WO2018070489A1 - Élément photosensible, dispositif à semi-conducteur et procédé de formation de motif de réserve - Google Patents

Élément photosensible, dispositif à semi-conducteur et procédé de formation de motif de réserve Download PDF

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Publication number
WO2018070489A1
WO2018070489A1 PCT/JP2017/037049 JP2017037049W WO2018070489A1 WO 2018070489 A1 WO2018070489 A1 WO 2018070489A1 JP 2017037049 W JP2017037049 W JP 2017037049W WO 2018070489 A1 WO2018070489 A1 WO 2018070489A1
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group
photosensitive
layer
component
photosensitive layer
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PCT/JP2017/037049
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English (en)
Japanese (ja)
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加藤　哲也
健一 岩下
絵厘 坂井
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日立化成株式会社
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Priority to JP2018545057A priority Critical patent/JPWO2018070489A1/ja
Publication of WO2018070489A1 publication Critical patent/WO2018070489A1/fr

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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • 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
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • 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
    • G03F7/075—Silicon-containing 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
    • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
    • 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
    • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
    • G03F7/11—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having cover layers or intermediate layers, e.g. subbing layers
    • 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
    • G03F7/20—Exposure; Apparatus therefor
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits

Definitions

  • the present disclosure relates to a photosensitive element, a semiconductor device, and a method for forming a resist pattern.
  • a negative photosensitive resin composition is used to form a fine pattern.
  • a photosensitive layer is formed on a base material (for example, a chip in the case of a semiconductor element or a substrate in the case of a printed wiring board) by application of a photosensitive resin composition, and irradiated with actinic rays through a predetermined pattern. By doing so, the exposed portion is cured.
  • the resist pattern which is a cured film of the photosensitive resin composition is formed on a base material by selectively removing an unexposed part using a developing solution.
  • the photosensitive resin composition is required to have high sensitivity to actinic rays and to be able to form a fine pattern (resolution). Therefore, it contains a photosensitive resin composition containing components such as a novolak resin, an epoxy resin and a photoacid generator that are soluble in an alkaline aqueous solution, a component such as an alkali-soluble epoxy compound having a carboxyl group and a photocationic polymerization initiator.
  • a photosensitive resin composition has been proposed (see, for example, Patent Documents 1 to 3).
  • the surface protective film and the interlayer insulating film used in the semiconductor element are required to have insulation reliability such as heat resistance, electrical characteristics, and mechanical characteristics.
  • a photosensitive resin composition in which the photosensitive resin composition further contains a crosslinkable monomer has been proposed (see, for example, Patent Document 4).
  • the photosensitive layer of the photosensitive element is transferred to the substrate by peeling the protective layer from the photosensitive element, laminating the photosensitive layer and the substrate using a laminator, and peeling the support.
  • the protective layer is peeled off
  • the photosensitive layer may be transferred to the unintended protective layer side.
  • the support is peeled off
  • the photosensitive layer may be transferred to the unintended support side.
  • the site where unintentional transcription occurs cannot be used, so that productivity at the time of manufacture is lowered. Therefore, from the viewpoint of productivity, it is required not to transfer the photosensitive layer of the photosensitive element to the protective layer, preferably to the protective layer and the support.
  • a first object of the present disclosure is to provide a photosensitive element in which a photosensitive layer is difficult to transfer to a protective layer and a support.
  • a second object of the present disclosure is to provide a photosensitive element that can form a resist pattern that is difficult to transfer to a protective layer and that is particularly excellent in resolution.
  • an object of the present disclosure is to provide a semiconductor device obtained using the photosensitive element, and a resist pattern forming method using the photosensitive element.
  • the photosensitive element of the first embodiment of the present disclosure includes a support, a photosensitive layer, and a protective layer in this order, and the support is an olefin resin layer or amino acid as a surface layer on the photosensitive layer side.
  • An alkyd resin layer, the ratio of the peel strength between the photosensitive layer and the support to the peel strength between the photosensitive layer and the protective layer is 1.0 or more, and the photosensitive layer The peel strength between the support and the support is 6.0 N / m or less.
  • the photosensitive layer is composed of (A) component: a resin having a phenolic hydroxyl group, (B) component: a photosensitive acid generator, and (C) component: an aromatic ring, a heterocyclic ring, and an alicyclic ring.
  • a photosensitive element formed from a photosensitive resin composition containing an aliphatic compound having two or more functional groups selected from the group consisting of a vinyl ether group and a hydroxyl group.
  • the photosensitive element of the second embodiment of the present disclosure includes a support, a photosensitive layer, and a protective layer in this order, and the protective layer has a silicone resin layer as a surface layer on the photosensitive layer side
  • the photosensitive layer is selected from the group consisting of (A) component: a resin having a phenolic hydroxyl group, (B) component: a photosensitive acid generator, and (C) component: an aromatic ring, a heterocyclic ring and an alicyclic ring. It is formed from a photosensitive resin composition containing at least one kind and a compound having at least one of a methylol group and an alkoxyalkyl group.
  • the photosensitive resin composition is one or more selected from the group consisting of component (D): acryloyloxy group, methacryloyloxy group, glycidyloxy group, oxetanyl alkyl ether group, vinyl ether group and hydroxyl group.
  • component (D) acryloyloxy group, methacryloyloxy group, glycidyloxy group, oxetanyl alkyl ether group, vinyl ether group and hydroxyl group.
  • a photosensitive element further containing an aliphatic compound having two or more functional groups.
  • 1st and 2nd embodiment provides the photosensitive element whose content of said (D) component is 1-70 mass parts with respect to 100 mass parts of said (A) component.
  • 1st and 2nd embodiment provides the photosensitive element in which the said photosensitive resin composition further contains the compound which has (G) component: Si-O bond.
  • 1st and 2nd embodiment provides a semiconductor device provided with the hardened
  • the first and second embodiments include a step of forming a photosensitive layer on a substrate using the photosensitive element, a step of exposing the photosensitive layer to a predetermined pattern, and a photosensitive layer after exposure. And a step of heat-treating the obtained resin pattern.
  • a method for forming a resist pattern is provided.
  • the first embodiment of the present disclosure it is possible to provide a photosensitive element in which the photosensitive layer is difficult to transfer to the protective layer and the support.
  • the second embodiment of the present disclosure it is possible to provide a photosensitive element that can form a resist pattern that is difficult to transfer to a protective layer and that is particularly excellent in resolution.
  • the terms “layer” and “film” refer to a structure formed in part in addition to a structure formed over the entire surface when observed as a plan view. Is included.
  • the term “process” is not limited to an independent process, and is included in the term if the intended purpose of the process is achieved even if it cannot be clearly distinguished from other processes.
  • EO-modified means a compound having a (poly) oxyethylene group
  • PO-modified means a compound having a (poly) oxypropylene group.
  • (poly) oxyethylene group” means at least one of an oxyethylene group and a polyoxyethylene group in which two or more ethylene groups are linked by an ether bond.
  • the “(poly) oxypropylene group” means at least one of an oxypropylene group and a polyoxypropylene group in which two or more propylene groups are linked by an ether bond.
  • the term “Si—O bond” refers to a bond between a silicon atom and an oxygen atom, and may be part of a siloxane bond (Si—O—Si bond).
  • the numerical range indicated by using “to” indicates a range including the numerical values described before and after “to” as the minimum value and the maximum value, respectively. In the numerical ranges described stepwise in the present specification, the upper limit value or lower limit value of a numerical range of a certain step may be replaced with the upper limit value or lower limit value of the numerical range of another step.
  • the upper limit value or the lower limit value of the numerical range may be replaced with the values shown in the examples. “A or B” only needs to include either A or B, and may include both.
  • the materials exemplified below can be used singly or in combination of two or more unless otherwise specified.
  • the content of each component in the composition means the total amount of the plurality of substances present in the composition unless there is a specific notice when there are a plurality of substances corresponding to each component in the composition.
  • FIG. 1 is a schematic cross-sectional view of a photosensitive element 10 according to the first embodiment.
  • the photosensitive element 10 according to the present embodiment includes a support 11, a photosensitive layer 15, and a protective layer 17 in this order.
  • the photosensitive element 10 can be used for manufacturing the semiconductor device of this embodiment.
  • the support 11 has a support substrate 12 and an olefin resin layer 13.
  • the olefin resin layer 13 forms a surface layer on the photosensitive layer 15 side of the support 11 and is disposed so as to be in contact with the photosensitive layer 15.
  • the support 11 may include an amino alkyd resin layer at the same position instead of the olefin resin layer 13.
  • a polymer film having heat resistance and solvent resistance such as polyester (polyethylene terephthalate, etc.), polypropylene, and polyethylene can be used.
  • a polymer film having an olefin resin layer or an aminoalkyd resin layer on at least one surface can be used.
  • the support 11 has the olefin resin layer 13 or the amino alkyd resin layer as the surface layer on the photosensitive layer 15 side, when the photosensitive layer 15 is laminated on the substrate, the photosensitive layer 15 is easily transferred to the substrate, Productivity can be improved.
  • the olefin resin layer 13 only needs to contain an olefin resin.
  • the olefin component that is a monomer constituting the olefin resin is not particularly limited, but is an alkene having 2 to 6 carbon atoms such as ethylene, propylene, isobutylene, 2-butene, 1-butene, 1-pentene, 1-hexene and the like. Etc., and a mixture thereof may be used.
  • a (meth) acrylic acid ester component, an acid-modified component, etc. may be contained in the olefin resin.
  • the content of the olefin resin in the olefin resin layer 13 may be, for example, 1 to 100% by mass, and may be 50 to 100% by mass.
  • the amino alkyd resin layer only needs to contain an amino alkyd resin.
  • the amino alkyd resin is a resin obtained by using an amino resin and an alkyd resin.
  • the olefin resin layer 13 or amino alkyd resin layer may be formed, for example, by treating at least the surface of the support substrate 12 on the photosensitive layer 15 side with an olefin resin or amino alkyd resin.
  • the treatment with the olefin resin or amino alkyd resin refers to a chemical treatment in which the olefin resin containing the olefin component or the like or the amino alkyd resin is thinly coated (coated) on the surface of the support substrate 12.
  • the olefin resin or aminoalkyd resin When applying (coating) the olefin resin or aminoalkyd resin to the support substrate 12, it is preferable to apply (coat) thinly as long as the effect of releasing is obtained. After coating (coating), the olefin resin or aminoalkyd resin may be fixed to the support substrate 12 by heat, UV treatment or the like. It is more preferable to apply an undercoat layer to the support substrate 12 before applying (coating) the olefin resin or aminoalkyd resin.
  • the preferred thickness of the olefin resin layer 13 or amino alkyd resin layer is about 0.005 to 1 ⁇ m, and particularly preferably 0.01 to 0.1 ⁇ m. When the thickness of the olefin resin layer 13 or the amino alkyd resin layer is within the above range, the adhesion between the support substrate 12 and the olefin resin layer 13 or the amino alkyd resin layer is improved.
  • a PET film treated with an olefin resin for example, a product name “A170” manufactured by Unitika Ltd. is available.
  • a PET film treated with an aminoalkyd resin for example, a product name “NSP-5” manufactured by Fujimori Kogyo Co., Ltd. is available.
  • the thickness of the support 11 and the support substrate 12 may be 5 to 100 ⁇ m, preferably 15 to 100 ⁇ m, and more preferably 25 to 50 ⁇ m.
  • the thickness of the support 11 or the support substrate 12 is 15 ⁇ m or more, the strain at the time of treatment with the olefin resin or aminoalkyd resin is less likely to remain, and the wrinkle is generated when the film is wound. There is a tendency to be suppressed.
  • the thickness of the support 11 is 50 ⁇ m or less, bubbles tend not to be caught between the substrate and the photosensitive layer 15 during thermocompression bonding when the photosensitive layer 15 is laminated on the substrate.
  • the protective layer 17 in the photosensitive element 10 for example, a polymer film having heat resistance and solvent resistance such as polyester (polyethylene terephthalate, etc.), polypropylene, and polyethylene can be used.
  • the thickness of the protective layer 17 is preferably 5 to 100 ⁇ m.
  • the 180 ° peel strength at 23 ° C. between the surface of the support 11 on the olefin resin layer 13 or aminoalkyd resin layer side and the photosensitive layer 15 is 0 It is preferably 0.1 to 6.0 N / m, more preferably 0.2 to 5.5 N / m, still more preferably 0.2 to 4.0 N / m, and 1.0 to Particularly preferred is 2.0 N / m.
  • the 180 ° peel strength is 1.0 N / m or more, the adhesive strength between the photosensitive layer 15 and the support 11 is sufficiently high, and when the protective layer 17 is peeled from the photosensitive layer 15, the photosensitive layer 15 is supported by the support.
  • the photosensitive layer 15 tends to be less easily transferred to the protective layer 17.
  • the 180 ° peel strength is 4.0 N / m or less, the adhesive strength between the photosensitive layer 15 and the support 11 is sufficiently low, and after the photosensitive layer 15 is laminated on the substrate, the support from the photosensitive layer 15 to the support is obtained. 11 tends to be more easily peeled off.
  • the ratio of the peel strength between the photosensitive layer 15 and the support 11 to the peel strength between the photosensitive layer 15 and the protective layer 17 is 1.0 or more.
  • the adhesive strength between the photosensitive layer 15 and the support 11 is relatively high, and the photosensitive layer 15 is adhered to the support 11 when the protective layer 17 is peeled off from the photosensitive layer 15. The state is sufficiently maintained and the photosensitive layer 15 tends to be difficult to be transferred to the protective layer 17.
  • the peel strength a value of 180 ° peel strength at 23 ° C. is used.
  • the ratio of the peel strength between the photosensitive layer 15 and the support 11 to the peel strength between the photosensitive layer 15 and the protective layer 17 may be 1.1 to 4.0, and 1.2 to 3. 0 is preferable, and 1.3 to 2.0 is more preferable.
  • the 180 ° peel strength can be measured by a general method (for example, a method according to JIS K6854-2) using an adhesive tape (manufactured by Nitto Denko Corporation, product name: “NITTO31B”). .
  • the photosensitive layer 15 can be formed by applying a photosensitive resin composition described later on the support 11 or the protective layer 17.
  • the coating method include a dipping method, a spray method, a bar coating method, a roll coating method, and a spin coating method.
  • the thickness of the photosensitive layer 15 varies depending on the application, it is preferably 1 to 100 ⁇ m after drying the photosensitive layer 15, more preferably 3 to 60 ⁇ m, still more preferably 5 to 60 ⁇ m, 5 to 40 ⁇ m is particularly preferable, and 5 to 25 ⁇ m is very preferable. Further, from the viewpoint of excellent insulation reliability (insulation between wirings in the thickness direction of the layer) and productivity in mounting a chip, the thickness of the photosensitive layer 15 is preferably over 20 ⁇ m. 20 ⁇ m or less.
  • FIG. 2 is a schematic cross-sectional view of the photosensitive element 20 according to this embodiment.
  • the photosensitive element 20 according to this embodiment includes a protective layer 21, a photosensitive layer 25, and a support 27 in this order.
  • the photosensitive element 20 can be used for manufacturing the semiconductor device of this embodiment.
  • the protective layer 21 has a protective layer base material 22 and a silicone resin layer 23.
  • the silicone resin layer 23 forms a surface layer on the photosensitive layer 25 side of the protective layer 21 and is disposed so as to be in contact with the photosensitive layer 25.
  • the protective layer base material 22 for example, a polymer film having heat resistance and solvent resistance, such as polyester (polyethylene terephthalate, etc.), polypropylene, and polyethylene can be used.
  • the thickness of the protective layer 21 is preferably 5 to 100 ⁇ m.
  • a polymer film having a silicone resin layer on at least one surface can be used.
  • the silicone resin layer 23 may be formed, for example, by treating at least the surface of the protective layer base material 22 on the photosensitive layer 25 side with a silicone resin.
  • the treatment with a silicone resin refers to a chemical treatment in which a silicone compound such as a silicone surfactant or silicone resin is thinly coated (coated) on the surface of the protective layer substrate 22.
  • the silicone resin include silicone-modified resin and polydimethylsiloxane.
  • the silicone resin When the silicone resin is applied (coated) to the protective layer base material 22, it is preferably applied thinly (coated) to the extent that a release effect can be obtained. After application (coating), the silicone resin may be fixed to the protective layer base material 22 by heat, UV treatment or the like. It is more preferable to apply an undercoat layer to the protective layer base material 22 before applying (coating) the silicone resin.
  • the preferable thickness of the silicone resin layer 23 is about 0.005 to 1 ⁇ m, and particularly preferably 0.01 to 0.1 ⁇ m. When the thickness of the silicone resin layer 23 is in the above range, the adhesion between the protective layer base material 22 and the silicone resin layer 23 becomes good.
  • a PET film treated with a silicone resin for example, a product name “38-T25C-4” manufactured by Mitsui Chemicals Tosero Co., Ltd. is available.
  • each of the protective layer 21 and the protective layer base material 22 is preferably 15 to 50 ⁇ m, and more preferably 25 to 40 ⁇ m.
  • the thickness of the protective layer 21 or the protective layer base material 22 is 15 ⁇ m or more, distortion during the treatment with the silicone resin hardly remains, and when the film is wound, the generation of wrinkles tends to be suppressed. is there.
  • the 180 ° peel strength at 23 ° C. between the surface of the protective layer 21 on the silicone resin layer side and the photosensitive layer 25 is 0.010 to 0.30 N. / Cm is preferable, 0.015 to 0.25 N / cm is more preferable, and 0.020 to 0.20 N / cm is still more preferable.
  • the 180 ° peel strength is 0.020 N / cm or more, the adhesive strength between the photosensitive layer 25 and the protective layer 21 is sufficiently high, and the photosensitive resin composition is coated on the support 27 and dried. There exists a tendency for the laminating property of the layer 25 and the protective layer 21 to become favorable.
  • the 180 ° peel strength is 0.20 N / cm or less, the adhesive strength between the photosensitive layer 25 and the protective layer 21 is sufficiently low, and the photosensitive layer 25 is transferred to the protective layer 21 when the protective layer 21 is peeled off. There is a tendency to become difficult.
  • the 180 ° peel strength can be measured by a general method (for example, a method according to JIS K6854-2) using an adhesive tape (manufactured by Nitto Denko Corporation, product name: “NITTO31B”). .
  • a polymer film having heat resistance and solvent resistance such as polyester (polyethylene terephthalate, etc.), polypropylene, and polyethylene can be used.
  • the thickness of the support (polymer film) 27 is preferably 5 to 100 ⁇ m.
  • the support (polymer film) 27 may have a silicone resin layer, an olefin resin layer, or the like as a release layer.
  • the photosensitive layer 25 can be formed by applying a photosensitive resin composition described later on the support 27 or the protective layer 21.
  • the coating method include a dipping method, a spray method, a bar coating method, a roll coating method, and a spin coating method.
  • the thickness of the photosensitive layer 25 varies depending on the application, but is preferably 1 to 100 ⁇ m after drying the photosensitive layer 25, more preferably 3 to 60 ⁇ m, still more preferably 5 to 60 ⁇ m. 5 to 40 ⁇ m is particularly preferable, and 5 to 25 ⁇ m is very preferable.
  • the thickness of the photosensitive layer 25 is preferably over 20 ⁇ m. 20 ⁇ m or less.
  • the photosensitive resin composition for forming the photosensitive layer 15 in the first embodiment includes (A) component: a resin having a phenolic hydroxyl group, (B) component: a photosensitive acid generator, and (C) component: A compound having at least one selected from the group consisting of an aromatic ring, a heterocyclic ring and an alicyclic ring, and having at least one of a methylol group and an alkoxyalkyl group; and component (D): an acryloyloxy group, a methacryloyloxy group, And an aliphatic compound having two or more functional groups selected from the group consisting of a glycidyloxy group, an oxetanyl alkyl ether group, a vinyl ether group and a hydroxyl group.
  • these components may be simply referred to as (A) component, (B) component, (C) component and the like. If the photosensitive layer is formed from the photosensitive resin composition, the resolution of the photosensitive layer is formed from the photosensitive
  • the photosensitive resin composition for forming the photosensitive layer 25 in the second embodiment includes (A) component: a resin having a phenolic hydroxyl group, (B) component: a photosensitive acid generator, and (C) component: And a compound having at least one selected from the group consisting of an aromatic ring, a heterocyclic ring and an alicyclic ring and having at least one of a methylol group and an alkoxyalkyl group.
  • the photosensitive resin composition in this embodiment is selected from the group consisting of component (D): an acryloyloxy group, a methacryloyloxy group, a glycidyloxy group, an oxetanyl alkyl ether group, a vinyl ether group, and a hydroxyl group as necessary.
  • component (D) an acryloyloxy group, a methacryloyloxy group, a glycidyloxy group, an oxetanyl alkyl ether group, a vinyl ether group, and a hydroxyl group as necessary.
  • An aliphatic compound having two or more kinds of functional groups can be contained.
  • the present inventors consider the reason why the photosensitive resin composition is excellent in resolution as follows.
  • the solubility of the component (A) in the developer is improved by the addition of the component (C).
  • the methylol groups or alkoxyalkyl groups in the component (C) or the methylol groups or alkoxyalkyl groups in the component (C) When the component (A) reacts with dealcoholization, the solubility of the composition in the developer is greatly reduced. Thereby, when developed, sufficient resolution can be obtained due to a remarkable difference in solubility in the unexposed and exposed portion of the developer.
  • the photosensitive resin composition may contain (E) component: benzophenone compound, (F) component: solvent, (G) component: compound having Si—O bond, and (H) component: sensitizer. Can be contained.
  • the photosensitive resin composition in the present embodiment contains a resin having a phenolic hydroxyl group.
  • resin which has a phenolic hydroxyl group Resin soluble in alkaline aqueous solution (alkali-soluble resin) is preferable, and a novolak resin is more preferable from a viewpoint of further improving resolution.
  • the novolak resin can be obtained, for example, by condensing phenols and aldehydes in the presence of a catalyst.
  • Phenols include phenol, o-cresol, m-cresol, p-cresol, o-ethylphenol, m-ethylphenol, p-ethylphenol, o-butylphenol, m-butylphenol, p-butylphenol, 2,3- Xylenol, 2,4-xylenol, 2,5-xylenol, 2,6-xylenol, 3,4-xylenol, 3,5-xylenol, 2,3,5-trimethylphenol, 3,4,5-trimethylphenol, Catechol, resorcinol, pyrogallol, ⁇ -naphthol, ⁇ -naphthol and the like can be mentioned. Phenols can be used alone or in combination of two or more.
  • aldehydes examples include formaldehyde, paraformaldehyde, acetaldehyde, benzaldehyde and the like. Aldehydes can be used singly or in combination of two or more.
  • the novolac resin for example, a cresol novolac resin can be used.
  • the novolak resin include phenol / formaldehyde condensed novolak resin, phenol-cresol / formaldehyde condensed novolak resin, cresol / formaldehyde condensed novolak resin, phenol-naphthol / formaldehyde condensed novolak resin, and the like.
  • component (A) other than the novolak resin examples include polyhydroxystyrene and copolymers thereof, phenol-xylylene glycol condensation resin, cresol-xylylene glycol condensation resin, phenol-dicyclopentadiene condensation resin, and the like.
  • a component can be used individually by 1 type or in mixture of 2 or more types.
  • the weight average molecular weight of the component (A) is 100,000 or less, 1000 to 80000, 2000 to 50000, from the viewpoint of further improving the resolution, developability, thermal shock resistance, heat resistance and the like of the resulting resin pattern (cured film). It may be 2000-20000, 3000-15000, or 5000-15000.
  • the weight average molecular weight of each component can be measured on condition of the following by the gel permeation chromatography method (GPC) using a standard polystyrene calibration curve, for example.
  • GPC gel permeation chromatography method
  • Equipment used Hitachi L-6000 type (manufactured by Hitachi, Ltd.)
  • Eluent Tetrahydrofuran Measurement temperature: 40 ° C
  • Flow rate 1.75 ml / min
  • Detector L-3300RI (manufactured by Hitachi, Ltd.)
  • the content of the component (A) is 10 to 90% by mass, 30 to 90% by mass based on the total amount of the photosensitive resin composition (however, when the component (F) is used, the component (F) is excluded). 30 to 80% by mass, 40 to 80% by mass, or 40 to 60% by mass.
  • the content of the component (A) is in the above range, the developability of the photosensitive layer formed using the photosensitive resin composition with respect to the aqueous alkali solution tends to be further improved.
  • the photosensitive resin composition in the present embodiment contains a photosensitive acid generator.
  • the photosensitive acid generator is a compound that generates an acid upon irradiation with an actinic ray or the like. Due to the catalytic effect of the acid generated from the photosensitive acid generator, the methylol groups in the component (C) or the alkoxyalkyl groups, or the methylol group or the alkoxyalkyl group in the component (C) and the component (A) However, by reacting with dealcoholization, the solubility of the composition in the developer is greatly reduced, and a negative pattern can be formed.
  • the component (B) is not particularly limited as long as it is a compound that generates an acid upon irradiation with actinic rays or the like.
  • the component (B) include onium salt compounds, halogen-containing compounds, diazoketone compounds, sulfone compounds, sulfonic acid compounds, sulfonimide compounds, and diazomethane compounds.
  • the component (B) is preferably at least one selected from the group consisting of an onium salt compound and a sulfonimide compound.
  • the component (B) is preferably an onium salt compound from the viewpoint of excellent solubility in the solvent.
  • onium salt compounds examples include iodonium salts, sulfonium salts, phosphonium salts, diazonium salts, pyridinium salts, and the like.
  • preferred onium salt compounds include diphenyliodonium trifluoromethanesulfonate, diphenyliodonium nonafluorobutanesulfonate, diphenyliodonium heptadecafluorooctanesulfonate, diphenyliodonium p-toluenesulfonate, diphenyliodonium hexafluoroantimonate, diphenyliodonium hexafluorophosphate Diaryl iodonium salts such as diphenyliodonium tris (pentafluoroethyl) trifluorophosphate, diphenyliodonium tetrafluoroborate, diphenyliodonium tetra
  • a sulfonium salt is preferable from the viewpoint of further improving sensitivity and thermal stability, and a triarylsulfonium salt is more preferable from the viewpoint of further improving thermal stability.
  • An onium salt compound can be used singly or in combination of two or more.
  • the triarylsulfonium salt of the component (B) for example, a compound represented by the following general formula (b1), a compound represented by the following general formula (b2), a compound represented by the following general formula (b3), And at least one cation selected from the group consisting of compounds represented by the following general formula (b4), a tetraphenylborate skeleton, an alkyl sulfonate skeleton having 1 to 20 carbon atoms, a phenyl sulfonate skeleton, and a 10-camphor sulfonate skeleton
  • the hydrogen atom of the phenyl group in the general formulas (b1) to (b4) includes a hydroxyl group, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an alkylcarbonyl group having 2 to 12 carbon atoms, and carbon It may be substituted with at least one selected from the group consisting of alkoxycarbonyl groups of 2 to 12, and when there are a plurality of substituents, they may be the same or different.
  • the hydrogen atom of the phenyl group of the tetraphenylborate skeleton is a fluorine atom, chlorine atom, bromine atom, iodine atom, cyano group, nitro group, hydroxyl group, alkyl group having 1 to 12 carbon atoms, alkoxy group having 1 to 12 carbon atoms, It may be substituted with at least one selected from the group consisting of an alkylcarbonyl group having 2 to 12 carbon atoms and an alkoxycarbonyl group having 2 to 12 carbon atoms, and when there are a plurality of substituents, they are the same as each other. Or different.
  • the hydrogen atom of the alkyl sulfonate skeleton is at least one selected from the group consisting of a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a cyano group, a nitro group, a hydroxyl group, an alkoxy group, an alkylcarbonyl group, and an alkoxycarbonyl group. It may be substituted, and when there are a plurality of substituents, they may be the same or different.
  • the hydrogen atom of the phenyl group of the phenylsulfonate skeleton is a fluorine atom, chlorine atom, bromine atom, iodine atom, cyano group, nitro group, hydroxyl group, alkyl group having 1 to 12 carbon atoms, alkoxy group having 1 to 12 carbon atoms, carbon It may be substituted with at least one selected from the group consisting of an alkylcarbonyl group having 2 to 12 carbon atoms and an alkoxycarbonyl group having 2 to 12 carbon atoms. May be different.
  • the hydrogen atom of the trisalkylsulfonylmethanide skeleton is at least selected from the group consisting of a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a cyano group, a nitro group, a hydroxyl group, an alkoxy group, an alkylcarbonyl group, and an alkoxycarbonyl group. It may be substituted with one kind, and when there are a plurality of substituents, they may be the same or different.
  • the fluorine atom of the hexafluorophosphate skeleton may be substituted with at least one selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, and a perfluoroalkyl group having 1 to 12 carbon atoms, When there are a plurality of substituents, they may be the same or different.
  • the sulfonium salt used as the component (B) has, as a cation, [4- (4-biphenylylthio) phenyl] -4-biphenylylphenylsulfonium, (2) from the viewpoint of further excellent sensitivity, resolution, and insulation.
  • the sulfonium salt used as component (B) includes trifluoromethanesulfonate, nonafluorobutanesulfonate, hexafluoroantimonate, tris [(trifluoromethyl) sulfonyl] methanide, 10-camphorsulfonate, tris (pentafluoroethyl) as anions.
  • a compound having at least one selected from the group consisting of trifluorophosphate and tetrakis (pentafluorophenyl) borate is preferable.
  • the sulfonium salt examples include (2-ethoxy) phenyl [4- (4-biphenylylthio) -3-ethoxyphenyl] 4-biphenylylsulfonium nonafluorobutanesulfonate, [4- (4-biphenylylthio) Phenyl] -4-biphenylylphenylsulfonium tetrakis (pentafluorophenyl) borate, tris [4- (4-acetylphenylsulfanyl) phenyl] sulfonium tetrakis (pentafluorophenyl) borate, and the like.
  • a sulfonium salt can be used individually by 1 type or in mixture of 2 or more types.
  • sulfonimide compound examples include N- (trifluoromethylsulfonyloxy) succinimide, N- (trifluoromethylsulfonyloxy) phthalimide, N- (trifluoromethylsulfonyloxy) diphenylmaleimide, N- (trifluoromethylsulfonyl).
  • a sulfonimide compound can be used individually by 1 type or in mixture of 2 or more types.
  • a component can be used individually by 1 type or in mixture of 2 or more types.
  • the content of the component (B) is 0.1 to It may be 15 parts by weight, 0.3 to 10 parts by weight, 1 to 10 parts by weight, 3 to 10 parts by weight, 5 to 10 parts by weight, or 6 to 10 parts by weight.
  • 100 mass parts of (A) component means that it is 100 mass parts of solid content of (A) component.
  • the photosensitive resin composition in the present embodiment is at least one selected from the group consisting of an aromatic ring, a heterocyclic ring, and an alicyclic ring as the component (C), and at least selected from the group consisting of a methylol group and an alkoxyalkyl group.
  • a compound having one kind is contained (however, the component (D) and the component (E) are not included).
  • the aromatic ring means an aromatic hydrocarbon group (for example, a hydrocarbon group having 6 to 10 carbon atoms), and examples thereof include a benzene ring and a naphthalene ring.
  • the heterocyclic ring means a cyclic group having at least one hetero atom such as a nitrogen atom, oxygen atom, sulfur atom (for example, a cyclic group having 3 to 10 carbon atoms), such as a pyridine ring, an imidazole ring, Examples include a pyrrolidinone ring, an oxazolidinone ring, an imidazolidinone ring and a pyrimidinone ring.
  • An alicyclic ring means a cyclic hydrocarbon group having no aromaticity (for example, a cyclic hydrocarbon group having 3 to 10 carbon atoms), such as a cyclopropane ring, a cyclobutane ring, a cyclopentane ring and a cyclohexane ring.
  • An alkoxyalkyl group means a group in which an alkyl group is bonded to another alkyl group via an oxygen atom. In the alkoxyalkyl group, the two alkyl groups may be the same as or different from each other, and may be, for example, an alkyl group having 1 to 10 carbon atoms.
  • the photosensitive resin composition contains the component (C)
  • component (C) when exposed to light (or when cured by heat treatment after exposure and exposure), methylol groups or alkoxyalkyl groups in the component (C)
  • the methylol group or alkoxyalkyl group in component (C) reacts with component (A) with dealcoholization to greatly reduce the solubility of the composition in the developer, resulting in a negative pattern. Can be formed.
  • the photosensitive layer after the resin pattern is formed is heated and cured, the (C) component reacts with the (A) component to form a bridge structure, thereby preventing the resin pattern from being weakened and melted. .
  • the component (C) includes a compound having a phenolic hydroxyl group (however, the component (A) is not included), a compound having a hydroxymethylamino group, and a compound having an alkoxymethylamino group. At least one selected from the above is preferred.
  • the compound having a phenolic hydroxyl group has a methylol group or an alkoxyalkyl group, it is possible to further increase the dissolution rate of the unexposed area when developing with an alkaline aqueous solution, and to further improve the sensitivity of the photosensitive layer.
  • a component can be used individually by 1 type or in mixture of 2 or more types.
  • the compound having a phenolic hydroxyl group As the compound having a phenolic hydroxyl group, a conventionally known compound can be used, but it is excellent in balance between the effect of promoting dissolution of the unexposed area and the effect of preventing melting at the time of curing of the photosensitive resin composition layer. From the viewpoint, a compound represented by the following general formula (1) is preferable.
  • Z represents a single bond or a divalent organic group
  • R 81 and R 82 each independently represent a hydrogen atom or a monovalent organic group
  • R 83 and R 84 represent Each independently represents a monovalent organic group
  • a and b each independently represent an integer of 1 to 3
  • c and d each independently represents an integer of 0 to 3.
  • the monovalent organic group for example, an alkyl group having 1 to 10 carbon atoms such as a methyl group, an ethyl group or a propyl group; a carbon group such as a vinyl group having 2 to 10 carbon atoms.
  • R 81 to R 84 When there are a plurality of R 81 to R 84 , they may be the same or different.
  • the compound represented by the general formula (1) is preferably a compound represented by the following general formula (2).
  • X 1 represents a single bond or a divalent organic group, and a plurality of R's each independently represents an alkyl group (for example, an alkyl group having 1 to 10 carbon atoms). Several R may mutually be same or different.
  • a plurality of R's each independently represents an alkyl group (for example, an alkyl group having 1 to 10 carbon atoms). Several R may mutually be same or different.
  • the compound in which Z is a single bond is a biphenol (dihydroxybiphenyl) derivative.
  • the divalent organic group represented by Z include an alkylene group having 1 to 10 carbon atoms such as a methylene group, an ethylene group and a propylene group; an ethylidene group and the like having 2 to 10 carbon atoms.
  • An alkylidene group an arylene group having 6 to 30 carbon atoms, such as a phenylene group; a group in which some or all of the hydrogen atoms of these hydrocarbon groups are substituted with halogen atoms such as fluorine atoms; a sulfonyl group; a carbonyl group Ether bond; sulfide bond; amide bond and the like.
  • Z is preferably a divalent organic group represented by the following general formula (4).
  • X is a single bond, an alkylene group (for example, an alkylene group having 1 to 10 carbon atoms), an alkylidene group (for example, an alkylidene group having 2 to 10 carbon atoms), A group in which part or all of the hydrogen atoms are substituted with a halogen atom, a sulfonyl group, a carbonyl group, an ether bond, a sulfide bond, or an amide bond is shown.
  • R 9 represents a hydrogen atom, a hydroxyl group, an alkyl group (for example, an alkyl group having 1 to 10 carbon atoms) or a haloalkyl group, and e represents an integer of 1 to 10.
  • a plurality of R 9 and X may be the same as or different from each other.
  • the haloalkyl group means an alkyl group substituted with a halogen atom.
  • the compound having an alkoxymethylamino group is at least one selected from the group consisting of a compound represented by the following general formula (5) and a compound represented by the following general formula (6). preferable.
  • a plurality of R's each independently represents an alkyl group (for example, an alkyl group having 1 to 10 carbon atoms). Several R may mutually be same or different.
  • a plurality of R's each independently represents an alkyl group (for example, an alkyl group having 1 to 10 carbon atoms). Several R may mutually be same or different.
  • Examples of the compound having a hydroxymethylamino group include (poly) (N-hydroxymethyl) melamine, (poly) (N-hydroxymethyl) glycoluril, (poly) (N-hydroxymethyl) benzoguanamine, (poly) (N -Hydroxymethyl) urea and the like.
  • Examples of the compound having an alkoxymethylamino group include nitrogen-containing compounds obtained by alkylating all or part of the methylol groups of the compound having a hydroxymethylamino group.
  • examples of the alkyl group of the alkyl ether include a methyl group, an ethyl group, a butyl group, or a mixture thereof, and may contain an oligomer component that is partially self-condensed.
  • Specific examples of the compound having an alkoxymethylamino group include hexakis (methoxymethyl) melamine, hexakis (butoxymethyl) melamine, tetrakis (methoxymethyl) glycoluril, tetrakis (butoxymethyl) glycoluril, tetrakis (methoxymethyl). Examples include urea.
  • the content of the component (C) is 5 parts by mass or more, 10 parts by mass or more, 15 parts by mass or more with respect to 100 parts by mass of the component (A) from the viewpoint that chemical resistance and heat resistance tend to be good. , 20 parts by mass or more, or 25 parts by mass or more.
  • the content of the component (C) is such that the resolution tends to be further improved, with respect to 100 parts by mass of the component (A), 80 parts by mass or less, 70 parts by mass or less, 55 parts by mass or less, or 40 mass parts or less may be sufficient.
  • the weight average molecular weight of the compound used as the component (C) is preferably 94 to 2000, more preferably 108 to 2000, and still more preferably 108 to 1500. In addition, about the compound with a low molecular weight, when it is difficult to measure by the above-mentioned measuring method of the weight average molecular weight, the molecular weight can be measured by another method, and the average can be calculated.
  • the photosensitive resin composition in the present embodiment includes at least one functional group selected from the group consisting of an acryloyloxy group, a methacryloyloxy group, a glycidyloxy group, an oxetanyl alkyl ether group, a vinyl ether group, and a hydroxyl group as the component (D). Containing an aliphatic compound having two or more.
  • (D) component may have at least 1 type of 2 or more types of different functional groups, and may have 2 or more types of 1 type of functional groups.
  • the compound is preferably an aliphatic compound having three or more functional groups. The upper limit of the number of functional groups is not particularly limited, but is 12 for example.
  • the “aliphatic compound” refers to a compound in which the main skeleton is an aliphatic skeleton and does not contain an aromatic ring or an aromatic heterocyclic ring.
  • the photosensitive resin composition is also required to have excellent adhesion to the substrate (tackiness) There is.
  • tackiness adhesion to the substrate
  • the photosensitive resin composition in the exposed area is easily removed by the development process, and the adhesion between the substrate and the resin pattern (resist pattern) deteriorates.
  • the photosensitive resin composition contains the component (D)
  • the adhesiveness that is, tackiness
  • the photosensitive resin composition containing component (D) can impart flexibility to the photosensitive layer (coating film), and increase the dissolution rate of unexposed areas when developing with an alkaline aqueous solution. This tends to improve the resolution of the resin pattern.
  • the weight average molecular weight of the component (D) may be 92 to 2000, 106 to 1500, or 134 to 1300 in consideration of balance. .
  • the molecular weight can be measured by another method, and the average can be calculated.
  • component (D) examples include compounds represented by the following general formulas (7) to (10).
  • examples of the alkyl group in the oxetanyl alkyl ether group include a methyl group, an ethyl group, and a propyl group, and a methyl group is preferable.
  • R 1 represents a hydrogen atom, a methyl group, an ethyl group, a hydroxyl group, or a group represented by the following General Formula (11), and R 2 , R 3, and R 4 are each independently Are an acryloyloxy group, a methacryloyloxy group, a glycidyloxy group, an oxetanyl alkyl ether group, a vinyl ether group, a hydroxyl group, a group represented by the following general formula (12), or a group represented by the following general formula (13). .
  • R 5 represents a hydrogen atom, a methyl group, an ethyl group, a hydroxyl group, or a group represented by the following General Formula (11), and R 6 , R 7, and R 8 are each independently Are an acryloyloxy group, a methacryloyloxy group, a glycidyloxy group, an oxetanyl alkyl ether group, a vinyl ether group, a hydroxyl group, a group represented by the following general formula (12), or a group represented by the following general formula (13). .
  • R 9 , R 10 , R 11 , R 12 , R 13 and R 14 are each independently acryloyloxy group, methacryloyloxy group, glycidyloxy group, oxetanyl alkyl ether group, vinyl ether group, hydroxyl group , A group represented by the following general formula (12), or a group represented by the following general formula (13).
  • R 15 , R 17 , R 18 and R 20 are each independently acryloyloxy group, methacryloyloxy group, glycidyloxy group, oxetanyl alkyl ether group, vinyl ether group, hydroxyl group, the following general formula (12 ) Or a group represented by the following general formula (13), R 16 and R 19 are each independently a hydrogen atom, a methyl group, an ethyl group, a hydroxyl group, or the following general formula ( The group represented by 11) is shown.
  • R 21 represents an acryloyloxy group, a methacryloyloxy group, a glycidyloxy group, an oxetanyl alkyl ether group, a vinyl ether group or a hydroxyl group.
  • R 22 represents an acryloyloxy group, a methacryloyloxy group, a glycidyloxy group, an oxetanyl alkyl ether group, a vinyl ether group or a hydroxyl group, and n is an integer of 1 to 10.
  • R 23 represents an acryloyloxy group, a methacryloyloxy group, a glycidyloxy group, an oxetanyl alkyl ether group, a vinyl ether group or a hydroxyl group, and m is an integer of 1 to 10, respectively.
  • the component (D) at least selected from the group consisting of an acryloyloxy group, a methacryloyloxy group, a glycidyloxy group, an oxetanyl alkyl ether group, and a vinyl ether group from the viewpoint of further improving sensitivity and resolution.
  • a compound having one kind is preferable, a compound having two or more glycidyloxy groups or two or more acryloyloxy groups is more preferable, and a compound having three or more glycidyloxy groups or three or more acryloyloxy groups is further included.
  • a component can be used individually by 1 type or in mixture of 2 or more types.
  • the component (D) includes a compound having an acryloyloxy group, a compound having a methacryloyloxy group, a compound having a glycidyloxy group, a compound having an oxetanyl alkyl ether group, a compound having a vinyl ether group, and a compound having a hydroxyl group. At least one selected from the group can be used.
  • a compound having at least one group selected from the group consisting of an acryloyloxy group, a methacryloyloxy group and a glycidyloxy group is preferable.
  • acryloyloxy A compound having at least one group selected from the group consisting of a group and a methacryloyloxy group is more preferable.
  • the component (D) is preferably an aliphatic compound having two or more glycidyloxy groups, and preferably an aliphatic compound having three or more glycidyloxy groups. More preferably, it is more preferably an aliphatic compound having 3 or more glycidyloxy groups having a weight average molecular weight of 1000 or less.
  • Examples of the compound having an acryloyloxy group include EO-modified dipentaerythritol hexaacrylate, PO-modified dipentaerythritol hexaacrylate, dipentaerythritol hexaacrylate, EO-modified ditrimethylolpropane tetraacrylate, PO-modified ditrimethylolpropane tetraacrylate, ditrile Methylolpropane tetraacrylate, EO-modified pentaerythritol tetraacrylate, PO-modified pentaerythritol tetraacrylate, pentaerythritol tetraacrylate, EO-modified pentaerythritol triacrylate, PO-modified pentaerythritol triacrylate, pentaerythritol triacrylate, EO-modified trimethylolpropane acrylate, PO modified birds Chi
  • Examples of the compound having a methacryloyloxy group include EO-modified dipentaerythritol hexamethacrylate, PO-modified dipentaerythritol hexamethacrylate, dipentaerythritol hexamethacrylate, EO-modified ditrimethylolpropane tetramethacrylate, PO-modified ditrimethylolpropane tetramethacrylate, ditriethyl.
  • the compound which has a methacryloyloxy group can be used individually by 1 type or in mixture of 2 or more
  • Examples of the compound having a glycidyloxy group include ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, and 1,6-hexanediol diglycidyl.
  • Ether glycerin diglycidyl ether, dipentaerythritol hexaglycidyl ether, pentaerythritol tetraglycidyl ether, pentaerythritol triglycidyl ether, trimethylolethane triglycidyl ether, trimethylolpropane triglycidyl ether, glycerol polyglycidyl ether, glycerin triglycidyl ether, Glycerol propoxyle Totori glycidyl ether, 1,4-cyclohexanedimethanol diglycidyl ether, diglycidyl 1,2-cyclohexane dicarboxylate, and the like.
  • the compound which has a glycidyloxy group can be used individually by 1 type or in mixture of 2 or more types.
  • Examples of the compound having a glycidyloxy group include dipentaerythritol hexaglycidyl ether, pentaerythritol tetraglycidyl ether, pentaerythritol triglycidyl ether, trimethylolethane triglycidyl ether, trimethylolpropane triglycidyl ether, glycerol polyglycidyl ether, and And at least one selected from the group consisting of glycerin triglycidyl ether is preferred.
  • the compound having a glycidyloxy group includes, for example, Epolite 40E, Epolite 100E, Epolite 70P, Epolite 200P, Epolite 1500NP, Epolite 1600, Epolite 80MF, Epolite 100MF (trade name, manufactured by Kyoeisha Chemical Co., Ltd.), alkyl type epoxy resin ZX-1542 (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., trade name), Denacol EX-212L, Denacol EX-214L, Denacol EX-216L, Denacol EX-321L and Denacol EX-850L (above, manufactured by Nagase ChemteX Corporation, product)
  • the name “Denacol” is a commercially available trademark).
  • Examples of the compound having an oxetanyl alkyl ether group include a compound having a 3-alkyl-3-oxetanyl alkyl ether group, and a compound having a 3-ethyl-3-oxetanyl alkyl ether group is preferable.
  • oxetane compounds include dipentaerythritol hexakis (3-ethyl-3-oxetanylmethyl) ether, pentaerythritol tetrakis (3-ethyl-3-oxetanylmethyl) ether, pentaerythritol tris (3-ethyl-3- Oxetanylmethyl) ether, trimethylolethanetris (3-ethyl-3-oxetanylmethyl) ether, trimethylolpropane tris (3-ethyl-3-oxetanylmethyl) ether, glycerol poly (3-ethyl-3-oxetanylmethyl) ether And glycerin tris (3-ethyl-3-oxetanylmethyl) ether.
  • the compound which has oxetanyl alkyl ether can be used individually by 1 type or in mixture of 2 or more types.
  • Examples of the compound having a hydroxyl group include polyhydric alcohols such as dipentaerythritol, pentaerythritol, and glycerin.
  • the compound which has a hydroxyl group can be used individually by 1 type or in mixture of 2 or more types.
  • At least one selected from the group consisting of trimethylolethane triglycidyl ether and trimethylolpropane triglycidyl ether is preferable from the viewpoint of further excellent sensitivity and resolution.
  • Component (D) is commercially available as an alkyl type epoxy resin (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., trade name ZX-1542), an alkyl type acrylic resin (manufactured by Nippon Kayaku Co., Ltd., trade name: PET-30), and the like. .
  • the content of the component (D) is such that the flexibility of the photosensitive layer (coating film) can be further imparted, and the dissolution rate of the unexposed area when developing with an alkaline aqueous solution is likely to further increase, so that the component (A) 100 1 mass part or more, 10 mass parts or more, 20 mass parts or more, 25 mass parts or more, 30 mass parts or more, or 40 mass parts or more may be sufficient with respect to a mass part.
  • the content of the component (D) is 70 parts by mass or less and 65 parts by mass with respect to 100 parts by mass of the component (A) from the viewpoint that the photosensitive resin composition tends to form a film on a desired support. Or 50 parts by mass or less.
  • the photosensitive resin composition in this embodiment may contain a benzophenone compound as the component (E).
  • a benzophenone compound By containing a benzophenone compound, the resolution of the photosensitive resin composition can be further improved. Moreover, the tolerance of the exposure amount which can form a fine resist pattern can be improved by containing (E) component, and productivity can be improved more.
  • benzophenone compound examples include benzophenone, 4,4′-diaminobenzophenone, 4,4′-bis (dimethylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone, 4,4′-bis (dibutylamino) Benzophenone, 4-ethylaminobenzophenone, 2,4-dihydroxybenzophenone, 3,4-dihydroxybenzophenone, 2,3,4-trihydroxybenzophenone, 2,3,4,4′-tetrahydroxybenzophenone, 2,2 ′, 4,4'-tetrahydroxybenzophenone, 2,2 ', 4,4'-tetramethoxybenzophenone, 2,2', 4,4'-tetraethoxybenzophenone, 2,2 ', 4,4'-tetrabutoxybenzophenone 2,2'-dihydroxy-4,4'-dimethoxybenzopheno 2,2′-dihydroxy-4,4′-diethoxybenz
  • the compound is selected from the group consisting of an amino group, a dimethylamino group, a diethylamino group, a dibutylamino group, a hydroxy group, a methoxy group, an ethoxy group, a butoxy group, and a phenyl group in that the resolution is further improved.
  • a benzophenone compound having one or more groups is preferred, and two or more groups selected from the group consisting of amino group, dimethylamino group, diethylamino group, dibutylamino group, hydroxy group, methoxy group, ethoxy group, butoxy group and phenyl group
  • Benzophenone compounds having 2 or more diethylamino groups or hydroxy groups are more preferable, and 4,4′-bis (dimethylamino) benzophenone and 2,2 ′, 4,4′-tetrahydroxybenzophenone are particularly preferable.
  • a component can be used individually by 1 type or in mixture of 2 or more types.
  • the content of component (E) is preferably 0.001 to 10 parts by weight, more preferably 0.01 to 1 part by weight, and 0.01 to 0.8 parts by weight with respect to 100 parts by weight of component (A). Is more preferable, and 0.05 to 0.1 part by mass is particularly preferable.
  • the content of the component (E) is in the range of 0.001 to 10 parts by mass, the resolution of the photosensitive resin composition can be further improved, and the exposure amount that can form a fine resist pattern is sufficient. Tolerance can be further improved and productivity is further improved.
  • the resolution is further improved.
  • a fine resist pattern that is, a fine resist pattern having a via opening diameter of 10 (unit: ⁇ m) or less.
  • a fine resist pattern having a via opening diameter of 10 (unit: ⁇ m) or less it is necessary to appropriately adjust the exposure amount, but by containing the component (E), The width of the exposure amount that can form a simple resist pattern can be widened, that is, the tolerance (allowable range) of the exposure amount can be improved, so that when a mass-produced product or the like is manufactured, a fine resist pattern is formed.
  • the photosensitive resin composition in this embodiment may further contain a solvent as the component (F) in order to improve the handleability of the photosensitive resin composition or to adjust the viscosity and storage stability. it can.
  • the component (F) is preferably an organic solvent.
  • the organic solvent is not particularly limited as long as it can exhibit the above performance, but ethylene glycol monoalkyl ether acetate such as ethylene glycol monomethyl ether acetate and ethylene glycol monoethyl ether acetate; propylene glycol monomethyl ether, propylene glycol monoethyl Propylene glycol monoalkyl ethers such as ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether; Propylene glycol dialkyl ethers such as propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol dipropyl ether, propylene glycol dibutyl ether; Propylene glycol monomethyl ether acetate Propylene glycol monoalkyl ether acetates such as propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate
  • the content of the component (F) may be 30 to 200 parts by mass or 40 to 120 parts by mass with respect to 100 parts by mass of the total amount of the photosensitive resin composition excluding the component (F).
  • the photosensitive resin composition in this embodiment may contain a compound having a Si—O bond (excluding compounds corresponding to the components (A) to (F)) as the component (G).
  • the compound having a Si—O bond may be a compound having a siloxane bond.
  • the component (G) is not particularly limited as long as it has a Si—O bond, and examples thereof include silica (silica filler) and silane compounds (silane coupling agent and the like).
  • a component can be used individually by 1 type or in mixture of 2 or more types.
  • the thermal expansion coefficient of the resin pattern can be reduced.
  • the inorganic filler is preferably silica such as fused spherical silica, fused pulverized silica, fumed silica, or sol-gel silica.
  • an inorganic filler having a Si—O bond may be used by treating the inorganic filler with a silane compound.
  • inorganic fillers treated with a silane compound examples include inorganic fillers derived from mineral products such as mica.
  • the average primary particle diameter of the inorganic filler is preferably 100 nm or less, more preferably 80 nm or less, and further preferably 50 nm or less from the viewpoint of further improving the photosensitivity of the photosensitive layer.
  • the average primary particle size is 100 nm or less, the photosensitive resin composition is less likely to become cloudy, and light for exposure is easily transmitted through the photosensitive layer. As a result, since the unexposed part is easily removed, the resolution of the resin pattern tends to be difficult to decrease.
  • the average primary particle diameter is a value obtained by converting from the BET specific surface area.
  • the thermal expansion coefficient of silica is preferably 5.0 ⁇ 10 ⁇ 6 / ° C. or less.
  • Silica is preferably silica such as fused spherical silica, fumed silica, sol-gel silica, and more preferably fumed silica or sol-gel silica from the viewpoint of easily obtaining a suitable particle size.
  • the silica is preferably silica (nanosilica) having an average primary particle diameter of 5 to 100 nm.
  • the particle size distribution meter is a laser diffraction / scattering type particle size distribution meter that calculates the particle size distribution by irradiating the particle group with laser light and calculating from the intensity distribution pattern of the diffracted light and scattered light emitted from the particle group; Examples thereof include a particle size distribution meter of nanoparticles for obtaining a particle size distribution using frequency analysis.
  • the adhesion strength between the photosensitive layer and the substrate after pattern formation can be improved.
  • a silane compound is used as the component (G)
  • the silane compound is not particularly limited as long as the silane compound has a Si—O bond.
  • the silane compound include alkyl silane, alkoxy silane, vinyl silane, epoxy silane, amino silane, acrylic silane, methacryl silane, mercapto silane, sulfide silane, isocyanate silane, sulfur silane, styryl silane, alkyl chlorosilane, and the like.
  • silane compound as component (G) a compound represented by the following general formula (14) is preferable. (R 101 O) 4-f -Si- (R 102 ) f (14)
  • R 101 represents an alkyl group having 1 to 10 carbon atoms, such as a methyl group, an ethyl group, or a propyl group
  • R 102 represents a monovalent organic group
  • f is An integer from 0 to 3 is shown.
  • f is 0, 1 or 2
  • the plurality of R 101 may be the same as or different from each other.
  • f is 2 or 3
  • the plurality of R 102 may be the same as or different from each other.
  • R 101 is preferably an alkyl group having 1 to 5 carbon atoms, more preferably an alkyl group having 1 to 2 carbon atoms, from the viewpoint of further improving resolution.
  • f is preferably 0 to 2 from the viewpoint of further improving the dispersibility of the inorganic filler. 0 to 1 are more preferable.
  • silane compound as component (G) examples include methyltrimethoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane, methyltriethoxysilane, methyltriphenoxysilane, ethyltrimethoxysilane, n-propyltrimethoxysilane, and diisopropyl.
  • Dimethoxysilane isobutyltrimethoxysilane, diisobutyldimethoxysilane, isobutyltriethoxysilane, n-hexyltrimethoxysilane, n-hexyltriethoxysilane, cyclohexylmethyldimethoxysilane, n-octyltriethoxysilane, n-dodecyltrimethoxysilane, Phenyltrimethoxysilane, diphenyldimethoxysilane, triphenylsilanol, tetraethoxysilane, 3-aminopropyltrimethoxysilane, -Aminopropyltriethoxysilane, 3- (2-aminoethyl) aminopropyltrimethoxysilane, 3- (2-aminoethyl) aminopropylmethyldimethoxysilane, 3-phenylamin
  • the component (G) is preferably an epoxy silane having at least one glycidyloxy group, more preferably an epoxy silane having at least one selected from the group consisting of a trimethoxysilyl group and a triethoxysilyl group. .
  • the content of the component (G) is preferably 1.8 to 420 parts by mass, more preferably 1.8 to 270 parts by mass with respect to 100 parts by mass of the component (A).
  • the content of component (G) may be 1 to 20 parts by mass or 3 to 10 parts by mass with respect to 100 parts by mass of component (A).
  • the photosensitive resin composition in the present embodiment may further contain a sensitizer as the component (H).
  • a sensitizer as the component (H).
  • the sensitizer include 9,10-dibutoxyanthracene.
  • (H) component can be used individually by 1 type or in mixture of 2 or more types.
  • the content of the component (H) is preferably 0.01 to 1.5 parts by mass, more preferably 0.05 to 0.5 parts by mass with respect to 100 parts by mass of the component (A).
  • the photosensitive resin composition of the present embodiment may contain a phenolic low molecular compound having a molecular weight of less than 1000 (hereinafter referred to as “phenol compound (a)”).
  • phenol compound (a) examples include 4,4′-dihydroxydiphenylmethane, 4,4′-dihydroxydiphenyl ether, tris (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, Tris (4-hydroxyphenyl) ethane, 1,3-bis [1- (4-hydroxyphenyl) -1-methylethyl] benzene, 1,4-bis [1- (4-hydroxyphenyl) -1-methylethyl ] Benzene, 4,6-bis [1- (4-hydroxyphenyl) -1-methylethyl] -1,3-dihydroxybenzene, 1,1-bis (4-hydroxyphenyl) -1- [4
  • the photosensitive resin composition of this embodiment may contain other components other than the above-mentioned components.
  • other components include a colorant, an adhesion aid, a leveling agent, and an inorganic filler having no Si—O bond.
  • the inorganic filler include, but are not limited to, aluminum compounds such as aluminum oxide and aluminum hydroxide; alkali metal compounds; alkalis such as calcium carbonate, calcium hydroxide, barium sulfate, barium carbonate, magnesium oxide, and magnesium hydroxide.
  • the inorganic filler may be used alone or in combination of two or more. Any inorganic filler is preferably dispersed with a maximum particle size of 2 ⁇ m or less when dispersed in the photosensitive resin composition. At that time, a silane coupling agent can be used in order to disperse the resin in the resin without aggregation.
  • the content of the inorganic filler is preferably 1 to 70% by mass based on the total amount of the photosensitive resin composition (however, when the component (F) is used, excluding the component (F)). More preferably, it is ⁇ 65 mass%.
  • the resist pattern forming method includes a step of forming a photosensitive layer on a substrate using a photosensitive element (photosensitive layer preparation step), a step of exposing the photosensitive layer to a predetermined pattern, and an exposure. Developing the subsequent photosensitive layer, and heat-treating the resulting resin pattern.
  • the resist pattern forming method of this embodiment may further include a step of heat-treating (post-exposure baking) the photosensitive layer between the exposure step and the development step.
  • the method for forming a resist pattern according to this embodiment includes a step of forming a photosensitive layer on a substrate using a photosensitive element, exposing the photosensitive layer to a predetermined pattern, and post-exposure heat treatment (after exposure). And a step of developing the photosensitive layer after the heat treatment (baking after exposure) and heat-treating the obtained resin pattern.
  • the above-described photosensitive layer is formed on a substrate on which a resist pattern is to be formed.
  • the process of forming a photosensitive layer can be performed by arrange
  • the photosensitive layer preparation step can also be referred to as a step of obtaining a base material (for example, a substrate) including a photosensitive layer containing a photosensitive resin composition.
  • the photosensitive layer can be formed, for example, by transferring (laminating) the photosensitive layer in the photosensitive element onto a substrate.
  • the substrate may be a substrate.
  • a substrate for example, a copper foil with resin, a copper clad laminate, a silicon wafer with a metal sputtered film, a silicon wafer with a copper plating film, an alumina substrate, or the like can be used.
  • the surface on which the photosensitive layer is formed on the substrate may be a cured resin layer formed using the photosensitive resin composition. In that case, there exists a tendency for adhesiveness with a base material to improve.
  • the photosensitive layer is exposed to a predetermined pattern through a predetermined mask pattern.
  • actinic rays used for exposure include rays using a g-line stepper as a light source; ultraviolet rays using a low-pressure mercury lamp, high-pressure mercury lamp, metal halide lamp, i-line stepper and the like as a light source; electron beams;
  • the exposure amount is appropriately selected depending on the light source used, the thickness of the photosensitive layer, and the like.
  • the exposure dose may be about 100 to 3000 mJ / cm 2 when the photosensitive layer thickness is 5 to 50 ⁇ m.
  • the curing reaction of the component (A) and the component (C) by the acid generated from the photosensitive acid generator can be promoted.
  • the post-exposure baking conditions vary depending on the composition of the photosensitive resin composition, the content of each component, the thickness of the photosensitive layer, and the like, but for example, heating at 50 to 150 ° C. for 1 to 60 minutes is preferable. It is more preferable to heat at 100 ° C. for 1 to 15 minutes. Further, it may be heated at 70 to 150 ° C. for 1 to 60 minutes, or at 80 to 120 ° C. for 1 to 60 minutes.
  • the photosensitive layer (coating film) that has been subjected to exposure and / or post-exposure baking is developed with an alkaline developer, and the unexposed areas (areas other than the cured areas) are dissolved and removed to obtain a desired resist pattern.
  • Examples of the developing method in this case include a shower developing method, a spray developing method, an immersion developing method, and a paddle developing method.
  • the development conditions are, for example, 20 to 40 ° C. and 10 to 300 seconds in the spray development method.
  • the alkaline developer examples include an alkaline aqueous solution in which an alkaline compound such as sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, and choline is dissolved in water so as to have a concentration of 1 to 10% by mass; Is mentioned.
  • An appropriate amount of a water-soluble organic solvent such as methanol or ethanol, a surfactant, or the like can be added to the alkaline developer.
  • the alkaline developer is preferably tetramethylammonium hydroxide from the viewpoint of further excellent resolution.
  • a cured film (resist pattern) of the photosensitive resin composition is obtained by performing a heat treatment to develop the insulating film characteristics.
  • the curing conditions of the photosensitive resin composition are not particularly limited, but can be adjusted according to the use of the cured product.
  • the photosensitive resin composition can be cured by heating at 50 to 250 ° C. for 30 minutes to 10 hours.
  • heating can be performed in two stages in order to sufficiently advance the curing and / or to prevent deformation of the obtained resin pattern.
  • it can be cured by heating at 50 to 120 ° C. for 5 minutes to 2 hours in the first stage and further heating at 80 to 200 ° C. for 10 minutes to 10 hours in the second stage.
  • the heating equipment is not particularly limited, and a general oven, infrared furnace, or the like can be used.
  • the semiconductor device includes a cured product of the photosensitive layer in the present embodiment.
  • the cured product of the photosensitive layer of this embodiment can be suitably used as, for example, a surface protective film and / or an interlayer insulating film of a semiconductor element, or a solder resist and / or an interlayer insulating film in a multilayer printed wiring board.
  • the semiconductor device of this embodiment includes a circuit substrate (for example, a circuit board) having a cured product of the photosensitive layer of this embodiment.
  • FIG. 3 is a view showing a method for producing a multilayer printed wiring board including the cured product of the photosensitive layer according to the present embodiment as a solder resist and / or an interlayer insulating film.
  • the multilayer printed wiring board 100A shown in FIG. 3F has a wiring pattern on the surface and inside.
  • the multilayer printed wiring board 100A is obtained by laminating a copper clad laminate, an interlayer insulating film, a metal foil, and the like and appropriately forming a wiring pattern by an etching method or a semi-additive method.
  • a method of manufacturing the multilayer printed wiring board 100A according to an embodiment of the present disclosure will be briefly described with reference to FIG.
  • an interlayer insulating film 103 is formed on both surfaces of a substrate 101 (such as a copper clad laminate) having a wiring pattern 102 on the surface (see FIG. 3A).
  • the interlayer insulating film 103 can be formed by preparing the above-described photosensitive element in advance and attaching the photosensitive layer of the photosensitive element to the surface of the printed wiring board using a laminator.
  • an opening 104 is formed by using a YAG laser or a carbon dioxide gas laser in a place that needs to be electrically connected to the outside (see FIG. 3B). Smear (residue) around the opening 104 is removed by desmear treatment.
  • a seed layer 105 is formed by an electroless plating method (see FIG. 3C).
  • a photosensitive layer containing a photosensitive resin composition (a semi-additive photosensitive resin composition) is formed on the seed layer 105, and a predetermined pattern is exposed and developed to form a resin pattern 106 (FIG. 3 ( d)).
  • a wiring pattern 107 is formed on the portion of the seed layer 105 where the resin pattern 106 is not formed by electrolytic plating, and the resin pattern 106 is removed by a peeling solution, and then the wiring pattern 107 of the seed layer 105 is formed.
  • the part which is not removed is removed by etching (see FIG. 3E).
  • the multilayer printed wiring board 100A can be manufactured by repeating the above operation and forming the solder resist 108 containing the cured product of the above-described photosensitive resin composition on the outermost surface (see FIG. 3 (f)).
  • the interlayer insulating film 103 and / or the solder resist 108 can be formed by using the resist pattern forming method described above. Moreover, it can form using the method provided with the process of forming a photosensitive layer, and the process of heat-processing. In the multilayer printed wiring board 100A thus obtained, semiconductor elements are mounted at corresponding locations, and electrical connection can be ensured.
  • A-1 Novolac resin (Asahi Organic Materials Co., Ltd., trade name: TR4020G, weight average molecular weight: 13000)
  • A-2 Novolac resin (manufactured by Asahi Organic Materials Co., Ltd., trade name: TR4080G, weight average molecular weight: 5000)
  • B-1 Triarylsulfonium salt (manufactured by San Apro Co., Ltd., trade name: CPI-310B, anion: tetrakis (pentafluorophenyl) borate)
  • C-1 1,3,4,6-tetrakis (methoxymethyl) glycoluril (manufactured by Sanwa Chemical Co., Ltd., trade name: Nicalak MX-270)
  • D-1 Pentaerythritol triacrylate (Nippon Kayaku Co., Ltd., trade name: PET-30)
  • E-1 4,4′-bis (diethylamino) be
  • photosensitive element As the support, those having an olefin resin layer, an aminoalkyd resin layer, or a silicone resin layer formed on a support substrate and those not formed were prepared.
  • the photosensitive resin composition was applied onto a support so that the thickness of the photosensitive resin composition was uniform, and dried for 10 minutes with a hot air convection dryer at 90 ° C.
  • a polyethylene film manufactured by Tamapoly Co., Ltd., product name: NF-15
  • NF-15 polyethylene film
  • the copper-clad laminate with the photosensitive element attached is attached to a rheometer (manufactured by Rheotech Co., Ltd., trade name: FUDOH RHEO METER RT-3010D-CW), peeled off at 23 ° C., 30 cm / min, angle 180 °
  • the support was peeled from the photosensitive layer, and the peel strength between the support and the photosensitive layer was evaluated.
  • the measured value fluctuated in a peak shape instead of a constant value
  • the average value of the peak was taken as the peel strength.
  • Table 1 The evaluation results are shown in Table 1.
  • the photosensitive element was cut into 2 cm ⁇ 10 cm with a cutter, and attached to a rigid copper-clad laminate with a double-sided tape so that the support and the copper-clad laminate were in contact.
  • the copper-clad laminate with the photosensitive element attached is attached to a rheometer (manufactured by Rheotech Co., Ltd., trade name: FUDOH RHEO METER RT-3010D-CW), peeled off at 23 ° C., 30 cm / min, angle 180 °
  • the protective layer was peeled from the photosensitive layer, and the peel strength between the protective layer and the photosensitive layer was evaluated.
  • the measured value fluctuated in a peak shape instead of a constant value
  • the average value of the peak was taken as the peel strength.
  • the peel strength ratio was evaluated as a value obtained by dividing the peel strength between the support and the photosensitive layer by the peel strength between the protective layer and the photosensitive layer. The evaluation results are shown in Table 1.
  • the photosensitive element from which the protective layer was peeled was laminated on a 6-inch diameter silicon wafer so that the photosensitive layer was in contact with the silicon wafer to obtain a laminate.
  • Lamination was performed using a vacuum pressurizing laminator with a heater at 60 ° C. (upper), a heater at 60 ° C. (lower), a vacuuming time of 20 seconds, a pressing time of 20 seconds, and a pressure of 0.4 MPa. .
  • the support of the laminate is peeled off, and reduced projection exposure is performed on the photosensitive layer through the mask with i-line (365 nm) using an i-line stepper (trade name: FPA-3000iW, manufactured by Canon Inc.). Went.
  • a negative pattern having via openings (unexposed portions) in 1 ⁇ m increments with a via diameter of 1 to 30 ⁇ m was used as the mask.
  • the exposure amount is in the range of 100 ⁇ 2000mJ / cm 2, was subjected to the reduction projection exposure while changing by 100 mJ / cm 2.
  • the exposed photosensitive layer (coating film) was heated at 65 ° C. for 1 minute and then at 75 ° C. for 8 minutes (post exposure bake). Next, a 2.38 mass% tetramethylammonium hydroxide aqueous solution (manufactured by Tama Chemical Industry Co., Ltd., trade name: TMAH 2.38%) is used as a developer, and a developing machine (trade name: AD- manufactured by Takizawa Sangyo Co., Ltd.) is used. 1200) and spray the developer onto the photosensitive layer (coating film) in a time corresponding to four times the shortest development time (the shortest time to remove the unexposed area) (pump discharge pressure [developer]: 0. 16 MPa) to remove the unexposed area.
  • TMAH 2.38 tetramethylammonium hydroxide aqueous solution
  • purified water (trade name: purified water, manufactured by Wako Pure Chemical Industries, Ltd.) was sprayed as a rinse solution for 60 seconds (pump discharge pressure [rinse solution]: 0.12 to 0.14 MPa) to wash away the developer. . And it was made to dry and the resin pattern was formed. The formed resin pattern was observed by enlarging the magnification to 1000 times using a metal microscope. The diameter of the smallest via opening was evaluated as the resolution among the patterns formed without the via opening (unexposed area) being removed cleanly and the insulating resin part (exposed area) being reduced in film thickness and without film roughness. . The evaluation results are shown in Table 1. In Comparative Example 1-1, since the peelability of the support was poor and the photosensitive layer was destroyed, the resolution was not evaluated.
  • Examples 1-1 and 1-2 using a support having an olefin resin layer or an amino alkyd resin layer having a peel strength of less than 4.0 N / m between the support and the photosensitive layer were used in Examples 1-1 and 1-2.
  • the peelability of the support body improved from B to A.
  • the resolution was 7 ⁇ m, and it was found that the resolution was extremely good as in Comparative Examples 1-2 to 1-6.
  • A-1 Novolac resin (Asahi Organic Materials Co., Ltd., trade name: TR4020G, weight average molecular weight: 13000)
  • A-2 Novolac resin (manufactured by Asahi Organic Materials Co., Ltd., trade name: TR4080G, weight average molecular weight: 5000)
  • B-1 Triarylsulfonium salt (manufactured by San Apro Co., Ltd., trade name: CPI-310B, anion: tetrakis (pentafluorophenyl) borate)
  • C-1 1,3,4,6-tetrakis (methoxymethyl) glycoluril (manufactured by Sanwa Chemical Co., Ltd., trade name: Nicalak MX-270)
  • D-1 Pentaerythritol triacrylate (Nippon Kayaku Co., Ltd., trade name: PET-30)
  • E-1 4,4′-bis (diethylamino) be
  • the above photosensitive resin composition is formed on a polyethylene terephthalate film (manufactured by Teijin DuPont Films, trade name: Purex A53, "Purex” is a registered trademark) (support), and the thickness of the photosensitive resin composition is uniform. And dried for 10 minutes with a hot air convection dryer at 90 ° C. After drying, any one of PET1, PE1-2, or OPP1-3 as a protective layer was laminated on the photosensitive layer to obtain a photosensitive element having a photosensitive layer thickness of 10 ⁇ m.
  • the protective layer having the silicone resin layer was laminated so that the support, the photosensitive layer, the silicone resin layer, and the protective layer substrate were in this order.
  • the photosensitive element from which the protective layer was peeled was laminated on a 6-inch diameter silicon wafer so that the photosensitive layer was in contact with the silicon wafer to obtain a laminate.
  • Lamination was performed using a vacuum pressurizing laminator with a heater at 60 ° C. (upper), a heater at 60 ° C. (lower), a vacuuming time of 20 seconds, a pressing time of 20 seconds, and a pressure of 0.4 MPa. .
  • the support of the laminate is peeled off, and reduced projection exposure is performed on the photosensitive layer through the mask with i-line (365 nm) using an i-line stepper (trade name: FPA-3000iW, manufactured by Canon Inc.). Went.
  • a negative pattern having via openings (unexposed portions) in 1 ⁇ m increments with a via diameter of 1 to 30 ⁇ m was used as the mask.
  • the exposure amount is in the range of 100 ⁇ 2000mJ / cm 2, was subjected to the reduction projection exposure while changing by 100 mJ / cm 2.
  • the exposed photosensitive layer (coating film) was heated at 65 ° C. for 1 minute and then at 75 ° C. for 8 minutes (post exposure bake). Next, a 2.38 mass% tetramethylammonium hydroxide aqueous solution (manufactured by Tama Chemical Industry Co., Ltd., trade name: TMAH 2.38%) is used as a developer, and a developing machine (trade name: AD- manufactured by Takizawa Sangyo Co., Ltd.) is used. 1200) and spray the developer onto the photosensitive layer (coating film) in a time corresponding to four times the shortest development time (the shortest time to remove the unexposed area) (pump discharge pressure [developer]: 0. 16 MPa) to remove the unexposed area.
  • TMAH 2.38 tetramethylammonium hydroxide aqueous solution
  • purified water (trade name: purified water, manufactured by Wako Pure Chemical Industries, Ltd.) was sprayed as a rinse solution for 60 seconds (pump discharge pressure [rinse solution]: 0.12 to 0.14 MPa) to wash away the developer. . And it was made to dry and the resin pattern was formed. The formed resin pattern was observed by enlarging the magnification to 1000 times using a metal microscope. The diameter of the smallest via opening was evaluated as the resolution among the patterns formed without the via opening (unexposed area) being removed cleanly and the insulating resin part (exposed area) being reduced in film thickness and without film roughness. . The evaluation results are shown in Table 2.
  • Example 2-1 As is apparent from Table 2, in Example 2-1 using the protective layer having the silicone resin layer, the peelability of the protective layer was improved from B to A as compared with Comparative Examples 2-1 to 2-5. did. In addition, Example 2-1 has a resolution of 7 ⁇ m, and it was found that the resolution was extremely good as in Comparative Examples 2-1 to 2-5.
  • the photosensitive element of the present disclosure can be applied to formation of a material used for a surface protective film or an interlayer insulating film of a semiconductor element, and formation of a material used for a solder resist of a wiring board material or an interlayer insulating film.
  • the photosensitive layer in the photosensitive element of the first embodiment of the present disclosure was thinned and densified because the resolution, the protective layer peelability, and the support peelability were all good. It is suitably used for a highly integrated package substrate.
  • the photosensitive element of the second embodiment of the present disclosure has good resolution and protective layer peeling properties, so that it is highly integrated with fine lines and high density. It is suitably used for a package substrate or the like.

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Abstract

L'invention concerne un élément photosensible qui est pourvu d'un support, d'une couche photosensible et d'une couche de protection dans cet ordre, le support ayant soit une couche de résine d'oléfine soit une couche de résine d'amino-alkyde en tant que couche superficielle sur le côté de la couche photosensible. Le rapport de la résistance à la séparation entre la couche photosensible et le support par rapport à la résistance à la séparation entre la couche photosensible et la couche de protection est d'au moins 1,0, et la résistance à la séparation entre la couche photosensible et le support est de 6,0 N/m ou moins.
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