by mass, 30 to 60 parts by mass, 35 to 50 parts by mass, or 40 to 50 parts by mass. A mass part may be sufficient.
  • the component (C) is not particularly limited as long as the component (B) can be polymerized by irradiation with actinic rays or the like, and can be appropriately selected from commonly used photopolymerization initiators.
  • component (C) examples include benzophenone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -1-butanone, 2-methyl-1- [4- (methylthio) phenyl] -2- Aromatic ketones such as morpholino-1-propanone; quinones such as alkylanthraquinones; benzoin ether compounds such as benzoin alkyl ether; benzoin compounds such as benzoin and alkylbenzoin; benzyl derivatives such as benzyldimethyl ketal; 2- (o-chlorophenyl) ) -4,5-diphenylimidazole dimer (for example, 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole), 2- (O-chlorophenyl) -4,5-di (methoxyphenyl) imidazole dimer, -(
  • the substituents of the two aryl groups of 2,4,5-triarylimidazole may give the same and symmetric compounds, or differently give asymmetric compounds.
  • the component (C) may contain a 2,4,5-triarylimidazole dimer from the viewpoint of further improving adhesion and sensitivity.
  • the content thereof may be 10 to 100 parts by mass with respect to 100 parts by mass of the solid content of the component (C). 30 to 100 parts by mass or 50 to 100 parts by mass.
  • the content of the 2,4,5-triarylimidazole dimer in the component (C) is 10 parts by mass or more, sensitivity and adhesion tend to be further improved.
  • the content of the component (C) may be in the following range with respect to 100 parts by mass of the total amount of the component (A) and the component (B).
  • the content of the component (C) may be 0.1 parts by mass or more, 1 part by mass or more, or 2 parts by mass or more from the viewpoint of further improving sensitivity and adhesion. There may be 3 mass parts or more.
  • the content of the component (C) may be 10 parts by mass or less, 6 parts by mass or less, or 5 parts by mass from the viewpoint that the shape of the opening forming part tends to be further improved. It may be the following. From these viewpoints, the content of the component (C) may be 0.1 to 10 parts by mass, 1 to 10 parts by mass, or 2 to 6 parts by mass. It may be up to 5 parts by mass.
  • the photosensitive resin composition according to the present embodiment may further contain (D) a sensitizing dye (hereinafter also referred to as “component (D)”).
  • component (D) a sensitizing dye
  • component (D) examples include dialkylaminobenzophenone compounds (such as 4,4′-bis (diethylamino) benzophenone), pyrazoline compounds, anthracene compounds, coumarin compounds, xanthone compounds, thioxanthone compounds, oxazole compounds, benzoxazole compounds, thiazoles.
  • dialkylaminobenzophenone compounds such as 4,4′-bis (diethylamino) benzophenone
  • pyrazoline compounds anthracene compounds
  • coumarin compounds xanthone compounds
  • thioxanthone compounds oxazole compounds
  • benzoxazole compounds examples include compounds, benzothiazole compounds, triazole compounds, stilbene compounds, triazine compounds, thiophene compounds, naphthalimide compounds, triarylamine compounds, and aminoacridine compounds.
  • a component can be used individually or in combination of 2 or more types.
  • the component (D) a sensitizing dye having an absorption maximum at 340 to 430 nm can be used.
  • the component (D) is a dialkylaminobenzophenone compound, a pyrazoline compound, an anthracene compound, It may contain at least one sensitizing dye selected from the group consisting of a coumarin compound, a triarylamine compound, a thioxanthone compound and an aminoacridine compound, and among them, from a dialkylaminobenzophenone compound, a pyrazoline compound, an anthracene compound and a triarylamine compound It may contain at least one selected from the group consisting of
  • the content of the component (D) may be in the following range with respect to 100 parts by mass of the total amount of the component (A) and the component (B). .
  • the content of the component (D) may be 0.01 parts by mass or more, may be 0.05 parts by mass or more, from the viewpoint that the sensitivity and adhesion tend to be further excellent. It may be 0.1 parts by mass or more.
  • the content of the component (D) may be 10 parts by mass or less, 5 parts by mass or less, or 3 parts by mass from the viewpoint that the resist shape of the opening forming part tends to be further improved. Part or less, 1 part by weight or less, 0.5 part by weight or less, or 0.3 part by weight or less.
  • the content of the component (D) may be 0.01 to 10 parts by mass, 0.05 to 5 parts by mass, or 0.1 to 3 parts by mass. Alternatively, it may be 0.1 to 1 part by mass, 0.1 to 0.5 part by mass, or 0.1 to 0.3 part by mass.
  • the photosensitive resin composition according to this embodiment may further contain (E) a hydrogen donor (hereinafter also referred to as “component (E)”).
  • component (E) can give hydrogen during the reaction in the exposed area.
  • the photosensitive resin composition according to the present embodiment further contains the component (E)
  • the contrast between the exposed portion and the unexposed portion also referred to as “imaging”.
  • component (E) examples include bis [4- (dimethylamino) phenyl] methane, bis [4- (diethylamino) phenyl] methane, and leucocrystal violet.
  • a component can be used individually or in combination of 2 or more types.
  • the content of the component (E) may be in the following range with respect to 100 parts by mass of the total amount of the component (A) and the component (B). .
  • the content of the component (E) may be 0.01 parts by mass or more, may be 0.05 parts by mass or more, from the viewpoint that the sensitivity tends to be further improved. It may be greater than or equal to part by mass, or greater than or equal to 0.2 parts by mass.
  • the content of the component (E) may be 10 parts by mass or less, or 5 parts by mass or less from the viewpoint that the component (E) tends to be difficult to precipitate as foreign matter after film formation. It may be 2 parts by mass or less, 1 part by mass or less, or 0.5 part by mass or less. From these viewpoints, the content of the component (E) may be 0.01 to 10 parts by mass, 0.05 to 5 parts by mass, or 0.1 to 2 parts by mass. It may be 0.2 to 1 part by mass, or 0.2 to 0.5 part by mass.
  • the photosensitive resin composition according to the present embodiment includes a photopolymerizable compound (such as an oxetane compound) having at least one cationically polymerizable cyclic ether group in the molecule, a cationic polymerization initiator, and a dye (malachite) as necessary.
  • thermochromic agent tribromophenylsulfone, leuco crystal violet, etc.
  • thermochromic inhibitor plasticizer (p-toluenesulfonamide, etc.)
  • pigment filler, antifoaming agent, flame retardant, stabilizer
  • You may further contain an adhesive imparting agent, a leveling agent, a peeling accelerator, antioxidant, a fragrance
  • the photosensitive resin composition which concerns on this embodiment may contain the solvent mentioned later in order to adjust a viscosity as needed.
  • the photosensitive resin composition according to this embodiment can be dissolved in a solvent and used as a solution (coating solution) having a solid content of 30 to 60% by mass.
  • the solvent include methanol, ethanol, acetone, methyl ethyl ketone, methyl cellosolve, ethyl cellosolve, toluene, N, N-dimethylformamide, propylene glycol monomethyl ether, and a mixed solvent thereof.
  • a photosensitive resin layer can be formed using the photosensitive resin composition according to the present embodiment by applying a coating solution onto the surface of a support of a photosensitive element, which will be described later, a substrate, and the like and drying the coating solution.
  • the thickness of the photosensitive resin layer varies depending on its use, but may be 2 to 50 ⁇ m after drying.
  • the surface of the photosensitive resin layer may be covered with a protective layer.
  • a protective layer polymer films, such as polyethylene and a polypropylene, are mentioned, for example.
  • the photosensitive element which concerns on this embodiment is provided with a support body and the photosensitive resin layer formed on the said support body using the photosensitive resin composition which concerns on this embodiment.
  • a photosensitive resin layer can be formed on the support using the photosensitive resin composition.
  • the photosensitive resin layer can contain the said photosensitive resin composition.
  • coated on a support body may be the coating liquid mentioned above.
  • a polymer film having heat resistance and solvent resistance such as polyethylene terephthalate (PET), polypropylene, polyethylene, and polyester can be used.
  • the photosensitive element may be provided with a protective layer that covers the surface of the photosensitive resin layer opposite to the support, if necessary.
  • the protective layer may have a lower adhesive force to the photosensitive resin layer than an adhesive force of the support to the photosensitive resin layer.
  • the protective layer may be a low fish eye film.
  • fish eye means that when a material is heat-melted, kneaded, extruded, biaxially stretched, casting method, etc., foreign materials, undissolved materials, oxidatively deteriorated materials, etc. are present in the film. It means what was taken in. That is, “low fish eye” means that the above-mentioned foreign matter or the like in the film is small.
  • a polymer film having heat resistance and solvent resistance such as polyethylene terephthalate, polypropylene, polyethylene, and polyester can be used.
  • examples of commercially available products include polypropylene films such as Alfan MA-410 and E-200C manufactured by Oji Paper Co., Ltd., Shin-Etsu Film Co., Ltd., and PS-25 such as PS-25 manufactured by Teijin DuPont Films Co., Ltd. A polyethylene terephthalate film is mentioned.
  • the protective layer may be the same as the support.
  • the photosensitive element can be produced as follows.
  • the photosensitive element includes a step of preparing a coating liquid containing the photosensitive resin composition according to the present embodiment, a step of coating the coating liquid on a support to form a coating layer, and drying the coating layer. And a step of forming a photosensitive resin layer.
  • the photosensitive resin composition can be applied to the support by a known method such as roll coating, comma coating, gravure coating, air knife coating, die coating, or bar coating.
  • the drying of the coating layer is not particularly limited as long as at least a part of the solvent can be removed from the coating layer.
  • the coating layer may be dried, for example, at 70 to 150 ° C. for 1 to 30 minutes. After drying, the amount of the remaining organic solvent in the photosensitive resin layer may be 2% by mass or less from the viewpoint of preventing diffusion of the organic solvent in the subsequent step.
  • the thickness of the photosensitive resin layer (after drying) can be appropriately adjusted as necessary.
  • the thickness (after drying) of the photosensitive resin layer may be, for example, 2 to 50 ⁇ m. When this thickness is 2 ⁇ m or more, it becomes easy to industrially form a photosensitive resin layer.
  • the transmittance of the photosensitive resin layer with respect to ultraviolet rays may be 5 to 75%, 10 to 65%, or 15 to 55% with respect to ultraviolet rays having a wavelength of 365 nm.
  • the transmittance can be measured with a UV spectrometer. Examples of the UV spectrometer include a 228A type W beam spectrophotometer manufactured by Hitachi, Ltd.
  • the photosensitive element may further have an intermediate layer such as a cushion layer, an adhesive layer, a light absorption layer, and a gas barrier layer.
  • an intermediate layer such as a cushion layer, an adhesive layer, a light absorption layer, and a gas barrier layer.
  • the obtained photosensitive element may be stored in the form of a sheet, or may be stored after being wound around a roll in a roll shape. When winding in a roll shape, it may be wound so that the support is on the outside.
  • the winding core include plastics such as polyethylene, polypropylene, polystyrene, polyvinyl chloride, and ABS resin (acrylonitrile-butadiene-styrene copolymer).
  • an end face separator may be installed from the viewpoint of end face protection, or a moisture-proof end face separator may be installed from the viewpoint of edge fusion resistance.
  • the packaging method may be a method of wrapping in a black sheet with low moisture permeability.
  • a resist pattern can be formed using the photosensitive resin composition or the photosensitive element.
  • the resist pattern forming method includes (i) a photosensitive resin layer forming step of forming a photosensitive resin layer on a substrate using the photosensitive resin composition or the photosensitive element, and (ii) ) An exposure step of irradiating a predetermined portion of the photosensitive resin layer with actinic rays to expose and cure the predetermined portion; and (iii) removing portions other than the predetermined portion of the photosensitive resin layer from the substrate. And a developing step of forming a resist pattern made of a cured product of the photosensitive resin composition on the substrate.
  • the photosensitive resin layer is formed on a board
  • a substrate circuit forming substrate
  • a conductor layer formed on the insulating layer can be used.
  • a method for forming the photosensitive resin layer on the substrate for example, a method in which the photosensitive resin composition is applied on the substrate and then dried, and the photosensitive resin layer in the photosensitive element described above is transferred onto the substrate. (Lamination) is mentioned.
  • photosensitive resin composition onto the substrate can be performed by a known method such as roll coating, comma coating, gravure coating, air knife coating, die coating, or bar coating.
  • the lamination of the photosensitive resin layer on the substrate is performed, for example, by removing the protective layer of the photosensitive element and then pressing the photosensitive resin layer on the substrate while heating the photosensitive resin layer of the photosensitive element. Is done.
  • the laminated body which consists of a board
  • Lamination conditions can be adjusted as needed. Lamination may be performed under reduced pressure from the viewpoint of further improving adhesion and followability.
  • the photosensitive resin layer and / or the substrate may be heated at the temperature of 70 to 130 ° C. during the pressure bonding.
  • the pressure bonding may be performed at a pressure of 0.1 to 1.0 MPa (1 to 10 kgf / cm 2 ). There are no particular restrictions on these conditions. If the photosensitive resin layer is heated to 70 to 130 ° C., it is not necessary to pre-heat the substrate in advance. In order to further improve the laminating property, the substrate may be heated in the above temperature range in advance.
  • Examples of the exposure method include a method of irradiating an image with active light through a negative or positive mask pattern called an artwork (mask exposure method).
  • a method of irradiating actinic rays in the form of an image by a direct drawing exposure method such as an LDI (Laser Direct Imaging) exposure method or a DLP (Digital Light Processing) exposure method may be employed.
  • LDI Laser Direct Imaging
  • DLP Digital Light Processing
  • a known light source can be used as the active light source.
  • active light sources include carbon arc lamps, mercury vapor arc lamps, high pressure mercury lamps, xenon lamps, gas lasers (such as argon lasers), solid state lasers (such as YAG lasers), and semiconductor lasers, such as ultraviolet rays and visible light. What emits effectively is used.
  • the wavelength of the actinic ray may be 340 to 430 nm or 350 to 420 nm from the viewpoint of obtaining the effect of the present embodiment more reliably.
  • development process In a development process, the resist pattern which consists of hardened
  • development is performed by a known development method using a developer corresponding to the photosensitive resin composition.
  • the developing method include a method using a dipping method, a paddle method, a spray method, brushing, slapping, scrubbing, rocking immersion, and the like. From the viewpoint of further improving the resolution, the high pressure spray method is most suitable. You may develop by combining these 2 or more types of methods.
  • the developer is appropriately selected according to the configuration of the photosensitive resin composition.
  • the developer include an alkaline aqueous solution and an organic solvent developer.
  • An alkaline aqueous solution is safe and stable when used as a developer, and has good operability.
  • Examples of the base of the alkaline aqueous solution include alkali hydroxides such as lithium, sodium, or potassium hydroxide; alkali carbonates such as lithium, sodium, potassium, or ammonium carbonate or bicarbonate; potassium phosphate, sodium phosphate Alkali metal phosphates such as sodium pyrophosphate and potassium pyrophosphate; borax (sodium tetraborate); sodium metasilicate; tetramethylammonium hydroxide; ethanolamine; ethylenediamine; diethylenetriamine; -Amino-2-hydroxymethyl-1,3-propanediol; 1,3-diamino-2-propanol; morpholine and the like are used.
  • Examples of the alkaline aqueous solution used for development include a dilute solution of 0.1 to 5% by mass of sodium carbonate, a dilute solution of 0.1 to 5% by mass of potassium carbonate, a dilute solution of 0.1 to 5% by mass of sodium hydroxide, It may be a dilute solution of 1 to 5% by mass sodium tetraborate.
  • the pH of the alkaline aqueous solution may be in the range of 9-11.
  • the temperature of the alkaline aqueous solution is adjusted according to the alkali developability of the photosensitive resin layer.
  • a surfactant, an antifoaming agent, a small amount of an organic solvent for promoting development, and the like may be mixed.
  • organic solvent used in the organic solvent developer examples include 1,1,1-trichloroethane, N-methylpyrrolidone, N, N-dimethylformamide, cyclohexanone, methyl isobutyl ketone and ⁇ -butyrolactone.
  • these organic solvents may be added with water in an amount of 1 to 20% by mass to form an organic solvent developer.
  • the photosensitive resin composition according to the present embodiment and the photosensitive element according to the present embodiment are suitably used for the manufacture of a structure (for example, a printed wiring board) for mounting a semiconductor element. It is preferably used for manufacturing a package substrate, and more preferably used for manufacturing a structure (a structure having a conductor circuit).
  • a structure a structure having a conductor circuit.
  • WLP Wafer Level Package
  • eWLB embedded Wafer Level Ball Grid Array
  • other board-less package rewiring methods can also be suitably used.
  • the size of the semiconductor element to be mounted is large, and it is particularly suitable for a printed wiring board for electrically connecting to tens of thousands of bumps arranged in an area array on the surface of the semiconductor element.
  • the structure according to the present embodiment is a structure in which an opening is provided in an insulating layer formed on the surface of a substrate having a conductor circuit, and a wiring portion connected to the conductor circuit is formed in the opening.
  • the photosensitive resin composition according to the present embodiment and the photosensitive element according to the present embodiment are provided with an opening in an insulating layer formed on the surface of a substrate having a conductor circuit, and connected to the conductor circuit. It can be used in a method for manufacturing a structure in which a wiring portion is formed in the opening.
  • the insulating layer is, for example, a thermosetting resin layer and / or a photosensitive resin layer.
  • the structure manufacturing method uses the photosensitive resin composition according to the present embodiment or the photosensitive element according to the present embodiment to form a first photosensitive material on a substrate so as to cover a conductor circuit.
  • a pattern exposing step for exposing from the curable resin layer and a predetermined portion of the pattern of the first photosensitive resin layer exposed from the thermosetting resin layer are removed, and an opening for exposing the conductor circuit is formed in the thermosetting resin layer.
  • the photosensitive resin composition which concerns on this embodiment, and the photosensitive element which concerns on this embodiment can be used for the manufacturing method of such a structure. That is, according to the present disclosure, the multilayer printed wiring board shown in FIG. 1 can be manufactured without using a laser.
  • a manufacturing method of the structure a manufacturing method described in Patent Document 5 may be used.
  • a manufacturing method described in Patent Document 5 may be used as the “substrate having a conductor circuit”, a flexible substrate or a rigid substrate may be used.
  • the “conductor circuit” can also be referred to as a “conductor pattern” or “wiring pattern”.
  • the shape of the opening is not particularly limited, and may be, for example, an ellipse, a polygon, an irregular shape, or other shapes in addition to a circle and a line. Note that when the line-shaped opening forming part is formed using the stripping solution, the stripping liquid penetrates more than when the opening forming part having a circular, elliptical, polygonal, or irregular shape is formed. It tends to be easy.
  • the multilayer printed wiring board which can be manufactured by this indication is equipped with the insulating layer formed so that a conductor circuit may be covered on a board
  • the insulating layer includes an opening formed so that at least a part of the conductor circuit on the substrate is exposed, and a conductor pattern can be formed in the opening.
  • various openings can be easily formed by patterning the first photosensitive resin layer in the first patterning step in accordance with the shape of the opening formed in the thermosetting resin layer. Can be formed. Also, in this method of manufacturing a structure (for example, a printed wiring board), unlike the case of forming openings with a laser, in addition to being able to form a plurality of openings at the same time, resin residues around the openings can be reduced. For this reason, even when the number of pins of the semiconductor element increases and a large number of fine openings need to be provided, a structure (eg, a printed wiring board) having excellent reliability can be efficiently manufactured. Further, even when an opening having a diameter of 30 ⁇ m or less is formed or a large opening having a diameter of 100 ⁇ m or more is formed, an opening having excellent insulation reliability can be more efficiently formed. it can.
  • a structure for example, a printed wiring board
  • thermosetting resin layer is heat-processed.
  • a part of the thermosetting resin layer after thermosetting is removed in the pattern exposure process, and the first photosensitive resin layer exposed from the thermosetting resin layer is removed in the opening forming process.
  • Examples of the method for removing a part of the thermosetting resin layer after thermosetting include mechanical polishing, plasma treatment, wet blasting, sand blasting, and chemical polishing.
  • the method for removing the first photosensitive resin layer exposed from the thermosetting resin layer include chemical treatment (also referred to as “desmear treatment”), plasma treatment, wet blasting, and sand blasting.
  • the method for removing a part of the thermosetting resin layer after the thermosetting may be mechanical polishing, and the method for removing the first photosensitive resin layer exposed from the thermosetting resin layer may be chemical treatment. .
  • the first photosensitive resin layer can be exposed more quickly, and residues around the opening can be more reliably reduced.
  • the residue around the opening can be more reliably reduced.
  • the method for removing a part of the thermosetting resin layer after the thermosetting and the method for removing the first photosensitive resin layer exposed from the thermosetting resin layer may be chemical treatment. .
  • the first photosensitive resin layer can be exposed more quickly, and residues around the opening can be more reliably reduced. Moreover, it can peel by using the aqueous solution which is stronger alkaline than the alkaline aqueous solution used for image development as a chemical solution used for a chemical solution process.
  • the strong alkaline aqueous solution include a sodium permanganate aqueous solution, a sodium hydroxide aqueous solution, and a potassium permanganate aqueous solution.
  • a developer composed of water or an alkaline aqueous solution and one or more organic solvents can be suitably used.
  • Examples of the base of the alkaline aqueous solution include tetramethylammonium hydroxide, ethanolamine, ethylenediamine, diethylenetriamine, 2-amino-2-hydroxymethyl-1,3-propanediol and the like.
  • Examples of the organic solvent used together include acetone, ethyl acetate, alkoxyethanol having an alkoxy group having 1 to 4 carbon atoms, ethyl alcohol, isopropyl alcohol, butyl alcohol, diethylene glycol monomethyl ether, and the like. It can be used alone or in combination of two or more bases. In addition, these chemical
  • medical solutions can be used individually or in combination of 2 or more types as a liquid mixture.
  • thermosetting may be performed in an inert gas atmosphere.
  • thermosetting in an inert gas atmosphere, copper oxidation on the surface of the conductor circuit can be suppressed in the thermosetting step.
  • the structure manufacturing method includes a seed layer forming step of forming a seed layer serving as a base of the wiring portion by an electroless plating method so as to cover at least a part of the thermosetting resin layer after the opening is formed.
  • a seed layer forming step of forming a seed layer serving as a base of the wiring portion by an electroless plating method so as to cover at least a part of the thermosetting resin layer after the opening is formed.
  • a seed layer removing step of removing the seed layer By forming the seed layer, the wiring part can be formed by electrolytic plating,
  • the thickness T 1 of the first photosensitive resin layer may be 2 to 50 ⁇ m.
  • the photosensitive resin composition used for forming the first photosensitive resin layer can be easily formed.
  • the thickness T1 of the first photosensitive resin layer is 50 ⁇ m or less, it becomes easy to form a fine pattern on the first photosensitive resin layer.
  • the thickness T 2 of the thermosetting resin layer may be 2 to 50 ⁇ m. If the thickness T 2 of the thermosetting resin layer is 2 ⁇ m or more, it becomes easier by forming a thermosetting resin composition used to form the thermosetting resin layer, the production of structures (e.g., printed circuit board) The film-like thermosetting resin composition used in the above can be easily produced. If the thickness T 2 of the thermosetting resin layer is 50 ⁇ m or less, it is easy to form a fine pattern in the thermosetting resin layer.
  • the structure according to the present embodiment is a structure (structure having a conductor circuit) manufactured by the above-described structure manufacturing method, and the diameter of the opening of the thermosetting resin layer is 30 ⁇ m or less. There may be.
  • the structure manufactured by the above-described manufacturing method can have fine openings in the insulating layer and can have excellent reliability.
  • the diameter of the opening of the thermosetting resin layer in the structure is 30 ⁇ m or less, it is suitable for mounting a semiconductor element having a large number of pins with tens of thousands to hundreds of thousands of pins. It will be.
  • thermosetting resin composition used in the above-described structure manufacturing method is not particularly limited as long as it can be cured by heat.
  • the thermosetting resin composition may be, for example, a resin composition containing at least one selected from the group consisting of an epoxy resin, a phenol resin, a cyanate ester resin, a polyamideimide resin, and a thermosetting polyimide resin.
  • the thermosetting resin composition may contain an inorganic filler having a maximum particle size of 5 ⁇ m or less and an average particle size of 1 ⁇ m or less in a state dispersed in the thermosetting resin composition.
  • thermosetting resin layer By forming a thermosetting resin layer using such a thermosetting resin composition, the surface of the opening formed in the thermosetting resin layer becomes smooth, and it becomes easy to form a seed layer on the opening.
  • the maximum particle size of the inorganic filler in a state dispersed in the thermosetting resin composition is one measured using a microtrack method or a nanotrack method, for example, a dynamic light scattering nanotrack particle size distribution.
  • binder polymer (A-1) A polymerizable monomer (monomer) obtained by mixing 54 g of methacrylic acid, 150 g of methyl methacrylate and 96 g of ethyl acrylate (mass ratio 18/50/32) and 2.5 g of azobisisobutyronitrile. The solution was designated as “Solution a”.
  • Solution b A solution obtained by dissolving 1.2 g of azobisisobutyronitrile in 150 g of a mixed solution (mass ratio 3: 2) of 100 g of methyl cellosolve and 50 g of toluene was designated as “Solution b”.
  • a flask equipped with a stirrer, reflux condenser, thermometer, dropping funnel and nitrogen gas introduction tube was charged with 300 g of a mixture of 180 g of methyl cellosolve and 120 g of toluene (mass ratio 3: 2), and nitrogen gas was introduced into the flask.
  • the mixture was heated with stirring while being blown, and the temperature was raised to 80 ° C.
  • the solution a was dropped into the mixed solution in the flask at a constant dropping rate over 4 hours, and then stirred at 80 ° C. for 2 hours.
  • the solution b was dropped into the solution in the flask at a constant dropping rate over 10 minutes, and then the solution in the flask was stirred at 80 ° C. for 3 hours.
  • the solution in the flask was heated to 90 ° C. over 30 minutes and stirred at 90 ° C. for 2 hours. Then, stirring was stopped and the solution was cooled to room temperature to obtain a solution of binder polymer (A-1).
  • room temperature means 25 ° C.
  • the nonvolatile content (solid content) of the binder polymer (A-1) was 44.6% by mass, the weight average molecular weight was 50000, and the acid value was 117 mgKOH / g.
  • x 10 ⁇ Vf ⁇ 56.1 / (Wp ⁇ I)
  • x represents an acid value (mgKOH / g)
  • Vf represents a titration amount (mL) of a 0.1N KOH aqueous solution
  • Wp represents a mass (g) of the measured resin solution
  • I Indicates the ratio (% by mass) of the non-volatile content in the measured resin solution.
  • Binder Polymers (A-2) and (A-3) As the polymerizable monomer (monomer), the binder polymer (A-2) was obtained in the same manner as that for obtaining a solution of the binder polymer (A-1) except that the materials shown in Table 1 were used in the mass ratio shown in Table 1. ) And (A-3) were obtained.
  • Binder polymer Binder polymers (A-1) to (A-3) synthesized as described above were used.
  • Sensitizing dye EAB 4,4′-bis (diethylamino) benzophenone (trade name, manufactured by Hodogaya Chemical Co., Ltd.)
  • a polyethylene film manufactured by Tamapoly Co., Ltd., trade name “NF-15” (protective layer) was laminated on the photosensitive resin layer, and a support film, a photosensitive resin layer, and a protective layer were laminated in order.
  • photosensitive element photosensitive elements according to Examples and Comparative Examples were obtained.
  • a copper clad laminate manufactured by Hitachi Chemical Co., Ltd., trade name “MCL-E-679FG” having a copper foil having a thickness of 18 ⁇ m adhered on both sides was prepared.
  • the thickness of the copper clad laminate was 400 ⁇ m.
  • the copper surface was roughened with a CZ treatment solution (trade name “MEC etch bond CZ-8100” manufactured by MEC Co., Ltd.). After heating this roughened copper substrate (hereinafter simply referred to as “substrate”) to 80 ° C., each of the photosensitive elements according to Examples and Comparative Examples was laminated on the copper surface of the substrate ( Layered).
  • Lamination was performed under conditions of a temperature of 120 ° C. and a lamination pressure of 0.39 MPa so that the photosensitive resin layer of each photosensitive element was in close contact with the copper surface of the substrate while removing the protective layer. Subsequently, it cooled until it became room temperature, and the laminated substrate A by which the photosensitive resin layer and the support film were laminated
  • the multilayer substrate A is divided into two regions, and a circular pattern having a diameter of 30 ⁇ m ⁇ , 40 ⁇ m ⁇ , and 50 ⁇ m ⁇ is arranged on a support film in one region at a pitch of 40 ⁇ m, 80 ⁇ m, and 100 ⁇ m, respectively.
  • a photo tool made of PET was placed.
  • the distance between the centers of two adjacent circular patterns is referred to as “pitch”.
  • a parallel light exposure machine (trade name “EXM-1201” manufactured by Oak Manufacturing Co., Ltd.) using a short arc UV lamp (trade name “AHD-5000R” manufactured by Oak Manufacturing Co., Ltd.) as a light source is used.
  • the photosensitive resin layer was exposed through a PET phototool and a support film with an exposure amount (energy amount) that allows the diameter of a 30 ⁇ m ⁇ circular pattern after development to be obtained as designed.
  • an ultraviolet illuminance meter (trade name “UV-350SN type” manufactured by Oak Manufacturing Co., Ltd.) using a 365 nm probe was used.
  • the support film was peeled off from the laminated substrate A to expose the photosensitive resin layer.
  • the unexposed part was removed by spraying 1 mass% sodium carbonate aqueous solution at 30 degreeC and 0.2 Mpa using the developing machine (made by HMS).
  • the development time was set to twice the shortest development time of each photosensitive resin composition.
  • the laminated substrate B was obtained by forming the cured film which consists of a hardened
  • the shortest development time was a value obtained by measurement as follows. First, the laminated substrate A was cut into a size of 30 mm ⁇ 30 mm to obtain a test piece.
  • spray development is performed at a pressure of 0.2 MPa using a 1% by mass sodium carbonate aqueous solution at 30 ° C., and the shortest time that can be visually confirmed that an unexposed portion of 1 mm or more has been removed. was set as the shortest development time.
  • thermosetting film type resin composition As a thermosetting resin composition used for forming a thermosetting resin layer (interlayer insulating layer) of a printed wiring board, 70 parts by mass of an epoxy resin, 30 parts by mass (solid content), and an inorganic filler component The solution of the thermosetting resin composition was prepared by mixing. In addition, the inorganic filler component was blended so as to be 30% by mass with respect to the resin content.
  • epoxy resin a biphenyl aralkyl type epoxy resin (manufactured by Nippon Kayaku Co., Ltd., trade name “NC-3000H”) was used.
  • a curing agent solution obtained as follows was used.
  • a volume of 2 L that can be heated and cooled 26.40 g of bis (4-aminophenyl) sulfone, and 2,2′- Bis [4- (4-maleimidophenoxy) phenyl] propane: 484.50 g, p-aminobenzoic acid: 29.10 g, and dimethylacetamide: 360.00 g were added and reacted at 140 ° C. for 5 hours.
  • a solution of a curing agent having a sulfone group in the molecular main chain and having an acidic substituent and an unsaturated N-substituted maleimide group was obtained.
  • the inorganic filler component a silica filler having an average particle diameter of 50 nm and silane coupling treatment with vinylsilane was used.
  • a dynamic light scattering nanotrack particle size distribution analyzer “UPA-EX150” manufactured by Nikkiso Co., Ltd.
  • a laser diffraction scattering type microtrack particle size distribution analyzer “MT-3100” manufactured by Nikkiso Co., Ltd.
  • the maximum particle size was confirmed to be 1 ⁇ m or less.
  • thermosetting resin composition obtained as described above is uniformly applied onto a 16 ⁇ m-thick polyethylene terephthalate film (G2-16, manufactured by Teijin Ltd., trade name) as a support layer. A resin composition layer was formed. Thereafter, the thermosetting resin composition layer was dried at 100 ° C. for about 10 minutes using a hot air convection dryer to obtain a film-like thermosetting resin composition. The film thickness of the film-like thermosetting resin composition was adjusted to 10 to 90 ⁇ m.
  • thermosetting resin composition layer a polyethylene film (manufactured by Tamapoly Co., Ltd., trade name “NF-15”) is provided on the surface opposite to the side in contact with the support layer. Bonding as a protective film, a thermosetting film type resin composition was obtained.
  • thermosetting resin layer was formed on the laminated substrate B using the obtained thermosetting film type resin composition. Specifically, first, only the protective film of the thermosetting film type resin composition made of the above thermosetting resin composition is peeled off, and heat is applied to both surfaces (on the photosensitive resin layer pattern and the conductor circuit) of the multilayer substrate B. A curable resin composition was placed. The thermosetting resin composition was laminated on the surface of the laminated substrate B using a press-type vacuum laminator (MVLP-500, manufactured by Meiki Seisakusho, trade name).
  • MVLP-500 press-type vacuum laminator
  • the press hot plate temperature was 80 ° C.
  • the evacuation time was 20 seconds
  • the lamination pressing time was 30 seconds
  • the atmospheric pressure was 4 kPa or less
  • the pressing pressure was 0.4 MPa.
  • the thermosetting resin layer was thermoset at a predetermined temperature and a predetermined time in a clean oven.
  • thermosetting resin layer was ground to form an exposed portion in the photosensitive resin layer pattern.
  • plasma treatment plasma ashing
  • the exposed portion of the photosensitive resin layer pattern is removed, and a via is formed by opening a part of the thermosetting resin layer and the photosensitive resin layer, thereby forming a printed wiring board.
  • the via opening (removability of the cylindrical resist) was evaluated based on the following criteria by observing vias having a diameter of 30 ⁇ m ⁇ , 40 ⁇ m ⁇ , and 50 ⁇ m ⁇ with an electron microscope (SEM). The evaluation results are shown in Tables 8 to 11.
  • C Residue derived from the photosensitive resin composition is generated at 50% or more of the volume in the via forming part (opening part).
  • An FPC board (trade name: F-30VC1, board thickness: 25 ⁇ m, copper thickness: 18 ⁇ m, manufactured by Nikkan Kogyo Co., Ltd.) was heated to 80 ° C., and the photosensitive elements according to Examples and Comparative Examples were formed on the copper surface.
  • the photosensitive resin composition layer and the support film were laminated at a speed of 1.5 m / min using a 110 ° C. heat roll while peeling off the protective film so that the photosensitive resin composition layer was opposed to the FPC substrate side.
  • the FPC board on which the photosensitive resin composition layer and the support film were laminated was used as a test piece for evaluating flexibility.
  • a parallel light exposure machine (trade name “EXM-1201” manufactured by Oak Manufacturing Co., Ltd.) using a short arc UV lamp (trade name “AHD-5000R” manufactured by Oak Manufacturing Co., Ltd.) as a light source is used for the above test piece.
  • the photosensitive resin composition layer was photocured by performing exposure with an energy amount of 20 steps in the number of remaining step steps after development of the 41 step tablet.
  • development was performed to obtain a flexibility evaluation substrate in which a resist pattern was laminated on the FPC substrate.
  • Flexibility was evaluated by a mandrel test.
  • the substrate for evaluation of flexibility was cut into a strip shape having a width of 2 cm and a length of 10 cm, and was rubbed back and forth 5 times at 180 ° to a cylindrical rod. Thereafter, the minimum diameter (mm) of the cylinder that could not be peeled between the FPC substrate and the resist pattern was determined. The smaller the diameter of the cylinder, the better the flexibility. The results are shown in Tables 8-11.
  • Adhesion was evaluated using the photosensitive resin compositions of Examples 2, 7, 12, and 14. As in the above (formation of photosensitive resin layer pattern), using a photo tool made of PET having a design in which circular patterns with diameters of 30 ⁇ m ⁇ , 40 ⁇ m ⁇ , and 50 ⁇ m ⁇ are arranged at pitches of 40 ⁇ m, 80 ⁇ m, and 100 ⁇ m, respectively, A columnar resist (also called a post) was formed. Observed with an electron microscope (SEM), the ratio of posts remaining after development (that is, post formability) was evaluated based on the following criteria as an index of adhesion. The results are shown in Table 12 and Table 13. A: 90% or more of the posts are formed over the entire opening of the mask design. B: The post is formed to be 50% or more and less than 90% of the entire opening of the mask design. C: The post is formed less than 50% of the entire opening of the mask design.
  • a printed wiring board was produced in the same manner as in the above evaluation except that the via diameter was changed to 100 ⁇ m, and the evaluation was performed in the same manner as described above. Furthermore, a printed wiring board was produced in the same manner as in the above evaluation except that the via diameter was changed to 200 ⁇ m, and the evaluation was performed in the same manner as described above. In any case, it was found that when the photosensitive resin compositions of Examples 1 to 14 were used, the opening property was good and the throughput was excellent even when the roughening time was reduced to one third.
  • DESCRIPTION OF SYMBOLS 100 Multilayer printed wiring board, 101 ... Copper clad laminated board, 102 ... Wiring pattern, 103 ... Interlayer insulation layer, 104 ... Opening, 105 ... Seed layer, 106 ... Wiring pattern, 107 ... Wiring pattern, 108 ... Solder resist.

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Abstract

La présente invention concerne une composition de résine photosensible contenant un polymère liant, un composé photopolymérisable, et un initiateur de photopolymérisation, lequel composé photopolymérisable contient un composé représenté par la formule générale (1), et un composé ayant une liaison éthyléniquement insaturée par molécule. (Dans la formule (1), R11 représente un groupe alkylène en C1 à C20, un groupe cycloalkylène en C1 à C10, ou un groupe phénylène. R12 et R13 représentent chacun indépendamment un atome d'hydrogène ou un groupe méthyle. X11 et X12 représentent chacun indépendamment un groupe oxyalkylène ou un groupe polyoxyalkylène contenant au moins un ou plusieurs types choisis dans un groupe constitué par un groupe oxyéthylène et un groupe oxypropylène. Le nombre total de groupes oxypropylène et de groupes oxyéthylène contenus dans X11 et X12 est de 12 à 80.)
PCT/JP2016/051294 2015-01-20 2016-01-18 Composition de résine photosensible, élément photosensible, procédé de formation de motif de résine photosensible, et procédé de production de structure Ceased WO2016117509A1 (fr)

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JP2011175135A (ja) * 2010-02-25 2011-09-08 Nissan Chem Ind Ltd アミドビニルエーテル基含有架橋剤を含む感光性レジスト下層膜形成組成物
WO2011114593A1 (fr) * 2010-03-19 2011-09-22 日立化成工業株式会社 Composition de résine photosensible et élément photosensible l'utilisant, procédé de formation d'un motif de réserve et procédé de fabrication d'une carte de circuits imprimés
WO2013054790A1 (fr) * 2011-10-11 2013-04-18 日立化成株式会社 Structure contenant un circuit conducteur, procédé de fabrication de celle-ci et composition de résine thermodurcissable

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JP2017167396A (ja) * 2016-03-17 2017-09-21 日立化成株式会社 感光性樹脂組成物、感光性エレメント、レジストパターン付き基板の製造方法、及びプリント配線板の製造方法

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JP2000171970A (ja) * 1998-12-04 2000-06-23 Hitachi Chem Co Ltd 感光性樹脂組成物及びこれを用いた感光性エレメント
JP2008102257A (ja) * 2006-10-18 2008-05-01 Hitachi Chem Co Ltd 感光性樹脂組成物これを用いた感光性エレメント、レジストパターンの製造法及びプリント配線板の製造法
JP2011175135A (ja) * 2010-02-25 2011-09-08 Nissan Chem Ind Ltd アミドビニルエーテル基含有架橋剤を含む感光性レジスト下層膜形成組成物
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WO2013054790A1 (fr) * 2011-10-11 2013-04-18 日立化成株式会社 Structure contenant un circuit conducteur, procédé de fabrication de celle-ci et composition de résine thermodurcissable

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