WO2017213056A1 - パターン付き基材の製造方法、及び、回路基板の製造方法 - Google Patents

パターン付き基材の製造方法、及び、回路基板の製造方法 Download PDF

Info

Publication number
WO2017213056A1
WO2017213056A1 PCT/JP2017/020695 JP2017020695W WO2017213056A1 WO 2017213056 A1 WO2017213056 A1 WO 2017213056A1 JP 2017020695 W JP2017020695 W JP 2017020695W WO 2017213056 A1 WO2017213056 A1 WO 2017213056A1
Authority
WO
WIPO (PCT)
Prior art keywords
resin composition
photosensitive resin
group
substrate
structural unit
Prior art date
Application number
PCT/JP2017/020695
Other languages
English (en)
French (fr)
Japanese (ja)
Inventor
藤本　進二
佐藤　守正
晃男 片山
Original Assignee
富士フイルム株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 富士フイルム株式会社 filed Critical 富士フイルム株式会社
Priority to KR1020187034333A priority Critical patent/KR102110818B1/ko
Priority to JP2018522459A priority patent/JP6573721B2/ja
Priority to CN201780033955.9A priority patent/CN109219777B/zh
Publication of WO2017213056A1 publication Critical patent/WO2017213056A1/ja

Links

Images

Classifications

    • 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
    • G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F1/00—Originals for photomechanical production of textured or patterned surfaces, e.g., masks, photo-masks, reticles; Mask blanks or pellicles therefor; Containers specially adapted therefor; Preparation thereof
    • G03F1/68—Preparation processes not covered by groups G03F1/20 - G03F1/50
    • G03F1/80—Etching
    • 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
    • G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
    • 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
    • G03F7/26—Processing photosensitive materials; Apparatus therefor
    • G03F7/38—Treatment before imagewise removal, e.g. prebaking
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/26—Processing photosensitive materials; Apparatus therefor
    • G03F7/42—Stripping or agents therefor
    • G—PHYSICS
    • G06—COMPUTING; CALCULATING OR COUNTING
    • G06F—ELECTRIC DIGITAL DATA PROCESSING
    • G06F3/00—Input arrangements for transferring data to be processed into a form capable of being handled by the computer; Output arrangements for transferring data from processing unit to output unit, e.g. interface arrangements
    • G06F3/01—Input arrangements or combined input and output arrangements for interaction between user and computer
    • G06F3/03—Arrangements for converting the position or the displacement of a member into a coded form
    • G06F3/041—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means
    • G—PHYSICS
    • G06—COMPUTING; CALCULATING OR COUNTING
    • G06F—ELECTRIC DIGITAL DATA PROCESSING
    • G06F3/00—Input arrangements for transferring data to be processed into a form capable of being handled by the computer; Output arrangements for transferring data from processing unit to output unit, e.g. interface arrangements
    • G06F3/01—Input arrangements or combined input and output arrangements for interaction between user and computer
    • G06F3/03—Arrangements for converting the position or the displacement of a member into a coded form
    • G06F3/041—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means
    • G06F3/044—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means by capacitive means

Definitions

  • the present disclosure relates to a method for manufacturing a substrate with a pattern and a method for manufacturing a circuit board.
  • a display device such as an organic electroluminescence (EL) display device and a liquid crystal display device
  • a touch panel such as a capacitance-type input device
  • an electrode pattern corresponding to a sensor in a visual recognition portion a wiring in a peripheral wiring portion
  • a wiring in a take-out wiring portion A conductive pattern such as is provided inside the touch panel.
  • a patterned layer is formed by a photosensitive resin composition layer provided on an arbitrary substrate using a photosensitive transfer material because the number of steps for obtaining a required pattern shape is small.
  • a method of developing after exposure through a mask having a desired pattern is widely used.
  • Patent Document 1 includes a support and a photosensitive resin composition layer, and the photosensitive resin composition layer has a structural unit (A) in which an acid group is protected by an acid-decomposable group.
  • a photosensitive transfer material comprising a polymer component comprising a polymer having (a1) and (B) a photoacid generator, wherein the photosensitive resin composition does not have an ethylenic crosslinked structure. ing.
  • the problem to be solved by an embodiment of the present invention is that the pattern shape obtained is less deformed and has a pattern obtained by the method for producing a patterned substrate having excellent resolution and the method for producing the patterned substrate. It is providing the manufacturing method of the circuit board using a base material.
  • Step 1 for pressure-bonding a photosensitive transfer material comprising a temporary support and a photosensitive resin composition layer to a base material provided with a conductive layer
  • Step 2 for exposing the photosensitive resin composition layer
  • Step 3 for winding and rolling the base material provided with the photosensitive resin composition layer, developing the roll-shaped base material, and developing the exposed photosensitive resin composition layer
  • a method for producing a patterned substrate which is a layer comprising a polymer component containing a polymer having a structural unit a1 having a group protected by a group, and a chemically amplified positive photosensitive resin composition containing a photoacid generator .
  • ⁇ 4> The method for producing a patterned substrate according to any one of ⁇ 1> to ⁇ 3>, wherein the step a is performed between the step 1 and the step 2.
  • the polymer includes a structural unit represented by the following formula A as the structural unit a1 and a structural unit having an acid group, and a polymer having a glass transition temperature of 90 ° C. or less ⁇
  • R 31 and R 32 each independently represent a hydrogen atom, an alkyl group or an aryl group, at least one of R 31 and R 32 is an alkyl group or an aryl group, and R 33 is an alkyl group or Represents an aryl group, R 31 or R 32 and R 33 may combine to form a cyclic ether, R 34 represents a hydrogen atom or a methyl group, X 0 represents a single bond or an arylene group, * Represents a bonding position with another structure.
  • ⁇ 6> The content of the polymer containing the structural unit represented by the formula A and the structural unit having an acid group in the photosensitive resin composition layer and having a glass transition temperature of 90 ° C. or lower is ⁇ 5>.
  • ⁇ 7> The patterned substrate according to any one of ⁇ 1> to ⁇ 6>, wherein the photoacid generator includes at least one compound selected from the group consisting of an onium salt compound and an oxime sulfonate compound. Manufacturing method.
  • ⁇ 8> The method for producing a patterned substrate according to any one of ⁇ 1> to ⁇ 7>, wherein the photoacid generator includes an oxime sulfonate compound.
  • ⁇ 9> The method for producing a patterned substrate according to any one of ⁇ 1> to ⁇ 8>, wherein conveyance of the substrate is stopped at the time of exposure in the step 2.
  • a base material provided with a temporary support, a photosensitive resin composition layer, and a conductive layer is wound up into a roll shape, and a roll shape is obtained.
  • the method for producing a patterned substrate according to any one of ⁇ 1> to ⁇ 9> further comprising a step of developing the substrate.
  • ⁇ 11> Manufacture of a circuit board including the step 5 of etching the conductive layer in the patterned base material obtained by the method for manufacturing a patterned base material according to any one of ⁇ 1> to ⁇ 10> Method.
  • ⁇ 12> The method for producing a circuit board according to ⁇ 11>, including a step 6 of peeling the photosensitive resin composition layer using a peeling liquid after the step 5.
  • a method for producing a patterned substrate having little resolution of a pattern shape to be obtained and excellent in resolution, and a substrate with a pattern obtained by the method for producing a patterned substrate are used. It is possible to provide a method of manufacturing a circuit board.
  • symbol may be abbreviate
  • a numerical range expressed using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.
  • (meth) acryl” represents both and / or acryl and methacryl
  • (meth) acrylate” represents both and / or acrylate and methacrylate.
  • the amount of each component in the composition is the total amount of the plurality of substances present in the composition unless there is a specific indication when there are a plurality of substances corresponding to each component in the composition. Means.
  • the term “process” is not only an independent process, but is included in this term if the intended purpose of the process is achieved even when it cannot be clearly distinguished from other processes.
  • the notation that does not indicate substitution and non-substitution includes not only those having no substituent but also those having a substituent.
  • the “alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
  • the chemical structural formula in this specification may be expressed as a simplified structural formula in which a hydrogen atom is omitted.
  • “mass%” and “weight%” are synonymous, and “part by mass” and “part by weight” are synonymous.
  • a combination of two or more preferred embodiments is a more preferred embodiment.
  • the weight average molecular weight and the number average molecular weight in the polymer component are the weight average molecular weight in terms of polystyrene measured by gel permeation chromatography (GPC) using tetrahydrofuran (THF) as a solvent. is there.
  • the manufacturing method of the base material with a pattern of this indication WHEREIN The process 1 which crimps
  • the method for producing a patterned substrate of the present disclosure preferably includes the steps 1 to 4 in this order.
  • the present inventors presume that the steps of transferring, exposing, and developing are arranged independently, and unwinding before and after each step and incorporating the winding are ideal within the scope of the present technology. is doing.
  • these steps of transfer, exposure, and development are arranged independently, and the chemically amplified positive photosensitive resin composition is used in a process incorporating unwinding and winding before and after each process.
  • the present inventors have found that pixel deformation may occur when the formed layer is imaged. As a result of intensive studies, the present inventors have found that this phenomenon is a characteristic phenomenon when a chemically amplified positive resin composition as described in Patent Document 1 is used.
  • the manufacturing method of the base material with a pattern of this indication includes the process 1 which crimps
  • the said photosensitive resin From the chemically amplified positive photosensitive resin composition, wherein the composition layer includes a polymer component including a polymer having a structural unit a1 having a group in which an acid group is protected by an acid-decomposable group, and a photoacid generator. It is a layer. Details of the chemically amplified positive photosensitive resin composition in the present disclosure will be described later.
  • the photosensitive resin composition layer is a layer made of a chemically amplified positive photosensitive resin composition (that is, a chemically amplified positive photosensitive resin composition).
  • the photoacid generator in the chemically amplified positive photosensitive resin composition is such that an acid generated in response to actinic light acts as a catalyst for deprotection of protected acid groups in the polymer. Therefore, an acid generated by the action of one photon contributes to a number of deprotection reactions, and the quantum yield exceeds 1, for example, a large value such as the power of 10, which is a result of so-called chemical amplification. High sensitivity can be obtained.
  • the substrate used in the present disclosure is preferably a glass substrate or a resin film substrate, and more preferably a resin film substrate.
  • a base material is a resin film base material.
  • the refractive index of the substrate is preferably 1.50 to 1.52.
  • the said base material may be comprised with translucent base materials (transparent base material), such as a glass base material.
  • the tempered glass represented by the gorilla glass of Corning, etc. can be used.
  • materials used in JP 2010-86684 A, JP 2010-152809 A, or JP 2010-257492 A can be preferably used.
  • transparent in the present disclosure means that the transmittance of all visible light is 85% or more, preferably 90% or more, and more preferably 95% or more.
  • a film substrate it is preferable to use a substrate that is optically undistorted and has high transparency.
  • Specific examples of the material include polyethylene terephthalate (PET), polyethylene naphthalate, polycarbonate, cellulose triacetate, and cycloolefin polymer.
  • the base material provided with the conductive layer has at least a conductive layer on the surface of the base material.
  • the conductivity in the present disclosure means that the volume resistivity is less than 1 ⁇ 10 7 ⁇ ⁇ cm.
  • the conductive layer include any conductive layer used for general circuit wiring or touch panel wiring.
  • the material for the conductive layer include metals and metal oxides. Examples of the metal include Al, Zn, Cu, Fe, Ni, Cr, Au, Ag, Ti, W, Si, and Mo. Examples of the metal oxide include ITO (Indium Tin Oxide) and IZO (Indium Zinc Oxide).
  • the conductive layer preferably contains a metal oxide.
  • the conductive layer may be formed of one layer or two or more layers, and the conductive layer on the substrate surface may be formed of different materials. For example, an aspect having two or more conductive layers formed of different materials on one surface of the substrate, a metal layer is formed on a part of one surface of the substrate, and the metal is formed on the other part An aspect in which a metal layer different from the layer is formed, and a metal layer is formed on a part of one surface of the substrate, and a metal oxide layer is formed on another part of the one surface. The aspect etc. which can be illustrated can be illustrated.
  • the shape and thickness of the base material and the conductive layer are not particularly limited, and may be appropriately set according to a desired base material with a pattern or a circuit board.
  • the photosensitive transfer material in the present disclosure includes a temporary support and a photosensitive resin composition layer.
  • the temporary support is preferably a support that supports the photosensitive resin composition layer and is peelable from the photosensitive resin composition layer.
  • a glass substrate, a resin film, paper, etc. are mentioned, From viewpoints, such as intensity
  • the resin film include a polyethylene terephthalate film, a polyethylene naphthalate film, a polypropylene film, a polyethylene film, a cellulose triacetate film, a polystyrene film, and a polycarbonate film.
  • a polyethylene terephthalate film is preferable, and a biaxially stretched polyethylene terephthalate film is particularly preferable.
  • the said temporary support body exposes the photosensitive resin composition layer through a temporary support body in the said process 2, it is preferable to have a light transmittance.
  • Having light transmittance means that the transmittance of the main wavelength of light used for exposure in the above step 2 is 50% or more, and the transmittance of the main wavelength of light used for exposure is improved in sensitivity. From the viewpoint, 60% or more is preferable, and 70% or more is more preferable.
  • the thickness of the temporary support is not particularly limited, but is preferably in the range of 5 ⁇ m to 200 ⁇ m, and more preferably in the range of 10 ⁇ m to 150 ⁇ m from the viewpoint of ease of handling and versatility.
  • the thickness of the temporary support is determined depending on the material from the viewpoints of strength as a temporary support, flexibility required for bonding with the base material, and light transmittance required in the exposure process. You may choose according to it.
  • the photosensitive transfer material includes a photosensitive resin composition layer, and the photosensitive resin composition layer includes a polymer having a structural unit a1 having a group in which an acid group is protected by an acid-decomposable group. It is a layer made of a chemically amplified positive photosensitive resin composition containing a component and a photoacid generator. Details of the chemically amplified positive photosensitive resin composition will be described later.
  • the temporary support and the photosensitive resin composition layer may or may not be in direct contact.
  • the thickness of the photosensitive resin composition layer is preferably 0.5 ⁇ m to 20 ⁇ m.
  • the thickness of the photosensitive resin composition layer is 20 ⁇ m or less, the pattern resolution is more excellent, and when it is 0.5 ⁇ m or more, it is preferable from the viewpoint of pattern linearity.
  • the thickness of the photosensitive resin composition layer is more preferably 0.8 ⁇ m to 15 ⁇ m, and particularly preferably 1.0 ⁇ m to 10 ⁇ m.
  • a photosensitive transfer material provided with the photosensitive resin composition layer on the temporary support can be obtained by applying the photosensitive resin composition to the temporary support and drying it.
  • the coating method is not particularly limited, and the coating can be performed by a known method such as slit coating, spin coating, curtain coating, and inkjet coating.
  • the photosensitive resin composition layer can also be apply
  • the photosensitive transfer material may have a layer other than the temporary support and the photosensitive resin composition layer (hereinafter may be referred to as “other layer”).
  • other layers include a contrast enhancement layer, an intermediate layer, a cover film, and a thermoplastic resin layer.
  • the photosensitive transfer material can have a contrast enhancement layer in addition to the photosensitive resin composition layer.
  • a contrast enhancement layer is a material that absorbs light at an exposure wavelength before exposure, but gradually decreases as it is exposed, that is, a material that increases light transmittance (light). It is a layer containing a decolorizable dye component.
  • the photodecolorable dye component include diazonium salts, stilbazolium salts, and aryl nitroso salts.
  • the film forming component include phenolic resins.
  • an intermediate layer is formed on the photosensitive resin composition layer, and a contrast enhancement layer (hereinafter sometimes referred to as “CEL” or “CE layer”) is formed on the intermediate layer. It can also be formed.
  • middle layer is provided in order to prevent mixing with CEL and the photosensitive resin composition layer.
  • the said photosensitive transfer material can also have a temporary support body, a thermoplastic resin layer, and the photosensitive resin composition layer in this order, for example.
  • the thermoplastic resin layer is preferably a non-photosensitive layer.
  • the photosensitive transfer material may have a cover film for the purpose of protecting the photosensitive resin composition layer.
  • the preferred embodiments of the thermoplastic resin layer are described in paragraphs 0189 to 0193 of JP 2014-85643 A, and the preferred embodiments of other layers are described in paragraphs 0194 to 0196 of JP 2014-85643 A, respectively. And the contents of these publications are incorporated herein.
  • the photosensitive transfer material When the photosensitive transfer material has other layers such as a thermoplastic resin layer, the photosensitive transfer material can be produced according to the method for producing a photosensitive transfer material described in paragraphs 0094 to 0098 of JP-A-2006-259138. it can.
  • a photosensitive transfer material having a thermoplastic resin layer and an intermediate layer when produced, a solution obtained by dissolving a thermoplastic organic polymer and an additive on a temporary support (a coating for a thermoplastic resin layer).
  • thermoplastic resin layer Liquid
  • intermediate layer a prepared liquid (intermediate layer) prepared by adding a resin and an additive to a solvent that does not dissolve the thermoplastic resin layer on the obtained thermoplastic resin layer Coating solution) is applied and dried to laminate the intermediate layer.
  • a photosensitive resin composition layer coating solution prepared using a solvent that does not dissolve the intermediate layer is further applied and dried to laminate the photosensitive resin composition layer. Can be suitably produced.
  • the photosensitive transfer material is pressure-bonded to a base material provided with the conductive layer. Moreover, in the said process 1, it is preferable to make it pressure-bond so that the said electroconductive layer and the said photosensitive resin composition layer may contact.
  • the photosensitive resin composition layer by which the pattern formation after exposure and image development can be used suitably as an etching resist at the time of etching a conductive layer.
  • a well-known transfer method and a lamination method can be used.
  • the photosensitive resin composition layer side of the photosensitive transfer material is overlaid on the conductive layer, and pressure is applied with a roll or the like, or pressure and heating are performed.
  • laminators such as a laminator, a vacuum laminator, and an auto-cut laminator that can further increase productivity can be used.
  • the manufacturing method of the base material with a pattern of this indication includes the process 2 which exposes the said photosensitive resin composition layer.
  • the step 2 it is preferable to irradiate the substrate provided with the coating film with actinic rays through a mask having a predetermined pattern.
  • the photoacid generator is decomposed to generate an acid.
  • the acid-decomposable group contained in the coating film component is hydrolyzed to produce an acid group, for example, a carboxyl group or a phenolic hydroxyl group.
  • the detailed arrangement and specific size of the pattern are not particularly limited.
  • the electrode pattern and the portion of the lead-out wiring are preferably fine wires of 100 ⁇ m or less, and more preferably 70 ⁇ m or less.
  • the exposure in step 2 may be exposure through a mask or digital exposure using a laser or the like, but is preferably exposure through an exposure mask. It is preferable that the manufacturing method of the base material with a pattern of this indication has the process b which makes the said photosensitive transfer material and exposure mask contact between the said process 1 and the said process 2. FIG. It is excellent in the resolution of the pattern obtained as it is the said aspect.
  • Visible light, ultraviolet light, and an electron beam are mentioned as actinic light, However, Visible light or ultraviolet light is preferable and an ultraviolet-ray is especially preferable.
  • an exposure light source using actinic light a low-pressure mercury lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a chemical lamp, a light-emitting diode (LED) light source, an excimer laser generator, and the like can be used.
  • Actinic rays having a wavelength of 300 nm to 450 nm, such as h-line (405 nm), can be preferably used.
  • irradiation light can also be adjusted through spectral filters, such as a long wavelength cut filter, a short wavelength cut filter, and a band pass filter, as needed.
  • spectral filters such as a long wavelength cut filter, a short wavelength cut filter, and a band pass filter
  • various types of exposure machines such as a mirror projection aligner, a stepper, a scanner, a proximity, a contact, a microlens array, and a laser exposure can be used.
  • Exposure dose depending on the photosensitive resin composition layer to be used may be appropriately selected, but is preferably from 5mJ / cm 2 ⁇ 200mJ / cm 2, it is 10mJ / cm 2 ⁇ 100mJ / cm 2 More preferred.
  • the apparatus becomes simple and the yield reduction due to the trouble of the apparatus can be reduced.
  • the base material provided with a temporary support body, the photosensitive resin composition layer, and an electroconductive layer is wound, the process made into roll shape, and the said roll-shaped said It is preferable to further include a step of developing the substrate.
  • the said photosensitive resin composition layer may be exposed with having a temporary support body, or a temporary support body is peeled and the said photosensitive resin is peeled off.
  • the composition layer may be exposed, it is preferable to peel the temporary support and expose the photosensitive resin composition layer. It is excellent in the resolution of the pattern obtained as it is the said aspect.
  • PEB post-exposure heat treatment
  • the temperature for performing PEB is preferably 30 ° C. or higher and 130 ° C. or lower, more preferably 40 ° C. or higher and 110 ° C. or lower, and particularly preferably 50 ° C. or higher and 100 ° C. or lower.
  • the acid-decomposable group in the present disclosure has a low activation energy for acid decomposition and is easily decomposed by an acid derived from an acid generator by exposure to generate an acid group, for example, a carboxyl group or a phenolic hydroxyl group.
  • a positive image can be formed by development without performing PEB.
  • the manufacturing method of the base material with a pattern of this indication includes the process 3 which winds up the said base material provided with the exposed said photosensitive resin composition layer, and makes it roll shape.
  • a winding roll is mentioned preferably.
  • the winding core used for winding conventionally known ones such as paper, resin, and metal can be used. From the viewpoints of dust generation, weight, and ease of handling, a resin winding core is preferable.
  • the material of the winding roll is not particularly limited as long as it has sufficient strength, and a known material can be used. For example, paper, resin, metal, and the like can be mentioned. From the viewpoint of dust generation, weight, ease of handling, and the like, a resin winding roll is preferable.
  • the step 3 it is preferable to repeat the winding and stopping in accordance with the conveyance stop at the time of exposure in the step 2. When winding and stopping are not repeated in accordance with the conveyance stop at the time of exposure in the above step 2, it is preferable to have a play mechanism such as a dancer roll.
  • the manufacturing method of the base material with a pattern of this indication includes the process a which peels the said temporary support body from the said photosensitive transfer material before the said process 3.
  • FIG. There is no restriction
  • the step a is preferably performed between the step 1 and the step 3, and more preferably performed between the step 1 and the step 2. It is excellent in the resolution of the pattern obtained as it is the said aspect.
  • the manufacturing method of the base material with a pattern of this indication includes the process b mentioned above, the said process a is performed between the said process 1 and the process b, or between the said process 2 and the process 3. It is preferable to carry out between step 1 and step b. It is excellent in the resolution of the pattern obtained as it is the said aspect.
  • Drawing 1 is a mimetic diagram showing typically process 2, process 3, and process a of one embodiment in a manufacturing method of a substrate with a pattern of this indication.
  • a base material 14 including a temporary support, a photosensitive resin composition layer, and a conductive layer is developed from an unwinding roll 12, and the base material 14 is transported to a transport roll 16.
  • the temporary support 18 is peeled from the base material 14, and the temporary support 18 is wound around the peeling roll 20.
  • the substrate 22 including the photosensitive resin composition layer and the conductive layer from which the temporary support 18 has been peeled is exposed in a pattern by an exposure light source 26 in an exposure device 24.
  • the exposed base material 22 is transported by a transport roll 28, wound up by a take-up roll 30, and becomes a roll-shaped base material 22.
  • FIG. 2 is a schematic diagram schematically showing Step 2, Step 3, and Step a of another embodiment in the method for manufacturing a patterned substrate of the present disclosure.
  • the base material 14 including the temporary support, the photosensitive resin composition layer, and the conductive layer is developed from the unwinding roll 12, transported to the transport roll 16, and further transported to the exposure device 24.
  • the substrate 14 is exposed in a pattern by an exposure light source 26 in the exposure device 24.
  • the exposed base material 14 is transported to a transport roll 28.
  • the temporary support 18 is peeled off from the substrate 14, and the temporary support 18 is wound around the peeling roll 20.
  • the base material 22 including the photosensitive resin composition layer and the conductive layer from which the temporary support 18 has been peeled is transported by a transport roll 28 and wound up by a take-up roll 30 to form a roll-shaped base material 22. .
  • a timing for performing step a it is also preferable to peel off the temporary support immediately before winding in step 1.
  • the manufacturing method of the base material with a pattern of this indication includes the process 4 which develops the said base material made into the said roll shape, develops the exposed said photosensitive resin composition layer, and forms a pattern.
  • deploy the said base material made into the said roll shape A well-known means can be used.
  • a winding roll an aspect in which the base material is developed while pulling an end of the base material and rotating the winding roll in a reverse direction to the winding time.
  • the developer is not particularly limited as long as the exposed portion of the photosensitive resin composition layer can be removed.
  • a known developer such as a developer described in JP-A-5-72724 may be used. Can do.
  • the developer is preferably a developer in which the exposed portion of the photosensitive resin composition layer exhibits a dissolution type development behavior.
  • the developer is preferably an alkaline aqueous solution, and more preferably, for example, an alkaline aqueous solution containing a compound having a pKa of 7 to 13 at a concentration of 0.05 mol / L (liter) to 5 mol / L.
  • the developer may further contain an organic solvent miscible with water, a surfactant, and the like. Examples of the developer suitably used in the present disclosure include the developer described in Paragraph 0194 of International Publication No. 2015/092731.
  • the development system is not particularly limited, and any of paddle development, shower development, shower and spin development, dip development, and the like may be used.
  • the shower development will be described.
  • the exposed portion can be removed by spraying a developer onto the photosensitive resin composition layer after exposure. Further, after the development, it is preferable to remove the development residue while spraying a cleaning agent or the like with a shower and rubbing with a brush or the like.
  • the liquid temperature of the developer is preferably 20 ° C. to 40 ° C.
  • the manufacturing method of the base material with a pattern of this indication may include well-known processes, such as the process of wash
  • the post-baking temperature is preferably 80 ° C. to 250 ° C., more preferably 110 ° C. to 170 ° C., and particularly preferably 130 ° C. to 150 ° C.
  • the post-baking time is preferably 1 to 30 minutes, more preferably 2 to 10 minutes, and particularly preferably 2 to 4 minutes.
  • the post-bake may be performed in an air environment or a nitrogen substitution environment. Further, the post-baking may be performed under atmospheric pressure or under reduced pressure.
  • the conveyance speed of the substrate at each step in the method for producing a patterned substrate of the present disclosure is not particularly limited, but is preferably 0.5 m / min to 10 m / min except during exposure, It is more preferably 2.0 m / min to 8.0 m / min except during exposure.
  • the manufacturing method of the base material with a pattern of this indication may have other processes, such as a post exposure process.
  • step 2 and other steps in the present disclosure the methods described in paragraphs 0035 to 0051 of JP-A-2006-23696 can be suitably used.
  • the manufacturing method of the circuit board of this indication includes the process 5 which etches the said electroconductive layer in the base material with a pattern obtained by the manufacturing method of the base material with a pattern of this indication.
  • Step 5 the pattern formed from the photosensitive resin composition layer in the patterned substrate obtained by the method for producing a patterned substrate of the present disclosure is used as an etching resist, and the conductive layer is etched.
  • Etching of the conductive layer can be performed by a known method such as the method described in paragraphs 0048 to 0054 of JP 2010-152155 A.
  • a commonly performed wet etching method in which the substrate is immersed in an etching solution can be used.
  • an etchant used for wet etching an acid type or alkaline type etchant may be appropriately selected in accordance with an object to be etched.
  • Acidic etchants include hydrochloric acid, sulfuric acid, nitric acid, acetic acid, hydrofluoric acid, oxalic acid, aqueous solutions of acidic components such as phosphoric acid, acidic components and ferric chloride, ammonium fluoride, or permanganese Examples thereof include a mixed aqueous solution of a salt such as potassium acid.
  • the acidic component a component obtained by combining a plurality of acidic components may be used.
  • Alkali type etching solutions include sodium hydroxide, potassium hydroxide, ammonia, organic amines, or aqueous solutions of alkali components such as salts of organic amines such as tetramethylammonium hydroxide, alkaline components and potassium permanganate.
  • alkali components such as salts of organic amines such as tetramethylammonium hydroxide, alkaline components and potassium permanganate.
  • a mixed aqueous solution of a salt such as As the alkali component, a component obtained by combining a plurality of alkali components may be used.
  • the temperature of the etching solution is not particularly limited, but is preferably 45 ° C. or lower.
  • the pattern used as an etching mask preferably exhibits particularly excellent resistance to acidic and alkaline etching solutions in a temperature range of 45 ° C. or lower. Therefore, the positive photosensitive resin layer is prevented from peeling off during the etching process, and the portion where the positive photosensitive resin layer does not exist is selectively etched.
  • a step of cleaning the substrate (cleaning step) and a step of drying the substrate (drying step) may be performed as necessary.
  • the cleaning step for example, the substrate may be cleaned with pure water for 10 seconds to 300 seconds at room temperature (10 ° C. to 35 ° C.).
  • the drying step for example, air blow may be used, and the air blow pressure (about 0.1 kg / cm 2 to about 5 kg / cm 2 ) may be appropriately adjusted for drying.
  • the manufacturing method of the circuit board of this indication includes the process 6 which peels the said photosensitive resin composition layer using a peeling liquid after the said process 5.
  • FIG. 5 After completion of the step 5, the patterned photosensitive resin composition layer remains. If the photosensitive resin composition layer is unnecessary, all the remaining photosensitive resin composition layers may be removed.
  • a method of peeling using a peeling solution for example, a substrate having the above-mentioned photosensitive resin composition layer in a peeling solution preferably stirred at 30 ° C. to 80 ° C., more preferably 50 ° C. to 80 ° C. A method of dipping for 5 to 30 minutes can be mentioned.
  • an inorganic alkali component such as sodium hydroxide or potassium hydroxide, or an organic alkali component such as a tertiary amine or a quaternary ammonium salt, water, dimethyl sulfoxide, N-methylpyrrolidone, or And a stripping solution dissolved in a mixed solution thereof.
  • a stripping solution may be used and stripped by a spray method, a shower method, a paddle method, or the like.
  • the circuit board manufacturing method of the present disclosure may include other arbitrary steps.
  • the following processes are mentioned, it is not limited to these processes.
  • the manufacturing method of the circuit board of this indication may include the process of reducing the visible light reflectance of a part or all of the conductive layer on the above-mentioned substrate.
  • the treatment for reducing the visible light reflectance include an oxidation treatment.
  • the visible light reflectance can be reduced by blackening by oxidizing copper to copper oxide.
  • paragraphs 0017 to 0025 of JP2014-150118A and paragraphs 0041, 0042, 0048 and 0058 of JP2013-206315A are described. And the contents of these publications are incorporated herein.
  • the method for manufacturing a circuit board according to the present disclosure includes a step of forming an insulating film on the formed circuit wiring (the etched conductive layer), and a step of forming a new conductive layer on the insulating film.
  • a step of forming an insulating film on the formed circuit wiring (the etched conductive layer) Is also preferable.
  • an insulating film having a desired pattern may be formed by photolithography using a photosensitive material having insulating properties.
  • a new conductive layer having a desired pattern may be formed by photolithography using a photosensitive material having conductivity.
  • the new conductive layer may be etched by forming an etching resist by the same method (step 1 to step 5 and step a) as described above, or separately. Etching may be performed by a known method. Even if the circuit board obtained by the method for manufacturing a circuit board of the present disclosure has only one layer of circuit wiring formed from the conductive layer, the circuit wiring of two or more layers formed from the conductive layer You may have.
  • the substrate has a plurality of conductive layers on both surfaces, and circuit formation is performed sequentially or simultaneously on the conductive layers formed on both surfaces of the substrate. It is also preferable to do.
  • a circuit wiring preferably a touch panel circuit wiring, in which the first conductive pattern is formed on one surface of the substrate and the second conductive pattern is formed on the other surface.
  • the circuit board of this indication is a circuit board manufactured by the manufacturing method of the circuit board of this indication.
  • the use of the circuit board manufactured by the manufacturing method of the circuit board of this indication is not limited, for example, it is preferred that it is a circuit board for touch panels. A preferred embodiment of the touch panel circuit board will be described later in the description of the capacitive input device.
  • an input device may be mentioned.
  • the input device in the present disclosure is preferably a capacitive touch panel.
  • the display device according to the present disclosure preferably includes the input device according to the present disclosure.
  • the display device in the present disclosure is preferably an organic EL display device and an image display device such as a liquid crystal display device.
  • the touch panel of this indication is a touch panel which has at least the circuit board manufactured by the manufacturing method of the circuit board of this indication. Moreover, it is preferable that the touchscreen of this indication has a transparent substrate, an electrode, and an insulating layer or a protective layer at least.
  • the touch panel display device of the present disclosure is a touch panel display device having at least a circuit board manufactured by the method of manufacturing a circuit board of the present disclosure, and is preferably a touch panel display device having the touch panel of the present disclosure.
  • the detection method in the touch panel of the present disclosure and the touch panel display device of the present disclosure may be any known method such as a resistive film method, a capacitance method, an ultrasonic method, an electromagnetic induction method, and an optical method.
  • the electrostatic capacity method is preferable.
  • As the touch panel type a so-called in-cell type (for example, those described in FIGS. 5, 6, 7, and 8 of JP-T-2012-517051), a so-called on-cell type (for example, JP 2013-168125 A). 19 of the gazette, those described in FIGS. 1 and 5 of JP 2012-89102 A, OGS (One Glass Solution) type, TOL (Touch-on-Lens) type (for example, JP No.
  • the chemically amplified positive photosensitive resin composition used for forming the photosensitive resin composition layer in the present disclosure includes a polymer having a structural unit a1 having a group in which an acid group is protected by an acid-decomposable group.
  • a coalescing component and a photoacid generator are included.
  • the preferred content of each component with respect to the total solid content of the chemically amplified positive photosensitive resin composition and the preferred content with respect to the total solid content of the photosensitive resin composition layer are in the same range, In the following description, it is assumed that they are interchangeable.
  • the said polymer is the following formula A applicable to the said structural unit a1 from a viewpoint of the adhesiveness of the said photosensitive resin composition layer and the base material provided with the said electroconductive layer, and the resolution of the pattern obtained.
  • a polymer having a structural unit (a) having an acid group and a glass transition temperature of 90 ° C. or lower also referred to as “specific polymer”.
  • the polymer having at least the structural unit a1 having a group in which an acid group is protected with an acid-decomposable group is more preferably a specific polymer.
  • R 31 and R 32 each independently represent a hydrogen atom, an alkyl group or an aryl group, at least one of R 31 and R 32 is an alkyl group or an aryl group, and R 33 is an alkyl group or Represents an aryl group, R 31 or R 32 and R 33 may combine to form a cyclic ether, R 34 represents a hydrogen atom or a methyl group, X 0 represents a single bond or an arylene group, * Represents a bonding position with another structure.
  • —C (R 31 ) (R 32 ) —O—R 33 in Formula A corresponds to the acid-decomposable group.
  • the chemically amplified positive photosensitive resin composition includes a polymer component including a polymer having a structural unit a1 having a group in which an acid group is protected with an acid-decomposable group.
  • a structural unit a1 having a group in which an acid group in the polymer is protected by an acid-decomposable group is subjected to a deprotection reaction to be an acid group by the action of a catalytic amount of an acidic substance generated by exposure. This acid group enables a curing reaction.
  • a structural unit a1 will be described.
  • the chemically amplified positive photosensitive resin composition may further contain a polymer other than a polymer having a structural unit having a group in which an acid group is protected by an acid-decomposable group. Moreover, it is preferable that all the polymers contained in the polymer component are polymers each having at least a structural unit a3 having an acid group.
  • the chemically amplified positive photosensitive resin composition may further contain a polymer other than these.
  • the polymer component in the present disclosure means a material including other polymers added as necessary. In addition, even if it is a high molecular compound, the compound applicable to the crosslinking agent and dispersing agent mentioned later shall not be contained in the said polymer component.
  • the above polymer is preferably an addition polymerization type resin, and more preferably a polymer having a structural unit derived from (meth) acrylic acid or an ester thereof.
  • the chemically amplified positive photosensitive resin composition has, as a polymer component, the structural unit (a) represented by the formula A as the structural unit a1 and the structural unit (b) having an acid group, And it is preferable that the specific polymer whose glass transition temperature is 90 degrees C or less is included.
  • the specific polymer contained in the chemically amplified positive photosensitive resin composition may be only one kind or two or more kinds.
  • the polymer component includes a polymer having at least a structural unit a1 having a group in which an acid group is protected with an acid-decomposable group.
  • an extremely sensitive chemically amplified positive photosensitive resin composition can be obtained.
  • the “group in which the acid group is protected with an acid-decomposable group” in the present disclosure can be any known acid group and acid-decomposable group, and is not particularly limited. Specific examples of the acid group preferably include a carboxyl group and a phenolic hydroxyl group.
  • Examples of the group in which the acid group is protected with an acid-decomposable group include groups that are relatively easily decomposed by an acid (for example, an ester group protected with a group represented by the formula A, a tetrahydropyranyl ester group, or a tetrahydrofuran group).
  • An acetal functional group such as a nyl ester group) or a group that is relatively difficult to decompose with an acid (for example, a tertiary alkyl group such as a tert-butyl ester group or a tertiary alkyl carbonate group such as a tert-butyl carbonate group).
  • the acid-decomposable group is preferably a group having a structure protected in the form of an acetal.
  • the structural unit (a) represented by the above formula A is a structural unit having a carboxy group protected with an acid-decomposable group.
  • the polymer contains the structural unit (a) represented by the formula A, the sensitivity at the time of pattern formation is excellent and the resolution is superior.
  • R 31 or R 32 when R 31 or R 32 is an alkyl group, an alkyl group having 1 to 10 carbon atoms is preferable. When R 31 or R 32 is an aryl group, a phenyl group is preferable. R 31 and R 32 are each preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
  • R 33 represents an alkyl group or an aryl group, preferably an alkyl group having 1 to 10 carbon atoms, and more preferably an alkyl group having 1 to 6 carbon atoms. The alkyl group and aryl group in R 33 may have a substituent.
  • R 31 or R 32 and R 33 may be linked to form a cyclic ether, and R 31 or R 32 and R 33 are preferably linked to form a cyclic ether.
  • the number of ring members of the cyclic ether is not particularly limited, but is preferably 5 or 6, and more preferably 5.
  • X 0 represents a single bond or an arylene group, and a single bond is preferable.
  • the arylene group may have a substituent.
  • R 34 represents a hydrogen atom or a methyl group, and is preferably a hydrogen atom from the viewpoint of lowering the Tg of the specific polymer. More specifically, the structural unit in which R 34 in Formula A is a hydrogen atom is preferably 20% by mass or more based on the total amount of the structural unit (a) contained in the polymer. In the structural unit (a), the content (content ratio: mass ratio) of the structural unit in which R 34 in formula A is a hydrogen atom is calculated by a conventional method from 13 C-nuclear magnetic resonance spectrum (NMR) measurement. It can be confirmed by the intensity ratio of the peak intensity.
  • NMR 13 C-nuclear magnetic resonance spectrum
  • the structural unit represented by the following formula A1 is more preferable from the viewpoint of further increasing the sensitivity during pattern formation.
  • R 34 represents a hydrogen atom or a methyl group, in each of R 35 ⁇ R 41 independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, * represents a bonding position to other structures .
  • R 34 is preferably a hydrogen atom.
  • R 35 to R 41 are preferably hydrogen atoms.
  • R 34 represents a hydrogen atom or a methyl group.
  • the structural unit (a) contained in the specific copolymer may be one type or two or more types.
  • the content of the structural unit (a) represented by the formula A in the specific polymer is preferably 20% by mass or more, and 20% by mass to 90% by mass with respect to the total mass of the specific polymer. Is more preferable, and 30 to 70% by mass is still more preferable.
  • the content (content ratio: mass ratio) of the structural unit (a) in the specific polymer can be confirmed by the intensity ratio of the peak intensity calculated by a conventional method from 13 C-NMR measurement.
  • the proportion of the structural unit (a) having a protected carboxy group in which the acid group is protected by an acid-decomposable group is the total of the polymer components.
  • the mass is preferably 5% by mass to 80% by mass, more preferably 10% by mass to 80% by mass, and particularly preferably 30% by mass to 70% by mass.
  • the polymer preferably includes a structural unit (b) having an acid group. Moreover, the said specific polymer contains the structural unit (b) which has an acid group.
  • the structural unit (b) is a structural unit containing an acid group that is not protected by an acid-decomposable group, that is, an acid group that does not have an acid-decomposable group.
  • the specific copolymer has good sensitivity at the time of pattern formation, becomes easily soluble in an alkaline developer in the development process after pattern exposure, and shortens the development time. Can be achieved.
  • the acid group in this specification means a proton dissociable group having a pKa of 12 or less.
  • the acid group is usually incorporated into the polymer as a structural unit [structural unit (b)] containing an acid group, using a monomer capable of forming an acid group.
  • the pKa of the acid group is preferably 10 or less, and more preferably 6 or less.
  • the pKa of the acid group is preferably ⁇ 5 or more.
  • the specific polymer contains the structural unit (a) and the structural unit (b) having an acid group that is not protected by a protective device as a copolymerization component, and the glass transition temperature is 90 ° C.
  • the positive photosensitive resin layer containing the coalescence has better resolution and sensitivity at the time of pattern formation while maintaining transferability and peelability from the temporary support at good levels.
  • the acid group examples include a carboxylic acid group, a sulfonamide group, a phosphonic acid group, a sulfonic acid group, a phenolic hydroxyl group, and a sulfonylimide group.
  • at least one acid group selected from the group consisting of a carboxylic acid group and a phenolic hydroxyl group is preferable.
  • Introduction of a structural unit having an acid group into the polymer can be carried out by copolymerizing a monomer having an acid group.
  • the structural unit containing an acid group which is the structural unit (b), is derived from a structural unit derived from styrene or a structural unit derived from a vinyl compound by an acid group, or derived from (meth) acrylic acid. More preferably, it is a structural unit.
  • the structural unit which has a carboxylic acid group, or the structural unit which has a phenolic hydroxyl group is preferable from a viewpoint that the sensitivity at the time of pattern formation becomes more favorable.
  • the monomer having an acid group that can form the structural unit (b) is not limited to the examples described above.
  • the structural unit (b) contained in the polymer may be only one type or two or more types.
  • the polymer preferably contains 0.1% by mass to 20% by mass, and 0.5% by mass to 15% by mass of a structural unit having an acid group [structural unit (b)] based on the total mass of the polymer. %, More preferably 1% by mass to 10% by mass. When it is in the above range, the pattern formability becomes better.
  • the content (content ratio: mass ratio) of the structural unit (b) in the polymer can be confirmed by the intensity ratio of peak intensity calculated by 13 C-NMR measurement by a conventional method.
  • the structural substrate other than the structural unit (a) and the structural unit (b) described above may be used as the patterned substrate of the present disclosure. In the range which does not impair the effect of this manufacturing method.
  • a monomer which forms a structural unit (c) For example, styrenes, (meth) acrylic acid alkyl ester, (meth) acrylic acid cyclic alkyl ester, (meth) acrylic acid aryl ester, unsaturated dicarboxylic acid Acid diesters, bicyclounsaturated compounds, maleimide compounds, unsaturated aromatic compounds, conjugated diene compounds, unsaturated monocarboxylic acids, unsaturated dicarboxylic acids, unsaturated dicarboxylic acid anhydrides, groups having an aliphatic cyclic skeleton, etc. Of unsaturated compounds.
  • the Tg of the specific polymer can be easily adjusted to 90 ° C. or lower by appropriately using the structural unit (c).
  • the said polymer may contain only 1 type of structural units (c), and may contain 2 or more types.
  • the structural unit (c) is styrene, tert-butoxystyrene, methylstyrene, hydroxystyrene, ⁇ -methylstyrene, acetoxystyrene, methoxystyrene, ethoxystyrene, chlorostyrene, methyl vinylbenzoate, vinylbenzoic acid.
  • the compounds described in paragraphs 0021 to 0024 of JP-A No. 2004-264623 can be given.
  • a group having an aromatic ring or a group having an aliphatic cyclic skeleton is preferable from the viewpoint of improving the electrical characteristics of the obtained transfer material.
  • styrene, tert-butoxystyrene, methylstyrene, hydroxystyrene, ⁇ -methylstyrene, dicyclopentanyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, and benzyl (meth) An acrylate etc. are mentioned.
  • the structural unit derived from a cyclohexyl (meth) acrylate is mentioned preferably.
  • (meth) acrylic acid alkyl ester is preferable from the viewpoint of adhesion.
  • (meth) acrylic acid alkyl esters having an alkyl group having 4 to 12 carbon atoms are more preferable from the viewpoint of adhesion.
  • Specific examples include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate.
  • content of a structural unit (c) is preferable with respect to the total mass of the said polymer, content of a structural unit (c) has more preferable 60 mass% or less, and 50 mass% or less is still more preferable.
  • the lower limit may be 0% by mass, but is preferably 1% by mass or more, and more preferably 5% by mass or more.
  • the content of the structural unit (c) is preferably 1% by mass to 70% by mass, more preferably 5% by mass to 60% by mass, and more preferably 10% by mass to 50% by mass with respect to the total mass of the polymer. Further preferred. When it is within the above numerical range, the resolution and adhesion are further improved.
  • the polymer may contain, as the structural unit (c), a structural unit having an ester of an acid group in the structural unit (b), solubility in a developer, and physical properties of the photosensitive resin composition layer. It is preferable from the viewpoint of optimizing.
  • the specific polymer preferably includes a structural unit having a carboxylic acid group as the structural unit (b), and further includes a structural unit (c) including a carboxylic acid ester group as a copolymerization component.
  • a polymer comprising a structural unit (b) derived from (meth) acrylic acid and a structural unit (c) derived from cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate or n-butyl (meth) acrylate. More preferred.
  • this indication is not limited to the following illustrations.
  • the ratio of the structural unit and the weight average molecular weight in the following exemplary compounds are appropriately selected in order to obtain preferable physical properties.
  • the glass transition temperature (Tg) of the polymer in the present disclosure, particularly the specific polymer, is preferably 90 ° C. or lower.
  • the said photosensitive resin composition layer has high adhesiveness because Tg is 90 degrees C or less.
  • the Tg is more preferably 60 ° C. or less, and further preferably 40 ° C. or less.
  • the lower limit of Tg is not particularly limited, but is preferably ⁇ 20 ° C. or higher, and more preferably ⁇ 10 ° C. or higher.
  • the glass transition temperature of the polymer can be measured using differential scanning calorimetry (DSC).
  • DSC differential scanning calorimetry
  • the specific measuring method was performed in accordance with the method described in JIS K 7121 (1987) or JIS K 6240 (2011).
  • Tig extrapolated glass transition start temperature
  • the method for measuring the glass transition temperature will be described more specifically.
  • the apparatus is kept at a temperature about 50 ° C. lower than the expected Tg of the polymer until the apparatus is stabilized, and then heated at a rate of 20 ° C./min, about 30 times higher than the temperature at which the glass transition is completed. Heat to a higher temperature and draw a DTA or DSC curve.
  • the extrapolated glass transition start temperature (Tig) that is, the glass transition temperature Tg in the present specification, is a straight line obtained by extending the low-temperature base line to the high-temperature side in the DTA curve or DSC curve, and Calculated as the temperature of the intersection with the tangent drawn at the point where the slope of the curve is maximum.
  • the FOX formula is used as a guideline based on the Tg of the homopolymer of each constituent unit of the target polymer and the mass ratio of each constituent unit.
  • the FOX formula is used as a guideline based on the Tg of the homopolymer of each constituent unit of the target polymer and the mass ratio of each constituent unit.
  • Tg of the homopolymer of the first structural unit contained in the polymer is Tg1
  • W1 is the mass fraction in the copolymer of the first structural unit
  • the homopolymer of the second structural unit is When Tg is Tg2 and the mass fraction in the copolymer of the second structural unit is W2, Tg0 (K) of the copolymer containing the first structural unit and the second structural unit is It is possible to estimate according to the following equation.
  • FOX formula: 1 / Tg0 (W1 / Tg1) + (W2 / Tg2)
  • a copolymer having a desired Tg can be obtained by adjusting the type and mass fraction of each constituent unit contained in the copolymer using the FOX formula described above. It is also possible to adjust the Tg of the polymer by adjusting the weight average molecular weight of the polymer.
  • the molecular weight of the polymer is preferably 60,000 or less in terms of polystyrene-equivalent weight average molecular weight.
  • the weight average molecular weight of the polymer is 60,000 or less, the melt viscosity of the photosensitive resin composition layer is kept low, and bonding at a low temperature (for example, 130 ° C. or less) is realized when bonding to the substrate. can do.
  • the weight average molecular weight of the polymer is preferably 2,000 to 60,000, and more preferably 3,000 to 50,000.
  • the weight average molecular weight of the polymer can be measured by GPC (gel permeation chromatography), and various commercially available devices can be used as the measuring device.
  • HLC registered trademark
  • -8220GPC manufactured by Tosoh Corp.
  • TSKgel registered trademark
  • Super HZM-M 4 .6 mm ID ⁇ 15 cm, manufactured by Tosoh Corp.
  • Super HZ4000 4 mm ID ⁇ 15 cm, manufactured by Tosoh Corp.
  • Super HZ3000 4 mm ID ⁇ 15 cm, manufactured by Tosoh Corp.
  • Super HZ2000 4 mm ID
  • THF tetrahydrofuran
  • the measurement conditions are 0.2 mass%, the flow rate is 0.35 ml / min, the sample injection amount is 10 ⁇ l, the measurement temperature is 40 ° C., and a differential refractive index (RI) detector is used. be able to.
  • the calibration curve is “Standard sample TSK standard, polystyrene” manufactured by Tosoh Corporation: “F-40”, “F-20”, “F-4”, “F-1”, “A-5000”, “ It can be produced using any of the seven samples of “A-2500” and “A-1000”.
  • the ratio (dispersity) between the number average molecular weight and the weight average molecular weight of the polymer is preferably 1.0 to 5.0, more preferably 1.05 to 3.5.
  • the production method (synthesis method) of the above polymer is not particularly limited.
  • a polymerizable monomer for forming the structural unit (a) represented by the formula A, a structural unit having an acid group (b ), And, if necessary, in an organic solvent containing a polymerizable monomer for forming other structural unit (c), polymerization is performed using a polymerization initiator.
  • a polymerization initiator for example, a polymerization initiator, if necessary, in an organic solvent containing a polymerizable monomer for forming other structural unit (c), polymerization is performed using a polymerization initiator.
  • the photosensitive resin composition layer has 50% by mass to 99% by mass of the polymer component with respect to the total solid content of the photosensitive resin composition layer from the viewpoint of developing good adhesion to the substrate. It is preferably included in a proportion of .9% by mass, more preferably in a proportion of 70% by mass to 98% by mass.
  • the photosensitive resin composition layer has a specific polymer content of 50% by mass to 99.99% based on the total solid content of the photosensitive resin composition layer. It is preferably contained in a proportion of 9% by mass, more preferably in a proportion of 70% by mass to 98% by mass.
  • the chemical amplification positive photosensitive resin composition is a structural unit (a ) May be further included (sometimes referred to as “other polymers”).
  • the blending amount of the other polymer is preferably 50% by mass or less, and 30% by mass or less in the total polymer components. Is more preferable, and it is still more preferable that it is 20 mass% or less.
  • the chemically amplified positive photosensitive resin composition may contain only one type of other polymer in addition to the polymer, or may contain two or more types.
  • polyhydroxystyrene can be used, which are commercially available, such as SMA 1000P, SMA 2000P, SMA 3000P, SMA 1440F, SMA 17352P, SMA 2625P, and SMA 3840F (above, manufactured by Sartomer).
  • ARUFON UC-3000, ARUFON UC-3510, ARUFON UC-3900, ARUFON UC-3910, ARUFON UC-3920, and ARUFON UC-3080 above, manufactured by Toagosei Co., Ltd.
  • Joncryl 690, Joncryl 6 Joncryl 67, Joncryl 586 manufactured by BASF or the like can also be used.
  • the chemically amplified positive photosensitive resin composition contains a photoacid generator.
  • the photoacid generator used in the present disclosure is a compound capable of generating an acid by irradiation with radiation such as ultraviolet rays, far ultraviolet rays, X-rays, and charged particle beams.
  • the photoacid generator used in the present disclosure is preferably a compound that reacts with actinic rays having a wavelength of 300 nm or more, preferably 300 nm to 450 nm, and generates an acid, but is not limited to its chemical structure.
  • a photoacid generator that is not directly sensitive to an actinic ray having a wavelength of 300 nm or more can also be used as a sensitizer if it is a compound that reacts with an actinic ray having a wavelength of 300 nm or more and generates an acid when used in combination with the sensitizer It can be preferably used in combination.
  • the photoacid generator used in the present disclosure is preferably a photoacid generator that generates an acid having a pKa of 4 or less, more preferably a photoacid generator that generates an acid having a pKa of 3 or less, and a pKa of 2 or less.
  • a photoacid generator that generates an acid is particularly preferable.
  • the lower limit value of pKa is not particularly defined, but is preferably ⁇ 10.0 or more, for example.
  • the photoacid generator examples include an ionic photoacid generator and a nonionic photoacid generator.
  • the photoacid generator preferably contains at least one compound selected from the group consisting of an onium salt compound described later and an oxime sulfonate compound described later from the viewpoint of sensitivity and resolution, and an oxime sulfonate compound. It is more preferable to contain.
  • nonionic photoacid generators examples include trichloromethyl-s-triazines, diazomethane compounds, imide sulfonate compounds, and oxime sulfonate compounds.
  • the photoacid generator is preferably an oxime sulfonate compound from the viewpoints of sensitivity, resolution, and adhesion.
  • These photoacid generators can be used singly or in combination of two or more.
  • Specific examples of trichloromethyl-s-triazines and diazomethane derivatives include the compounds described in paragraphs 0083 to 0088 of JP 2011-212494A.
  • oxime sulfonate compound that is, a compound having an oxime sulfonate structure
  • a compound containing an oxime sulfonate structure represented by the following formula (B1) is preferable.
  • R 21 represents an alkyl group or an aryl group
  • * represents a bonding site with another atom or another group.
  • any group may be substituted, and the alkyl group in R 21 may be linear or have a branched structure. , May have a ring structure. Acceptable substituents are described below.
  • the alkyl group for R 21 is preferably a linear or branched alkyl group having 1 to 10 carbon atoms.
  • the alkyl group of R 21 is an aryl group having 6 to 11 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a cycloalkyl group (7,7-dimethyl-2-oxonorbornyl group or other bridged alicyclic group) , Preferably a bicycloalkyl group or the like) or a halogen atom.
  • a aryl group for R 21 an aryl group having 6 to 18 carbon atoms is preferable, and a phenyl group or a naphthyl group is more preferable.
  • the aryl group of R 21 may be substituted with one or more groups selected from the group consisting of an alkyl group having 1 to 4 carbon atoms, an alkoxy group, and a halogen atom.
  • the compound containing an oxime sulfonate structure represented by the formula (B1) is preferably an oxime sulfonate compound described in paragraphs 0078 to 0111 of JP-A No. 2014-85643.
  • Examples of the ionic photoacid generator include onium salt compounds such as diaryliodonium salts and triarylsulfonium salts, quaternary ammonium salts, and the like. Of these, onium salt compounds are preferable, and triarylsulfonium salts and diaryliodonium salts are particularly preferable.
  • ionic photoacid generators described in paragraphs 0114 to 0133 of JP-A-2014-85643 can also be preferably used.
  • the photoacid generator is 0.1% relative to 100 parts by mass of the total solid content in the chemically amplified positive photosensitive resin composition from the viewpoint of sensitivity and resolution. It is preferable to use from 10 to 10 parts by mass, and more preferably from 0.5 to 5 parts by mass. Two or more kinds can be used in combination.
  • the chemically amplified positive photosensitive resin composition may contain a solvent. Further, the chemical amplification positive photosensitive resin composition, in order to easily form the photosensitive resin composition layer, to adjust the viscosity of the chemical amplification positive photosensitive resin composition once containing a solvent, The said chemically amplified positive photosensitive resin composition containing a solvent can be apply
  • a known solvent can be used as the solvent used in the present disclosure.
  • Solvents include ethylene glycol monoalkyl ethers, ethylene glycol dialkyl ethers, ethylene glycol monoalkyl ether acetates, propylene glycol monoalkyl ethers, propylene glycol dialkyl ethers, propylene glycol monoalkyl ether acetates, diethylene glycol dialkyl ethers And diethylene glycol monoalkyl ether acetates, dipropylene glycol monoalkyl ethers, dipropylene glycol dialkyl ethers, dipropylene glycol monoalkyl ether acetates, esters, ketones, amides, and lactones.
  • Specific examples of the solvent include the solvents described in paragraphs 0174 to 0178 of JP2011-221494A, the contents of which are incorporated herein.
  • the solvent which can be used for this indication may be used individually by 1 type, and it is more preferable to use 2 types together.
  • two or more solvents for example, combined use of propylene glycol monoalkyl ether acetates and dialkyl ethers, combined use of diacetates and diethylene glycol dialkyl ethers, or esters and butylene glycol alkyl ether acetates A combination with the above is preferred.
  • the solvent is preferably a solvent having a boiling point of 130 ° C. or higher and lower than 160 ° C., a solvent having a boiling point of 160 ° C. or higher, or a mixture thereof. Solvents having a boiling point of 130 ° C. or higher and lower than 160 ° C.
  • propylene glycol monomethyl ether acetate (boiling point 146 ° C.), propylene glycol monoethyl ether acetate (boiling point 158 ° C.), propylene glycol methyl-n-butyl ether (boiling point 155 ° C.), and An example is propylene glycol methyl-n-propyl ether (boiling point 131 ° C.).
  • Solvents having a boiling point of 160 ° C or higher include ethyl 3-ethoxypropionate (boiling point 170 ° C), diethylene glycol methyl ethyl ether (boiling point 176 ° C), propylene glycol monomethyl ether propionate (boiling point 160 ° C), dipropylene glycol methyl ether acetate.
  • the content of the solvent in applying the chemically amplified positive photosensitive resin composition is preferably 50 parts by mass to 1,900 parts by mass per 100 parts by mass of the total solid content in the photosensitive resin composition. 100 parts by weight to 900 parts by weight is more preferable. Further, the content of the solvent in the photosensitive resin composition layer is preferably 2% by mass or less, more preferably 1% by mass or less, with respect to the total mass of the photosensitive resin composition layer. More preferably, it is 0.5 mass% or less.
  • the chemically amplified positive photosensitive resin composition in the present disclosure may contain a known additive as necessary in addition to the polymer and the photoacid generator.
  • the chemically amplified positive photosensitive resin composition may contain a plasticizer for the purpose of improving plasticity.
  • the plasticizer preferably has a weight average molecular weight smaller than that of the polymer.
  • the weight average molecular weight of the plasticizer is preferably 500 or more and less than 10,000, more preferably 700 or more and less than 5,000, and still more preferably 800 or more and less than 4,000 from the viewpoint of imparting plasticity.
  • the plasticizer is not particularly limited as long as it is a compound that is compatible with the polymer and exhibits plasticity, but from the viewpoint of imparting plasticity, the plasticizer preferably has an alkyleneoxy group in the molecule.
  • the alkyleneoxy group contained in the plasticizer preferably has the following structure.
  • R represents an alkyl group having 2 to 8 carbon atoms
  • n represents an integer of 1 to 50
  • * represents a bonding site with another atom.
  • a chemically amplified positive photosensitive resin composition obtained by mixing compound X, the polymer and the photoacid generator, even if the compound has an alkyleneoxy group referred to as “compound X”.
  • compound X an alkyleneoxy group
  • the optionally added surfactant is generally not used in an amount that brings plasticity to the photosensitive resin composition, and thus does not correspond to the plasticizer in the present specification.
  • plasticizer examples include, but are not limited to, compounds having the following structure.
  • the content of the plasticizer is 1 part by mass to 50 parts by mass with respect to 100 parts by mass of the total solid content in the above chemically amplified positive photosensitive resin composition from the viewpoint of adhesion.
  • Part by weight preferably 2 parts by weight to 20 parts by weight.
  • the chemically amplified positive photosensitive resin composition may contain only one kind of plasticizer or two or more kinds.
  • the chemically amplified positive photosensitive resin composition may further contain a sensitizer.
  • the sensitizer absorbs actinic rays and enters an electronically excited state.
  • the sensitizer in an electronically excited state comes into contact with the photoacid generator, and effects such as electron transfer, energy transfer, and heat generation occur. Thereby, a photo-acid generator raise
  • anthracene derivative a compound selected from the group consisting of an anthracene derivative, an acridone derivative, a thioxanthone derivative, a coumarin derivative, a base styryl derivative, and a distyrylbenzene derivative is preferable, and an anthracene derivative is more preferable.
  • Anthracene derivatives include anthracene, 9,10-dibutoxyanthracene, 9,10-dichloroanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9-hydroxymethylanthracene, 9-bromoanthracene, 9-chloroanthracene, 9 1,10-dibromoanthracene, 2-ethylanthracene, or 9,10-dimethoxyanthracene is preferred.
  • Examples of the sensitizer include compounds described in paragraphs 0139 to 0141 of International Publication No. 2015/092731.
  • the content of the sensitizer is preferably 0 to 10 parts by mass, and 0.1 to 10 parts by mass with respect to 100 parts by mass of the total solid content of the above chemically amplified positive photosensitive resin composition. More preferably, it is a part.
  • the chemically amplified positive photosensitive resin composition preferably further contains a basic compound.
  • the basic compound can be arbitrarily selected from basic compounds used in chemically amplified resists. Examples thereof include aliphatic amines, aromatic amines, heterocyclic amines, quaternary ammonium hydroxides, and quaternary ammonium salts of carboxylic acids. Specific examples thereof include compounds described in JP-A-2011-212494, paragraphs 0204 to 0207, the contents of which are incorporated herein.
  • aliphatic amine examples include trimethylamine, diethylamine, triethylamine, di-n-propylamine, tri-n-propylamine, di-n-pentylamine, tri-n-pentylamine, diethanolamine, triethanolamine, and the like.
  • examples include ethanolamine, dicyclohexylamine, and dicyclohexylmethylamine.
  • aromatic amine examples include aniline, benzylamine, N, N-dimethylaniline, and diphenylamine.
  • heterocyclic amine examples include pyridine, 2-methylpyridine, 4-methylpyridine, 2-ethylpyridine, 4-ethylpyridine, 2-phenylpyridine, 4-phenylpyridine, N-methyl-4-phenylpyridine, 4-dimethylaminopyridine, imidazole, benzimidazole, 4-methylimidazole, 2-phenylbenzimidazole, 2,4,5-triphenylimidazole, nicotine, nicotinic acid, nicotinamide, quinoline, 8-oxyquinoline, pyrazine, Pyrazole, pyridazine, purine, pyrrolidine, piperidine, piperazine, morpholine, 4-methylmorpholine, 1,5-diazabicyclo [4.3.0] -5-nonene, and 1,8-diazabicyclo [5.3.0] -7-Undecene.
  • Examples of the quaternary ammonium hydroxide include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetra-n-butylammonium hydroxide, and tetra-n-hexylammonium hydroxide.
  • Examples of the quaternary ammonium salt of carboxylic acid include tetramethylammonium acetate, tetramethylammonium benzoate, tetra-n-butylammonium acetate, and tetra-n-butylammonium benzoate.
  • the said basic compound may be used individually by 1 type, or may use 2 or more types together.
  • the content of the basic compound is preferably 0.001 parts by mass to 5 parts by mass, and preferably 0.005 parts by mass to 100 parts by mass with respect to 100 parts by mass of the total solid content of the chemical amplification positive photosensitive resin composition. More preferably, it is 3 parts by mass.
  • the photosensitive resin composition layer in this embodiment can contain the compound containing a heterocyclic compound.
  • a heterocyclic compound there is no restriction
  • heterocyclic monomers having d electrons such as silicon, sulfur, and phosphorus can be added.
  • the amount of the heterocyclic compound added in the photosensitive resin composition layer is 0.01 to 50 parts by mass with respect to 100 parts by mass of the total solid content of the positive photosensitive resin layer when the heterocyclic compound is transferred. It is preferably 0.1 parts by mass to 10 parts by mass, more preferably 1 part by mass to 5 parts by mass. Addition within this range is preferable from the viewpoint of adhesion and etching resistance. Only 1 type may be used for a heterocyclic compound and it can also use 2 or more types together. When using 2 or more types together, the said preferable content points out the total content of 2 or more types of heterocyclic compounds.
  • Specific examples of the compound having an epoxy group in the molecule include bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, aliphatic epoxy resin and the like.
  • a compound having an epoxy group in the molecule can be obtained as a commercial product.
  • JER828, JER1007, JER157S70 (manufactured by Mitsubishi Chemical Co., Ltd.), JER157S65 (manufactured by Mitsubishi Chemical Holdings Co., Ltd.), and the like commercially available products described in paragraph 0189 of JP2011-221494A, and the like can be mentioned.
  • bisphenol A type epoxy resin bisphenol F type epoxy resin, phenol novolac type epoxy resin and aliphatic epoxy resin are more preferable, and aliphatic epoxy resin is particularly preferable.
  • the compound containing an oxetanyl group is preferably used alone or mixed with a compound containing an epoxy group.
  • the positive photosensitive resin layer in the present embodiment is preferably a compound in which the heterocyclic compound has an epoxy group from the viewpoint of etching resistance and line width stability.
  • the chemically amplified positive photosensitive resin composition may contain an alkoxysilane compound.
  • Preferred examples of the alkoxysilane compound include trialkoxysilane compounds.
  • Examples of the alkoxysilane compound include ⁇ -aminopropyltrimethoxysilane, ⁇ -aminopropyltriethoxysilane, ⁇ -glycidoxypropyltriacoxysilane, ⁇ -glycidoxypropylalkyldialkoxysilane, and ⁇ -methacryloxy.
  • ⁇ -glycidoxypropyltrialkoxysilane and ⁇ -methacryloxypropyltrialkoxysilane are more preferable, ⁇ -glycidoxypropyltrialkoxysilane is more preferable, and 3-glycidoxypropyltrimethoxysilane is particularly preferable. preferable. These can be used alone or in combination of two or more.
  • the chemically amplified positive photosensitive resin composition preferably contains a surfactant from the viewpoint of film thickness uniformity.
  • a surfactant any of anionic, cationic, nonionic or amphoteric can be used, but a preferred surfactant is a nonionic surfactant.
  • nonionic surfactants include polyoxyethylene higher alkyl ethers, polyoxyethylene higher alkyl phenyl ethers, higher fatty acid diesters of polyoxyethylene glycol, silicone-based and fluorine-based surfactants. .
  • KP manufactured by Shin-Etsu Chemical Co., Ltd.
  • Polyflow manufactured by Kyoeisha Chemical Co., Ltd.
  • F-Top manufactured by JEMCO
  • MegaFac manufactured by DIC Corporation
  • Florard Suditomo 3M
  • Surflon manufactured by Asahi Glass Co., Ltd.
  • PolyFox manufactured by OMNOVA
  • SH-8400 Toray Dow Corning Silicone
  • a surfactant it contains a structural unit A and a structural unit B represented by the following formula I-1, and is a weight average in terms of polystyrene measured by gel permeation chromatography using tetrahydrofuran (THF) as a solvent.
  • a preferable example is a copolymer having a molecular weight (Mw) of 1,000 or more and 10,000 or less.
  • R 401 and R 403 each independently represent a hydrogen atom or a methyl group
  • R 402 represents a linear alkylene group having 1 to 4 carbon atoms
  • R 404 represents a hydrogen atom or a carbon group.
  • L represents an alkylene group having 3 to 6 carbon atoms
  • p and q are mass percentages representing a polymerization ratio
  • p is a numerical value of 10 mass% to 80 mass%.
  • Q represents a numerical value of 20% to 90% by mass
  • r represents an integer of 1 to 18, and s represents an integer of 1 to 10.
  • L is preferably a branched alkylene group represented by the following formula (I-2).
  • R 405 in formula (I-2) represents an alkyl group having 1 to 4 carbon atoms, and is preferably an alkyl group having 1 to 3 carbon atoms in terms of compatibility and wettability to the coated surface. Two or three alkyl groups are more preferred.
  • the weight average molecular weight (Mw) of the copolymer is more preferably from 1,500 to 5,000.
  • Surfactant may be used individually by 1 type and may use 2 or more types together.
  • the addition amount of the surfactant is preferably 10 parts by mass or less, and preferably 0.001 to 10 parts by mass with respect to 100 parts by mass of the total solid content in the chemically amplified positive photosensitive resin composition. More preferably, the content is 0.01 to 3 parts by mass.
  • metal oxide particles an antioxidant, a dispersant, an acid multiplier, a development accelerator, conductive fibers, a colorant, a thermal radical polymerization initiator, a thermal acid generator, Known additives such as ultraviolet absorbers, thickeners, crosslinking agents, and organic or inorganic suspending agents can be further added.
  • Preferred embodiments of the other components are described in paragraphs 0165 to 0184 of JP-A-2014-85643, respectively, and the contents of this publication are incorporated in this specification.
  • the chemical amplification positive type photosensitive resin composition for forming the photosensitive resin composition layer can be prepared by mixing each component at a predetermined ratio and by any method, and dissolving by stirring. For example, it is possible to prepare a composition by preparing each solution of each component in advance in a solvent and then mixing the obtained solution at a predetermined ratio.
  • the composition prepared as described above can be used after being filtered using a filter having a pore size of 0.2 ⁇ m or the like.
  • Example 1 A positive photosensitive resin composition 1 was produced according to the following formulation.
  • ⁇ Positive Photosensitive Resin Composition 1 Prescription> Specific polymer 3 (the following compound, weight average molecular weight 15,000): 9.66 parts (Tg of specific polymer 3 was measured by the method described above, and was 40 ° C. The GPC method described above The weight average molecular weight measured at 15,000 was 15,000.) Photoacid generator (compound A-1 below): 0.25 parts Surfactant (surfactant C below): 0.01 parts Additive (compound D below): 0.08 parts Propylene glycol monomethyl Ether acetate (solvent): 90.00 parts In the following structure, the numerical value of each structural unit represents the content (% by mass) of the structural unit. The same applies to other specific polymers described below.
  • Surfactant C Perfluoroalkyl group-containing nonionic surfactant (F-554, manufactured by DIC Corporation)
  • Compound D Basic compound having the following structure (manufacturer: Toyo Kasei Kogyo Co., Ltd., product number: CMTU)
  • the produced positive photosensitive resin composition 1 was slit on a 50 ⁇ m-thick polyethylene terephthalate film (26 cm wide ⁇ 1,000 m roll) (hereinafter referred to as “PET (A)”) as a temporary support. Applied in an amount such that the dry film thickness becomes 5.0 ⁇ m using a cylindrical nozzle, and dried for 1 minute by passing through a dryer whose temperature was continuously adjusted to 100 ° C. to form a photosensitive resin composition layer, On the photosensitive resin composition layer, a polyethylene film (OSM-N, manufactured by Tredegar Co., Ltd.) was pressure bonded as a cover film to prepare photosensitive transfer material 1 (26 cm width ⁇ 1,000 m roll).
  • OSM-N polyethylene film
  • the laminate roll temperature is 90 ° C. so that the cover film of the photosensitive transfer material 1 is peeled off and the surface of the conductive substrate having the copper layer and the photosensitive resin composition layer of the photosensitive transfer material 1 are combined.
  • a roll-shaped base material (26 cm width) in which the conductive substrate and the photosensitive transfer material 1 are integrated by laminating and winding under a lamination condition of a linear pressure of 0.6 MPa and a linear velocity (laminate velocity) of 3.6 m / min. ⁇ 500 m long).
  • the wound roll-shaped substrate is unwound from the unwinding device at a transport speed of 3.6 m / min, the temporary support is peeled off, and transport is stopped during exposure.
  • Image quality evaluation was performed by observing the resolution pattern of the obtained copper film base material with a resist pattern with an optical microscope. As for the image quality, various resolution patterns from 1 ⁇ mL & S to 50 ⁇ mL & S were observed, and the minimum pattern that could be resolved was defined as the resolution. In addition, the presence or absence of pixel deformation (pattern deformation) was evaluated. The evaluation criteria are as follows:
  • the minimum pattern that can be resolved is an L & S pattern of 2.0 ⁇ m or less.
  • 4 The minimum pattern that can be resolved is an L & S pattern of more than 2.0 ⁇ m and not more than 3.0 ⁇ m.
  • 3 The minimum pattern that can be resolved is an L & S pattern of more than 3.0 ⁇ m and 4.0 ⁇ m or less.
  • 2 The minimum pattern that can be resolved is an L & S pattern of more than 4.0 ⁇ m and 5.0 ⁇ m or less.
  • Example 2 As shown in FIG. 2, a copper film substrate with a resist pattern was produced in the same manner as in Example 1 except that the temporary support was peeled off immediately after contact pattern exposure.
  • Example 1 A copper film substrate with a resist pattern was formed in the same manner as in Example 1 except that the temporary support was peeled off after unrolling the roll-shaped substrate after exposure from the unwinding device and before the shower developing tank. Produced.
  • Example 3 A photosensitive transfer material 3 was produced in the same manner as in Example 1 except that the specific polymer 3 was replaced with the following specific polymer 2. It was 20 degreeC when Tg of the specific polymer 2 was measured by the above-mentioned method. The weight average molecular weight measured by the GPC method described above was 15,000.
  • Example 4 A photosensitive transfer material 4 was produced in the same manner as in Example 1 except that the specific polymer 3 was replaced with the following specific polymer 4. It was 50 degreeC when Tg of the specific polymer 4 was measured by the above-mentioned method. The weight average molecular weight measured by the GPC method described above was 15,000.
  • Example 5 A photosensitive transfer material 5 was produced in the same manner as in Example 1 except that the specific polymer 3 was replaced with the following specific polymer 5. It was 56 degreeC when Tg of the specific polymer 5 was measured by the above-mentioned method. The weight average molecular weight measured by the GPC method described above was 15,000.
  • FIG. 3 the schematic diagram of the pattern image of Example 1 at the time of the said evaluation is shown in FIG. 3, and the schematic diagram of the pattern image of the comparative example 1 is shown in FIG.
  • the pattern of the first embodiment reproduces a pattern according to a mask without pixel deformation.
  • the pattern of Comparative Example 1 the pixels are greatly deformed, and the pattern according to the mask cannot be reproduced.

Landscapes

  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • General Engineering & Computer Science (AREA)
  • Theoretical Computer Science (AREA)
  • Human Computer Interaction (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Structural Engineering (AREA)
  • Architecture (AREA)
  • Materials For Photolithography (AREA)
  • Photosensitive Polymer And Photoresist Processing (AREA)
  • Exposure And Positioning Against Photoresist Photosensitive Materials (AREA)
  • Manufacturing Of Printed Circuit Boards (AREA)
PCT/JP2017/020695 2016-06-10 2017-06-02 パターン付き基材の製造方法、及び、回路基板の製造方法 WO2017213056A1 (ja)

Priority Applications (3)

Application Number Priority Date Filing Date Title
KR1020187034333A KR102110818B1 (ko) 2016-06-10 2017-06-02 패턴이 형성된 기재의 제조 방법, 및 회로 기판의 제조 방법
JP2018522459A JP6573721B2 (ja) 2016-06-10 2017-06-02 パターン付き基材の製造方法、及び、回路基板の製造方法
CN201780033955.9A CN109219777B (zh) 2016-06-10 2017-06-02 带图案的基材的制造方法及电路板的制造方法

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2016116201 2016-06-10
JP2016-116201 2016-06-10

Publications (1)

Publication Number Publication Date
WO2017213056A1 true WO2017213056A1 (ja) 2017-12-14

Family

ID=60577824

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2017/020695 WO2017213056A1 (ja) 2016-06-10 2017-06-02 パターン付き基材の製造方法、及び、回路基板の製造方法

Country Status (4)

Country Link
JP (1) JP6573721B2 (zh)
KR (1) KR102110818B1 (zh)
CN (1) CN109219777B (zh)
WO (1) WO2017213056A1 (zh)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2019194007A (ja) * 2018-05-01 2019-11-07 旭化成株式会社 感光性積層体及びその製造方法
WO2019225363A1 (ja) * 2018-05-22 2019-11-28 富士フイルム株式会社 感光性転写材料、樹脂パターンの製造方法、回路配線の製造方法、及び、タッチパネルの製造方法
WO2020066351A1 (ja) * 2018-09-28 2020-04-02 富士フイルム株式会社 パターン付き基材の製造方法、回路基板の製造方法及びタッチパネルの製造方法
TWI690774B (zh) * 2018-01-30 2020-04-11 日商旭化成股份有限公司 感光性樹脂積層體及抗蝕劑圖案之製造方法
CN111712763A (zh) * 2018-02-16 2020-09-25 富士胶片株式会社 抗蚀剂图案的制造方法、电路基板的制造方法及触摸面板的制造方法

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR102648550B1 (ko) * 2019-04-05 2024-03-18 후지필름 가부시키가이샤 감광성 전사 재료, 수지 패턴의 제조 방법, 회로 배선의 제조 방법, 및, 터치 패널의 제조 방법

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001125274A (ja) * 1999-10-26 2001-05-11 Matsushita Electric Works Ltd 回路板製造用露光装置
JP2002266085A (ja) * 2001-03-08 2002-09-18 Dainippon Screen Mfg Co Ltd シャドウマスクの製造方法
JP2003140335A (ja) * 2001-11-02 2003-05-14 Asahi Kasei Corp 感光性樹脂積層体及びその用途
JP2005266347A (ja) * 2004-03-18 2005-09-29 Asahi Kasei Electronics Co Ltd レジストパターン形成方法および回路形成方法
JP2013152645A (ja) * 2012-01-25 2013-08-08 Dainippon Printing Co Ltd タッチパネルの製造方法
JP2014016935A (ja) * 2012-07-11 2014-01-30 Toppan Printing Co Ltd フィルム状静電容量型タッチパネルの製造方法
JP2014085643A (ja) * 2012-10-26 2014-05-12 Fujifilm Corp 感光性転写材料、パターン形成方法およびエッチング方法
JP2016099374A (ja) * 2014-11-18 2016-05-30 日立化成株式会社 感光性エレメント、レジストパターン付き基材の製造方法、プリント配線板の製造方法、及びタッチパネルの製造方法

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002122986A (ja) * 2000-10-16 2002-04-26 Kansai Paint Co Ltd ポジ型感光性樹脂組成物、ポジ型感光性ドライフィルム、その組成物を使用して得られる材料及びパターン形成方法
JP2003149803A (ja) * 2001-11-13 2003-05-21 Kanegafuchi Chem Ind Co Ltd 感光性ドライフィルムレジスト
JP3902169B2 (ja) * 2003-09-08 2007-04-04 日東電工株式会社 配線回路基板の製造方法および製造装置
TW200707106A (en) * 2005-05-17 2007-02-16 Kyowa Hakko Chemical Co Ltd Photoresist composition
JP6267951B2 (ja) 2013-12-18 2018-01-24 富士フイルム株式会社 感光性転写材料、パターン形成方法およびエッチング方法
US10114287B2 (en) * 2014-10-02 2018-10-30 Shin-Etsu Chemical Co., Ltd. Silicone skeleton-containing polymer compound and method for producing same, chemically amplified negative resist composition, photo-curable dry film and method for producing same, patterning process, layered product, and substrate

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001125274A (ja) * 1999-10-26 2001-05-11 Matsushita Electric Works Ltd 回路板製造用露光装置
JP2002266085A (ja) * 2001-03-08 2002-09-18 Dainippon Screen Mfg Co Ltd シャドウマスクの製造方法
JP2003140335A (ja) * 2001-11-02 2003-05-14 Asahi Kasei Corp 感光性樹脂積層体及びその用途
JP2005266347A (ja) * 2004-03-18 2005-09-29 Asahi Kasei Electronics Co Ltd レジストパターン形成方法および回路形成方法
JP2013152645A (ja) * 2012-01-25 2013-08-08 Dainippon Printing Co Ltd タッチパネルの製造方法
JP2014016935A (ja) * 2012-07-11 2014-01-30 Toppan Printing Co Ltd フィルム状静電容量型タッチパネルの製造方法
JP2014085643A (ja) * 2012-10-26 2014-05-12 Fujifilm Corp 感光性転写材料、パターン形成方法およびエッチング方法
JP2016099374A (ja) * 2014-11-18 2016-05-30 日立化成株式会社 感光性エレメント、レジストパターン付き基材の製造方法、プリント配線板の製造方法、及びタッチパネルの製造方法

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TWI690774B (zh) * 2018-01-30 2020-04-11 日商旭化成股份有限公司 感光性樹脂積層體及抗蝕劑圖案之製造方法
CN111712763A (zh) * 2018-02-16 2020-09-25 富士胶片株式会社 抗蚀剂图案的制造方法、电路基板的制造方法及触摸面板的制造方法
JP2019194007A (ja) * 2018-05-01 2019-11-07 旭化成株式会社 感光性積層体及びその製造方法
CN110426917A (zh) * 2018-05-01 2019-11-08 旭化成株式会社 感光性层叠体和其制造方法
JP7317550B2 (ja) 2018-05-01 2023-07-31 旭化成株式会社 感光性積層体及びその製造方法
WO2019225363A1 (ja) * 2018-05-22 2019-11-28 富士フイルム株式会社 感光性転写材料、樹脂パターンの製造方法、回路配線の製造方法、及び、タッチパネルの製造方法
JPWO2019225363A1 (ja) * 2018-05-22 2021-04-22 富士フイルム株式会社 感光性転写材料、樹脂パターンの製造方法、回路配線の製造方法、及び、タッチパネルの製造方法
WO2020066351A1 (ja) * 2018-09-28 2020-04-02 富士フイルム株式会社 パターン付き基材の製造方法、回路基板の製造方法及びタッチパネルの製造方法
CN112740107A (zh) * 2018-09-28 2021-04-30 富士胶片株式会社 带图案的基材的制造方法、电路基板的制造方法及触摸面板的制造方法

Also Published As

Publication number Publication date
JP6573721B2 (ja) 2019-09-11
JPWO2017213056A1 (ja) 2019-03-07
KR102110818B1 (ko) 2020-05-14
KR20190003641A (ko) 2019-01-09
CN109219777A (zh) 2019-01-15
CN109219777B (zh) 2021-06-22

Similar Documents

Publication Publication Date Title
JP6573721B2 (ja) パターン付き基材の製造方法、及び、回路基板の製造方法
WO2018179640A1 (ja) 感光性転写材料、及び、回路配線の製造方法
JP6573545B2 (ja) ポジ型感光性転写材料及び回路配線の製造方法
JP2018169543A (ja) 感光性転写材料、及び回路配線の製造方法
JP2018031847A (ja) 感光性転写材料、及び、回路配線の製造方法
WO2019102771A1 (ja) 感光性転写材料、樹脂パターン製造方法、及び、配線製造方法
JP6502284B2 (ja) 感光性転写材料及び回路配線の製造方法
JP6821046B2 (ja) 回路配線の製造方法及びタッチパネルの製造方法
JP6893550B2 (ja) 感光性転写材料、及び回路配線の製造方法
JP6992097B2 (ja) レジストパターンの製造方法、回路基板の製造方法及びタッチパネルの製造方法
JP6812556B2 (ja) 感光性樹脂組成物、感光性転写材料、回路配線の製造方法、及び、タッチパネルの製造方法
JP6685461B2 (ja) 感光性転写材料、回路配線の製造方法及びタッチパネルの製造方法
JP6995873B2 (ja) 回路基板の製造方法及びタッチパネルの製造方法
WO2019225362A1 (ja) 感光性転写材料、樹脂パターンの製造方法、回路配線の製造方法、及び、タッチパネルの製造方法
JP7011047B2 (ja) 感光性転写材料、感光性転写材料の製造方法、レジストパターンの製造方法、回路配線の製造方法、タッチパネル、及び、タッチパネル表示装置
JP6808045B2 (ja) 感光性樹脂組成物、感光性転写材料、回路配線の製造方法、及び、タッチパネルの製造方法
JP7011046B2 (ja) 感光性転写材料、レジストパターンの製造方法、回路配線の製造方法、タッチパネル、及び、タッチパネル表示装置
JP6685460B2 (ja) 感光性転写材料、回路配線の製造方法及びタッチパネルの製造方法

Legal Events

Date Code Title Description
ENP Entry into the national phase

Ref document number: 2018522459

Country of ref document: JP

Kind code of ref document: A

ENP Entry into the national phase

Ref document number: 20187034333

Country of ref document: KR

Kind code of ref document: A

121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 17810234

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 17810234

Country of ref document: EP

Kind code of ref document: A1