WO2024185060A1 - 感光性樹脂組成物、感光性樹脂フィルム、多層プリント配線板及び半導体パッケージ、並びに多層プリント配線板の製造方法 - Google Patents

感光性樹脂組成物、感光性樹脂フィルム、多層プリント配線板及び半導体パッケージ、並びに多層プリント配線板の製造方法 Download PDF

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WO2024185060A1
WO2024185060A1 PCT/JP2023/008746 JP2023008746W WO2024185060A1 WO 2024185060 A1 WO2024185060 A1 WO 2024185060A1 JP 2023008746 W JP2023008746 W JP 2023008746W WO 2024185060 A1 WO2024185060 A1 WO 2024185060A1
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Prior art keywords
photosensitive resin
resin composition
component
group
composition according
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Ceased
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PCT/JP2023/008746
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English (en)
French (fr)
Japanese (ja)
Inventor
憂子 今野
秀行 片木
薫平 山田
剛 野尻
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Resonac Corp
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Resonac Corp
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Priority to JP2025504980A priority Critical patent/JPWO2024185060A1/ja
Priority to CN202380037457.7A priority patent/CN119234184A/zh
Priority to PCT/JP2023/008746 priority patent/WO2024185060A1/ja
Priority to KR1020257021925A priority patent/KR20250151361A/ko
Publication of WO2024185060A1 publication Critical patent/WO2024185060A1/ja
Anticipated expiration legal-status Critical
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/0042—Photosensitive materials with inorganic or organometallic light-sensitive compounds not otherwise provided for, e.g. inorganic resists
    • 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
    • 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

Definitions

  • the present disclosure relates to a photosensitive resin composition, a photosensitive resin film, a multilayer printed wiring board and a semiconductor package, and a method for producing a multilayer printed wiring board.
  • a conventional method for manufacturing a printed wiring board is a build-up method (see, for example, Patent Document 1) for sequentially laminating an interlayer insulating layer and a conductor circuit layer.
  • a semi-additive method for forming circuits by plating has become mainstream for multilayer printed wiring boards.
  • the conventional semi-additive method for example, (1) a thermosetting resin film is laminated on a conductor circuit, and then the thermosetting resin film is heated to harden the film to form an "interlayer insulating layer”.
  • vias for interlayer connection are formed by laser processing, and then desmearing and roughening are performed by alkaline permanganate treatment or the like.
  • the board is subjected to electroless copper plating, and then a pattern is formed using a resist, and then electrolytic copper plating is performed to form a copper circuit layer.
  • the resist is peeled off, and then flash etching of the electroless layer is performed to form a copper circuit.
  • laser processing is the mainstream method for forming vias in an interlayer insulating layer formed by hardening a thermosetting resin film, but the ability to reduce the diameter of vias by irradiating a laser with a laser processing machine is reaching its limit. Furthermore, when forming vias with a laser processing machine, each via hole must be formed one by one, and when a large number of vias are required to achieve high density, it takes a long time to form the vias, resulting in poor manufacturing efficiency.
  • Patent Document 2 one of the problems is to suppress the decrease in adhesion with copper plating caused by using a photosensitive resin composition instead of a conventional thermosetting resin composition as a material for an interlayer insulating layer or a surface protective layer, and further, the resolution of vias and adhesion with silicon substrates and chip components are also identified as problems, and these are claimed to have been solved.
  • substrate materials are being required to be applied to fifth generation mobile communication system (5G) antennas that use radio waves in a high frequency band and millimeter wave radars that use radio waves in an even higher frequency band.
  • 5G fifth generation mobile communication system
  • one of the goals is the development of a resin composition with a further improved relative dielectric constant in the "10 GHz band”.
  • the technology of Patent Document 2 has room for improvement in the relative dielectric constant in the 10 GHz band.
  • the inventors have investigated the inclusion of polytetrafluoroethylene (hereinafter referred to as PTFE) particles, which have a very low dielectric constant, in a photosensitive resin composition in order to reduce the dielectric constant in the 10 GHz band.
  • PTFE polytetrafluoroethylene
  • the dielectric constant can certainly be reduced by simply adding PTFE to a photosensitive resin composition, the problem of reduced adhesive strength with copper plating arises, and it has been found that it is difficult to achieve both a high dielectric constant in the 10 GHz band and high adhesive strength with copper plating.
  • the purpose of this disclosure is to provide a photosensitive resin composition that exhibits an excellent dielectric constant in the 10 GHz band and high adhesive strength with copper plating, a photosensitive resin film formed using the photosensitive resin composition, and to provide a multilayer printed wiring board and a method for producing the same, and a semiconductor package.
  • the present disclosure includes the following embodiments [1] to [18].
  • [1] (X) A photosensitive resin composition comprising an inorganic filler that is a solid particle having a true density of 1,500 kg/ m3 or less.
  • the component (A) contains an alicyclic skeleton represented by the following general formula (A-1): (In the formula, R A1 represents an alkyl group having 1 to 12 carbon atoms and may be substituted anywhere in the alicyclic skeleton. m 1 is an integer of 0 to 6.
  • a photosensitive resin composition for forming a photovia comprising the photosensitive resin composition according to any one of [1] to [13] above.
  • a multilayer printed wiring board comprising an interlayer insulating layer formed using the photosensitive resin composition according to any one of [1] to [13] above or the photosensitive resin film according to [15] above.
  • a semiconductor package comprising the multilayer printed wiring board according to [16] above and a semiconductor element.
  • a method for producing a multilayer printed wiring board comprising the following (1), (2), and (4): (1): The photosensitive resin film according to the above item [15] is laminated onto one or both sides of a circuit board. (2) Forming an interlayer insulating layer having vias by exposing and developing the photosensitive resin film laminated in (1) above. (4): Forming a circuit pattern on the interlayer insulating layer.
  • a photosensitive resin composition that exhibits an excellent relative dielectric constant in the 10 GHz band and high adhesive strength with copper plating. It is also possible to provide a photosensitive resin film formed using the photosensitive resin composition. It is also possible to provide a multilayer printed wiring board that contains an interlayer insulating layer formed using the photosensitive resin composition or the photosensitive resin film, and it is also possible to provide a method for manufacturing the multilayer printed wiring board. It is also possible to provide a semiconductor package that includes the multilayer printed wiring board and a semiconductor element.
  • FIG. 2 is a schematic diagram showing one embodiment of a process for producing a multilayer printed wiring board using the photosensitive resin film of the present embodiment as at least one of the materials for a surface protective layer and an interlayer insulating layer.
  • the upper or lower limit of the numerical range may be replaced with the values shown in the examples.
  • the lower and upper limits of a numerical range may be arbitrarily combined with the lower or upper limit of another numerical range.
  • the numerical values AA and BB at both ends are included in the numerical range as the lower and upper limits, respectively.
  • the expression “10 or more” means 10 or a numerical value exceeding 10, and the same applies when the numerical values are different.
  • the expression "10 or less” means 10 or a numerical value less than 10, and the same applies when the numerical values are different.
  • the content of each component means the total content of the multiple substances present in the photosensitive resin composition, unless otherwise specified.
  • the term “number of ring carbon atoms” refers to the number of carbon atoms necessary to form a ring, and does not include the number of carbon atoms of the substituents on the ring. For example, both the cyclohexane skeleton and the methylcyclohexane skeleton have 6 ring carbon atoms.
  • (meth)acrylic XX means one or both of acrylic XX and the corresponding methacrylic XX.
  • (meth)acryloyl group means one or both of an acryloyl group and a methacryloyl group.
  • dielectric constant refers to the dielectric constant in the 10 GHz band unless otherwise specified. Additionally, any combination of the descriptions in this specification is also included in this embodiment.
  • the photosensitive resin composition according to one embodiment of the present disclosure (hereinafter, sometimes simply referred to as the present embodiment) comprises (X) an inorganic solid particle having a true density of 1,500 kg/ m3 or less.
  • a photosensitive resin composition comprising a filler.
  • component (X) the above component may be abbreviated to "component (X)", and other components may be abbreviated in the same manner.
  • the term "resin component” refers to the components (A) and (B) described below, and other components that may be contained as necessary (e.g., (C), (D) ), (E), (F), (G), (H) and (I), but does not include component (X) and inorganic compounds such as other inorganic fillers and pigments.
  • solid content refers to non-volatile content excluding water and the diluent described below contained in the photosensitive resin composition, and includes liquid, starch syrup, and wax-like substances at room temperature around 25°C. .
  • the photosensitive resin composition of the present embodiment has an excellent relative dielectric constant in the 10 GHz band and is suitable for via formation by photolithography (also referred to as photovia formation), and is therefore suitable for forming one or more types selected from the group consisting of photovias and interlayer insulating layers.
  • layer when the term "layer” is used, for example, as in an interlayer insulating layer, the term “layer” includes not only a solid layer, but also a layer that is not a solid layer but at least a part of which is island-like, a layer that has holes, and a layer in which the interface with an adjacent layer is unclear.
  • the solid layer refers to a sheet-like layer that has not been particularly processed.
  • the photosensitive resin composition of the present embodiment is suitable as a negative type photosensitive resin composition.
  • the component (X) will be described in detail, and then other components that may be contained in the photosensitive resin composition of this embodiment will be described in detail.
  • the photosensitive resin composition of the present embodiment exhibits an excellent relative dielectric constant in the 10 GHz band and high adhesive strength with copper plating by containing, as the component (X), an inorganic filler that is a solid particle with a true density of 1,500 kg/m3 or less.
  • the true density of the component (X) is a value measured by a dry automatic densitometer "AccuPycII 1340" (manufactured by Shimadzu Corporation), more specifically, a value measured according to the method described in the Examples.
  • solid particles refers to particles having a hollow ratio of 60% or less (including 0%, that is, 0 to 60%) calculated from the true density measured by a dry automatic densitometer (more specifically, the method described in the Examples), and when the hollow ratio measured by this method exceeds 60%, they are called “hollow particles”. Therefore, for example, even if a particle has a porous interior, it is included in the solid particles if the hollow ratio is 60% or less.
  • the hollow ratio in the solid particles is preferably 55% or less, more preferably 50% or less, even more preferably 45% or less, and particularly preferably 43% or less.
  • the lower limit of the hollow ratio there is no particular restriction on the lower limit of the hollow ratio, and it may be 0% or more, 5% or more, 15% or more, 25% or more, 30% or more, 32% or more, 34% or more, or 37% or more.
  • the method for determining the hollow ratio is as described in the Examples.
  • the true density of component (X) is preferably 1,000 to 1,500 kg/m 3 , more preferably 1,100 to 1,500 kg/m 3 , even more preferably 1,200 to 1,500 kg/m 3 , particularly preferably 1,250 to 1,450 kg/m 3 , and most preferably 1,250 to 1,400 kg/m 3 .
  • Examples of the (X) component include silica (SiO 2 ), alumina (Al 2 O 3 ), titania (TiO 2 ), tantalum oxide (Ta 2 O 5 ), zirconia (ZrO 2 ), silicon nitride (Si 3 N 4 ), barium titanate (BaO.TiO 2 ), barium carbonate (BaCO 3 ), magnesium carbonate (MgCO 3 ), aluminum hydroxide (Al(OH) 3 ), magnesium hydroxide (Mg(OH) 2 ), lead titanate (PbO.TiO 2 ), lead zirconate titanate (PZT), lead lanthanum zirconate titanate (PLZT), gallium oxide (Ga 2 O 3 ), spinel (MgO.Al 2 O 3 ), mullite (3Al 2 O 3.2SiO 2 ), cordierite (2MgO.2Al 2 O 3 ) .
  • silica is preferred from the viewpoints of heat resistance, low thermal expansion, and relative dielectric constant.
  • the (X) component commercially available products can be used.
  • examples of silica that is a solid particle having a true density of 1,500 kg/ m3 or less include "BQQ-0710SCB” (manufactured by TAT Co., Ltd.) and “BQQ-0310SCB” (manufactured by TAT Co., Ltd.).
  • silica that is a solid particle having a true density of 1,500 kg/ m3 or less
  • the silica has a Si-R X bond (R X represents an organic group) in addition to the Si-O- bond.
  • the (X) component may or may not be surface-treated with a coupling agent, but is preferably surface-treated with a coupling agent.
  • coupling agents include silane coupling agents such as aminosilane coupling agents, epoxysilane coupling agents, phenylsilane coupling agents, alkylsilane coupling agents, alkenylsilane coupling agents, alkynylsilane coupling agents, haloalkylsilane coupling agents, siloxane coupling agents, hydrosilane coupling agents, silazane coupling agents, alkoxysilane coupling agents, chlorosilane coupling agents, (meth)acrylic silane coupling agents, isocyanurate silane coupling agents, ureidosilane coupling agents, mercaptosilane coupling agents, sulfide silane coupling agents, and isocyanate silane coupling agents.
  • the volume average particle diameter of the (X) component is preferably 0.3 to 3 ⁇ m, more preferably 0.3 to 2.5 ⁇ m, even more preferably 0.3 to 2.0 ⁇ m, and particularly preferably 0.3 to 1.7 ⁇ m, and may be 0.3 to 1.2 ⁇ m or 1.2 to 2.0 ⁇ m. If the volume average particle diameter of the (X) component is equal to or greater than the lower limit, the component tends to have excellent low thermal expansion properties, and if the volume average particle diameter is equal to or less than the upper limit, the component tends to have excellent via resolution. If the volume average particle diameter of the (X) component is 2.5 ⁇ m or less, the via resolution tends to be very good.
  • the component (X) may contain two or more inorganic fillers having different volume average particle sizes.
  • the volume average particle diameter can be determined by measuring particles dispersed in a solvent with a refractive index of 1.38 in accordance with ISO 13321 using a submicron particle analyzer (manufactured by Beckman Coulter, Inc., product name: N5), and determining the volume average particle diameter as the particle diameter equivalent to an integrated value of 50% (volume basis) in the particle size distribution.
  • the content of component (X) is not particularly limited, but is preferably 1 to 45 volume %, more preferably 3 to 40 volume %, and even more preferably 5 to 40 volume %, based on the total solid content of the photosensitive resin composition, and may be 5 to 25 volume % or 25 to 40 volume %. If the content of component (X) is equal to or greater than the lower limit, a lower relative dielectric constant and thermal expansion coefficient tend to be obtained, and if it is equal to or less than the upper limit, better adhesion strength with copper plating and via resolution tend to be obtained.
  • the photosensitive resin composition of this embodiment preferably further contains (A) a photopolymerizable compound having an ethylenically unsaturated group and an acidic substituent, and (B) a thermosetting resin.
  • A a photopolymerizable compound having an ethylenically unsaturated group and an acidic substituent
  • B a thermosetting resin
  • the component (A) is a photopolymerizable compound having an ethylenically unsaturated group and an acidic substituent.
  • the component (A) may be used alone or in combination of two or more types.
  • the component (A) is a compound that has an ethylenically unsaturated group and thus exhibits photopolymerizability, in particular radical polymerizability.
  • the ethylenically unsaturated group contained in the component (A) include photopolymerizable functional groups such as a vinyl group, an allyl group, a propargyl group, a butenyl group, an ethynyl group, a phenylethynyl group, a maleimide group, a nadimide group, a (meth)acryloyl group, etc.
  • a (meth)acryloyl group is preferred from the viewpoints of reactivity and via resolution.
  • the component (A) has an acidic substituent from the viewpoint of enabling alkaline development.
  • the acidic substituent that the component (A) has include a carboxy group, a sulfonic acid group, a phenolic hydroxyl group, etc. Of these, from the viewpoint of via resolution, a carboxy group is preferred.
  • the acid value of component (A) is preferably 20 to 200 mgKOH/g, more preferably 40 to 180 mgKOH/g, further preferably 70 to 150 mgKOH/g, and particularly preferably 90 to 120 mgKOH/g.
  • component (A) When the acid value of component (A) is equal to or more than the lower limit, the solubility of the photosensitive resin film in a dilute alkaline solution tends to be excellent, and when it is equal to or less than the upper limit, the relative dielectric constant tends to be excellent.
  • the acid value of component (A) can be measured by the method described in the Examples. Two or more types of (A) components having different acid values may be used in combination. In this case, it is preferable that the weighted average acid value of the acid values of the two or more types of (A) components falls within any one of the above ranges.
  • the weight average molecular weight (Mw) of component (A) is preferably 600 to 30,000, more preferably 800 to 25,000, even more preferably 1,000 to 18,000, even more preferably 1,000 to 8,000, particularly preferably 1,200 to 5,000, and most preferably 1,200 to 3,500.
  • the weight average molecular weight (Mw) of component (A) is within the above range, the adhesive strength with copper plating, heat resistance, and insulation reliability tend to be excellent.
  • the weight average molecular weight is a value determined by gel permeation chromatography (GPC) using tetrahydrofuran as a solvent and converted into standard polystyrene, and in detail, is a value measured according to the method described in the examples.
  • the component (A) preferably contains an alicyclic skeleton.
  • an alicyclic skeleton having 5 to 20 ring carbon atoms is preferred, an alicyclic skeleton having 5 to 18 ring carbon atoms is more preferred, an alicyclic skeleton having 6 to 18 ring carbon atoms is even more preferred, an alicyclic skeleton having 8 to 14 ring carbon atoms is particularly preferred, and an alicyclic skeleton having 8 to 12 ring carbon atoms is most preferred.
  • the alicyclic skeleton preferably consists of two or more rings, more preferably consists of two to four rings, and even more preferably consists of three rings.
  • Examples of alicyclic skeletons having two or more rings include a norbornane skeleton, a decalin skeleton, a bicycloundecane skeleton, and a saturated dicyclopentadiene skeleton.
  • a saturated dicyclopentadiene skeleton is preferred.
  • the component (A) preferably contains an alicyclic skeleton represented by the following general formula (A-1).
  • R A1 represents an alkyl group having 1 to 12 carbon atoms and may be substituted anywhere in the alicyclic skeleton.
  • m 1 is an integer of 0 to 6. * represents a bonding site to another structure.
  • examples of the alkyl group having 1 to 12 carbon atoms represented by R A1 include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a t-butyl group, an n-pentyl group, etc.
  • an alkyl group having 1 to 6 carbon atoms is preferable, an alkyl group having 1 to 3 carbon atoms is more preferable, and a methyl group is further preferable.
  • m1 is an integer of 0 to 6, preferably an integer of 0 to 2, and more preferably 0.
  • the multiple R A1 may be the same or different from each other. Furthermore, the multiple R A1 may be substituted on the same carbon atom or on different carbon atoms, to the extent possible.
  • * denotes a bonding site to another structure, and may be bonded to any carbon atom on the alicyclic skeleton. However, it is preferable that the bond is formed at a carbon atom at a site represented by 1 or 2, and at a carbon atom at a site represented by 3 or 4 in the following general formula (A-1').
  • the (A) component is preferably an acid-modified vinyl-group-containing epoxy resin obtained by reacting (a1) an epoxy resin with (a2) an ethylenically unsaturated group-containing organic acid (hereinafter sometimes referred to as (A') component) with (a3) a saturated or unsaturated group-containing polybasic acid anhydride.
  • the term "acid-modified” in the acid-modified vinyl-group-containing epoxy resin means that it has an acidic substituent
  • "vinyl group” means that it has an ethylenically unsaturated group
  • "epoxy resin” means that an epoxy resin is used as a raw material, and the acid-modified vinyl-group-containing epoxy resin does not necessarily have to have an epoxy group, and may not have an epoxy group.
  • preferred embodiments of the component (A) obtained from (a1) an epoxy resin, (a2) an ethylenically unsaturated group-containing organic acid, and (a3) a saturated or unsaturated group-containing polybasic acid anhydride will be described.
  • the (a1) epoxy resin is preferably an epoxy resin having two or more epoxy groups.
  • the epoxy resin (a1) may be used alone or in combination of two or more kinds.
  • Epoxy resins are classified into glycidyl ether type epoxy resins, glycidyl amine type epoxy resins, glycidyl ester type epoxy resins, etc. Among these, glycidyl ether type epoxy resins are preferred.
  • Epoxy resins can be classified into various epoxy resins based on the difference in the main skeleton, such as epoxy resins having an alicyclic skeleton, novolac type epoxy resins, bisphenol type epoxy resins, aralkyl type epoxy resins, and other epoxy resins. Among these, epoxy resins having an alicyclic skeleton and novolac type epoxy resins are preferred.
  • Epoxy resin with alicyclic skeleton The alicyclic skeleton of the epoxy resin having an alicyclic skeleton is explained in the same manner as the alicyclic skeleton of the component (A) described above, and preferred embodiments are also the same.
  • an epoxy resin represented by the following general formula (A-2) is preferred.
  • R A1 represents an alkyl group having 1 to 12 carbon atoms and may be substituted anywhere in the alicyclic skeleton.
  • R A2 represents an alkyl group having 1 to 12 carbon atoms.
  • m 1 is an integer of 0 to 6
  • m 2 is an integer of 0 to 3
  • n is a number of 0 to 50.
  • R A1 is the same as R A1 in formula (A-1), and the preferred embodiments are also the same.
  • Examples of the alkyl group having 1 to 12 carbon atoms represented by R in general formula (A-2) include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a t-butyl group, an n-pentyl group, etc.
  • the alkyl group an alkyl group having 1 to 6 carbon atoms is preferable, an alkyl group having 1 to 3 carbon atoms is more preferable, and a methyl group is further preferable.
  • n in formula (A-2) is the same as m1 in formula (A-1), and the preferred embodiments are also the same.
  • m2 represents an integer of 0 to 3, preferably 0 or 1, and more preferably 0.
  • n represents the repeating number of the structural unit in parentheses and is a number from 0 to 50.
  • an epoxy resin is a mixture of resins having different repeating numbers of the structural unit in parentheses, and in that case, n represents the average value of the mixture.
  • a number from 0 to 30 is preferable as n.
  • epoxy resin having an alicyclic skeleton commercially available products may be used, such as XD-1000 (trade name, manufactured by Nippon Kayaku Co., Ltd.) and EPICLON (registered trademark) HP-7200 (trade name, manufactured by DIC Corporation).
  • novolac type epoxy resin examples include bisphenol novolac type epoxy resins such as bisphenol A novolac type epoxy resin, bisphenol F novolac type epoxy resin, and bisphenol S novolac type epoxy resin; phenol novolac type epoxy resin, cresol novolac type epoxy resin, biphenyl novolac type epoxy resin, and naphthol novolac type epoxy resin.
  • the novolac type epoxy resin an epoxy resin having a structural unit represented by the following general formula (A-3) is preferable.
  • R A3 represents a hydrogen atom or a methyl group
  • Y A1 each independently represents a hydrogen atom or a glycidyl group.
  • the two R A3 may be the same or different.
  • At least one of the two Y A1 represents a glycidyl group.
  • each of R A3 is a hydrogen atom
  • each of Y A1 is a glycidyl group.
  • the number of structural units in the epoxy resin (a1) having a structural unit represented by general formula (A-3) is a number of 1 or more, preferably a number from 10 to 100, more preferably a number from 15 to 80, and further preferably a number from 15 to 70. When the number of structural units is within the above range, the adhesive strength with copper plating, heat resistance, and insulation reliability tend to be improved.
  • Examples of the bisphenol type epoxy resin include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, 3,3',5,5'-tetramethyl-4,4'-diglycidyloxydiphenylmethane, and the like.
  • Examples of the aralkyl type epoxy resin include phenol aralkyl type epoxy resin, biphenyl aralkyl type epoxy resin, and naphthol aralkyl type epoxy resin.
  • epoxy resins include stilbene type epoxy resins, naphthalene skeleton-containing epoxy resins, biphenyl type epoxy resins, dihydroanthracene type epoxy resins, cyclohexanedimethanol type epoxy resins, trimethylol type epoxy resins, alicyclic epoxy resins, aliphatic linear epoxy resins, heterocyclic epoxy resins, spiro ring-containing epoxy resins, and rubber-modified epoxy resins.
  • the ethylenically unsaturated group-containing organic acid (a2) is preferably an ethylenically unsaturated group-containing monocarboxylic acid.
  • Examples of the ethylenically unsaturated group contained in the component (a2) include the same ethylenically unsaturated groups as those exemplified as the ethylenically unsaturated group contained in the component (A).
  • the component (a2) examples include acrylic acid, acrylic acid dimers, methacrylic acid, ⁇ -furfurylacrylic acid, ⁇ -styrylacrylic acid, cinnamic acid, crotonic acid, and ⁇ -cyanocinnamic acid and other acrylic acid derivatives; Half-ester compounds which are reaction products of hydroxyl-containing acrylates and dibasic acid anhydrides; half-ester compounds which are reaction products of vinyl-containing monoglycidyl ethers or vinyl-containing monoglycidyl esters and dibasic acid anhydrides, etc. Examples include: The component (a2) may be used alone or in combination of two or more types.
  • the half-ester compound is obtained by reacting one or more ethylenically unsaturated group-containing compounds selected from the group consisting of hydroxyl group-containing acrylates, vinyl group-containing monoglycidyl ethers, and vinyl group-containing monoglycidyl esters with a dibasic acid anhydride.
  • the reaction is preferably carried out by reacting the ethylenically unsaturated group-containing compound with the dibasic acid anhydride in equimolar amounts.
  • Examples of the hydroxyl group-containing acrylate used in the synthesis of the semi-ester compound include hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate, polyethylene glycol mono(meth)acrylate, trimethylolpropane di(meth)acrylate, pentaerythritol tri(meth)acrylate, and dipentaerythritol penta(meth)acrylate.
  • Examples of vinyl group-containing monoglycidyl ethers include glycidyl (meth)acrylate.
  • the dibasic acid anhydride used in the synthesis of the half ester compound may contain either a saturated group or an unsaturated group.
  • dibasic acid anhydrides include succinic anhydride, maleic anhydride, tetrahydrophthalic anhydride, phthalic anhydride, methyltetrahydrophthalic anhydride, ethyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, ethylhexahydrophthalic anhydride, and itaconic anhydride.
  • the amount of component (a2) used per equivalent of epoxy groups in component (a1) is preferably 0.6 to 1.05 equivalents, more preferably 0.7 to 1.02 equivalents, and even more preferably 0.8 to 1.0 equivalents.
  • the components (a1) and (a2) are preferably dissolved in an organic solvent and reacted with each other.
  • the organic solvent include ketones such as methyl ethyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene; glycol ether compounds such as methyl cellosolve, butyl cellosolve, methyl carbitol, butyl carbitol, propylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol diethyl ether, and triethylene glycol monoethyl ether; esters such as ethyl acetate, butyl acetate, butyl cellosolve acetate, and carbitol acetate; aliphatic hydrocarbons such as octane and decane; and petroleum solvents such as petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha, and
  • a catalyst for promoting the reaction.
  • the catalyst include amine-based catalysts such as triethylamine and benzylmethylamine; quaternary ammonium salt catalysts such as methyltriethylammonium chloride, benzyltrimethylammonium chloride, benzyltrimethylammonium bromide and benzyltrimethylammonium iodide; and phosphine-based catalysts such as triphenylphosphine. Among these, phosphine-based catalysts are preferred, and triphenylphosphine is more preferred.
  • the catalyst may be used alone or in combination of two or more.
  • the amount of the catalyst used is preferably 0.01 to 10 parts by mass, more preferably 0.05 to 5 parts by mass, and even more preferably 0.1 to 2 parts by mass, per 100 parts by mass of the total of the components (a1) and (a2), from the viewpoint of obtaining an appropriate reaction rate.
  • a polymerization inhibitor for the purpose of preventing polymerization during the reaction.
  • the polymerization inhibitor include hydroquinone, methylhydroquinone, hydroquinone monomethyl ether, catechol, pyrogallol, etc.
  • the polymerization inhibitor may be used alone or in combination of two or more kinds.
  • the amount used is preferably 0.01 to 1 part by mass, more preferably 0.02 to 0.8 parts by mass, and even more preferably 0.1 to 0.5 parts by mass, per 100 parts by mass of the total of the components (a1) and (a2).
  • the reaction temperature between components (a1) and (a2) is preferably 60 to 150°C, more preferably 80 to 120°C, and even more preferably 90 to 110°C, from the viewpoint of ensuring sufficient reactivity and allowing the reaction to proceed homogeneously.
  • the (A') component obtained by reacting the (a1) component with the (a2) component has a hydroxyl group formed by a ring-opening addition reaction between the epoxy group of the (a1) component and the carboxyl group of the (a2) component.
  • an acid-modified vinyl group-containing epoxy resin can be obtained in which the hydroxyl group of the (A') component (including the hydroxyl group originally present in the (a1) component) and the acid anhydride group of the (a3) component are semi-esterified.
  • the (a3) component may contain a saturated group or an unsaturated group.
  • examples of the (a3) component include succinic anhydride, maleic anhydride, tetrahydrophthalic anhydride, phthalic anhydride, methyltetrahydrophthalic anhydride, ethyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, ethylhexahydrophthalic anhydride, and itaconic anhydride.
  • tetrahydrophthalic anhydride is preferred from the viewpoint of via resolution.
  • the (a3) component may be used alone or in combination of two or more.
  • the acid value of the acid-modified vinyl group-containing epoxy resin can be adjusted by reacting 0.1 to 1.0 equivalent of component (a3) with 1 equivalent of hydroxyl groups in component (A').
  • the reaction temperature between component (A') and component (a3) is preferably 50 to 150°C, more preferably 60 to 120°C, and even more preferably 70 to 100°C, from the viewpoint of ensuring sufficient reactivity and allowing the reaction to proceed homogeneously.
  • the content of component (A) in the photosensitive resin composition of this embodiment is not particularly limited, but from the viewpoints of heat resistance, dielectric constant, and chemical resistance, it is preferably 10 to 80 mass%, more preferably 10 to 60 mass%, even more preferably 15 to 45 mass%, particularly preferably 15 to 35 mass%, and most preferably 20 to 35 mass%, based on the total amount of resin components in the photosensitive resin composition.
  • the component (B) is a thermosetting resin.
  • the component (B) does not include the component (A).
  • thermosetting resins include epoxy resins, phenolic resins, unsaturated imide resins, cyanate resins, isocyanate resins, benzoxazine resins, oxetane resins, amino resins, unsaturated polyester resins, allyl resins, dicyclopentadiene resins, silicone resins
  • Examples of the thermosetting resin include triazine resin, melamine resin, etc.
  • the present invention is not particularly limited to these, and any known thermosetting resin can be used.
  • any known thermosetting resin can be used.
  • Epoxy resins are preferred.
  • the component (B) may be used alone or in combination of two or more types.
  • the epoxy resin is preferably an epoxy resin having two or more epoxy groups.
  • Epoxy resins are classified into glycidyl ether type epoxy resins, glycidyl amine type epoxy resins, glycidyl ester type epoxy resins, etc. Among these, glycidyl ether type epoxy resins are preferred.
  • Epoxy resins are also classified into various types based on the differences in the main skeleton, and each of the above types of epoxy resins is further classified as follows: Specifically, bisphenol-based epoxy resins such as bisphenol A type epoxy resin, bisphenol F type epoxy resin, and bisphenol S type epoxy resin; bisphenol-based novolac type epoxy resins such as bisphenol A novolac type epoxy resin and bisphenol F novolac type epoxy resin; novolac type epoxy resins other than the above bisphenol-based novolac type epoxy resins, such as phenol novolac type epoxy resin, cresol novolac type epoxy resin, and biphenyl novolac type epoxy resin; phenol aralkyl type epoxy resin; stilbene type epoxy resin; naphthol They are classified into naphthalene skeleton-containing epoxy resins such as novolac type epoxy resins, naphthol type epoxy resins, naphthol aralkyl type epoxy resins, and naphthylene ether type epoxy resins; biphenyl type epoxy resins;
  • the epoxy resin preferably contains at least one selected from the group consisting of bisphenol-based epoxy resins, naphthalene skeleton-containing epoxy resins, and biphenylaralkyl-type epoxy resins, particularly from the viewpoints of heat resistance, electrical insulation reliability, developability, and adhesive strength with copper plating, and more preferably contains at least one selected from the group consisting of naphthalene skeleton-containing epoxy resins and biphenylaralkyl-type epoxy resins.
  • the equivalent ratio [epoxy group/acidic substituent] of the acidic substituent of component (A) to the epoxy group of component (B) in the photosensitive resin composition of this embodiment is not particularly limited, but from the viewpoints of insulation reliability, relative dielectric constant, heat resistance, and adhesive strength with copper plating, it is preferably 0.5 to 6.0, more preferably 0.7 to 4.0, even more preferably 0.8 to 2.0, and particularly preferably 0.9 to 1.8.
  • the content of component (B) in the photosensitive resin composition of this embodiment is not particularly limited, but from the viewpoints of insulation reliability, relative dielectric constant, heat resistance, and adhesive strength with copper plating, it is preferably 1 to 50 mass %, more preferably 5 to 30 mass %, and even more preferably 10 to 25 mass %, based on the total amount of resin components in the photosensitive resin composition.
  • the photosensitive resin composition of the present embodiment further preferably contains a crosslinking agent as component (C).
  • the crosslinking agent is preferably a crosslinking agent having two or more ethylenically unsaturated groups and no acidic substituent.
  • the crosslinking agent reacts with the ethylenically unsaturated group of component (A) to increase the crosslinking density of the photosensitive resin film after curing. Therefore, the photosensitive resin composition of the present embodiment tends to further improve the heat resistance and the relative dielectric constant by containing a crosslinking agent.
  • the component (C) may be used alone or in combination of two or more types.
  • Examples of the component (C) include a bifunctional monomer having two ethylenically unsaturated groups and a polyfunctional monomer having three or more ethylenically unsaturated groups.
  • the component (C) preferably contains the polyfunctional monomer.
  • Examples of the ethylenically unsaturated group contained in the component (C) include the same as the ethylenically unsaturated group contained in the component (A), and the preferred examples are also the same.
  • bifunctional monomer examples include aliphatic di(meth)acrylates such as trimethylolpropane di(meth)acrylate, polypropylene glycol di(meth)acrylate, and polyethylene glycol di(meth)acrylate; di(meth)acrylates having an alicyclic skeleton such as dicyclopentadiene di(meth)acrylate and tricyclodecane dimethanol di(meth)acrylate; and aromatic di(meth)acrylates such as 2,2-bis(4-(meth)acryloxypolyethoxypolypropoxyphenyl)propane and bisphenol A diglycidyl ether di(meth)acrylate.
  • di(meth)acrylates having an alicyclic skeleton are preferred, and tricyclodecane dimethanol diacrylate is more preferred.
  • polyfunctional monomer examples include (meth)acrylate compounds having a skeleton derived from trimethylolpropane, such as trimethylolpropane tri(meth)acrylate; (meth)acrylate compounds having a skeleton derived from tetramethylolmethane, such as tetramethylolmethane tri(meth)acrylate and tetramethylolmethane tetra(meth)acrylate; (meth)acrylate compounds having a skeleton derived from pentaerythritol, such as pentaerythritol tri(meth)acrylate and pentaerythritol tetra(meth)acrylate; (meth)acrylate compounds having a skeleton derived from dipentaerythritol, such as dipentaerythritol penta(meth)acrylate and dipentaerythritol hexa(meth)acrylate; (meth)acrylate
  • a (meth)acrylate compound having a skeleton derived from trimethylolpropane is preferred, and trimethylolpropane tri(meth)acrylate is more preferred.
  • the "(meth)acrylate compound having a skeleton derived from XXX” (wherein XXX is the name of the compound) means an esterification product of XXX and (meth)acrylic acid, and the esterification product also includes a compound modified with an alkyleneoxy group.
  • the content of the crosslinking agent (C) is not particularly limited, but from the viewpoint of heat resistance and relative dielectric constant, it is preferably 10 to 85 parts by mass, more preferably 25 to 80 parts by mass, even more preferably 35 to 75 parts by mass, and particularly preferably 35 to 60 parts by mass, per 100 parts by mass of component (A).
  • the photosensitive resin composition of this embodiment preferably further contains an elastomer as component (D).
  • the photosensitive resin composition of this embodiment tends to further improve the adhesive strength with the copper plating.
  • the photosensitive resin composition of this embodiment tends to have an effect of suppressing "reduction in flexibility and adhesive strength with the copper plating" caused by distortion (internal stress) that may occur due to cure shrinkage of the component (A).
  • the elastomer (D) may be used alone or in combination of two or more kinds.
  • the elastomer (D) may have a reactive functional group at the molecular end or in the molecular chain.
  • the reactive functional group include an acid anhydride group, an epoxy group, a hydroxyl group, a carboxyl group, an amino group, an amide group, an isocyanato group, an acrylic group, a methacrylic group, a vinyl group, etc.
  • an acid anhydride group, an epoxy group, a hydroxyl group, a carboxyl group, an amino group, and an amide group are preferred, an acid anhydride group and an epoxy group are more preferred, and an acid anhydride group is even more preferred.
  • the acid anhydride group is preferably an acid anhydride group derived from phthalic anhydride, maleic anhydride, trimellitic anhydride, pyromellitic anhydride, hexahydrophthalic anhydride, tetrahydrophthalic anhydride, methylnadic anhydride, nadic anhydride, glutaric anhydride, dimethylglutaric anhydride, diethylglutaric anhydride, succinic anhydride, methylhexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, or the like, and more preferably an acid anhydride group derived from maleic anhydride.
  • the (D) elastomer has an acid anhydride group, from the viewpoints of via resolution and dielectric constant, the number of acid anhydride groups in one molecule is preferably 1 to 10, more preferably 3 to 10, and even more preferably 6 to 10.
  • the photosensitive resin composition of the present embodiment preferably contains, as the elastomer (D), an elastomer having an ethylenically unsaturated group and an acidic substituent.
  • the acidic substituent and the ethylenically unsaturated group include the same as those of the acidic substituent and the ethylenically unsaturated group contained in the component (A).
  • the elastomer (D) has the above-mentioned acid anhydride group as the acidic substituent and the below-mentioned 1,2-vinyl group as the ethylenically unsaturated group.
  • elastomers examples include polybutadiene-based elastomers, polyester-based elastomers, styrene-based elastomers, olefin-based elastomers, urethane-based elastomers, polyamide-based elastomers, acrylic-based elastomers, silicone-based elastomers, and derivatives of these elastomers.
  • polybutadiene-based elastomers are preferred from the viewpoints of improving the adhesive strength with copper plating, and further improving compatibility and solubility with resin components.
  • the polybutadiene elastomer examples include those containing 1,2-vinyl groups and having 1,4-trans structural units and 1,4-cis structural units.
  • the polybutadiene-based elastomer is preferably a polybutadiene-based elastomer having an acid anhydride group that has been modified with an acid anhydride, and more preferably a polybutadiene-based elastomer having an acid anhydride group derived from maleic anhydride.
  • Polybutadiene-based elastomers are commercially available, and specific examples thereof include “POLYVEST (registered trademark) MA75” and “POLYVEST (registered trademark) EP MA120” (all of which are product names manufactured by Evonik Corporation), "Ricon (registered trademark) 100", “Ricon (registered trademark) 130MA8", “Ricon (registered trademark) 131MA5", “Ricon (registered trademark) 131MA17”, and “Ricon (registered trademark) 184MA6” (all of which are product names manufactured by Cray Valley Corporation).
  • the polybutadiene-based elastomer may be polybutadiene having an epoxy group (hereinafter, may be referred to as epoxidized polybutadiene).
  • the epoxidized polybutadiene is preferably an epoxidized polybutadiene represented by the following general formula (D-1).
  • y represents the number of structural units in square brackets and is an integer of 10 to 250.
  • the structural units in the square brackets may be bonded in any order.
  • the structural unit shown on the left, the structural unit shown in the center, and the structural unit shown on the right may be interchanged, and when they are represented as (a), (b), and (c), respectively, various bonding orders are possible, such as -[(a)-(b)-(c)]-[(a)-(b)-(c)-]-, -[(a)-(c)-(b)]-[(a)-(c)-(b)-]-, -[(b)-(a)-(c)]-[(b)-(a)-(c)-]-, -[(a)-(b)-(c)]-[(c)-(b)-(a)-]-, -[(a)-(b)-(a)]-[(c)-(b)-(a)-]-, -[(a)-(b)-(a)]-[(c)
  • a is preferably 0.10 to 0.30
  • b is preferably 0.10 to 0.30
  • c is preferably 0.40 to 0.80
  • y is preferably an integer of 30 to 180.
  • polyester-based elastomers include those obtained by polycondensation of a dicarboxylic acid or a derivative thereof with a diol compound or a derivative thereof.
  • dicarboxylic acids include aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, and naphthalenedicarboxylic acid, and aromatic dicarboxylic acids in which the hydrogen atoms of the aromatic nuclei of these dicarboxylic acids are substituted with a methyl group, an ethyl group, a phenyl group, or the like; aliphatic dicarboxylic acids having 2 to 20 carbon atoms such as adipic acid, sebacic acid, and dodecanedicarboxylic acid; and alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid.
  • diol compound examples include aliphatic diols such as ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, and 1,10-decanediol; alicyclic diols such as 1,4-cyclohexanediol; and aromatic diols such as bisphenol A, bis(4-hydroxyphenyl)methane, bis(4-hydroxy-3-methylphenyl)propane, and resorcin.
  • aliphatic diols such as ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, and 1,10-decanediol
  • alicyclic diols such as 1,4-cyclohexanediol
  • aromatic diols such as bisphenol A, bis(4-hydroxyphenyl)methane, bis
  • a multiblock copolymer having an aromatic polyester (e.g., polybutylene terephthalate) portion as a hard segment component and an aliphatic polyester (e.g., polytetramethylene glycol) portion as a soft segment component is preferably used.
  • Multiblock copolymers are available in various grades depending on the types, ratios, and molecular weights of the hard and soft segments.
  • the number average molecular weight of the (D) elastomer is not particularly limited, but is preferably 10,000 to 80,000, may be 20,000 to 70,000, may be 30,000 to 65,000, or may be 40,000 to 60,000.
  • the number average molecular weight of the (D) elastomer is determined by gel permeation chromatography (GPC) using tetrahydrofuran as a solvent, and converted into standard polystyrene.
  • the content of the elastomer (D) is not particularly limited, but from the viewpoint of heat resistance and adhesive strength with copper plating, it is preferably 0.5 to 15 mass %, more preferably 1 to 10 mass %, even more preferably 1 to 8 mass %, and particularly preferably 3 to 8 mass %, based on the total amount of the resin components of the photosensitive resin composition.
  • the photosensitive resin composition of the present embodiment may further contain an organic filler as component (E).
  • the photosensitive resin composition of the present embodiment contains an organic filler (E).
  • the photosensitive resin composition and the photosensitive resin film tend to have a low specific gravity, and depending on the material, the relative dielectric constant tends to be further reduced.
  • the component (E) preferably contains resin particles formed from at least one selected from the group consisting of a resin having a fluorine atom, polyethylene, polypropylene, polystyrene, polyphenylene ether, and silicone.
  • the component (E) preferably contains resin particles formed from a resin having fluorine atoms, and more preferably contains resin particles formed from a polytetrafluoroethylene (PTFE) resin.
  • PTFE polytetrafluoroethylene
  • the volume average particle size of the resin particles is not particularly limited, but is preferably 20 to 1,000 nm, more preferably 30 to 800 nm, further preferably 50 to 500 nm, and particularly preferably 100 to 300 nm.
  • the method for measuring the volume average particle size is as described above.
  • the content of the organic filler (E) is not particularly limited, but is preferably 1 to 45 mass%, more preferably 3 to 40 mass%, even more preferably 5 to 30 mass%, and particularly preferably 10 to 30 mass%, based on the total amount of the resin components of the photosensitive resin composition.
  • the content of the organic filler (E) is equal to or more than the lower limit based on the total amount of the resin components of the photosensitive resin composition, the relative dielectric constant tends to be further reduced, and when it is equal to or less than the upper limit, the decrease in the adhesive strength with the copper plating tends to be suppressed.
  • the content of the resin having a fluorine atom is preferably 1 to 45 mass%, more preferably 3 to 40 mass%, even more preferably 5 to 30 mass%, and particularly preferably 10 to 30 mass%, based on the total amount of the resin components of the photosensitive resin composition.
  • the total amount of the (X) component and the (E) component is preferably 50% by volume or less, more preferably 45% by volume or less, and even more preferably 40% by volume or less, based on the total amount of the resin components of the photosensitive resin composition, from the viewpoint of adhesive strength with copper plating.
  • the lower limit of the total amount of the (X) component and the (E) component is preferably 2% by volume or more, more preferably 10% by volume or more, even more preferably 20% by volume or more, and particularly preferably 30% by volume or more.
  • the photosensitive resin composition of the present embodiment preferably further contains a curing agent as component (F).
  • a curing agent as component (F)
  • the photosensitive resin composition of the present embodiment tends to be able to further improve the heat resistance, the relative dielectric constant, and the like.
  • the curing agent (F) may be used alone or in combination of two or more kinds.
  • a curing agent for the (B) thermosetting resin may be used.
  • the (B) thermosetting resin is an epoxy resin
  • the epoxy resin curing agent include guanamines such as acetoguanamine and benzoguanamine; polyamines such as diaminodiphenylmethane, m-phenylenediamine, m-xylylenediamine, diaminodiphenylsulfone, dicyandiamide, urea, urea derivatives, melamine, and polybasic hydrazides; organic acid salts and/or epoxy adducts thereof; amine complexes of boron trifluoride; triazine derivatives such as ethyldiamino-S-triazine, 2,4-diamino-S-triazine, and 2,4-diamino-6-xylyl-S
  • the polyphenol may be, for example, a modified polyphenol modified with melamine, benzoguanamine, etc.
  • the hydroxyl equivalent of the polyphenol is not particularly limited, but is preferably 40 to 300 g/eq, may be 40 to 250 g/eq, may be 60 to 200 g/eq, may be 80 to 160 g/eq, or may be 100 to 140 g/eq.
  • the hydroxyl equivalent (g/eq) can be determined by titration using an acetylation method with acetic anhydride.
  • the content of the curing agent (F) is not particularly limited, but from the viewpoint of further improving the heat resistance and relative dielectric constant, it is preferably 0.01 to 10 mass %, more preferably 0.05 to 5 mass %, and even more preferably 0.1 to 1 mass %, based on the total amount of the resin components of the photosensitive resin composition.
  • the photosensitive resin composition of the present embodiment preferably further contains a curing accelerator as component (G).
  • a curing accelerator as component (G)
  • the photosensitive resin composition of the present embodiment tends to be able to further improve the heat resistance, the relative dielectric constant, and the like.
  • the curing accelerator (G) may be used alone or in combination of two or more kinds.
  • Examples of the curing accelerator include imidazole compounds such as 2-methylimidazole, 2-ethyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 2-phenylimidazole, 2-phenyl-1-benzyl-1H-imidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, and isocyanate masked imidazole (an addition reaction product of hexamethylene diisocyanate resin and 2-ethyl-4-methylimidazole); trimethylamine, N,N-dimethyloctylamine, N-benzyldimethylamine, pyridine, N-methylmorpholine, hexa(N-methyl)melamine, 2,4,6-tris(dimethylaminophenol), and tetramethylamine.
  • imidazole compounds such as 2-methylimidazole, 2-ethyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 2-phenylimidazole
  • tertiary amines such as ethylguanidine and m-aminophenol
  • organic phosphines such as tributylphosphine, triphenylphosphine and tris-2-cyanoethylphosphine
  • phosphonium salts such as tri-n-butyl(2,5-dihydroxyphenyl)phosphonium bromide and hexadecyltributylphosphonium chloride
  • quaternary ammonium salts such as benzyltrimethylammonium chloride and phenyltributylammonium chloride
  • the above-mentioned polybasic acid anhydrides diphenyliodonium tetrafluoroborate, triphenylsulfonium hexafluoroantimonate, 2,4,6-triphenylthiopyrylium hexafluorophosphate, and the like.
  • imidazole-based compounds are preferred from the
  • the content of the curing accelerator (G) is not particularly limited, but from the viewpoint of further improving the heat resistance and relative dielectric constant, it is preferably 0.01 to 10 mass %, more preferably 0.05 to 5 mass %, and even more preferably 0.1 to 2 mass %, based on the total amount of the resin components of the photosensitive resin composition.
  • the photosensitive resin composition of the present embodiment preferably further contains a photopolymerization initiator as component (H).
  • a photopolymerization initiator As component (H), the photosensitive resin composition of the present embodiment tends to further improve the resolution of vias.
  • the photopolymerization initiator (H) may be used alone or in combination of two or more. From the viewpoint of via resolution, the photosensitive resin composition of the present embodiment preferably contains two or more types of the component (H).
  • the photopolymerization initiator (H) is not particularly limited as long as it can photopolymerize an ethylenically unsaturated group, and can be appropriately selected from commonly used photopolymerization initiators.
  • Photopolymerization initiators include benzoin-based compounds such as benzoin, benzoin methyl ether, and benzoin isopropyl ether; acetophenone-based compounds such as acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 1-hydroxycyclohexyl phenyl ketone, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-1-butanone, 2-[4-(methylthio)benzoyl]-2-(4-morpholinyl)propane, and N,N-dimethylaminoacetophenone; 2-methylanthraquinone, 2-
  • oxime ester compounds and acylphosphine oxide compounds are preferred, with 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone 1-(O-acetyloxime) and bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide being more preferred.
  • Oxime ester compounds have the advantage of improving photocurability, while acylphosphine oxide compounds have the advantage of improving the degree of curing at the bottom of the cured product obtained by curing a photosensitive resin film, and suppressing undercut.
  • the combined use of oxime ester compounds and acylphosphine oxide compounds tends to further increase the resolution of vias.
  • the content of the photopolymerization initiator (H) is not particularly limited, but is preferably 0.01 to 20 mass%, more preferably 0.05 to 10 mass%, even more preferably 0.05 to 3 mass%, and particularly preferably 0.05 to 1.0 mass%, based on the total amount of the resin components of the photosensitive resin composition. If the content of the photopolymerization initiator (H) is equal to or greater than the lower limit, there is a tendency for the exposed portion to be less likely to dissolve during development, and if it is equal to or less than the upper limit, there is a tendency for heat resistance to be improved.
  • the photosensitive resin composition of the present embodiment may contain a photosensitizer as the component (I) as necessary.
  • the photosensitizer (I) may be used alone or in combination of two or more. From the viewpoint of via resolution, the photosensitive resin composition of the present embodiment may contain two or more types of component (I).
  • photosensitizers include thioxanthone compounds such as 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, and 2,4-diisopropylthioxanthone; tertiary amines such as trialkylamines and triethanolamine; dialkylaminobenzoic acid alkyl esters such as ethyl N,N-dimethylaminobenzoate and amyl N,N-dimethylaminobenzoate; bis(dialkylamino)benzophenones such as 4,4'-bis(dimethylamino)benzophenone and 4,4'-bis(diethylamino)benzophenone; phosphine compounds such as triphenylphosphine; toluidine compounds such as N,N-dimethyltoluidine; anthracene compounds such as 9,10-dimethoxyanthrac
  • the content of the photosensitizer (I) is not particularly limited, but is preferably 0.01 to 5 mass%, more preferably 0.05 to 3 mass%, even more preferably 0.1 to 1.5 mass%, and particularly preferably 0.1 to 1.0 mass%, based on the total amount of resin components in the photosensitive resin composition. If the content of the photosensitizer (I) is equal to or greater than the lower limit, the degree of cure of the bottom of the cured product obtained by curing the photosensitive resin film tends to be sufficiently high, and if it is equal to or less than the upper limit, the degree of cure of the bottom of the cured product tends to be appropriately low.
  • the photosensitive resin composition of the present embodiment may contain, as necessary, various known and commonly used additives, such as an inorganic filler other than the component (X); a pigment such as phthalocyanine blue, phthalocyanine green, iodine green, diazo yellow, crystal violet, titanium oxide, carbon black, or naphthalene black; an adhesion aid such as melamine; a foam stabilizer such as a silicone compound; a polymerization inhibitor; a thickener; and a flame retardant.
  • an inorganic filler other than the component (X) such as phthalocyanine blue, phthalocyanine green, iodine green, diazo yellow, crystal violet, titanium oxide, carbon black, or naphthalene black
  • an adhesion aid such as melamine
  • a foam stabilizer such as a silicone compound
  • a polymerization inhibitor such as a polymerization inhibitor
  • a thickener such as a flame retardant.
  • each content of these (J) additives may be appropriately adjusted depending on each purpose, but each content is preferably 0.01 to 5 mass %, alternatively 0.05 to 3 mass %, or alternatively 0.1 to 1 mass % based on the total amount of the resin components in the photosensitive resin composition.
  • the photosensitive resin composition of the present embodiment may contain a diluent as necessary.
  • a diluent an organic solvent or the like can be used.
  • the organic solvent include ketones such as methyl ethyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene; glycol ether compounds such as methyl cellosolve, butyl cellosolve, methyl carbitol, butyl carbitol, propylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol diethyl ether, and triethylene glycol monoethyl ether; esters such as ethyl acetate, butyl acetate, propylene glycol monoethyl ether acetate, butyl cellosolve acetate, and carbitol acetate; aliphatic hydrocarbons such as
  • the content of the diluent may be appropriately selected for the purpose of adjusting the concentration of the total solid content in the photosensitive resin composition to a range of preferably 40 to 90 mass%, more preferably 50 to 85 mass%, and even more preferably 60 to 80 mass%.
  • the amount of diluent used to within the above range the coatability of the photosensitive resin composition is improved, making it possible to form a more precise pattern.
  • the photosensitive resin composition of the present embodiment can be obtained by kneading and mixing the components using a roll mill, a bead mill, or the like.
  • the photosensitive resin composition of the present embodiment may be used in a liquid state (liquid type) or in a film state (film type).
  • the method for applying the photosensitive resin composition of the present embodiment is not particularly limited, and examples of the application method include printing, spin coating, spray coating, jet dispensing, inkjet, dip coating, etc. Among these, printing and spin coating are preferred from the viewpoint of more easily forming the photosensitive layer.
  • a photosensitive resin film When used in the form of a film, it can be used in the form of a photosensitive resin film described later, for example, and in this case, a photosensitive layer of a desired thickness can be formed by laminating it on a carrier film using a laminator, etc. Note that using it in the form of a film is preferable because it increases the production efficiency of multilayer printed wiring boards.
  • the photosensitive resin composition of this embodiment is suitable for via formation by photolithography (also referred to as photovia formation), so this disclosure also provides a photosensitive resin composition for photovia formation that is made of the photosensitive resin composition of this embodiment.
  • the photosensitive resin film of the present embodiment is formed using the photosensitive resin composition of the present embodiment.
  • the photosensitive resin film is useful as a photosensitive layer for forming an interlayer insulating layer.
  • the photosensitive resin film of the present embodiment may be provided on a carrier film.
  • the photosensitive resin film of the present embodiment can be formed, for example, by applying the photosensitive resin composition of the present embodiment onto a carrier film using a known coating device such as a comma coater, a bar coater, a kiss coater, a roll coater, a gravure coater, or a die coater, and then drying the applied composition.
  • a known coating device such as a comma coater, a bar coater, a kiss coater, a roll coater, a gravure coater, or a die coater, and then drying the applied composition.
  • the carrier film include polyesters such as polyethylene terephthalate and polybutylene terephthalate, and polyolefins such as polypropylene and polyethylene.
  • the thickness of the carrier film is preferably 5 to 100 ⁇ m, more preferably 10 to 60 ⁇ m, and even more preferably 15 to 45 ⁇ m.
  • the photosensitive resin film of this embodiment can also have a protective film on the surface opposite to the surface in contact with the carrier film.
  • a protective film a polymer film such as polyethylene or polypropylene can be used.
  • the same polymer film as the carrier film described above may be used, or a different polymer film may be used.
  • the coating film formed by applying the photosensitive resin composition can be dried using hot air drying, a dryer using far infrared rays, or a dryer using near infrared rays.
  • the drying temperature is preferably 60 to 150°C, more preferably 70 to 120°C, and even more preferably 80 to 110°C.
  • the drying time is preferably 1 to 60 minutes, more preferably 2 to 30 minutes, and even more preferably 5 to 20 minutes.
  • the content of the remaining diluent in the photosensitive resin film after drying is preferably 3 mass% or less, more preferably 2 mass% or less, and even more preferably 1 mass% or less, from the viewpoint of avoiding diffusion of the diluent during the manufacturing process of the multilayer printed wiring board.
  • the thickness (thickness after drying) of the photosensitive resin film (photosensitive layer) is not particularly limited, but from the viewpoint of making the multilayer printed wiring board thinner, it is preferably 1 to 100 ⁇ m, more preferably 3 to 50 ⁇ m, and even more preferably 5 to 40 ⁇ m.
  • the photosensitive resin film of this embodiment has excellent via resolution and adhesive strength with copper plating, making it suitable as an interlayer insulating layer for multilayer printed wiring boards.
  • the multilayer printed wiring board of the present embodiment contains an interlayer insulating layer formed using the photosensitive resin composition of the present embodiment or the photosensitive resin film of the present embodiment.
  • the expression "containing an interlayer insulating layer” includes a case where the interlayer insulating layer is contained as it is, and a case where the interlayer insulating layer is contained after being subjected to, for example, processing such as via formation, various treatments such as roughening treatment, wiring formation, etc.
  • the multilayer printed wiring board of this embodiment is not particularly limited in its manufacturing method as long as it includes a step of forming an interlayer insulating layer using the photosensitive resin composition or photosensitive resin film of this embodiment, and can be more easily manufactured, for example, by the following manufacturing method for the multilayer printed wiring board of this embodiment.
  • Multilayer printed wiring board 100A can be manufactured, for example, by a manufacturing method including the following steps (1) to (4) (wherein (3) is optional).
  • photovia forming step (2) Forming an interlayer insulating layer having vias by exposing and developing the photosensitive resin film laminated in step (1) (hereinafter referred to as "photovia forming step (2)”).
  • circuit pattern forming step (4) Forming a circuit pattern on the interlayer insulating layer (hereinafter referred to as “circuit pattern forming step (4)").
  • circuit pattern forming step (4) Forming a circuit pattern on the interlayer insulating layer (hereinafter referred to as “circuit pattern forming step (4)").
  • the lamination step (1) is a step of laminating the photosensitive resin film of this embodiment onto one or both sides of a circuit board (substrate 101 having a circuit pattern 102) using a vacuum laminator.
  • the vacuum laminator include a vacuum applicator manufactured by Nichigo-Morton Co., Ltd., a vacuum pressure laminator manufactured by Meiki Co., Ltd., a roll-type dry coater manufactured by Hitachi, Ltd., and a vacuum laminator manufactured by Showa Denko Materials Electronics K.K.
  • the photosensitive resin film When a protective film is provided on the photosensitive resin film, after peeling or removing the protective film, the photosensitive resin film can be laminated to the circuit board by pressing and heating while being in contact with the circuit board.
  • the lamination can be carried out, for example, after preheating the photosensitive resin film and the circuit board as necessary, under reduced pressure at a pressure of 70 to 130° C., a pressure of 0.1 to 1.0 MPa, and an air pressure of 20 mmHg (26.7 hPa) or less, but is not particularly limited to these conditions.
  • the lamination method may be a batch method or a continuous method using a roll.
  • the photosensitive resin film laminated to the circuit board is cooled to about room temperature to form the interlayer insulating layer 103. If the photosensitive resin film has a carrier film, the carrier film may be peeled off at this stage, or may be peeled off after exposure, as described below.
  • Photovia Forming Process (2) In the photovia forming process (2), at least a part of the photosensitive resin film laminated on the circuit board is exposed to light, and then developed. By exposure, the part irradiated with active light is photocured to form a pattern.
  • the exposure method There is no particular limitation on the exposure method, and for example, a method of irradiating active light in an image-like manner by passing through a negative or positive mask pattern called artwork (mask exposure method) may be adopted, or a method of irradiating active light in an image-like manner by a direct writing exposure method such as LDI (Laser Direct Imaging) exposure method or DLP (Digital Light Processing) exposure method may be adopted.
  • LDI Laser Direct Imaging
  • DLP Digital Light Processing
  • the light source include gas lasers such as carbon arc lamps, mercury vapor arc lamps, high pressure mercury lamps, xenon lamps, and argon lasers; solid-state lasers such as YAG lasers; and semiconductor lasers that effectively radiate ultraviolet or visible light.
  • gas lasers such as carbon arc lamps, mercury vapor arc lamps, high pressure mercury lamps, xenon lamps, and argon lasers
  • solid-state lasers such as YAG lasers
  • semiconductor lasers that effectively radiate ultraviolet or visible light.
  • the exposure amount is appropriately selected depending on the light source used and the thickness of the photosensitive layer, and for example, in the case of ultraviolet irradiation from a high pressure mercury lamp, when the photosensitive layer has a thickness of 1 to 100 ⁇ m, it is usually preferably about 10 to 1,000 mJ/cm 2 , more preferably 50 to 700 mJ/cm 2 , even more preferably 150 to 550 mJ/cm 2 , and particularly preferably 250 to 500 mJ/cm 2 .
  • the uncured portions of the photosensitive layer are removed from the substrate, and the photocured portions are formed on the substrate as an interlayer insulating layer.
  • a carrier film is present on the photosensitive layer, the carrier film is removed before removing (developing) the unexposed portion.
  • the developing method includes wet development and dry development, either of which may be adopted, but wet development is widely used and can be adopted in the present embodiment.
  • wet development a developer corresponding to the photosensitive resin composition is used to develop the photosensitive resin composition by a known development method. Examples of the development method include a dip method, a battle method, a spray method, a brushing method, a slapping method, a scraping method, a swing immersion method, and the like.
  • the spray method is preferred, and among the spray methods, the high pressure spray method is more preferred.
  • the development may be performed by one method, or may be performed by combining two or more methods.
  • the composition of the developer is appropriately selected depending on the composition of the photosensitive resin composition. Examples of the developer include an alkaline aqueous solution, a water-based developer, and an organic solvent-based developer, and among these, an alkaline aqueous solution is preferred.
  • a post UV cure with an exposure amount of about 0.2 to 10 J/cm2 (preferably 0.5 to 5 J/ cm2 ) and a post thermal cure at a temperature of about 60 to 250°C (preferably 120 to 200°C) may be performed as necessary to further harden the interlayer insulating layer, and further hardening is also preferred.
  • a post UV cure with an exposure amount of about 0.2 to 10 J/cm2 (preferably 0.5 to 5 J/ cm2 ) and a post thermal cure at a temperature of about 60 to 250°C (preferably 120 to 200°C) may be performed as necessary to further harden the interlayer insulating layer, and further hardening is also preferred.
  • the shape of the vias there is no particular limitation on the shape of the vias, and examples of the cross-sectional shape include a rectangle and an inverted trapezoid (the upper side is longer than the lower side), and examples of the shape as viewed from the front (the direction from which the via bottom is visible) include a circle and a rectangle.
  • a via having a cross-sectional shape of an inverted trapezoid (the upper side is longer than the lower side) can be formed, which is preferable because it increases the adhesion of copper plating to the via wall surface.
  • the size (diameter) of the via 104 formed by this process can be less than 40 ⁇ m, and can also be 35 ⁇ m or less or 30 ⁇ m or less, which is smaller than the size of a via created by laser processing. There is no particular limit to the lower limit of the size (diameter) of the via formed by this process, but it may be 15 ⁇ m or more, or 20 ⁇ m or more. However, the size (diameter) of the vias 104 formed in this process is not limited to less than 40 ⁇ m, and may be arbitrarily selected within the range of, for example, 15 to 300 ⁇ m.
  • a roughening treatment is performed on the surfaces of the vias and the interlayer insulating layer using a roughening liquid. If a smear occurs in the photovia formation step (2), the smear may be removed by the roughening liquid.
  • the roughening treatment and the removal of the smear (desmear) can be performed simultaneously.
  • the roughening solution include a chromium/sulfuric acid roughening solution, an alkaline permanganate roughening solution (for example, a sodium permanganate roughening solution), and a sodium fluoride/chromium/sulfuric acid roughening solution.
  • the roughening treatment forms uneven anchors on the surface of the via and the interlayer insulating layer.
  • the circuit pattern forming step (4) is a step of forming a circuit pattern on the interlayer insulating layer after the roughening treatment step (3). From the viewpoint of forming fine wiring, it is preferable to form the circuit pattern by a semi-additive process, which forms the circuit pattern and also provides electrical continuity through the vias. In the semi-additive process, first, the via bottom, via wall surface, and the entire surface of the interlayer insulating layer after the roughening process (3) are subjected to electroless copper plating using a palladium catalyst or the like to form a seed layer 105.
  • the seed layer 105 is for forming a power supply layer for electrolytic copper plating, and is preferably formed to a thickness of about 0.1 to 2.0 ⁇ m. If the seed layer 105 has a thickness of 0.1 ⁇ m or more, there is a tendency to suppress a decrease in connection reliability during electrolytic copper plating, and if it is 2.0 ⁇ m or less, there is no need to increase the amount of etching when flash etching the seed layer between wirings, and there is a tendency to suppress damage to wiring during etching.
  • the electroless copper plating process is carried out by depositing metallic copper on the surface of the vias and the interlayer insulating layer through a reaction between copper ions and a reducing agent.
  • the electroless plating method and the electrolytic plating method may be any known method and are not particularly limited.
  • As the electroless copper plating solution a commercially available product can be used, and examples of the commercially available product include "MSK-DK” manufactured by Atotech Japan KK and "ThruCup (registered trademark) PEA series” manufactured by Uemura Kogyo Co., Ltd.
  • a dry film resist is thermocompressed onto the electroless copper plating using a roll laminator.
  • the thickness of the dry film resist must be greater than the wiring height after electrolytic copper plating, and from this viewpoint, a dry film resist having a thickness of 5 to 30 ⁇ m is preferred.
  • the dry film resist the "Photec (registered trademark)" series manufactured by Showa Denko Materials Co., Ltd., or the like is used.
  • the dry film resist is thermocompressed, the dry film resist is exposed to light, for example, through a mask on which a desired wiring pattern is drawn. The exposure can be performed using the same device and light source as those that can be used when forming vias in the photosensitive resin film.
  • the dry film resist is developed using an alkaline aqueous solution, and the unexposed parts are removed to form a resist pattern 106. Thereafter, if necessary, a process of removing development residues of the dry film resist using plasma or the like may be performed. After development, electrolytic copper plating is performed to form a copper circuit layer (circuit pattern) 107 and to fill vias.
  • the dry film resist is stripped using an alkaline aqueous solution or an amine-based stripper. After the dry film resist is stripped, the seed layer between the wiring is removed (flash etching). Flash etching is performed using an acidic solution such as sulfuric acid and hydrogen peroxide, and an oxidizing solution. After flash etching, palladium and other materials adhering to the portions between the wiring are removed as necessary. Palladium can be removed preferably using an acidic solution such as nitric acid or hydrochloric acid.
  • a post-baking process is preferably performed.
  • the post-baking process can sufficiently heat-cure unreacted thermosetting components, which tends to improve the insulation reliability, curing characteristics, and adhesive strength with copper plating.
  • the heat-curing conditions vary depending on the type of resin composition, but a curing temperature of 150 to 240°C and a curing time of 15 to 100 minutes are preferable.
  • the post-baking process completes the manufacturing process of the multilayer printed wiring board 100A using the photovia method, but the substrate is manufactured by repeating this process according to the number of interlayer insulating layers required. Then, a solder resist layer 108 is preferably formed on the outermost layer.
  • the above describes a method for manufacturing a multilayer printed wiring board in which vias are formed using the photosensitive resin composition of this embodiment.
  • the photosensitive resin composition of this embodiment has excellent pattern resolution, it is also suitable for forming cavities for incorporating chips or passive elements, for example.
  • the cavities can be suitably formed, for example, by forming a drawing pattern when exposing the photosensitive resin film to light in the above description of the multilayer printed wiring board, so that the desired cavity can be formed.
  • the photosensitive resin composition of this embodiment is also useful as a solder resist.
  • the present disclosure also provides a semiconductor package including the multilayer printed wiring board of the present embodiment and a semiconductor element.
  • the semiconductor package of the present embodiment can be manufactured by mounting a semiconductor element such as a semiconductor chip or memory at a predetermined position on the multilayer printed wiring board of the present embodiment, and then sealing the semiconductor element with a sealing resin or the like.
  • the present embodiment will be described in more detail below with reference to examples, but the present disclosure is not limited to these examples.
  • the acid value and weight average molecular weight of component (A) were measured according to the following method, and the true densities of components (X), (X') and (E) were measured according to the following method.
  • the photosensitive resin compositions obtained in each example were evaluated for their properties by the methods shown below.
  • the acid value of component (A) was calculated from the amount of aqueous potassium hydroxide solution required to neutralize component (A).
  • the weight average molecular weight of the component (A) was measured using the following GPC measuring device and measuring conditions, and the value converted using the calibration curve of standard polystyrene was used as the weight average molecular weight.
  • the calibration curve was created using a 5-sample set of standard polystyrene ("PStQuick MP-H" and "PStQuick B", manufactured by Tosoh Corporation).
  • GPC measuring device High-speed GPC apparatus "HCL-8320GPC", detector is differential refractometer or UV, manufactured by Tosoh Corporation Column: Column TSKgel SuperMultipore HZ-H (column length: 15 cm, column inner diameter: 4.6 mm), manufactured by Tosoh Corporation (measurement conditions) Solvent: Tetrahydrofuran (THF) Measurement temperature: 40°C Flow rate: 0.35 ml/min Sample concentration: 10 mg/5 ml THF Injection volume: 20 ⁇ l
  • component (X) or (X') was placed in a mortar and ground with a pestle to obtain component (X) or (X') having a particle size of 0.1 ⁇ m or less.
  • the ground component (X) or (X') was filled to 80% in a 1 cm3 cell of a dry automatic density meter "AccuPycII 1340" (manufactured by Shimadzu Corporation).
  • the weight of the cell filled with the components was measured, and the weight of the cell alone was subtracted to obtain the weight of the components filled in the cell.
  • the cell filled with the component was set in the dry-type automatic density meter, and the weight of the component was input.
  • the apparent density (specific gravity) of the (X) component or the (X') component was measured by the dry automatic densitometer.
  • the apparent density (specific gravity) was measured as follows. The (X) component or the (X') component (however, neither was ground, but was in its original state) was filled to 80% in a 1 cm3 cell of a dry automatic densitometer "AccuPycII 1340" (manufactured by Shimadzu Corporation).
  • the weight of the cell filled with the component was measured, and the weight of the component filled in the cell was calculated by subtracting the weight of the cell alone.
  • the obtained laminate was exposed to light at 400 mJ/ cm2 (wavelength 365 nm) using a parallel light exposure machine (manufactured by ORC Manufacturing Co., Ltd., product name "EXM-1201") with an ultra-high pressure mercury lamp as the light source. Next, it was exposed to light at an exposure dose of 2,000 mJ/ cm2 (wavelength 365 nm) using an ultraviolet exposure device, and then heated at 170°C for 1 hour to obtain a "laminate for evaluation" in which a cured product was formed on the copper-clad laminate substrate.
  • an aqueous solution of "diethylene glycol monobutyl ether: 200 ml/L, sodium hydroxide: 5 g/L” was prepared as a swelling liquid, and then heated to 70°C, and the evaluation laminate was immersed for 10 minutes.
  • an aqueous solution of potassium permanganate: 60 g/L, sodium hydroxide: 40 g/L was prepared as a roughening liquid, and then heated to 70°C, and the evaluation laminate was immersed for 15 minutes.
  • an aqueous solution of neutralizing liquid (tin chloride (SnCl 2 ): 30 g/L, hydrogen chloride: 300 ml/L) was prepared, and then heated to 40°C, and the evaluation laminate was immersed for 5 minutes to reduce potassium permanganate. In this manner, the surface of the cured evaluation laminate was desmeared.
  • the surface of the cured product of the desmeared evaluation laminate was treated with an alkaline cleaner "Cleaner Securigant 902" (trade name, manufactured by Atotech Japan Co., Ltd.) at 60°C for 5 minutes, and then degreased and washed.
  • the desmeared cured product was treated with a pre-dip liquid "Pre-dip Neogant B” (trade name, manufactured by Atotech Japan Co., Ltd.) at 23°C for 1 minute. Thereafter, the cured product was treated with an activator liquid "Activator Neogant 834" (trade name, manufactured by Atotech Japan Co., Ltd.) at 35°C for 5 minutes, and then the cured product was treated with a reducing liquid "Reducer Neogant WA” (trade name, manufactured by Atotech Japan Co., Ltd.) at 30°C for 5 minutes.
  • Pre-dip Neogant B trade name, manufactured by Atotech Japan Co., Ltd.
  • the laminate for evaluation thus obtained was placed in a chemical copper solution ("Basic Printganth MSK-DK”, “Copper Printganth MSK”, “Stabilizer Printganth MSK” (all product names manufactured by Atotech Japan K.K.)) and electroless plating was carried out until the plating thickness reached approximately 0.5 ⁇ m. After the electroless plating, an annealing treatment was carried out at a temperature of 120° C. for 30 minutes in order to remove residual hydrogen gas. Thereafter, copper sulfate electrolytic plating was carried out, and an annealing treatment was carried out at 180° C. for 60 minutes to form a conductor layer with a thickness of 25 ⁇ m.
  • the laminate for evaluation having the conductor layer formed thereon as described above was measured for perpendicular peel strength at 23° C. in accordance with JIS C6481 (1996) and evaluated according to the following evaluation criteria.
  • D The adhesive strength to the copper plating was 0.1 kN/m or less.
  • the surface of the evaluation laminate after the annealing treatment was visually observed to check for the occurrence of peeling of the plating. If peeling of the plating occurred, the plating surface had irregularities, and if no peeling of the plating occurred, the plating surface was flat.
  • the photosensitive resin composition prepared in each example was applied onto the carrier film while adjusting the film thickness after drying to 25 ⁇ m, and a photosensitive resin film (photosensitive layer) was formed by drying at 100° C. for 10 minutes using a hot air convection dryer.
  • a polyethylene film manufactured by Tamapoly Corporation, product name "NF-15" was laminated as a protective film onto the surface of the photosensitive resin film (photosensitive layer) opposite to the side in contact with the carrier film, and a photosensitive resin film in which the carrier film and the protective film were laminated was produced.
  • the prepared photosensitive resin film was used to carry out various evaluations according to the methods described above. The results are shown in Table 1.
  • D1 "Ricon (registered trademark) 131MA17” (manufactured by Cray Valley Corporation, maleic acid modified polybutadiene, number average molecular weight 54,000 (catalog value))
  • D2 "Ricon (registered trademark) 100” (manufactured by Cray Valley Corporation, butadiene-styrene random copolymer, number average molecular weight 45,000 (catalog value))
  • X1 Solid particles of spherical fused silica (volume average particle size: 0.7 ⁇ m) with a true density of 1,350 kg/ m3 , treated with a silane coupling agent, hollow ratio: 39%
  • X2 Solid particles of spherical fused silica (volume average particle size: 1.5 ⁇ m) with a true density of 1,350 kg/ m3 , treated with a silane coupling agent, hollow ratio: 39%
  • X3 Solid particles of spherical fused silica (volume average particle size: 3.0 ⁇ m) with a true density of 1,350 kg/ m3 , treated with a silane coupling agent, hollow ratio: 39%
  • F1 "Phenolite (registered trademark) LA7052" (manufactured by DIC Corporation, novolac-type phenolic resin modified with melamine, benzoguanamine, etc., hydroxyl group equivalent: 120 g/eq)
  • H1 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone 1-(O-acetyloxime) (oxime ester compound)
  • H2 Bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide (acylphosphine oxide compound)
  • the photosensitive resin compositions of Examples 1 to 5 of this embodiment were able to reduce the relative dielectric constant while maintaining a high adhesive strength with copper plating, compared to the photosensitive resin composition of Comparative Example 1 which used an inorganic filler with a true density of 2,210 kg/ m3 .
  • the photosensitive resin composition of Comparative Example 2 which contained a large amount of PTFE with the aim of significantly reducing the dielectric constant, achieved that aim, but it was found that the adhesive strength with the copper plating was significantly reduced and the plating was prone to peeling. Furthermore, even if the true density was 1,500 kg/ m3 or less, in the case of hollow particles, the adhesive strength with the copper plating was significantly reduced, and the plating peeled off.
  • Multilayer printed wiring board 101
  • Substrate 102
  • Circuit pattern 103
  • Interlayer insulating layer 104
  • Via (via hole) 105
  • seed layer 106
  • resist pattern 107
  • copper circuit layer 108 solder resist layer

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PCT/JP2023/008746 2023-03-08 2023-03-08 感光性樹脂組成物、感光性樹脂フィルム、多層プリント配線板及び半導体パッケージ、並びに多層プリント配線板の製造方法 Ceased WO2024185060A1 (ja)

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