WO2022138468A1 - Matériau de transfert, et procédé de fabrication de stratifié - Google Patents

Matériau de transfert, et procédé de fabrication de stratifié Download PDF

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Publication number
WO2022138468A1
WO2022138468A1 PCT/JP2021/046631 JP2021046631W WO2022138468A1 WO 2022138468 A1 WO2022138468 A1 WO 2022138468A1 JP 2021046631 W JP2021046631 W JP 2021046631W WO 2022138468 A1 WO2022138468 A1 WO 2022138468A1
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WIPO (PCT)
Prior art keywords
intermediate layer
mass
temporary support
layer
photosensitive layer
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PCT/JP2021/046631
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English (en)
Japanese (ja)
Inventor
進二 藤本
守正 佐藤
晃男 片山
隆志 有冨
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富士フイルム株式会社
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Priority to CN202180086959.XA priority Critical patent/CN116710845A/zh
Priority to JP2022571391A priority patent/JPWO2022138468A1/ja
Publication of WO2022138468A1 publication Critical patent/WO2022138468A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/02—Physical, chemical or physicochemical properties
    • B32B7/023—Optical properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/06—Interconnection of layers permitting easy separation
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
    • G03F7/11—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having cover layers or intermediate layers, e.g. subbing layers

Definitions

  • This disclosure relates to a transfer material and a method for manufacturing a laminate.
  • Patent Document 1 has a photosensitive layer, an intermediate layer, an adhesive layer, and a temporary support in this order on a cover film, the intermediate layer containing particles, and the intermediate layer and the adhesive layer.
  • the intermediate layer and the adhesive layer can be peeled off from each other, and the surface of the intermediate layer after peeling the intermediate layer and the adhesive layer has irregularities formed by the particles.
  • the photosensitive transfer material having is disclosed.
  • Patent Document 1 International Publication No. 2019/146380
  • the photosensitive layer is temporarily supported together with the adhesive layer before exposure.
  • a method of exfoliating the body may be used.
  • the intermediate layer exposed by the peeling of the temporary support may adhere to a transport device such as a roller, and the transportability may be deteriorated.
  • the above phenomenon is likely to occur when the temporarily stationary conveyed object is moved again.
  • the photomask is brought into contact with the intermediate layer exposed by peeling of the temporary support to expose the photosensitive layer, the intermediate layer may adhere to the photomask and it may be difficult to align the photomask.
  • One embodiment of the present disclosure is intended to provide a transfer material comprising an intermediate layer having excellent slipperiness.
  • Another embodiment of the present disclosure is an object of the present invention to provide a method for producing a laminate using a transfer material containing an intermediate layer having excellent slipperiness.
  • the disclosure includes the following aspects: ⁇ 1>
  • the temporary support, the intermediate layer in contact with the temporary support, and the photosensitive layer are included in this order, and the surface roughness of the intermediate layer exposed when the temporary support is peeled from the intermediate layer is rough.
  • ⁇ 2> The transfer material according to ⁇ 1>, wherein the roughness Ra of the surface of the temporary support exposed when the temporary support is peeled from the intermediate layer is 2 nm or more.
  • ⁇ 3> The transfer material according to ⁇ 1> or ⁇ 2>, wherein the surface roughness Ra of the intermediate layer exposed when the temporary support is peeled off from the intermediate layer is 1,000 nm or less.
  • ⁇ 4> One of ⁇ 1> to ⁇ 3>, wherein the roughness Ra of the surface of the temporary support exposed when the temporary support is peeled from the intermediate layer is 1,000 nm or less.
  • ⁇ 5> The invention according to any one of ⁇ 1> to ⁇ 4>, wherein the static friction coefficient of the surface of the intermediate layer exposed when the temporary support is peeled off from the intermediate layer is 1.0 or less.
  • Transfer material. ⁇ 6> The transfer material according to any one of ⁇ 1> to ⁇ 5>, wherein the intermediate layer contains a water-soluble resin.
  • the water-soluble resin is at least one selected from the group consisting of cellulose derivatives, polyhydric alcohol compounds, oxide adducts of polyhydric alcohol compounds, polyether compounds, phenol derivatives and amide compounds, ⁇ 6.
  • the transfer material described in. ⁇ 8> The transfer material according to any one of ⁇ 1> to ⁇ 7>, wherein the intermediate layer contains a surfactant.
  • the photosensitive layer contains a polymerizable compound having two or more polymerizable groups.
  • the photosensitive layer comprises any one of ⁇ 1> to ⁇ 8>, which comprises a polymerizable compound having two polymerizable groups and a polymerizable compound having three or more polymerizable groups.
  • the described transfer material ⁇ 11> The transfer material according to ⁇ 9> or ⁇ 10>, wherein the polymerizable compound contains an oxyethylene chain.
  • the transfer material containing the temporary support, the intermediate layer in contact with the temporary support, and the photosensitive layer in this order is bonded to the substrate, and the photosensitive layer, the intermediate layer, and the temporary support are placed on the substrate.
  • a method for producing a laminated body wherein the surface roughness Ra of the intermediate layer exposed by peeling the temporary support from the intermediate layer is 2 nm or more.
  • the exposure process comprises contacting the intermediate layer with a photomask to expose the intermediate layer and the photosensitive layer.
  • a transfer material containing an intermediate layer having excellent slipperiness is provided.
  • a method for producing a laminate using a transfer material containing an intermediate layer having excellent slipperiness is provided.
  • the numerical range represented by using “-” means a range including the numerical values before and after "-" as the lower limit value and the upper limit value.
  • “(meth) acrylic” represents both acrylic and methacrylic, or either, and "(meth) acrylate” represents both acrylate and methacrylate, or either, and "(meth) acryloyl”. Represents both acryloyl and / or methacryloyl.
  • the amount of each component in the composition means the total amount of the plurality of applicable substances present in the composition when a plurality of the substances corresponding to each component are present in the composition, unless otherwise specified. do.
  • the term "process" is included in this term not only as an independent process but also as long as the intended purpose of the process is achieved even if it cannot be clearly distinguished from other processes.
  • the notation not describing substitution and non-substitution includes those having no substituent as well as 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).
  • "exposure” includes not only exposure using light but also drawing using particle beams such as an electron beam and an ion beam, unless otherwise specified.
  • the light used for exposure generally, the emission line spectrum of a mercury lamp, far ultraviolet rays typified by an excima laser, extreme ultraviolet rays (EUV light), X-rays, active rays such as electron beams (active energy rays) are used. Can be mentioned.
  • the chemical structural formula in the present disclosure may be described as a simplified structural formula omitting a hydrogen atom.
  • a combination of two or more preferred embodiments is a more preferred embodiment.
  • "transparent" means that the average transmittance of visible light having a wavelength of 400 nm to 700 nm is 80% or more, and is preferably 90% or more.
  • the average transmittance of visible light is a value measured by using a spectrophotometer, and can be measured by, for example, a spectrophotometer U-3310 manufactured by Hitachi, Ltd.
  • the weight average molecular weight (Mw) and the number average molecular weight (Mn) in the present disclosure are gel permeations using columns of TSKgel GMHxL, TSKgel G4000HxL, and TSKgel G2000HxL (all are trade names manufactured by Tosoh Corporation). It is a molecular weight converted by detecting with a solvent THF (tetrahydrofuran) and a differential refraction meter by an ion chromatography (GPC) analyzer and using polystyrene as a standard substance.
  • the content of the metal element is a value measured by using an inductively coupled plasma (ICP) spectroscopic analyzer.
  • ICP inductively coupled plasma
  • the refractive index is a value measured using an ellipsometer at a wavelength of 550 nm.
  • alkali-soluble means that the solubility of sodium carbonate having a liquid temperature of 22 ° C. in 100 g of a 1% by mass aqueous solution is 0.1 g or more.
  • water-soluble means that the solubility in 100 g of water having a liquid temperature of 22 ° C. and a pH of 7.0 is 0.1 g or more. Therefore, for example, the water-soluble resin is intended to be a resin satisfying the above-mentioned solubility conditions.
  • solid content means all components except solvents.
  • the layer thickness of each layer provided in the transfer material is determined by observing a cross section in a direction perpendicular to the main surface of the transfer material with a scanning electron microscope (SEM) and determining the thickness of each layer based on the obtained observation image. It is measured by measuring any 5 or more points and calculating the average value.
  • SEM scanning electron microscope
  • the transfer material according to the embodiment of the present disclosure includes a temporary support, an intermediate layer in contact with the temporary support, and a photosensitive layer in this order, and when the temporary support is peeled off from the intermediate layer.
  • the roughness Ra of the surface of the exposed intermediate layer is 2 nm or more.
  • a transfer material including an intermediate layer having excellent slipperiness is provided.
  • the presumed reason for the improvement in the slipperiness of the intermediate layer is considered as follows. When the roughness Ra of the surface of the exposed intermediate layer when the temporary support is peeled from the intermediate layer is 2 nm or more, the friction generated on the surface of the intermediate layer is reduced. Therefore, it is presumed that the slipperiness of the surface of the intermediate layer is improved.
  • the transfer material will be specifically described.
  • the surface of the temporary support facing the intermediate layer in the transfer material is referred to as the "first surface of the temporary support”
  • the surface of the intermediate layer facing the temporary support in the transfer material is referred to as the "first surface of the intermediate layer”. May be said.
  • the first surface of the temporary support faces the first surface of the intermediate layer.
  • another layer may be laminated on the surface of the photosensitive layer opposite to the surface facing the temporary support.
  • the other layer include a refractive index adjusting layer and a protective film.
  • each layer may be a single layer or a plurality of layers.
  • An example of the composition of the transfer material is shown below. However, the composition of the transfer material is not limited to the following examples.
  • the photosensitive layer is preferably a negative photosensitive layer. Further, it is also preferable that the photosensitive layer is a colored resin layer.
  • FIG. 1 is a schematic diagram showing the configuration of a transfer material according to an embodiment.
  • the transfer material 100 shown in FIG. 1 includes a temporary support 10, an intermediate layer 20, a photosensitive layer 30, and a protective film 40 in this order.
  • the protective film 40 of the transfer material 100 does not have to be arranged.
  • the total thickness of the other layers may be 0.1% to 30% with respect to the thickness of the photosensitive layer. It is preferably 0.1% to 20%, more preferably 0.1% to 20%.
  • the maximum width of the swell of the transfer material is preferably 300 ⁇ m or less, more preferably 200 ⁇ m or less, and further preferably 60 ⁇ m or less.
  • the maximum width of the waviness of the transfer material is preferably 0 ⁇ m or more, more preferably 0.1 ⁇ m or more, and further preferably 1 ⁇ m or more.
  • the maximum width of the swell of the transfer material is measured by the following procedure. First, the transfer material is cut in a direction perpendicular to the main surface so as to have a size of 20 cm in length ⁇ 20 cm in width, and a test sample is prepared. If the transfer material contains a protective film, the protective film is peeled off.
  • test sample is placed on a stage having a smooth surface and a horizontal surface so that the surface of the temporary support faces the stage.
  • the surface of the test sample was scanned with a laser microscope (for example, VK-9700SP manufactured by Keyence Co., Ltd.) for a range of 10 cm square in the center of the test sample to obtain a three-dimensional surface image, and the obtained three-dimensional surface was obtained.
  • a laser microscope for example, VK-9700SP manufactured by Keyence Co., Ltd.
  • the above operation is performed on 10 test samples, and the arithmetic mean value is defined as the "maximum width of the waviness of the transfer material".
  • the transfer material according to one embodiment of the present disclosure includes a temporary support.
  • the temporary support is a support that supports at least the intermediate layer and the photosensitive layer and is removable.
  • the temporary support is in contact with the intermediate layer.
  • the surface of the temporary support facing the intermediate layer that is, the first surface of the temporary support is in contact with the intermediate layer and can be exposed by peeling the temporary support from the intermediate layer.
  • the roughness of the first surface of the temporary support can affect the roughness of the first surface of the intermediate layer, which will be described later. For example, when the roughness of the first surface of the temporary support becomes smaller in the process of manufacturing the transfer material, the roughness of the first surface of the intermediate layer tends to become smaller. On the other hand, as the roughness of the first surface of the temporary support increases, the roughness of the first surface of the intermediate layer also tends to increase. From the above viewpoint, the roughness Ra of the surface of the temporary support exposed when the temporary support is peeled from the intermediate layer, that is, the roughness Ra of the first surface of the temporary support is preferably 1,000 nm or less. , 500 nm or less, more preferably 200 nm or less.
  • the roughness Ra of the first surface of the temporary support is preferably 2 nm or more, more preferably 50 nm or more, and further preferably 100 nm or more.
  • the roughness Ra of the first surface of the temporary support is preferably 2 nm to 1,000 nm, more preferably 50 nm to 500 nm, and even more preferably 100 nm to 200 nm.
  • the method of adjusting the roughness of the first surface of the temporary support is not limited.
  • a method for adjusting the roughness Ra of the first surface of the temporary support for example, a method of bringing a matted roll (hereinafter, may be referred to as “matted roll”) into contact with the first surface of the temporary support.
  • the roughness Ra of the first surface of the temporary support is adjusted according to the surface roughness of the matted roll.
  • a method of projecting fine sand on the first surface of the temporary support to make the surface uneven for example, a sandblast method
  • the roughness Ra of the first surface of the temporary support is adjusted according to the size of the projected sand and the projected strength.
  • the roughness Ra of the first surface of the temporary support is measured using a surface roughness and surface shape measuring machine (NewView6300, manufactured by Zygo).
  • a surface roughness and surface shape measuring machine manufactured by Zygo.
  • the temporary support is peeled off from the photosensitive layer.
  • a 50x objective lens set "Image Zoom of Measurement Control” to x0.5, set “Scan Lens” to 40 ⁇ m, and select "CYLDER” in "Remov” of "Average Control”.
  • the value of the central surface average roughness Ra shown in "Surface map” is adopted as the roughness Ra.
  • the temporary support may have a single-layer structure or a multi-layer structure.
  • the temporary support is preferably a film, more preferably a resin film.
  • the temporary support is preferably a film that is flexible and does not undergo significant deformation, shrinkage, or elongation under pressure, or under pressure and heating.
  • the film include polyethylene terephthalate (PET) film (for example, biaxially stretched polyethylene terephthalate film), polymethylmethacrylate film, cellulose triacetate film, polystyrene film, polyimide film and polycarbonate film.
  • PET polyethylene terephthalate
  • the temporary support a polyethylene terephthalate film is preferable. Further, it is preferable that the film used as the temporary support is free from deformation such as wrinkles and scratches.
  • the layer constituting the first surface of the temporary support preferably contains a thermoplastic resin.
  • the temporary support preferably includes a thermoplastic resin layer in contact with the intermediate layer.
  • the fact that the temporary support includes a thermoplastic resin layer in contact with the intermediate layer, that is, that the first surface of the temporary support is composed of the thermoplastic resin layer controls the roughness of the first surface of the temporary support. Is preferable because it facilitates.
  • thermoplastic resin examples include polyolefin resins (eg, polyethylene, polypropylene, ethylene- (meth) acrylic acid copolymer resin, ethylene- (meth) acrylic acid metal salt copolymer resin, ethylene-vinyl acetate copolymer resin and Ethylene-vinyl alcohol copolymer resin), polyester resin, styrene-butadiene copolymer resin, acrylic resin, urethane resin, epoxy resin and polyamide resin can be mentioned.
  • polyolefin-based resin is preferable because it can be easily peeled off from the intermediate layer.
  • the reason why the peeling from the intermediate layer is easy is due to the interaction between the molecules between the thermoplastic resin layer and the intermediate layer, and by using the polyolefin resin as the thermoplastic resin, the hydrogen bonding interaction and the hydrogen bonding interaction and It is presumed that the bipolar interaction is suppressed.
  • the polyolefin-based resins polyethylene having a low hydrogen-bonding interaction and a dipole interaction and a low softening temperature is most preferable.
  • the transparency of the temporary support is preferably high.
  • the transmittance of the temporary support with respect to light having a wavelength of 365 nm is preferably 60% or more, and more preferably 70% or more.
  • the haze of the temporary support is preferably small.
  • the haze value of the temporary support is preferably 2% or less, more preferably 0.5% or less, still more preferably 0.1% or less. From the viewpoint of the transparency of the temporary support, it is preferable that the number of coarse particles, foreign substances, and defects contained in the temporary support is small.
  • the number of particles, foreign substances, and defects having a diameter of 1 ⁇ m or more in the temporary support is preferably 50/10 mm 2 or less, more preferably 10/10 mm 2 or less, and 3/10 mm 2 or less. Is more preferable, and 0 pieces / 10 mm 2 is particularly preferable.
  • the thickness of the temporary support is preferably 5 ⁇ m to 200 ⁇ m, more preferably 10 ⁇ m to 150 ⁇ m, and further preferably 10 ⁇ m to 50 ⁇ m from the viewpoint of ease of handling and versatility.
  • the thickness of the temporary support is calculated as an average value of the thicknesses of any five points measured by cross-sectional observation using a scanning electron microscope (SEM).
  • Examples of the temporary support include a biaxially stretched polyethylene terephthalate film having a thickness of 16 ⁇ m, a biaxially stretched polyethylene terephthalate film having a thickness of 12 ⁇ m, and a biaxially stretched polyethylene terephthalate film having a thickness of 9 ⁇ m.
  • Preferred embodiments of the provisional support include, for example, paragraphs 0017 to 0018 of JP2014-85643A, paragraphs 0019 to 0026 of JP2016-27363, and paragraphs 0041 to 0057 of International Publication No. 2012/081680. It is described in paragraphs 0029 to 0040 of International Publication No. 2018/179370 and paragraphs 0012 to 0032 of JP-A-2019-101405, and the contents of these publications are incorporated in the present specification.
  • the temporary support may have a layer (also referred to as a "lubricant layer") containing fine particles on the surface.
  • the lubricant layer may be provided on one side of the temporary support or on both sides.
  • the diameter of the particles contained in the lubricant layer is preferably 0.05 ⁇ m to 0.8 ⁇ m.
  • the thickness of the lubricant layer is preferably 0.05 ⁇ m to 1.0 ⁇ m.
  • the transfer material includes an intermediate layer in contact with the temporary support.
  • the intermediate layer is arranged between the temporary support and the photosensitive layer.
  • the surface of the intermediate layer facing the temporary support that is, the first surface of the intermediate layer is in contact with the temporary support and can be exposed by peeling the temporary support from the intermediate layer.
  • the intermediate layer can suppress the mixing of the components when the plurality of layers are applied in the production of the transfer material and when the intermediate layer is stored after the application.
  • the intermediate layer is preferably a water-soluble layer from the viewpoint of developability and suppressing mixing of components during application of the plurality of layers and storage after application.
  • the roughness Ra of the surface of the intermediate layer exposed when the temporary support is peeled off from the intermediate layer is 2 nm or more.
  • the roughness Ra of the first surface of the intermediate layer is preferably 10 nm or more, more preferably 50 nm or more, and further preferably 100 nm or more.
  • the roughness Ra of the first surface of the intermediate layer is preferably 1,000 nm or less, more preferably 500 nm or less, and further preferably 200 nm or less.
  • the roughness Ra of the first surface of the intermediate layer may be 100 nm or less in some embodiments.
  • the roughness Ra of the first surface of the intermediate layer is 1,000 nm or less, the linearity of the pattern formed from the intermediate layer is improved.
  • the roughness Ra of the first surface of the intermediate layer is preferably 2 nm to 1,000 nm, more preferably 50 nm to 500 nm, and 100 nm to 200 nm. Is more preferable.
  • the roughness Ra of the first surface of the intermediate layer is measured by a method according to the method for measuring the roughness Ra of the first surface of the temporary support described in the section of “Temporary support”.
  • the static friction coefficient of the surface of the intermediate layer exposed when the temporary support is peeled off from the intermediate layer is preferably less than 2.0, and preferably 1.0 or less. More preferably, it is more preferably 0.6 or less.
  • the coefficient of static friction of the first surface of the intermediate layer is less than 2.0, the slipperiness of the surface of the intermediate layer is improved.
  • the intermediate layer exposed by the peeling of the temporary support adheres to the exposure mask and the transport device such as the transport roller in the transport process after the temporary support is peeled. Can be suppressed and the temporarily stationary transported object can be smoothly moved again.
  • the coefficient of static friction of the first surface of the intermediate layer is preferably 0.1 or more, more preferably 0.2 or more, and further preferably 0.3 or more.
  • the coefficient of static friction of the first surface of the intermediate layer is preferably 0.1 or more and less than 2.0, more preferably 0.2 to 1.0, and preferably 0.3 to 0.6. More preferred.
  • the dynamic friction coefficient of the surface of the intermediate layer exposed when the temporary support is peeled from the intermediate layer is preferably less than 1.5, more preferably 1.0 or less. It is preferably 0.5 or less, and more preferably 0.5 or less. When the coefficient of dynamic friction of the first surface of the intermediate layer is less than 1.5, the slipperiness of the surface of the intermediate layer is improved.
  • the coefficient of dynamic friction of the first surface of the intermediate layer is preferably 0.05 or more, more preferably 0.1 or more, and further preferably 0.2 or more.
  • the coefficient of dynamic friction of the first surface of the intermediate layer is 0.05 or more, the holding force for a transport device such as a transport roller is improved, and the occurrence of meandering and unwinding is suppressed.
  • the coefficient of dynamic friction of the first surface of the intermediate layer is preferably 0.05 or more and less than 1.5, more preferably 0.1 to 1.0, and preferably 0.2 to 0.5. More preferred.
  • the static friction coefficient and the dynamic friction coefficient of the first surface of the intermediate layer are measured by the following methods.
  • the transfer material is laminated on a polyethylene terephthalate (PET) substrate with a copper layer under laminating conditions of a linear pressure of 0.6 MPa and a linear velocity (laminating speed) of 0.5 m / min.
  • PET polyethylene terephthalate
  • laminating speed 0.5 m / min.
  • the temporary support is peeled off, and the exposed intermediate layer is brought into contact with a transparent soda glass (200 x 200 mm ⁇ ) having a thickness of 5 mm.
  • Plastic-film and sheet friction coefficient using Tencilon universal material tester (RTF1210, manufactured by A & D Co., Ltd.) and plastic friction coefficient jig (J-PZ2-50N, manufactured by A & D Co., Ltd.) The coefficient of static friction and the coefficient of dynamic friction are measured by a test method (JIS K7125: 1999). The test conditions are shown below. Load: 200g Contact area: 63 mm x 63 mm Test speed: 100 mm / min
  • the intermediate layer examples include an oxygen blocking layer having an oxygen blocking function, which is described as a "separation layer" in JP-A-5-72724.
  • an oxygen blocking layer having an oxygen blocking function
  • the sensitivity at the time of exposure is improved, the time load of the exposure machine is reduced, and the productivity is improved, which is preferable.
  • the oxygen blocking layer used as the intermediate layer may be appropriately selected from the known layers described in the above publications and the like. Of these, an oxygen blocking layer that exhibits low oxygen permeability and is dispersed or dissolved in water or an alkaline aqueous solution (1% by mass aqueous solution of sodium carbonate at 22 ° C.) is preferable.
  • the intermediate layer preferably contains a resin.
  • the resin contained in the intermediate layer include polyvinyl alcohol-based resin, polyvinylpyrrolidone-based resin, cellulose-based resin, acrylamide-based resin, polyethylene oxide-based resin, gelatin, vinyl ether-based resin, polyamide resin, and their co-weight. Examples include resins such as coalescing.
  • a water-soluble resin is preferable.
  • the resin contained in the intermediate layer is preferably a resin different from the polymer A contained in the photosensitive layer from the viewpoint of suppressing mixing of the components between the plurality of layers.
  • the water-soluble resin is preferably at least one selected from the group consisting of cellulose derivatives, polyhydric alcohol compounds, oxide adducts of polyhydric alcohol compounds, polyether compounds, phenol derivatives and amide compounds.
  • Examples of the cellulose derivative include hydroxypropylmethyl cellulose and hydroxypropyl cellulose.
  • Examples of commercially available hydroxypropylmethylcellulose include Metrose 60SH-03 (manufactured by Shin-Etsu Chemical Co., Ltd.).
  • polyhydric alcohol compound examples include polyvinyl alcohol and modified polyvinyl alcohol.
  • Commercially available products of polyvinyl alcohol include, for example, PVA-105 (manufactured by Kuraray Co., Ltd.), PVA-117 (manufactured by Kuraray Co., Ltd.), PVA-205 (manufactured by Kuraray Co., Ltd.) PVA-217 (manufactured by Kuraray Co., Ltd.), JMR. -3M (manufactured by Japan Vam & Poval Co., Ltd.) and JMR-3H (manufactured by Japan Vam & Poval Co., Ltd.) can be mentioned.
  • Examples of commercially available modified polyvinyl alcohols include Gosenol CKS-50 (manufactured by Mitsubishi Chemical Corporation) and Gosenol K-434 (manufactured by Mitsubishi Chemical Corporation).
  • oxide adduct of the polyhydric alcohol compound examples include Gosenol WO-320N (manufactured by Mitsubishi Chemical Corporation).
  • polyether compound examples include polyethylene glycol 4000 (manufactured by Wako Pure Chemical Industries, Ltd.).
  • phenol derivative examples include Phenolite GG-1402 (manufactured by DIC Corporation) and Phenolite OG-660 (manufactured by DIC Corporation).
  • Examples of the amide compound include polyvinylpyrrolidone and water-soluble nylon.
  • Examples of commercially available products of the amide compound include polyvinylpyrrolidone K-30 (manufactured by Nippon Shokubai Co., Ltd.) and polyvinylpyrrolidone K-90 (manufactured by Nippon Shokubai Co., Ltd.).
  • Examples of the water-soluble nylon include AQ nylon P-95 (manufactured by Toray Industries, Inc.).
  • the intermediate layer preferably contains polyvinyl alcohol, and contains both polyvinyl alcohol and polyvinylpyrrolidone, from the viewpoint of oxygen blocking property and suppressing mixing of components during application of the plurality of layers and storage after application. It is more preferable to contain it.
  • the intermediate layer may contain the above resin alone or in combination of two or more.
  • the content of the resin in the intermediate layer is not particularly limited, but with respect to the total mass of the intermediate layer from the viewpoint of oxygen blocking property and suppressing the mixing of components during application of the plurality of layers and storage after application. , 50% by mass to 100% by mass, more preferably 70% by mass to 100% by mass, further preferably 80% by mass to 100% by mass, and particularly preferably 90% by mass to 100% by mass.
  • the intermediate layer may contain an additive such as a surfactant, if necessary.
  • the intermediate layer preferably contains a surfactant.
  • the surfactant include the surfactants described in the section "Photosensitive layer” below.
  • the preferred embodiment of the surfactant in the intermediate layer is the same as the preferred embodiment of the surfactant described in the section "Photosensitive layer” below.
  • the thickness of the intermediate layer is preferably 0.1 ⁇ m to 5 ⁇ m, more preferably 0.5 ⁇ m to 3 ⁇ m.
  • the oxygen barrier property is not deteriorated, the mixing of the components during the application of the plurality of layers and the storage after the application can be suppressed, and the intermediate layer during development is intermediate. It is possible to suppress an increase in layer removal time.
  • the method for forming the intermediate layer is not particularly limited, and for example, a composition for an intermediate layer containing the above resin and any additive is prepared, applied to the surface of the temporary support, and coated with the composition for the intermediate layer.
  • a method of forming an intermediate layer by drying the mixture can be mentioned.
  • the intermediate layer is preferably formed by applying the composition for the intermediate layer to the surface of the temporary support.
  • the composition for the intermediate layer preferably contains a solvent in order to adjust the viscosity of the composition for the intermediate layer and facilitate the formation of the intermediate layer.
  • the solvent contained in the composition for the intermediate layer is not particularly limited as long as the above resin can be dissolved or dispersed, and at least one selected from the group consisting of water and a water-miscible organic solvent is preferable, and water is preferable. Alternatively, a mixed solvent of water and a water-miscible organic solvent is more preferable.
  • the water-miscible organic solvent include alcohols having 1 to 3 carbon atoms, acetone, ethylene glycol and glycerin, and alcohols having 1 to 3 carbon atoms are preferable, and methanol or ethanol is more preferable.
  • the transfer material according to one embodiment of the present disclosure includes a photosensitive layer.
  • the photosensitive layer can form a pattern by exposure and development, for example, after being transferred onto a substrate.
  • the photosensitive layer may be a negative type photosensitive layer or a positive type photosensitive layer.
  • the photosensitive layer is preferably a negative photosensitive layer.
  • the formed pattern corresponds to a cured layer.
  • the photosensitive layer is a negative photosensitive layer, the negative photosensitive layer preferably contains a resin, a polymerizable compound and a polymerization initiator.
  • an alkali-soluble resin is contained as a part or all of the resin. That is, in one embodiment, the photosensitive layer preferably contains a resin containing an alkali-soluble resin, a polymerizable compound, and a polymerization initiator.
  • the photosensitive layer is 10% by mass to 90% by mass of an alkali-soluble resin, 5% by mass to 70% by mass of an ethylenically unsaturated compound, and 0.01% by mass to 20% by mass of photopolymerization with respect to the total mass of the photosensitive layer. It is preferable to include an initiator.
  • the photosensitive layer preferably contains an alkali-soluble resin.
  • the alkali-soluble resin include known alkali-soluble resins used in etching resists.
  • the alkali-soluble resin is preferably a binder polymer.
  • the alkali-soluble resin is preferably an alkali-soluble resin having an acid group.
  • polymer A which will be described later, is preferable.
  • the photosensitive layer preferably contains the polymer A as the alkali-soluble resin.
  • the acid value of the polymer A is preferably 220 mgKOH / g or less, and more preferably less than 200 mgKOH / g, from the viewpoint that the resolution is more excellent by suppressing the swelling of the photosensitive layer due to the developing solution. , 190 mgKOH / g or less, more preferably.
  • the lower limit of the acid value of the polymer A is not particularly limited.
  • the acid value of the polymer A is preferably 60 mgKOH / g or more, more preferably 120 mgKOH / g or more, further preferably 150 mgKOH / g or more, and 170 mgKOH / g or more. It is particularly preferable that it is g or more.
  • the acid value is the mass [mg] of potassium hydroxide required to neutralize 1 g of the sample, and in the present disclosure, the unit is described as mgKOH / g.
  • the acid value can be calculated, for example, from the average content of acid groups in the compound.
  • the acid value of the polymer A may be adjusted according to the type of the structural unit constituting the polymer A and the content of the structural unit containing an acid group.
  • the weight average molecular weight of the polymer A is preferably 5,000 to 500,000. It is preferable that the weight average molecular weight is 500,000 or less from the viewpoint of improving the resolvability and the developability.
  • the weight average molecular weight of the polymer A is more preferably 100,000 or less, further preferably 60,000 or less, and particularly preferably 50,000 or less.
  • the weight average molecular weight of the polymer A is more preferably 10,000 or more, further preferably 20,000 or more, and particularly preferably 30,000 or more.
  • the edge fuse property refers to the degree of ease with which the photosensitive layer protrudes from the end face of the roll when the transfer material is wound into a roll.
  • the cut chip property refers to the degree of ease of chip flying when the unexposed film is cut with a cutter. If this chip adheres to the upper surface of the photosensitive layer or the like, it is transferred to the mask in a later exposure step or the like, which causes a defective product.
  • the dispersity of the polymer A is preferably 1.0 to 6.0, more preferably 1.0 to 5.0, and even more preferably 1.0 to 4.0. It is particularly preferably 0.0 to 3.0.
  • the degree of dispersion is the ratio of the weight average molecular weight to the number average molecular weight (weight average molecular weight / number average molecular weight).
  • the polymer A preferably has an aromatic hydrocarbon group, and has a structural unit having an aromatic hydrocarbon group. Is more preferable.
  • the aromatic hydrocarbon group include a substituted or unsubstituted phenyl group and a substituted or unsubstituted aralkyl group.
  • the content ratio of the structural unit having an aromatic hydrocarbon group in the polymer A is preferably 20% by mass or more, more preferably 30% by mass or more, more preferably 40% by mass, based on the total mass of the polymer A. It is more preferably mass% or more, particularly preferably 45% by mass or more, and most preferably 50% by mass or more.
  • the upper limit is not particularly limited, but is preferably 95% by mass or less, and more preferably 85% by mass or less.
  • the content ratio of the structural unit having an aromatic hydrocarbon group is determined as a weight average value.
  • Examples of the monomer forming a structural unit having an aromatic hydrocarbon group include a monomer having an aralkyl group, styrene, and a polymerizable styrene derivative (for example, methyl styrene, vinyl toluene, t-butoxy styrene, acetoxy). Styrene, 4-vinyl benzoic acid, styrene dimer, styrene trimer, etc.) can be mentioned. Of these, a monomer having an aralkyl group or styrene is preferable.
  • the content ratio of the structural unit derived from styrene is 20 based on the total mass of the polymer A. It is preferably mass% to 50% by mass, more preferably 25% by mass to 45% by mass, further preferably 30% by mass to 40% by mass, and 30% by mass to 35% by mass. Is particularly preferable.
  • the content ratio of the structural unit derived from styrene is based on the total mass of the polymer A. It is preferably 40% by mass to 60% by mass, and more preferably 45% by mass to 55% by mass.
  • aralkyl group examples include a substituted or unsubstituted phenylalkyl group, and a substituted or unsubstituted benzyl group is preferable.
  • Examples of the monomer having a phenylalkyl group other than the substituted or unsubstituted benzyl group include phenylethyl (meth) acrylate and the like.
  • a (meth) acrylate having a substituted or unsubstituted benzyl group for example, benzyl (meth) acrylate, chlorobenzyl (meth) acrylate, etc.
  • vinyl monomers eg, vinylbenzyl chloride, vinylbenzyl alcohol, etc.
  • benzyl (meth) acrylate is preferable.
  • the content ratio of the structural unit derived from the benzyl (meth) acrylate is the polymer A. It is preferably 50% by mass to 95% by mass, more preferably 60% by mass to 90% by mass, further preferably 70% by mass to 90% by mass, and 75% by mass based on the total mass of the above. It is particularly preferably% to 90% by mass.
  • the polymer A having a structural unit having an aromatic hydrocarbon group is a monomer having an aromatic hydrocarbon group, at least one of the first monomer described later, and / or a second single amount described later. It is preferably a polymer obtained by polymerizing with at least one of the bodies.
  • the polymer A having no structural unit having an aromatic hydrocarbon group is preferably a polymer obtained by polymerizing at least one of the first monomers described later, and is preferably the first single amount. It is more preferable that the polymer is obtained by copolymerizing at least one kind of the body and at least one kind of the second monomer described later.
  • the first monomer is a monomer having a carboxy group in the molecule.
  • the first monomer include (meth) acrylic acid, fumaric acid, cinnamic acid, crotonic acid, itaconic acid, 4-vinylbenzoic acid, maleic acid anhydride, maleic acid semi-ester and the like.
  • (meth) acrylic acid is preferable.
  • the content ratio of the structural unit derived from the first monomer in the polymer A is preferably 5% by mass to 50% by mass, preferably 10% by mass or more, based on the total mass of the polymer A. It is more preferably 40% by mass, further preferably 15% by mass to 30% by mass.
  • the content ratio of the structural unit derived from the first monomer is preferably 10% by mass to 50% by mass based on the total mass of the polymer A. It is preferable to set the above ratio to 10% by mass or more from the viewpoint of exhibiting good developability, controlling edge fuseability, and the like, more preferably 15% by mass or more, and further preferably 20% by mass or more. It is preferable that the content ratio is 50% by mass or less from the viewpoint of high resolution and the shape of the resist pattern, and further from the viewpoint of chemical resistance of the resist pattern, and from these viewpoints, it is 35% by mass or less. Is more preferable, 30% by mass or less is further preferable, and 27% by mass or less is particularly preferable.
  • the second monomer is a monomer that is non-acidic and has at least one ethylenically unsaturated group in the molecule.
  • Examples of the second monomer include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, and isobutyl (meth) acrylate.
  • T-butyl (meth) acrylate 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate and other (meth) acrylates; vinyl acetate And the like, esters of vinyl alcohols; as well as (meth) acrylonitrile and the like.
  • methyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and n-butyl (meth) acrylate are preferable, and methyl (meth) acrylate is particularly preferable.
  • the content ratio of the structural unit derived from the second monomer in the polymer A is preferably 5% by mass to 60% by mass, preferably 15% by mass to 50% by mass, based on the total mass of the polymer A. It is more preferably 20% by mass to 45% by mass.
  • the polymer A contains at least one structural unit selected from the group consisting of a structural unit having an aralkyl group and a structural unit derived from styrene, when the focal position at the time of exposure shifts. It is preferable from the viewpoint of suppressing the line width thickening and the deterioration of the resolution.
  • the polymer A include a polymer containing methacrylic acid, benzyl methacrylate and styrene, a polymer containing methacrylic acid, methyl methacrylate, benzyl methacrylate and styrene, a polymer containing methacrylic acid, methyl methacrylate and styrene, and the like. Is preferable.
  • the polymer A contains 25% by mass to 40% by mass of a structural unit having an aromatic hydrocarbon group, 20% by mass to 35% by mass of a structural unit derived from the first monomer, and a second. It is preferable that the polymer contains 30% by mass to 45% by mass of the structural unit derived from the monomer of. In another embodiment, the polymer contains 70% by mass to 90% by mass of a structural unit having an aromatic hydrocarbon group and 10% by mass to 25% by mass of a structural unit derived from the first monomer. Is preferable. In still another embodiment, the structural unit having an aromatic hydrocarbon group is 40% by mass to 60% by mass, the structural unit derived from the first monomer is 15% by mass to 30% by mass, and the second. A polymer containing 20% by mass to 45% by mass of a constituent unit derived from a monomer is preferable.
  • the polymer A may have a branched structure and / or an alicyclic structure in the side chain.
  • a monomer having a group having a branched structure in the side chain or a monomer having a group having an alicyclic structure in the side chain a branched structure or an alicyclic structure can be introduced into the side chain of the polymer A. ..
  • the alicyclic structure may be a monocyclic structure or a polycyclic structure.
  • the monomer containing a group having a branched structure in the side chain examples include isopropyl (meth) acrylate, isobutyl (meth) acrylate, s-butyl (meth) acrylate, t-butyl (meth) acrylate, and (. Examples thereof include t-amyl (meth) acrylate, iso-amyl (meth) acrylate, 2-octyl (meth) acrylate, 3-octyl (meth) acrylate, and t-octyl (meth) acrylate.
  • isopropyl (meth) acrylate, isobutyl (meth) acrylate, or t-butyl methacrylate are preferable, and isopropyl methacrylate or t-butyl methacrylate is more preferable.
  • the monomer having a group having an alicyclic structure in the side chain examples include a monomer having a monocyclic aliphatic hydrocarbon group and a monomer having a polycyclic aliphatic hydrocarbon group.
  • a (meth) acrylate having an alicyclic hydrocarbon group having 5 to 20 carbon atoms (carbon atoms) can be mentioned. More specific examples include (meth) acrylic acid (bicyclo [2.2.1] heptyl-2), (meth) acrylic acid-1-adamantyl, (meth) acrylic acid-2-adamantyl, (meth).
  • (meth) acrylic acid esters (meth) acrylic acid cyclohexyl, (meth) acrylic acid (nor) boronyl, (meth) acrylic acid isobornyl, (meth) acrylic acid-1-adamantyl, (meth) acrylic acid- 2-adamantyl, fentyl (meth) acrylate, -1-mentyl (meth) acrylate or tricyclodecane (meth) acrylate are preferred, cyclohexyl (meth) acrylate, (nor) bornyl, (meth) acrylate, ( Isobornyl acrylate, -2-adamantyl (meth) acrylate or tricyclodecane (meth) acrylate are more preferred.
  • the photosensitive layer may contain the polymer A alone or in combination of two or more.
  • two kinds of the polymer A having an aromatic hydrocarbon group may be mixed and used, or the polymer A having an aromatic hydrocarbon group and the polymer A having no aromatic hydrocarbon group may not be used. It is preferable to use the polymer A in combination.
  • the content ratio of the polymer A having an aromatic hydrocarbon group is preferably 50% by mass or more, more preferably 70% by mass or more, based on the total mass of the polymer A. It is more preferably 80% by mass or more, and particularly preferably 90% by mass or more.
  • a radical polymerization initiator such as benzoyl peroxide and azoisobutyronitrile is added to a solution obtained by diluting the one or more monomers described above with a solvent such as acetone, methyl ethyl ketone and isopropanol. Is preferably added in an appropriate amount and heated and stirred. In some cases, a part of the mixture is added dropwise to the reaction solution for synthesis. After completion of the reaction, a solvent may be further added to adjust the concentration to a desired level.
  • a radical polymerization initiator such as benzoyl peroxide and azoisobutyronitrile is added to a solution obtained by diluting the one or more monomers described above with a solvent such as acetone, methyl ethyl ketone and isopropanol. Is preferably added in an appropriate amount and heated and stirred. In some cases, a part of the mixture is added dropwise to the reaction solution for synthesis. After completion of the reaction,
  • the glass transition temperature Tg of the polymer A is preferably 30 ° C. or higher and 135 ° C. or lower.
  • the Tg of the polymer A is more preferably 130 ° C. or lower, further preferably 120 ° C. or lower, and particularly preferably 110 ° C. or lower.
  • the polymer A having a Tg of 30 ° C. or higher from the viewpoint of improving the edge fuse resistance.
  • the Tg of the polymer A is more preferably 40 ° C. or higher, further preferably 50 ° C. or higher, particularly preferably 60 ° C. or higher, and most preferably 70 ° C. or higher. ..
  • the alkali-soluble resin may be used alone or in combination of two or more.
  • the ratio of the alkali-soluble resin to the total mass of the photosensitive layer is preferably 10% by mass to 90% by mass, more preferably 30% by mass to 70% by mass, and further preferably 40% by mass to 60% by mass. be. It is preferable that the ratio of the alkali-soluble resin to the photosensitive layer is 90% by mass or less from the viewpoint of controlling the developing time. On the other hand, it is preferable to make the ratio of the alkali-soluble resin to the photosensitive layer 10% by mass or more from the viewpoint of improving the edge fuse resistance.
  • the photosensitive layer may contain a resin other than the alkali-soluble resin.
  • the resin other than the alkali-soluble resin may be a resin having a solubility of less than 0.1 g in 100 g of a 1 mass% aqueous solution of sodium carbonate having a liquid temperature of 22 ° C., for example, an acrylic resin or a styrene-acrylic co-weight.
  • polyurethane resin polyvinyl alcohol, polyvinyl formal, polyamide resin, polyester resin, polyamide resin, epoxy resin, polyacetal resin, polyhydroxystyrene resin, polyimide resin, poly Examples thereof include benzoxazole resin, polysiloxane resin, polyethyleneimine, polyallylamine, and polyalkylene glycol.
  • the photosensitive layer When the photosensitive layer is a negative photosensitive layer, the negative photosensitive layer preferably contains a polymerizable compound having a polymerizable group.
  • the "polymerizable compound” means a compound that polymerizes under the action of a polymerization initiator described later, and is different from the above-mentioned alkali-soluble resin.
  • the molecular weight of the polymerizable compound is preferably 1,500 or less.
  • the molecular weight of the polymerizable compound is preferably 150 or more.
  • the type of polymerizable group is not limited as long as it is a group involved in the polymerization reaction.
  • the polymerizable group include a group having an ethylenically unsaturated group such as a vinyl group, an acryloyl group, a methacryloyl group, a styryl group and a maleimide group.
  • examples of the polymerizable group include groups having a cationically polymerizable group such as an epoxy group and an oxetane group.
  • a group having an ethylenically unsaturated group is preferable, and an acryloyl group or a methacryloyl group is more preferable.
  • the polymerizable compound preferably contains a polymerizable compound having two or more polymerizable groups.
  • the polymerizable compound more preferably contains a polymerizable compound having two polymerizable groups and a polymerizable compound having three or more polymerizable groups.
  • a compound having one or more ethylenically unsaturated groups that is, an ethylenically unsaturated compound
  • two or more in one molecule because the negative photosensitive layer is more excellent in photosensitivity.
  • a compound having an ethylenically unsaturated group that is, a polyfunctional ethylenically unsaturated compound
  • the number of ethylenically unsaturated groups contained in one molecule of the ethylenically unsaturated compound is preferably 6 or less, more preferably 3 or less, and 2 or less in terms of excellent resolution and peelability. More preferred.
  • the photosensitive layer is a compound having two or three ethylenically unsaturated groups in one molecule (ie, bifunctional or bifunctional or) in that the balance between the photosensitivity, the resolution and the peelability of the negative photosensitive layer is better. It is preferable to contain a trifunctional ethylenically unsaturated compound), and more preferably to contain a compound having two ethylenically unsaturated groups in one molecule (that is, a bifunctional ethylenically unsaturated compound).
  • the content of the bifunctional ethylenically unsaturated compound with respect to the total mass of the polymerizable compound is preferably 20% by mass or more, more preferably more than 40% by mass, still more preferably 55% by mass or more from the viewpoint of excellent peelability.
  • the upper limit is not particularly limited and may be 100% by mass. That is, all the polymerizable compounds may be bifunctional ethylenically unsaturated compounds. Further, as the ethylenically unsaturated compound, a (meth) acrylate compound having a (meth) acryloyl group as a polymerizable group is preferable.
  • the photosensitive layer preferably contains an aromatic ring and an ethylenically unsaturated compound B1 having two ethylenically unsaturated groups.
  • the ethylenically unsaturated compound B1 is a bifunctional ethylenically unsaturated compound having one or more aromatic rings in one molecule among the above-mentioned ethylenically unsaturated compounds.
  • the mass ratio of the content of the ethylenically unsaturated compound B1 to the content of the ethylenically unsaturated compound in the photosensitive layer is preferably 40% by mass or more, preferably 50% by mass or more, from the viewpoint of better resolution. It is more preferably 55% by mass or more, and particularly preferably 60% by mass or more.
  • the upper limit is not particularly limited, but from the viewpoint of peelability, 99% by mass or less is preferable, 95% by mass or less is more preferable, 90% by mass or less is further preferable, and 85% by mass or less is particularly preferable.
  • Examples of the aromatic ring contained in the ethylenically unsaturated compound B1 include an aromatic hydrocarbon ring such as a benzene ring, a naphthalene ring and an anthracene ring, a thiophene ring, a furan ring, a pyrrole ring, an imidazole ring, a triazole ring and a pyridine ring.
  • Aromatic heterocycles and fused rings thereof are mentioned, and aromatic hydrocarbon rings are preferable, and benzene rings are more preferable.
  • the aromatic ring may have a substituent.
  • the ethylenically unsaturated compound B1 may have only one aromatic ring or may have two or more aromatic rings.
  • the ethylenically unsaturated compound B1 preferably has a bisphenol structure from the viewpoint of improving the resolution by suppressing the swelling of the photosensitive layer due to the developing solution.
  • the bisphenol structure include a bisphenol A structure derived from bisphenol A (2,2-bis (4-hydroxyphenyl) propane), a bisphenol F structure derived from bisphenol F (bis (4-hydroxyphenyl) methane), and a bisphenol F structure.
  • bisphenol A structure is preferable.
  • Examples of the ethylenically unsaturated compound B1 having a bisphenol structure include a compound having a bisphenol structure and two polymerizable groups (preferably (meth) acryloyl groups) bonded to both ends of the bisphenol structure. Both ends of the bisphenol structure and the two polymerizable groups may be directly bonded or may be bonded via one or more alkyleneoxy groups. As the alkyleneoxy group added to both ends of the bisphenol structure, an ethyleneoxy group or a propyleneoxy group is preferable, and an ethyleneoxy group is more preferable.
  • the number of alkyleneoxy groups added to the bisphenol structure is not particularly limited, but is preferably 4 to 16 per molecule, more preferably 6 to 14.
  • the ethylenically unsaturated compound B1 having a bisphenol structure is described in paragraphs 0072 to 0080 of JP-A-2016-224162, and the contents described in this publication are incorporated in the present specification.
  • ethylenically unsaturated compound B1 a bifunctional ethylenically unsaturated compound having a bisphenol A structure is preferable, and 2,2-bis (4-((meth) acryloxypolyalkoxy) phenyl) propane is more preferable.
  • 2,2-bis (4-((meth) acryloxypolyalkoxy) phenyl) propane examples include 2,2-bis (4- (methacryloxydiethoxy) phenyl) propane (FA-324M, Showa Denko Materials Co., Ltd.).
  • the ethylenically unsaturated compound B1 preferably contains a compound represented by the following formula (Bis) from the viewpoint of the change in the line width of the leaving time, the change in the line width of the developing temperature, and the sensitivity.
  • R 1 and R 2 independently represent a hydrogen atom or a methyl group
  • A is C 2 H 4
  • B is C 3 H 6
  • n 1 and n 3 are independent, respectively.
  • n 1 + n 3 is an integer of 1 to 39
  • n 1 + n 3 is an integer of 2 to 40
  • n 2 and n 4 are independently integers of 0 to 29, and n 2 + n 4 is an integer of 0 to 40.
  • n 1 + n 2 + n 3 + n 4 is preferably an integer of 2 to 20, more preferably an integer of 2 to 16, and even more preferably an integer of 4 to 12. Further, n 2 + n 4 is preferably an integer of 0 to 10, more preferably an integer of 0 to 4, further preferably an integer of 0 to 2, and particularly preferably 0.
  • the ethylenically unsaturated compound B1 may be used alone or in combination of two or more.
  • the content of the ethylenically unsaturated compound B1 in the photosensitive layer is preferably 10% by mass or more, more preferably 20% by mass or more, based on the total mass of the photosensitive layer, from the viewpoint of better resolution.
  • the upper limit is not particularly limited, but is preferably 70% by mass or less, more preferably 60% by mass or less, from the viewpoint of transferability and edge fusion (a phenomenon in which the components in the photosensitive layer exude from the edge of the transfer material).
  • the photosensitive layer may contain an ethylenically unsaturated compound other than the above-mentioned ethylenically unsaturated compound B1.
  • the ethylenically unsaturated compound other than the ethylenically unsaturated compound B1 is not particularly limited and can be appropriately selected from known compounds.
  • a compound having one ethylenically unsaturated group in one molecule (monofunctional ethylenically unsaturated compound), a bifunctional ethylenically unsaturated compound having no aromatic ring, and a trifunctional or higher ethylenically unsaturated compound. Examples include compounds.
  • Examples of the monofunctional ethylenically unsaturated compound include ethyl (meth) acrylate, ethylhexyl (meth) acrylate, 2- (meth) acryloyloxyethyl succinate, polyethylene glycol mono (meth) acrylate, and polypropylene glycol mono (meth) acrylate. , And phenoxyethyl (meth) acrylate.
  • bifunctional ethylenically unsaturated compound having no aromatic ring examples include alkylene glycol di (meth) acrylate, polyalkylene glycol di (meth) acrylate, urethane di (meth) acrylate, and trimethylolpropane diacrylate. Be done.
  • alkylene glycol di (meth) acrylate examples include tricyclodecanedimethanol diacrylate (A-DCP, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.) and tricyclodecanedimethanol dimethacrylate (DCP, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.).
  • 1,9-Nonandiol diacrylate (A-NOD-N, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), 1,6-hexanediol diacrylate (A-HD-N, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), Examples thereof include ethylene glycol dimethacrylate, 1,10-decanediol diacrylate, and neopentyl glycol di (meth) acrylate.
  • polyalkylene glycol di (meth) acrylate examples include polyethylene glycol di (meth) acrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, and polypropylene glycol di (meth) acrylate.
  • urethane di (meth) acrylate examples include propylene oxide-modified urethane di (meth) acrylate, and ethylene oxide and propylene oxide-modified urethane di (meth) acrylate.
  • Commercially available urethane di (meth) acrylates include, for example, 8UX-015A (manufactured by Taisei Fine Chemical Co., Ltd.), UA-32P (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), and UA-1100H (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.). ).
  • Examples of the trifunctional or higher functional ethylenically unsaturated compound include dipentaerythritol (tri / tetra / penta / hexa) (meth) acrylate, pentaerythritol (tri / tetra) (meth) acrylate, and trimethylolpropane tri (meth).
  • Examples thereof include acrylates, trimethylolpropane tetra (meth) acrylates, trimethylolethanetri (meth) acrylates, isocyanuric acid tri (meth) acrylates, glycerintri (meth) acrylates, and alkylene oxide-modified products thereof.
  • (tri / tetra / penta / hexa) (meth) acrylate) is a concept including tri (meth) acrylate, tetra (meth) acrylate, penta (meth) acrylate, and hexa (meth) acrylate.
  • (Tri / tetra) (meth) acrylate” is a concept that includes tri (meth) acrylate and tetra (meth) acrylate.
  • the photosensitive layer preferably contains the above-mentioned ethylenically unsaturated compound B1 and a trifunctional or higher ethylenically unsaturated compound, and the above-mentioned ethylenically unsaturated compound B1 and two or more trifunctional or higher ethylenes. It is more preferable to contain a sex unsaturated compound.
  • the mass ratio of the ethylenically unsaturated compound B1 to the trifunctional or higher ethylenically unsaturated compound is (total mass of the ethylenically unsaturated compound B1): (total mass of the trifunctional or higher ethylenically unsaturated compound).
  • the photosensitive layer preferably contains the above-mentioned ethylenically unsaturated compound B1 and two or more trifunctional ethylenically unsaturated compounds.
  • alkylene oxide-modified product of the trifunctional or higher ethylenically unsaturated compound examples include caprolactone-modified (meth) acrylate compound (KAYARAD (registered trademark) DPCA-20 manufactured by Nippon Kayaku Co., Ltd. and A-9300 manufactured by Shin-Nakamura Chemical Industry Co., Ltd.). -1CL, etc.), alkylene oxide-modified (meth) acrylate compound (KAYARAD RP-1040 manufactured by Nippon Kayaku Co., Ltd., ATM-35E and A-9300 manufactured by Shin-Nakamura Chemical Industry Co., Ltd., EBECRYL manufactured by Daicel Ornex Co., Ltd.
  • caprolactone-modified (meth) acrylate compound (KAYARAD (registered trademark) DPCA-20 manufactured by Nippon Kayaku Co., Ltd. and A-9300 manufactured by Shin-Nakamura Chemical Industry Co., Ltd.).
  • -1CL, etc. alkylene oxide-modified (meth
  • A-GLY-9E ethoxylated glycerin triacrylate
  • A-GLY-9E ethoxylated glycerin triacrylate
  • Aronix registered trademark
  • TO-2349 manufactured by Shin-Nakamura Chemical Industry Co., Ltd.
  • Aronix M-520 manufactured by Toa Synthetic Co., Ltd.
  • Aronix M-510 manufactured by Toa Synthetic Co., Ltd.
  • the ethylenically unsaturated compound other than the ethylenically unsaturated compound B1 the ethylenically unsaturated compound having an acid group described in paragraphs 0025 to 0030 of JP-A-2004-239942 may be used.
  • the value of the ratio Mm / Mb of the content Mm of the ethylenically unsaturated compound and the content Mb of the alkali-soluble resin in the photosensitive layer is preferably 1.0 or less from the viewpoint of resolution and linearity. It is more preferably 0.9 or less, and particularly preferably 0.5 or more and 0.9 or less. Further, the ethylenically unsaturated compound in the photosensitive layer preferably contains a (meth) acrylic compound, and more preferably contains a (meth) acrylate compound, from the viewpoint of curability and resolvability.
  • the ethylenically unsaturated compound in the photosensitive layer contains a (meth) acrylic compound from the viewpoint of curability, resolution and linearity, and acrylic with respect to the total mass of the (meth) acrylic compound contained in the photosensitive layer. It is more preferable that the content of the compound is 60% by mass or less.
  • the molecular weight (weight average molecular weight (Mw) when having a distribution) of the ethylenically unsaturated compound containing the ethylenically unsaturated compound B1 is preferably 200 to 3,000, more preferably 280 to 2,200, and 300. -2,200 is more preferable.
  • the polymerizable compound preferably contains an oxyethylene chain.
  • the oxyethylene chain is a partial structure represented by ⁇ CH2 - CH2 -O—.
  • Examples of the polymerizable compound containing an oxyethylene chain include 2,2-bis (4- (methacryloxydiethoxy) phenyl) propane (FA-324M, manufactured by Showa Denko Materials Co., Ltd.) and 2,2-bis (4).
  • the polymerizable compound may be used alone or in combination of two or more.
  • the content of the polymerizable compound in the photosensitive layer is preferably 10% by mass to 70% by mass, more preferably 20% by mass to 60% by mass, still more preferably 20% by mass to 50% by mass, based on the total mass of the photosensitive layer. ..
  • the negative photosensitive layer preferably contains a polymerization initiator.
  • the polymerization initiator is selected according to the type of the polymerization reaction, and examples thereof include a thermal polymerization initiator and a photopolymerization initiator. Further, examples of the polymerization initiator include a radical polymerization initiator and a cationic polymerization initiator.
  • the negative photosensitive layer preferably contains a photopolymerization initiator.
  • the photopolymerization initiator is a compound that initiates the polymerization of a polymerizable compound by receiving active rays such as ultraviolet rays, visible rays and X-rays.
  • the photopolymerization initiator is not particularly limited, and a known photopolymerization initiator can be used. Examples of the photopolymerization initiator include a photoradical polymerization initiator and a photocationic polymerization initiator, and a photoradical polymerization initiator is preferable.
  • Examples of the photoradical polymerization initiator include a photopolymerization initiator having an oxime ester structure, a photopolymerization initiator having an ⁇ -aminoalkylphenone structure, a photopolymerization initiator having an ⁇ -hydroxyalkylphenone structure, and an acylphosphine oxide. Examples thereof include a photopolymerization initiator having a structure and a photopolymerization initiator having an N-phenylglycine structure.
  • the negative photosensitive layer is a 2,4,5-triarylimidazole dimer and a derivative thereof as a photoradical polymerization initiator from the viewpoints of photosensitive, visibility and resolution of exposed and unexposed areas. It is preferable to include at least one selected from the group consisting of.
  • the two 2,4,5-triarylimidazole structures in the 2,4,5-triarylimidazole dimer and its derivatives may be the same or different.
  • Derivatives of the 2,4,5-triarylimidazole dimer include, for example, 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer, 2- (o-chlorophenyl) -4,5-di.
  • the photoradical polymerization initiator for example, the polymerization initiator described in paragraphs 0031 to 0042 of JP-A-2011-95716 and paragraphs 0064-0081 of JP-A-2015-14783 may be used.
  • photoradical polymerization initiator examples include ethyl dimethylaminobenzoate (DBE, CAS No. 10287-53-3), benzoin methyl ether, anisyl (p, p'-dimethoxybenzyl), and TAZ-110 (Midori Chemical Co., Ltd.).
  • photoradical polymerization initiators examples include 1- [4- (phenylthio) phenyl] -1,2-octanedione-2- (O-benzoyloxime) (trade name: IRGACURE (registered trademark) OXE-.
  • the photocationic polymerization initiator is a compound that generates an acid by receiving active light rays.
  • a compound that is sensitive to active light having a wavelength of 300 nm or more, preferably a wavelength of 300 nm to 450 nm and generates an acid is preferable, but its chemical structure is not limited.
  • a photocationic polymerization initiator that is not directly sensitive to active light with a wavelength of 300 nm or more is also a sensitizer if it is a compound that is sensitive to active light with a wavelength of 300 nm or more and generates an acid when used in combination with a sensitizer. Can be preferably used in combination with.
  • a photocationic polymerization initiator that generates an acid having a pKa of 4 or less is preferable, a photocationic polymerization initiator that generates an acid having a pKa of 3 or less is more preferable, and an acid having a pKa of 2 or less is used.
  • the generated photocationic polymerization initiator is particularly preferred.
  • the lower limit of pKa is not particularly defined, but is preferably -10.0 or higher, for example.
  • Examples of the photocationic polymerization initiator include an ionic photocationic polymerization initiator and a nonionic photocationic polymerization initiator.
  • Examples of the ionic photocationic polymerization initiator include onium salt compounds such as diaryliodonium salts and triarylsulfonium salts, and quaternary ammonium salts.
  • the ionic photocationic polymerization initiator described in paragraphs 0114 to 0133 of JP-A-2014-85643 may be used.
  • nonionic photocationic polymerization initiator examples include trichloromethyl-s-triazines, diazomethane compounds, imide sulfonate compounds, and oxime sulfonate compounds.
  • trichloromethyl-s-triazines the diazomethane compound and the imide sulfonate compound
  • the compounds described in paragraphs 0083 to 0088 of JP-A-2011-22149 may be used.
  • the oxime sulfonate compound the compound described in paragraphs 0084 to 0088 of International Publication No. 2018/179640 may be used.
  • the photosensitive layer may contain one type of photopolymerization initiator alone or two or more types.
  • the content of the photopolymerization initiator in the photosensitive layer is not particularly limited, but is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and more preferably 1.0% by mass or more, based on the total mass of the photosensitive layer. Is more preferable.
  • the upper limit is not particularly limited, but is preferably 10% by mass or less, more preferably 5% by mass or less, based on the total mass of the photosensitive layer.
  • the photosensitive layer preferably contains a dye from the viewpoints of visibility of exposed and unexposed areas, pattern visibility after development, and resolution, and has a maximum absorption wavelength in the wavelength range of 400 nm to 780 nm at the time of color development. It is more preferable to contain a dye having a wavelength of 450 nm or more and whose maximum absorption wavelength is changed by an acid, a base, or a radical (also referred to simply as “dye N”). When the dye N is contained, the detailed mechanism is unknown, but the adhesion to the adjacent layer (for example, a temporary support and the intermediate layer) is improved, and the resolution is more excellent.
  • the maximum absorption wavelength is changed by an acid, a base or a radical means that the dye in a color-developing state is decolorized by an acid, a base or a radical, and the dye in a decolorized state is an acid or a base.
  • it may mean any aspect of a mode in which a color is developed by a radical and a mode in which a dye in a color-developing state changes to a color-developing state of another hue.
  • the dye N may be a compound that changes its color from the decolorized state by exposure and may be a compound that changes its color from the decolorized state by exposure.
  • it may be a dye whose color development or decolorization state is changed by the acid, base or radical generated and acted on in the photosensitive layer by exposure, and the state in the photosensitive layer (for example, pH) by the acid, base or radical. It may be a dye whose color development or decolorization state changes by changing. Further, it may be a dye that changes its color development or decolorization state by directly receiving an acid, a base or a radical as a stimulus without going through exposure.
  • the dye N is preferably a dye whose maximum absorption wavelength is changed by an acid or a radical, and more preferably a dye whose maximum absorption wavelength is changed by a radical.
  • the photosensitive layer preferably contains both a dye whose maximum absorption wavelength is changed by radicals as dye N and a photoradical polymerization initiator.
  • the dye N is preferably a dye that develops color by an acid, a base, or a radical.
  • a photoradical polymerization initiator, a photocationic polymerization initiator (photoacid generator) or a photobase generator is added to the photosensitive layer, and a photoradical polymerization initiator is added after exposure.
  • a radical-reactive dye, an acid-reactive dye or a base-reactive dye for example, a leuco dye
  • a radical-reactive dye, an acid-reactive dye or a base-reactive dye for example, a leuco dye
  • the dye N preferably has a maximum absorption wavelength of 550 nm or more in the wavelength range of 400 nm to 780 nm at the time of color development, more preferably 550 nm to 700 nm. It is more preferably ⁇ 650 nm. Further, the dye N may have only one maximum absorption wavelength in the wavelength range of 400 nm to 780 nm at the time of color development, or may have two or more. When the dye N has two or more maximum absorption wavelengths in the wavelength range of 400 nm to 780 nm at the time of color development, the maximum absorption wavelength having the highest absorbance among the two or more maximum absorption wavelengths may be 450 nm or more.
  • the maximum absorption wavelength of the dye N is the transmission spectrum of the solution (liquid temperature 25 ° C.) containing the dye N in the range of 400 nm to 780 nm using a spectrophotometer: UV3100 (manufactured by Shimadzu Corporation) in an atmospheric atmosphere. Is measured, and the wavelength at which the light intensity becomes the minimum (maximum absorption wavelength) is detected.
  • Examples of the dye that develops or decolorizes by exposure include a leuco compound.
  • Examples of the dye to be decolorized by exposure include leuco compounds, diarylmethane dyes, oxadin dyes, xanthene dyes, iminonaphthoquinone dyes, azomethine dyes and anthraquinone dyes.
  • As the dye N a leuco compound is preferable from the viewpoint of visibility of the exposed portion and the non-exposed portion.
  • the leuco compound examples include a leuco compound having a triarylmethane skeleton (triarylmethane dye), a leuco compound having a spiropyran skeleton (spiropylan dye), a leuco compound having a fluorane skeleton (fluorane dye), and a diarylmethane skeleton.
  • leuco compounds leuco auramine-based dyes having a leuco compound.
  • a triarylmethane dye or a fluorane dye is preferable, and a leuco compound having a triphenylmethane skeleton (triphenylmethane dye) or a fluorane dye is more preferable.
  • the leuco compound preferably has a lactone ring, a surujin ring, or a sultone ring from the viewpoint of visibility of the exposed portion and the non-exposed portion.
  • the lactone ring, sultin ring, or sulton ring of the leuco compound is reacted with the radical generated from the photoradical polymerization initiator or the acid generated from the photocationic polymerization initiator to change the leuco compound into a closed ring state.
  • the color can be decolorized or the leuco compound can be changed to an open ring state to develop a color.
  • the leuco compound is preferably a compound having a lactone ring, a sultone ring or a sultone ring, and the lactone ring, the sultone ring or the sultone ring is opened by a radical or an acid to develop color, and the lactone ring is formed by a radical or an acid.
  • a compound in which the lactone ring is opened to develop a color is more preferable.
  • Examples of the dye N include the following dyes and leuco compounds. Specific examples of the dyes among the dyes N include Brilliant Green, Ethyl Violet, Methyl Green, Crystal Violet, Basic Fuxin, Methyl Violet 2B, Kinaldine Red, Rose Bengal, Metanyl Yellow, Timor Sulfophthalein, Xylenol Blue, and Methyl.
  • leuco compound among the dyes N include p, p', p "-hexamethyltriaminotriphenylmethane (leucocrystal violet), Pergascript Blue SRB (manufactured by Ciba Geigy), crystal violet lactone, and malakite green lactone.
  • the dye N is preferably a dye whose maximum absorption wavelength is changed by radicals from the viewpoints of visibility of exposed and unexposed areas, pattern visibility after development, and resolution, and is a dye that develops color by radicals. Is more preferable.
  • As the dye N leuco crystal violet, crystal violet lactone, brilliant green, or Victoria pure blue-naphthalene sulfonate is preferable.
  • the dye may be used alone or in combination of two or more.
  • the content of the dye is preferably 0.1% by mass or more, preferably 0% by mass, based on the total mass of the photosensitive layer from the viewpoints of visibility of the exposed and non-exposed areas, pattern visibility after development, and resolution. .1% by mass to 10% by mass is more preferable, 0.1% by mass to 5% by mass is further preferable, and 0.1% by mass to 1% by mass is particularly preferable.
  • the content of the dye N is 0.1% by mass or more with respect to the total mass of the photosensitive layer from the viewpoints of visibility of the exposed portion and the non-exposed portion, pattern visibility after development, and resolution. It is preferable, 0.1% by mass to 10% by mass, more preferably 0.1% by mass to 5% by mass, and particularly preferably 0.1% by mass to 1% by mass.
  • the content of the dye N means the content of the dye when all of the dye N contained in the photosensitive layer is in a colored state.
  • a method for quantifying the content of dye N will be described by taking a dye that develops color by radicals as an example.
  • Two kinds of solutions in which 0.001 g or 0.01 g of the dye is dissolved in 100 mL of methyl ethyl ketone are prepared.
  • Irradicure OXE01 (trade name, manufactured by BASF), a photoradical polymerization initiator, is added to each of the obtained solutions, and radicals are generated by irradiating with light of 365 nm to bring all the dyes into a colored state.
  • the absorbance of each solution having a liquid temperature of 25 ° C. is measured using a spectrophotometer (UV3100, manufactured by Shimadzu Corporation), and a calibration curve is prepared.
  • UV3100 UV3100, manufactured by Shimadzu Corporation
  • the absorbance of the solution in which all the dyes are developed is measured by the same method as above except that 3 g of the photosensitive layer is dissolved in methyl ethyl ketone instead of the dye. From the absorbance of the obtained solution containing the photosensitive layer, the content of the dye contained in the photosensitive layer is calculated based on the calibration curve.
  • the photosensitive layer preferably contains a heat-crosslinkable compound from the viewpoint of the strength of the obtained cured film and the adhesiveness of the obtained uncured film.
  • the heat-crosslinkable compound having an ethylenically unsaturated group which will be described later, is not treated as an ethylenically unsaturated compound, but is treated as a heat-crosslinkable compound.
  • the heat-crosslinkable compound include a methylol compound and a blocked isocyanate compound. Of these, a blocked isocyanate compound is preferable from the viewpoint of the strength of the obtained cured film and the adhesiveness of the obtained uncured film.
  • the blocked isocyanate compound reacts with the hydroxy group and the carboxy group, for example, when the alkali-soluble resin and / or the ethylenically unsaturated compound has at least one of the hydroxy group and the carboxy group, the film formed.
  • the hydrophilicity is lowered, and the function when a film obtained by curing the photosensitive layer is used as a protective film tends to be enhanced.
  • the blocked isocyanate compound refers to "a compound having a structure in which the isocyanate group of isocyanate is protected (so-called masked) with a blocking agent".
  • the dissociation temperature of the blocked isocyanate compound is not particularly limited, but is preferably 100 ° C to 160 ° C, more preferably 130 ° C to 150 ° C.
  • the dissociation temperature of the blocked isocyanate means "the temperature of the heat absorption peak associated with the deprotection reaction of the blocked isocyanate when measured by DSC (Differential scanning calorimetry) analysis using a differential scanning calorimeter".
  • DSC Different scanning calorimeter
  • a differential scanning calorimeter model: DSC6200 manufactured by Seiko Instruments Inc. can be preferably used.
  • the differential scanning calorimeter is not limited to this.
  • the blocking agent having a dissociation temperature of 100 ° C. to 160 ° C. examples include active methylene compounds [malonic acid diester (dimethyl malonate, diethyl malonate, din-butyl malonate, di2-ethylhexyl malonic acid, etc.)] and oxime compounds.
  • the blocking agent having a dissociation temperature of 100 ° C. to 160 ° C. preferably contains, for example, an oxime compound from the viewpoint of storage stability.
  • the blocked isocyanate compound preferably has an isocyanurate structure, for example, from the viewpoint of improving the brittleness of the membrane and improving the adhesion to the transferred body.
  • the blocked isocyanate compound having an isocyanurate structure can be obtained, for example, by subjecting hexamethylene diisocyanate to isocyanurate to protect it.
  • a compound having an oxime structure using an oxime compound as a blocking agent is more likely to have a dissociation temperature in a preferable range than a compound having no oxime structure, and has a smaller development residue. It is preferable from the viewpoint of ease.
  • the blocked isocyanate compound may have a polymerizable group.
  • the polymerizable group is not particularly limited, and a known polymerizable group can be used, and a radically polymerizable group is preferable.
  • the polymerizable group include an ethylenically unsaturated group such as a (meth) acryloxy group, a (meth) acrylamide group and a styryl group, and a group having an epoxy group such as a glycidyl group.
  • an ethylenically unsaturated group is preferable, a (meth) acryloxy group is more preferable, and an acryloxy group is further preferable.
  • blocked isocyanate compound a commercially available product can be used.
  • examples of commercially available blocked isocyanate compounds include Karenz (registered trademark) AOI-BM, Karenz (registered trademark) MOI-BM, Karenz (registered trademark) MOI-BP (all manufactured by Showa Denko KK), and block type.
  • Duranate series for example, Duranate (registered trademark) TPA-B80E, Duranate (registered trademark) WT32-B75P, etc., manufactured by Asahi Kasei Chemicals Co., Ltd.
  • the blocked isocyanate compound a compound having the following structure can also be used.
  • the heat-crosslinkable compound may be used alone or in combination of two or more.
  • the content of the heat-crosslinkable compound is preferably 1% by mass to 50% by mass, more preferably 5% by mass to 30% by mass, based on the total mass of the photosensitive layer.
  • the photosensitive layer may contain components other than the above-mentioned alkali-soluble resin, polymerizable compound, polymerization initiator, dye and heat-crosslinkable compound.
  • examples of other components include radical polymerization inhibitors, surfactants, sensitizers, various additives and the like.
  • the other components may be used alone or in combination of two or more.
  • the photosensitive layer may contain a radical polymerization inhibitor.
  • the radical polymerization inhibitor include the thermal polymerization inhibitor described in paragraph 0018 of Japanese Patent No. 4502784. Of these, phenothiazine, phenoxazine, or 4-methoxyphenol is preferable.
  • examples of other radical polymerization inhibitors include naphthylamine, cuprous chloride, nitrosophenylhydroxyamine aluminum salt, diphenylnitrosamine and the like. It is preferable to use a nitrosophenylhydroxylamine aluminum salt as a radical polymerization inhibitor so as not to impair the sensitivity of the photosensitive layer.
  • the radical polymerization inhibitor may be used alone or in combination of two or more.
  • the content of the radical polymerization inhibitor is preferably 0.001% by mass to 5.0% by mass, preferably 0.01% by mass to 3% by mass, based on the total mass of the photosensitive layer. 0.0% by mass is more preferable, and 0.02% by mass to 2.0% by mass is further preferable.
  • the content of the radical polymerization inhibitor is preferably 0.005% by mass to 5.0% by mass, more preferably 0.01% by mass to 3.0% by mass, based on the total mass of the polymerizable compound. , 0.01% by mass to 1.0% by mass is more preferable.
  • the photosensitive layer preferably contains a surfactant.
  • the surfactant include the surfactants described in paragraphs 0017 of Japanese Patent No. 4502784 and paragraphs 0060 to 0071 of Japanese Patent Application Laid-Open No. 2009-237362. Further, as the surfactant, a nonionic surfactant, a fluorine-based surfactant or a silicone-based surfactant is preferable.
  • fluorine-based surfactants include, for example, Megafax (trade names) F-171, F-172, F-173, F-176, F-177, F-141, F-142, F-143. , F-144, F-437, F-444, F-475, F-477, F-479, F-482, F-551-A, F-552, F-554, F-555-A, F -556, F-557, F-558, F-559, F-560, F-561, F-565, F-563, F-568, F-575, F-780, EXP. MFS-330, EXP. MFS-578, EXP. MFS-578-2, EXP. MFS-579, EXP.
  • the fluorine-based surfactant has a molecular structure having a functional group containing a fluorine atom, and an acrylic compound in which a portion of the functional group containing a fluorine atom is cut off and the fluorine atom volatilizes when heat is applied.
  • fluorine-based surfactants include Megafuck (trade name) DS series manufactured by DIC Corporation (The Chemical Daily (February 22, 2016), Nikkei Sangyo Shimbun (February 23, 2016)).
  • Megafuck (trade name) DS-21 can be mentioned.
  • the fluorine-based surfactant it is also preferable to use a polymer of a fluorine atom-containing vinyl ether compound having a fluorinated alkyl group or a fluorinated alkylene ether group and a hydrophilic vinyl ether compound.
  • a block polymer can also be used as the fluorine-based surfactant.
  • the fluorine-based surfactant has a structural unit derived from a (meth) acrylate compound having a fluorine atom and 2 or more (preferably 5 or more) alkyleneoxy groups (preferably ethyleneoxy groups and propyleneoxy groups) (meth).
  • a fluorine-containing polymer compound containing a structural unit derived from an acrylate compound can also be preferably used.
  • fluorine-based surfactant a fluorine-containing polymer having an ethylenically unsaturated group in the side chain can also be used. Megafuck (trade name) RS-101, RS-102, RS-718K, RS-72-K (all manufactured by DIC Corporation) and the like can be mentioned.
  • a fluorine-based surfactant for example, a compound having a linear perfluoroalkyl group having 7 or more carbon atoms may be used. However, from the viewpoint of improving environmental aptitude, it is preferable to use a substitute material of perfluorooctanoic acid (PFOA) or perfluorooctanesulfonic acid (PFOS) as the fluorosurfactant.
  • PFOA perfluorooctanoic acid
  • PFOS perfluorooctanesulfonic acid
  • Nonionic surfactants include glycerol, trimethylolpropane, trimethylolethane, their ethoxylates and propoxylates (eg, glycerol propoxylates, glycerol ethoxylates, etc.), polyoxyethylene lauryl ethers, polyoxyethylene stearyl ethers, etc.
  • silicone-based surfactant examples include a linear polymer composed of a siloxane bond and a modified siloxane polymer having an organic group introduced into a side chain or a terminal.
  • Specific examples of the silicone-based surfactant include EXP. S-309-2, EXP. S-315, EXP. S-503-2, EXP.
  • the photosensitive layer may contain one type of surfactant alone or two or more types.
  • the content of the surfactant is preferably 0.001% by mass to 10% by mass, more preferably 0.01% by mass to 3% by mass, based on the total mass of the photosensitive layer.
  • the photosensitive layer may contain a sensitizer.
  • the sensitizer is not particularly limited, and known sensitizers, dyes and pigments can be used.
  • Examples of the sensitizer include dialkylaminobenzophenone compounds, pyrazoline compounds, anthracene compounds, coumarin compounds, xanthone compounds, thioxanthone compounds, acridone compounds, oxazole compounds, benzoxazole compounds, thiazole compounds, benzothiazole compounds, and triazole compounds (for example). 1,2,4-triazole), stilben compounds, triazine compounds, thiophene compounds, naphthalimide compounds, triarylamine compounds, and aminoacridin compounds.
  • the sensitizer may be used alone or in combination of two or more.
  • the content of the sensitizer can be appropriately selected depending on the purpose, but from the viewpoint of improving the sensitivity to the light source and improving the curing rate by balancing the polymerization rate and the chain transfer, the photosensitive layer is selected. 0.01% by mass to 5% by mass is preferable, and 0.05% by mass to 1% by mass is more preferable, based on the total mass of the above.
  • the photosensitive layer may contain known additives, if necessary.
  • the additive include plasticizers, heterocyclic compounds, benzotriazoles, carboxybenzotriazoles, pyridines (isonicotinamide and the like), purine bases (adenine and the like), and solvents.
  • the photosensitive layer may contain one kind of each additive alone, or may contain two or more kinds of additives.
  • benzotriazoles include 1,2,3-benzotriazole, 1-chloro-1,2,3-benzotriazole, bis (N-2-ethylhexyl) aminomethylene-1,2,3-benzotriazole, and the like. Examples thereof include bis (N-2-ethylhexyl) aminomethylene-1,2,3-tolyltriazole and bis (N-2-hydroxyethyl) aminomethylene-1,2,3-benzotriazole.
  • carboxybenzotriazoles examples include 4-carboxy-1,2,3-benzotriazole, 5-carboxy-1,2,3-benzotriazole, and N- (N, N-di-2-ethylhexyl) aminomethylene. Examples thereof include carboxybenzotriazole, N- (N, N-di-2-hydroxyethyl) aminomethylenecarboxybenzotriazole, N- (N, N-di-2-ethylhexyl) aminoethylenecarboxybenzotriazole and the like.
  • a commercially available product such as CBT-1 (Johoku Chemical Industry Co., Ltd., trade name) can be used.
  • the total content of benzotriazoles and carboxybenzotriazoles is preferably 0.01% by mass to 3% by mass, and preferably 0.05% by mass to 1% by mass, based on the total mass of the photosensitive layer. More preferred. It is preferable that the content is 0.01% by mass or more from the viewpoint of imparting storage stability to the photosensitive layer. On the other hand, it is preferable to set the content to 3% by mass or less from the viewpoint of maintaining the sensitivity and suppressing the decolorization of the dye.
  • the photosensitive layer may contain at least one selected from the group consisting of a plasticizer and a heterocyclic compound.
  • a plasticizer and a heterocyclic compound include the compounds described in paragraphs 097 to 0103 and 0111 to 0118 of International Publication No. 2018/179640.
  • the photosensitive layer may contain a solvent.
  • the photosensitive layer is formed of a photosensitive resin composition containing a solvent, the solvent may remain on the photosensitive layer.
  • the photosensitive layer includes metal oxide particles, antioxidants, dispersants, acid growth agents, development accelerators, conductive fibers, thermal acid generators, ultraviolet absorbers, thickeners, cross-linking agents, and organic or organic layers. It may further contain known additives such as an inorganic anti-precipitation agent. Additives contained in the photosensitive layer are described in paragraphs 0165 to 0184 of JP-A-2014-85643, and the contents of this publication are incorporated in the present specification.
  • the photosensitive layer may contain a predetermined amount of impurities.
  • impurities include sodium, potassium, magnesium, calcium, iron, manganese, copper, aluminum, titanium, chromium, cobalt, nickel, zinc, tin, halogen and ions thereof.
  • halide ions, sodium ions, and potassium ions are likely to be mixed as impurities, so the following content is preferable.
  • the content of impurities in the photosensitive layer is preferably 80 ppm or less, more preferably 10 ppm or less, still more preferably 2 ppm or less on a mass basis.
  • the content of impurities may be 1 ppb or more, or 0.1 ppm or more, on a mass basis.
  • Examples of the method for keeping impurities within the above range include selecting a composition having a low content of impurities as a raw material, preventing impurities from being mixed during the production of the photosensitive layer, and cleaning and removing the impurities. By such a method, the amount of impurities can be kept within the above range.
  • the impurities can be quantified by known methods such as ICP (Inductively Coupled Plasma) emission spectroscopy, atomic absorption spectroscopy, and ion chromatography.
  • ICP Inductively Coupled Plasma
  • the content of compounds such as benzene, formaldehyde, trichlorethylene, 1,3-butadiene, carbon tetrachloride, chloroform, N, N-dimethylformamide, N, N-dimethylacetamide, and hexane in the photosensitive layer is preferably low. ..
  • the content of these compounds with respect to the total mass of the photosensitive layer is preferably 100 ppm or less, more preferably 20 ppm or less, still more preferably 4 ppm or less on a mass basis.
  • the lower limit can be 10 ppb or more and 100 ppb or more with respect to the total mass of the photosensitive layer on a mass basis.
  • the content of these compounds can be suppressed in the same manner as the above-mentioned metal impurities. Further, it can be quantified by a known measurement method.
  • the water content in the photosensitive layer is preferably 0.01% by mass to 1.0% by mass, more preferably 0.05% by mass to 0.5% by mass, from the viewpoint of improving reliability and laminateability.
  • the photosensitive layer may contain a residual monomer corresponding to each structural unit of the alkali-soluble resin described above.
  • the content of the residual monomer is preferably 5,000 mass ppm or less, more preferably 2,000 mass ppm or less, and 500 mass ppm or less with respect to the total mass of the alkali-soluble resin from the viewpoint of patterning property and reliability. Is more preferable.
  • the lower limit is not particularly limited, but 1 mass ppm or more is preferable, and 10 mass ppm or more is more preferable.
  • the residual monomer of each structural unit of the alkali-soluble resin is preferably 3,000 mass ppm or less, more preferably 600 mass ppm or less, and more preferably 100 mass ppm or less, based on the total mass of the photosensitive layer, from the viewpoint of patterning property and reliability. More preferably, the mass is ppm or less.
  • the lower limit is not particularly limited, but is preferably 0.1 mass ppm or more, and more preferably 1 mass ppm or more.
  • the amount of residual monomer of the monomer when synthesizing the alkali-soluble resin by the polymer reaction is also in the above range.
  • the content of glycidyl acrylate is preferably in the above range.
  • the amount of the residual monomer can be measured by a known method such as liquid chromatography and gas chromatography.
  • the thickness of the photosensitive layer is preferably 20 ⁇ m or less, more preferably 10 ⁇ m or less, further preferably 8 ⁇ m or less, and further preferably 5 ⁇ m or less. Is particularly preferable.
  • the thickness of the photosensitive layer may be 1 ⁇ m or more.
  • the thickness of the photosensitive layer is most preferably 1 ⁇ m or more and 5 ⁇ m or less.
  • the transmittance of light having a wavelength of 365 nm in the photosensitive layer is preferably 10% or more, preferably 30% or more, and more preferably 50% or more.
  • the upper limit is not particularly limited, but is preferably 99.9% or less.
  • the method for forming the photosensitive layer is not particularly limited as long as it is a method capable of forming a layer containing the above components.
  • a method for forming the photosensitive layer for example, a photosensitive resin composition containing an alkali-soluble resin, an ethylenically unsaturated compound, a photopolymerization initiator, a solvent and the like is prepared, and the photosensitive resin composition is formed on the surface of the intermediate layer or the like. Is applied, and a method of forming the coating film of the photosensitive resin composition by drying is mentioned.
  • a method for drying the coating film of the photosensitive resin composition heat drying and vacuum drying are preferable.
  • drying means removing at least a part of the solvent contained in the composition.
  • Examples of the drying method include natural drying, heat drying, and vacuum drying. The above methods can be applied alone or in combination.
  • the drying temperature is preferably 80 ° C. or higher, more preferably 90 ° C. or higher.
  • the upper limit thereof is preferably 130 ° C. or lower, more preferably 120 ° C. or lower. It can also be dried by continuously changing the temperature.
  • the drying time is preferably 20 seconds or longer, more preferably 40 seconds or longer, and even more preferably 60 seconds or longer.
  • the upper limit is not particularly limited, but is preferably 600 seconds or less, and more preferably 300 seconds or less.
  • Examples of the photosensitive resin composition used for forming the photosensitive layer include an alkali-soluble resin, an ethylenically unsaturated compound, a photopolymerization initiator, and a composition containing the above-mentioned optional components and a solvent.
  • the photosensitive resin composition preferably contains a solvent in order to adjust the viscosity of the photosensitive resin composition and facilitate the formation of the photosensitive layer.
  • the solvent contained in the photosensitive resin composition is not particularly limited as long as it can dissolve or disperse an alkali-soluble resin, an ethylenically unsaturated compound, a photopolymerization initiator and the above optional components, and a known solvent is used. can.
  • the solvent include an alkylene glycol ether solvent, an alkylene glycol ether acetate solvent, an alcohol solvent (methanol, ethanol, etc.), a ketone solvent (acetone, methyl ethyl ketone, etc.), an aromatic hydrocarbon solvent (toluene, etc.), and an aprotonic polar solvent.
  • the photosensitive resin composition preferably contains at least one selected from the group consisting of an alkylene glycol ether solvent and an alkylene glycol ether acetate solvent.
  • a mixed solvent containing at least one selected from the group consisting of an alkylene glycol ether solvent and an alkylene glycol ether acetate solvent and at least one selected from the group consisting of a ketone solvent and a cyclic ether solvent is more preferable.
  • a mixed solvent containing at least one selected from the group consisting of a glycol ether solvent and an alkylene glycol ether acetate solvent, a ketone solvent, and at least three types of a cyclic ether solvent is more preferable.
  • alkylene glycol ether solvent examples include ethylene glycol monoalkyl ether, ethylene glycol dialkyl ether, propylene glycol monoalkyl ether, propylene glycol dialkyl ether, diethylene glycol dialkyl ether, dipropylene glycol monoalkyl ether and dipropylene glycol dialkyl ether. ..
  • alkylene glycol ether acetate solvent examples include ethylene glycol monoalkyl ether acetate, propylene glycol monoalkyl ether acetate, diethylene glycol monoalkyl ether acetate and dipropylene glycol monoalkyl ether acetate.
  • the solvent described in paragraphs 0092 to 0094 of International Publication No. 2018/179640 and the solvent described in paragraph 0014 of JP-A-2018-177789 may be used, and the contents thereof are described in the present specification. Incorporated into the book.
  • the photosensitive resin composition may contain one type of solvent alone, or may contain two or more types of solvent.
  • the content of the solvent when the photosensitive resin composition is applied is preferably 50 parts by mass to 1,900 parts by mass, preferably 100 parts by mass to 900 parts by mass with respect to 100 parts by mass of the total solid content in the photosensitive resin composition. The part is more preferable.
  • the method for preparing the photosensitive resin composition is not particularly limited.
  • a photosensitive resin composition is prepared by preparing a solution in which each component is dissolved in the above solvent in advance and mixing the obtained solution in a predetermined ratio. There is a method of preparing.
  • the photosensitive resin composition is preferably filtered using a filter having a pore size of 0.2 ⁇ m to 30 ⁇ m before forming the photosensitive layer.
  • the method of applying the photosensitive resin composition is not particularly limited, and the photosensitive resin composition may be applied by a known method. Examples of the coating method include slit coating, spin coating, curtain coating and inkjet coating. Further, the photosensitive layer may be formed by applying a photosensitive resin composition on a protective film described later and drying the photosensitive layer.
  • the transfer material according to one embodiment of the present disclosure preferably contains a protective film as the outermost layer on the side opposite to the temporary support side. Further, the protective film is preferably in contact with the photosensitive layer.
  • Examples of the material constituting the protective film include a resin film and paper, and a resin film is preferable from the viewpoint of strength and flexibility.
  • Examples of the resin film include a polyethylene film, a polypropylene film, a polyethylene terephthalate film, a cellulose triacetate film, a polystyrene film, and a polycarbonate film. Of these, polyethylene film, polypropylene film, or polyethylene terephthalate film is preferable.
  • the thickness (layer thickness) of the protective film is not particularly limited, but is preferably 1 ⁇ m to 100 ⁇ m, more preferably 5 ⁇ m to 50 ⁇ m, further preferably 5 ⁇ m to 40 ⁇ m, and particularly preferably 15 ⁇ m to 30 ⁇ m.
  • the arithmetic mean roughness Ra value of the surface of the protective film in contact with the photosensitive layer (hereinafter, also simply referred to as “the surface of the protective film”) is preferably 0.3 ⁇ m or less, preferably 0.1 ⁇ m or less, from the viewpoint of excellent resolution. Is more preferable, and 0.05 ⁇ m or less is further preferable.
  • the Ra value on the surface of the protective film is within the above range, the uniformity of the layer thickness of the photosensitive layer and the formed resin pattern is improved, so that the resolution is improved.
  • the lower limit of the Ra value on the surface of the protective film is not particularly limited, but 0.001 ⁇ m or more is preferable.
  • the Ra value on the surface of the protective film is measured by the following method. Using a three-dimensional optical profiler (New View7300, manufactured by Zygo), the surface of the protective film is measured under the following conditions to obtain the surface profile of the optical film. As the measurement / analysis software, Microscope Application of MetroPro ver8.3.2 is used. Next, the Surface Map screen is displayed by the above analysis software, and the histogram data is obtained in the Surface Map screen. From the obtained histogram data, the arithmetic mean roughness is calculated, and the Ra value on the surface of the protective film is obtained. When the protective film is attached to the transfer material, the protective film may be peeled from the transfer material and the Ra value of the surface on the peeled side may be measured.
  • a transfer material can be manufactured by adhering a protective film to a photosensitive layer or the like.
  • the method of attaching the protective film to the photosensitive layer or the like is not particularly limited, and known methods can be mentioned.
  • Examples of the device for adhering the protective film to the photosensitive layer include a vacuum laminator and a known laminator such as an auto-cut laminator. It is preferable that the laminator is provided with an arbitrary heatable roller such as a rubber roller and can be pressurized and heated.
  • the transfer material according to one embodiment of the present disclosure may include a refractive index adjusting layer (that is, a contrast enhancement layer).
  • a refractive index adjusting layer that is, a contrast enhancement layer.
  • the contrast enhancement layer is described in paragraph 0134 of WO 2018/179640. Further, the other layers are described in paragraphs 0194 to 0196 of JP-A-2014-85643. The contents of these publications are incorporated herein.
  • the total thickness of each layer of the transfer material excluding the temporary support and the protective film is preferably 20 ⁇ m or less, more preferably 10 ⁇ m or less, and more preferably 8 ⁇ m, from the viewpoint of resolution and adhesion to the substrate. It is more preferably 2 ⁇ m or more, and particularly preferably 8 ⁇ m or less. Further, the total thickness of the photosensitive layer and the intermediate layer in the transfer material is preferably 20 ⁇ m or less, more preferably 10 ⁇ m or less, and more preferably 8 ⁇ m or less, from the viewpoint of resolution and adhesion to the substrate. It is more preferably 2 ⁇ m or more and 8 ⁇ m or less.
  • the breaking elongation of the cured film obtained by curing the photosensitive layer at 120 ° C. is 15% or more, and the arithmetic mean roughness Ra of the surface of the temporary support on the photosensitive layer side is 50 nm or less. It is preferable that the arithmetic mean roughness Ra of the surface of the protective film on the photosensitive layer side is 150 nm or less.
  • the transfer material according to the present disclosure preferably satisfies the following formula (R1).
  • X ⁇ Y ⁇ 1,500 formula (R1) X represents the value (%) of the elongation at break at 120 ° C. of the cured film obtained by curing the photosensitive layer, and Y is the arithmetic mean roughness of the surface of the temporary support on the photosensitive layer side. Represents the value (nm) of Ra.
  • X ⁇ Y is more preferably 750 or less.
  • the breaking elongation at 120 ° C. is twice or more larger than the breaking elongation at 23 ° C. of the cured film obtained by curing the photosensitive layer.
  • the breaking elongation is obtained after the photosensitive layer having a thickness of 20 ⁇ m is exposed to 120 mJ / cm 2 with an ultrahigh pressure mercury lamp and cured, then further exposed to 400 mJ / cm 2 with a high pressure mercury lamp and heated at 145 ° C. for 30 minutes. It is measured by a tensile test using a cured film.
  • the transfer material according to the present disclosure preferably satisfies the following formula (R2).
  • Y represents the arithmetic mean roughness Ra value (nm) of the surface of the temporary support on the photosensitive layer side
  • Z is the arithmetic mean of the surface of the protective film on the photosensitive layer side. Represents the value (nm) of roughness Ra.
  • the method for producing the transfer material according to the present disclosure is not particularly limited, and a known production method, for example, a known method for forming each layer can be used.
  • a method for producing a transfer material according to the present disclosure will be described with reference to FIG. 1.
  • the transfer material according to the present disclosure is not limited to the one having the configuration shown in FIG.
  • a step of applying the composition for the intermediate layer to the surface of the temporary support 10 and then drying the coating film of the composition for the intermediate layer to form the intermediate layer 20 is intermediate.
  • a step of applying a photosensitive resin composition containing, for example, an alkali-soluble resin and an ethylenically unsaturated compound to the surface of the layer 20 and then drying the coating film of the photosensitive resin composition to form the photosensitive layer 30 is included. The method can be mentioned.
  • a composition for an intermediate layer containing at least one selected from the group consisting of water and a water-miscible organic solvent is used, and further, an alkali-soluble resin, an ethylenically unsaturated compound, and an alkylene are used. It is preferable to use a photosensitive resin composition containing at least one selected from the group consisting of a glycol ether solvent and an alkylene glycol ether acetate solvent.
  • the transfer material 100 is manufactured by crimping the protective film 40 to the photosensitive layer 30 of the laminate manufactured by the above manufacturing method.
  • the method for producing the transfer material used in the present disclosure includes a step of providing the protective film 40 so as to be in contact with the surface of the photosensitive layer 30 opposite to the side on which the temporary support 10 is provided. It is preferable to manufacture the transfer material 100 including 10, the intermediate layer 20, the photosensitive layer 30, and the protective film 40. After the transfer material 100 is manufactured by the above-mentioned manufacturing method, the transfer material 100 may be wound up to prepare and store the transfer material in the form of a roll.
  • the roll-type transfer material can be provided as it is in the process of bonding with a substrate in the roll-to-roll method described later.
  • the transfer material according to the embodiment of the present disclosure can be suitably used for various applications requiring precision microfabrication by photolithography.
  • the photosensitive layer may be used as a coating for etching, or electroforming may be performed mainly by electroplating.
  • the cured film obtained by patterning may be used as a permanent film, or may be used, for example, as an interlayer insulating film, a wiring protective film, a wiring protective film having an index matching layer, or the like.
  • the transfer materials according to the embodiment of the present disclosure include semiconductor packages, printed circuit boards, various wiring forming applications for sensor boards, touch panels, electromagnetic wave shielding materials, conductive films such as film heaters, liquid crystal sealing materials, micromachines and micros. It can be suitably used for applications such as the formation of structures in the field of electronics.
  • the photosensitive layer is a colored resin layer containing a pigment
  • the colored resin layer is used for, for example, a liquid crystal display (LCD) and a color used for a solid-state image sensor [for example, a CCD (charge-coupled device) and a CMOS (complementary metal oxide semiconductor)]. It is suitable for forming colored pixels such as filters or a black matrix.
  • liquid crystal display windows of electronic devices may be provided with a cover glass having a black frame-shaped light-shielding layer formed on the peripheral edge of the back surface of a transparent glass substrate or the like in order to protect the liquid crystal display window. be.
  • a colored resin layer can be used to form such a light-shielding layer.
  • the embodiments other than the pigment in the colored resin layer are the same as those described above.
  • the pigment used for the colored resin layer may be appropriately selected according to the desired hue, and can be selected from black pigments, white pigments, and chromatic pigments other than black and white. Above all, when forming a black pattern, a black pigment is preferably selected as the pigment.
  • the black pigment a known black pigment (organic pigment, inorganic pigment, etc.) can be appropriately selected as long as the effect in the present disclosure is not impaired.
  • a known black pigment organic pigment, inorganic pigment, etc.
  • carbon black is particularly preferable.
  • carbon black from the viewpoint of surface resistance, carbon black having at least a part of the surface coated with a resin is preferable.
  • the particle size of the black pigment is preferably 0.001 ⁇ m to 0.1 ⁇ m, more preferably 0.01 ⁇ m to 0.08 ⁇ m in terms of number average particle size.
  • the particle size refers to the diameter of a circle when the area of the pigment particles is obtained from a photographic image of the pigment particles taken with an electronic microscope and a circle having the same area as the area of the pigment particles is considered, and the number average particle size. Is an average value obtained by obtaining the above particle size for any 100 particles and averaging the obtained 100 particle sizes.
  • the white pigment described in paragraphs 0015 and 0114 of JP-A-2005-007765 can be used as the white pigment.
  • the white pigments as the inorganic pigment, titanium oxide, zinc oxide, lithopone, light calcium carbonate, white carbon, aluminum oxide, aluminum hydroxide, or barium sulfate are preferable, and titanium oxide or zinc oxide is more preferable.
  • titanium oxide is more preferred.
  • rutile-type or anatase-type titanium oxide is particularly preferable, and rutile-type titanium oxide is extremely preferable.
  • the surface of titanium oxide may be treated with silica, alumina, titania, zirconia, or an organic substance, or may be subjected to two or more treatments.
  • the catalytic activity of titanium oxide is suppressed, and heat resistance, fading and the like are improved.
  • at least one of alumina treatment and zirconia treatment is preferable as the surface treatment of the surface of titanium oxide, and both alumina treatment and zirconia treatment are particularly preferable.
  • the photosensitive layer is a colored resin layer
  • the photosensitive layer further contains a chromatic pigment other than the black pigment and the white pigment from the viewpoint of transferability.
  • a chromatic pigment is contained, the particle size of the chromatic pigment is preferably 0.1 ⁇ m or less, more preferably 0.08 ⁇ m or less, in that the dispersibility is more excellent.
  • chromatic pigments include Victoria Pure Blue BO (Color Index (hereinafter CI) 42595), Auramine (CI41000), Fat Black HB (CI26150), and Monolite.
  • CI Pigment Yellow 12 Permanent Yellow GR
  • Permanent Yellow HR Permanent Yellow HR
  • Pigment Red 146 Hoster Balm Red ESB (CI Pigment Violet 19), Permanent Ruby FBH (CI Pigment Red 11), Fastel Pink B Supra (CI Pigment) Red 81), Monastral First Blue (CI Pigment Blue 15), Monolite First Black B (CI Pigment Black 1) and Carbon, C.I. I. Pigment Red 97, C.I. I. Pigment Red 122, C.I. I. Pigment Red 149, C.I. I. Pigment Red 168, C.I. I. Pigment Red 177, C.I. I. Pigment Red 180, C.I. I. Pigment Red 192, C.I. I. Pigment Red 215, C.I. I. Pigment Green 7, C.I. I.
  • Pigment Blue 15 1, C.I. I. Pigment Blue 15: 4, C.I. I. Pigment Blue 22, C.I. I. Pigment Blue 60, C.I. I. Pigment Blue 64, and C.I. I. Pigment Violet 23 and the like. Above all, C.I. I. Pigment Red 177 is preferred.
  • the content of the pigment is preferably more than 3% by mass and 40% by mass or less, more preferably more than 3% by mass and 35% by mass or less, based on the total mass of the photosensitive layer. It is more preferably more than mass% and 35% by mass or less, and particularly preferably 10% by mass or more and 35% by mass or less.
  • the content of the pigment other than the black pigment is preferably 30% by mass or less, preferably 1% by mass to 20% by mass, based on the black pigment. % Is more preferable, and 3% by mass to 15% by mass is further preferable.
  • the black pigment (preferably carbon black) is introduced into the photosensitive resin composition in the form of a pigment dispersion.
  • the dispersion liquid may be prepared by adding a mixture obtained by previously mixing a black pigment and a pigment dispersant to an organic solvent (or vehicle) and dispersing it with a disperser.
  • the pigment dispersant may be selected depending on the pigment and the solvent, and for example, a commercially available dispersant can be used.
  • the vehicle refers to a portion of the medium in which the pigment is dispersed when the pigment is dispersed, and is a liquid, a binder component that holds the black pigment in a dispersed state, and a solvent component that dissolves and dilutes the binder component. (Organic solvent) and.
  • the disperser is not particularly limited, and examples thereof include known dispersers such as a kneader, a roll mill, an attritor, a super mill, a dissolver, a homomixer, and a sand mill. Further, it may be finely pulverized by mechanical grinding using frictional force.
  • disperser and fine pulverization the description of "Encyclopedia of Pigments" (Kunizo Asakura, First Edition, Asakura Shoten, 2000, 438, 310) can be referred to.
  • a transfer material containing a temporary support, an intermediate layer in contact with the temporary support, and a photosensitive layer in this order and a substrate are bonded together, and the substrate is placed on the substrate.
  • Arranging the photosensitive layer, the intermediate layer, and the temporary support in this order (hereinafter, may be referred to as “bonding step”) and peeling the temporary support from the intermediate layer (hereinafter, “peeling”). It may be referred to as a "step”), and the intermediate layer and the photosensitive layer may be exposed and developed to form a pattern (hereinafter, may be referred to as a "pattern forming step").
  • the surface roughness Ra of the intermediate layer exposed by peeling the temporary support from the intermediate layer is 2 nm or more.
  • the transfer material described in the above-mentioned "transfer material" section is applied as the transfer material.
  • at least a part of the pattern obtained in the pattern forming step includes a line-and-space pattern.
  • the width of at least one set of lines and spaces in the line-and-space pattern is preferably 20 ⁇ m or less in total.
  • the transfer material containing the temporary support, the intermediate layer in contact with the temporary support, and the photosensitive layer are bonded to each other in this order, and the photosensitive layer, the intermediate layer, and the temporary support are arranged in this order on the substrate. do.
  • the conductive layer is provided on the surface of the substrate, it is preferable to bond the transfer material and the conductive layer of the substrate.
  • the bonding of the transfer material and the substrate preferably includes crimping the transfer material and the substrate. Since the adhesion between the transfer material and the substrate is improved, the patterned photosensitive layer after exposure and development can be suitably used as an etching resist when etching the conductive layer. If the transfer material includes a protective film, the protective film may be removed and then bonded.
  • the method of crimping the transfer material and the substrate is not particularly limited, and a known transfer method and laminating method can be used.
  • the bonding of the transfer material and the substrate is preferably performed by stacking the transfer material and the substrate and applying pressure and heating by means such as a roll.
  • a known laminator such as a laminator, a vacuum laminator, and an auto-cut laminator capable of further increasing productivity can be used.
  • the laminating temperature is not particularly limited, but is preferably 70 ° C to 130 ° C, for example.
  • the method for manufacturing the laminated body including the bonding step is performed by a roll-to-roll method.
  • the roll-to-roll method uses a substrate that can be wound and unwound as a substrate, and unwinds the substrate or a structure including the substrate before any of the steps included in the method for manufacturing a laminated body (a step of unwinding the substrate or a structure including the substrate).
  • a "unwinding step") and a step of winding the substrate or a structure including the substrate also referred to as a "winding step” after any of the steps, and at least one of the steps (also referred to as a "winding step”).
  • the unwinding method in the unwinding step and the winding method in the winding step are not particularly limited, and a known method may be used in the manufacturing method to which the roll-to-roll method is applied.
  • the substrate a known substrate may be used, but a substrate having a conductive layer is preferable, and it is more preferable to have a conductive layer on the surface of the substrate.
  • the substrate may have any layer other than the conductive layer, if necessary.
  • the substrate include a resin substrate, a glass substrate, and a semiconductor substrate. Preferred embodiments of the substrate include, for example, the description in paragraph 0140 of WO 2018/155193, which is incorporated herein.
  • the material of the resin substrate cycloolefin polymer and polyimide are preferable.
  • the thickness of the resin substrate is preferably 5 ⁇ m to 200 ⁇ m, more preferably 10 ⁇ m to 100 ⁇ m.
  • the conductive layer examples include a conductive layer used for general circuit wiring or touch panel wiring. Further, as the conductive layer, at least one layer selected from the group consisting of a metal layer, a conductive metal oxide layer, a graphene layer, a carbon nanotube layer and a conductive polymer layer is used from the viewpoint of conductivity and fine wire forming property. Preferably, a metal layer is more preferable, and a copper layer or a silver layer is further preferable.
  • the substrate may have one conductive layer alone, or may have two or more layers. When having two or more conductive layers, it is preferable to have conductive layers made of different materials.
  • Examples of the material of the conductive layer include metals and conductive metal oxides.
  • Examples of the metal include Al, Zn, Cu, Fe, Ni, Cr, Mo, Ag and Au.
  • Examples of the conductive metal oxide include ITO (Indium Tin Oxide), IZO (Indium Zinc Oxide) and SiO 2 .
  • conductivity means that the volume resistivity is less than 1 ⁇ 106 ⁇ cm.
  • the volume resistivity of the conductive metal oxide is preferably less than 1 ⁇ 10 4 ⁇ cm.
  • a resin pattern is manufactured using a substrate having a plurality of conductive layers
  • the conductive layer an electrode pattern corresponding to the sensor of the visual recognition portion used in the capacitive touch panel or wiring of the peripheral extraction portion is preferable.
  • Preferred embodiments of the conductive layer include, for example, the description in paragraph 0141 of WO 2018/155193, the contents of which are incorporated herein.
  • a substrate having at least one of a transparent electrode and a routing wire is preferable.
  • the above-mentioned substrate can be suitably used as a touch panel substrate.
  • the transparent electrode may function suitably as a touch panel electrode.
  • the transparent electrode is preferably composed of a metal oxide film such as ITO (indium tin oxide) and IZO (indium zinc oxide), a metal mesh, and a fine metal wire such as a metal nanowire.
  • the thin metal wire include thin wires such as silver and copper. Of these, silver conductive materials such as silver mesh and silver nanowires are preferable.
  • Metal is preferable as the material of the routing wiring.
  • the metal that is the material of the routing wiring include gold, silver, copper, molybdenum, aluminum, titanium, chromium, zinc, and manganese, and alloys composed of two or more of these metal elements.
  • copper, molybdenum, aluminum, or titanium is preferable, and copper is particularly preferable.
  • the electrode protective film for a touch panel formed by using the transfer material according to the present disclosure has an electrode or the like directly or another layer for the purpose of protecting the electrode or the like (that is, at least one of the electrode for the touch panel and the wiring for the touch panel). It is preferable that it is provided so as to cover the interposition.
  • peeling process the temporary support is peeled from the intermediate layer.
  • the method of peeling the temporary support is not limited.
  • the same mechanism as the cover film peeling mechanism described in paragraphs 0161 to 0162 of Japanese Patent Application Laid-Open No. 2010-072589 can be used.
  • the roughness Ra of the surface of the intermediate layer exposed by peeling the temporary support from the intermediate layer is 2 nm or more.
  • the roughness Ra of the first surface of the intermediate layer is 2 nm or more, the slipperiness of the surface of the intermediate layer is improved.
  • a preferred range of roughness Ra on the first surface of the intermediate layer is described in the section "Intermediate layer" above.
  • the static friction coefficient of the surface of the intermediate layer exposed by peeling the temporary support from the intermediate layer is preferably less than 2.0.
  • the coefficient of static friction of the first surface of the intermediate layer is less than 2.0, the slipperiness of the surface of the intermediate layer is improved.
  • the preferred range of the coefficient of static friction of the first surface of the intermediate layer is described in the above section "Intermediate layer".
  • the dynamic friction coefficient of the surface of the intermediate layer exposed by peeling the temporary support from the intermediate layer is preferably less than 1.5.
  • the coefficient of dynamic friction of the first surface of the intermediate layer is less than 1.5, the slipperiness of the surface of the intermediate layer is improved.
  • the preferred range of the coefficient of dynamic friction of the first surface of the intermediate layer is described in the above section "Intermediate layer".
  • Pattern formation process In the pattern forming step, the intermediate layer and the photosensitive layer are exposed and developed to form a pattern. The development process is usually performed after the exposure process.
  • the exposure treatment preferably includes pattern exposure of the intermediate layer and the photosensitive layer.
  • the "pattern exposure” refers to an exposure in a pattern of exposure, that is, a form in which an exposed portion and a non-exposed portion are present.
  • the positional relationship between the exposed area and the unexposed area in the pattern exposure is not particularly limited and is appropriately adjusted.
  • the intermediate layer and the photosensitive layer may be exposed from the side opposite to the side on which the substrate is provided, or may be exposed from the side on which the substrate is provided.
  • the detailed arrangement and specific size of the pattern in the pattern exposure are not particularly limited.
  • at least a part of the pattern so as to improve the display quality of a display device (for example, a touch panel) having an input device having a circuit wiring manufactured by a circuit wiring manufacturing method and to reduce the area occupied by the take-out wiring.
  • the electrode pattern of the touch panel and / or the portion of the take-out wiring includes a thin wire having a width of 20 ⁇ m or less, and more preferably a thin wire having a width of 10 ⁇ m or less.
  • the light source used for exposure can be appropriately selected and used as long as it is a light source that irradiates the photosensitive layer with light having a wavelength that allows exposure (for example, 365 nm or 405 nm).
  • a light source that irradiates the photosensitive layer with light having a wavelength that allows exposure for example, 365 nm or 405 nm.
  • Specific examples thereof include ultra-high pressure mercury lamps, high pressure mercury lamps, metal halide lamps and LEDs (Light Emitting Diodes).
  • the exposure amount is preferably 5 mJ / cm 2 to 200 mJ / cm 2 , more preferably 10 mJ / cm 2 to 100 mJ / cm 2 .
  • Preferred embodiments of the light source, exposure amount and exposure method used for exposure include, for example, the description of paragraphs 0146 to 0147 of International Publication No. 2018/155193, the contents of which are incorporated in the present specification.
  • the exposure method select the contact exposure method in the case of contact exposure, the proximity exposure method in the case of the non-contact exposure method, the projection exposure method of the lens system or the mirror system, the direct exposure method using an exposure laser, etc. as appropriate. Can be used.
  • an exposure machine having an appropriate numerical aperture (NA) of the lens can be used according to the required resolving power and depth of focus.
  • drawing may be performed directly on the photosensitive layer, or reduced projection exposure may be performed on the photosensitive layer via a lens. Further, the exposure may be performed not only in the atmosphere but also under reduced pressure or vacuum, or may be exposed by interposing a liquid such as water between the light source and the intermediate layer.
  • the intermediate layer and the photomask may be brought into contact with each other to expose the intermediate layer and the photosensitive layer, or the intermediate layer may be photo-photographed without contacting the photomask with the intermediate layer.
  • the intermediate layer and the photosensitive layer may be exposed by bringing the masks close to each other.
  • the exposure treatment preferably includes contacting the intermediate layer with the photomask to expose the intermediate layer and the photosensitive layer.
  • Development can be performed using a developer.
  • a developer for example, a known developer such as the developer described in JP-A-5-72724 can be used.
  • the developer may contain a water-soluble organic solvent and / or a surfactant.
  • the developer the developer described in paragraph 0194 of International Publication No. 2015/093271 is also preferably mentioned.
  • Preferred development methods include, for example, the development method described in paragraph 0195 of International Publication No. 2015/093271.
  • the development method is not particularly limited, and may be any of paddle development, shower development, shower and spin development, and dip development.
  • Shower development is a development process for removing an exposed portion or a non-exposed portion by spraying a developing solution on the photosensitive layer after exposure by a shower. After development, it is preferable to spray the cleaning agent with a shower and rub with a brush to remove the development residue.
  • the liquid temperature of the developing solution is not particularly limited, but is preferably 20 ° C to 40 ° C.
  • the method for producing the laminate preferably includes a step of peeling the protective film from the transfer material.
  • the method of peeling the protective film is not limited, and a known method can be applied.
  • the method for producing a laminate may include a step of exposing a pattern obtained by a pattern forming step (post-exposure step) and / or a step of heating (post-baking step).
  • post-exposure step a step of exposing a pattern obtained by a pattern forming step
  • post-baking step a step of heating
  • the exposure amount of the post exposure is preferably 100 mJ / cm 2 to 5,000 mJ / cm 2 , more preferably 200 mJ / cm 2 to 3,000 mJ / cm 2 .
  • the temperature of the post bake is preferably 80 ° C to 250 ° C, more preferably 90 ° C to 160 ° C.
  • the post-baking time is preferably 1 minute to 180 minutes, more preferably 10 minutes to 60 minutes.
  • the method for producing a laminate according to an embodiment of the present disclosure may include any step other than the above-mentioned steps.
  • the steps described in the circuit wiring manufacturing method or the touch panel manufacturing method shown below may be mentioned, but the steps are not limited to these steps.
  • the laminate manufactured by the method for producing a laminate according to an embodiment of the present disclosure can be applied to various devices.
  • the device provided with the laminated body include an input device and the like, and a touch panel is preferable, and a capacitive touch panel is more preferable.
  • the input device can be applied to a display device such as an organic electroluminescence display device and a liquid crystal display device.
  • the formed pattern is preferably used as a touch panel electrode or a protective film for touch panel wiring. That is, the transfer material according to the present disclosure is preferably used for forming an electrode protective film for a touch panel or wiring for a touch panel.
  • a transfer material including a temporary support, an intermediate layer in contact with the temporary support, and a photosensitive layer in this order and a substrate are bonded together, and the substrate is placed on the substrate.
  • Arranging the photosensitive layer, the intermediate layer and the temporary support in this order that is, “bonding step”
  • peeling the temporary support from the intermediate layer that is, “peeling step”
  • the intermediate layer and the photosensitive layer are exposed and developed to form a pattern (that is, a "pattern forming step”), and the substrate is etched in a region where the pattern is not arranged.
  • etching step the surface roughness Ra of the intermediate layer exposed by peeling the temporary support from the intermediate layer is 2 nm or more. ..
  • etching step the surface roughness Ra of the intermediate layer exposed by peeling the temporary support from the intermediate layer is 2 nm or more.
  • etching step the substrate is etched in the region where the pattern is not arranged. That is, in the etching step, a pattern formed from the photosensitive layer is used as an etching resist to perform an etching process.
  • a method of etching treatment a known method can be applied, and for example, the method described in paragraphs 0209 to 0210 of JP-A-2017-120435 and paragraphs 0048-paragraph 0054 of JP-A-2010-152155. Examples thereof include a wet etching method in which the material is immersed in an etching solution, and a dry etching method such as plasma etching.
  • an acidic or alkaline etching solution may be appropriately selected according to the etching target.
  • the acidic etching solution include an aqueous solution of an acidic component alone selected from hydrochloric acid, sulfuric acid, nitric acid, acetic acid, hydrofluoric acid, oxalic acid and phosphoric acid, and the acidic component, ferric chloride, ammonium fluoride and Examples thereof include a mixed aqueous solution with a salt selected from potassium permanganate.
  • the acidic component may be a component in which a plurality of acidic components are combined.
  • the alkaline etching solution includes an aqueous solution of an alkaline component alone selected from sodium hydroxide, potassium hydroxide, ammonia, an organic amine, and a salt of an organic amine (tetramethylammonium hydroxide, etc.), and an alkaline component and a salt. Examples thereof include a mixed aqueous solution with (potassium permanganate, etc.).
  • the alkaline component may be a component in which a plurality of alkaline components are combined.
  • the method for manufacturing a circuit wiring according to an embodiment of the present disclosure preferably includes a step of removing a remaining pattern (hereinafter, may be referred to as a "removal step").
  • the removal step is preferably performed after the etching step.
  • the method for removing the remaining pattern is not particularly limited, and examples thereof include a method for removing by chemical treatment, and a method for removing with a removing liquid is preferable.
  • a method for removing the remaining pattern a substrate having the remaining pattern is placed in a stirring removing liquid having a liquid temperature of preferably 30 ° C. to 80 ° C., more preferably 50 ° C. to 80 ° C. for 1 minute to 30 minutes. Examples include a method of dipping.
  • the removing liquid examples include a removing liquid in which an inorganic alkaline component or an organic alkaline component is dissolved in water, dimethyl sulfoxide, N-methylpyrrolidone, or a mixed solution thereof.
  • examples of the inorganic alkaline component include sodium hydroxide and potassium hydroxide.
  • examples of the organic alkali component include a primary amine compound, a secondary amine compound, a tertiary amine compound and a quaternary ammonium salt compound.
  • the removing liquid may be used and removed by a known method such as a spray method, a shower method and a paddle method.
  • the method for manufacturing a circuit wiring according to an embodiment of the present disclosure may include any process other than the above-mentioned process.
  • the following steps can be mentioned, but the steps are not limited to these steps.
  • examples of the exposure step, the developing step, and other steps applicable to the method for manufacturing the circuit wiring include the steps described in paragraphs 0035 to 0051 of JP-A-2006-23696.
  • a step of reducing the visible light reflectance described in paragraph 0172 of International Publication No. 2019/022089 a new step on the insulating film described in paragraph 0173 of International Publication No. 2019/022089. Examples thereof include a step of forming a conductive layer, but the process is not limited to these steps.
  • the method for manufacturing a circuit wiring may include a step of reducing the visible light reflectance of a part or all of a plurality of conductive layers included in the substrate.
  • the treatment for reducing the visible light reflectance include an oxidation treatment.
  • the visible light reflectance of the conductive layer can be lowered by oxidizing copper to copper oxide and blackening the conductive layer.
  • the treatment for reducing the visible light reflectance is described in paragraphs 0017 to 0025 of JP-A-2014-150118, and paragraphs 0041, 0042, 0048 and 0058 of JP-2013-206315. The contents of these publications are incorporated herein by reference.
  • the method for manufacturing a circuit wiring preferably includes a step of forming an insulating film on the surface of the circuit wiring and a step of forming a new conductive layer on the surface of the insulating film.
  • a second electrode pattern insulated from the first electrode pattern can be formed.
  • the step of forming the insulating film is not particularly limited, and examples thereof include a known method of forming a permanent film.
  • an insulating film having a desired pattern may be formed by photolithography using a photosensitive material having an insulating property.
  • the step of forming the new conductive layer on the insulating film is not particularly limited, and for example, a new conductive layer having a desired pattern may be formed by photolithography using a photosensitive material having conductivity.
  • a substrate having a plurality of conductive layers on both surfaces of the substrate is used, and the circuit is sequentially or simultaneously with respect to the conductive layers formed on both surfaces of the substrate. It is also preferable to form. With such a configuration, it is possible to form a circuit wiring for a touch panel in which a first conductive pattern is formed on one surface of a substrate and a second conductive pattern is formed on the other surface. It is also preferable to form the touch panel circuit wiring having such a configuration from both sides of the substrate by roll-to-roll.
  • the circuit wiring manufactured by the method for manufacturing a circuit wiring according to an embodiment of the present disclosure can be applied to various devices.
  • Examples of the device provided with the circuit wiring manufactured by the above manufacturing method include an input device, a touch panel is preferable, and a capacitance type touch panel is more preferable.
  • the input device can be applied to a display device such as an organic EL display device and a liquid crystal display device.
  • a transfer material containing a temporary support, an intermediate layer in contact with the temporary support, and a photosensitive layer in this order and a substrate are bonded together, and the photosensitive layer is placed on the photosensitive layer.
  • Arranging the layer, the intermediate layer and the temporary support in this order that is, “bonding step”
  • peeling the temporary support from the intermediate layer that is, “peeling step”
  • the intermediate layer and the photosensitive layer are exposed and developed to form a pattern (that is, a "pattern forming step”), and the substrate is etched in a region where the pattern is not arranged (that is, a "pattern forming step”). That is, the "etching step”) is included in this order, and the surface roughness Ra of the intermediate layer exposed by peeling the temporary support from the intermediate layer is 2 nm or more.
  • each step in the touch panel manufacturing method and the embodiment such as the order in which each step is performed are described in the above-mentioned sections of "Manufacturing method of laminated body" and "Manufacturing method of circuit wiring". The same is true for the preferred embodiment.
  • a known method for manufacturing the touch panel may be referred to, except that the wiring for the touch panel is formed by the above method.
  • the touch panel manufacturing method may include any process (other process) other than those described above.
  • FIGS. 2 and 3 show an example of a mask pattern used for manufacturing a touch panel.
  • GR is a non-image part (light-shielding part)
  • EX is an image part (exposure part)
  • DL virtualizes a frame for alignment. It is shown as a target.
  • a touch panel having a circuit wiring having the pattern A corresponding to EX can be manufactured. Specifically, it can be produced by the method shown in FIG. 1 of International Publication No. 2016/190405.
  • the central portion (pattern portion where the squares are connected) of the exposed portion EX is the portion where the transparent electrode (touch panel electrode) is formed, and the peripheral portion (thin line portion) of the exposed portion EX is. This is the part where the wiring of the peripheral extraction part is formed.
  • a touch panel having at least touch panel wiring is manufactured.
  • the touch panel preferably has a transparent substrate, electrodes, and an insulating layer or a protective layer.
  • Examples of the detection method on the touch panel include known methods such as a resistance film method, a capacitance method, an ultrasonic method, an electromagnetic induction method, and an optical method. Above all, the capacitance method is preferable.
  • the touch panel type includes a so-called in-cell type (for example, those shown in FIGS. 5, 6, 7, and 8 of JP-A-2012-51751), and a so-called on-cell type (for example, JP-A-2013-168125).
  • 2013-5472 (described in FIG. 2), various out-cell types (so-called GG, G1 / G2, GFF, GF2, GF1, G1F, etc.) and other configurations (for example, Japanese Patent Application Laid-Open No. 2013-164871).
  • Examples of the touch panel include those described in paragraph 0229 of JP-A-2017-120435.
  • the temporary support S-1 is a Lumirror 16Q62 manufactured by Toray Industries, Inc.
  • Temporal support S-2 Polyethylene was melt-extruded and laminated on a polyethylene terephthalate (PET) film having a thickness of 16 ⁇ m so that the thickness of the polyethylene was 10 ⁇ m. In the laminating, a matted roll having a surface roughness Ra of 0.1 ⁇ m was pressed against the polyethylene layer. By the above procedure, a PET film with matted polyethylene was produced as the temporary support S-2.
  • the roughness Ra of the first surface of the temporary support S-2 shown in Table 1 is a value measured on the surface of the polyethylene layer.
  • Temporal support S-3 A temporary support S-3 was obtained by a method according to the method for manufacturing the temporary support S-2, except that the surface roughness Ra of the matted roll was changed to 0.2 ⁇ m.
  • the roughness Ra of the first surface of the temporary support S-3 shown in Table 1 is a value measured on the surface of the polyethylene layer.
  • the temporary support S-4 is a sand matte processed film type S manufactured by Kaisei Kogyo Co., Ltd.
  • Temporal support S-5 is a sand matte processed film type A manufactured by Kaisei Kogyo Co., Ltd.
  • A-1 Composition containing 30% by mass polymer A-1 produced by the method described below
  • A-2 Composition containing 30% by mass polymer A-2 produced by the method described below.
  • a composition containing 30% by mass of the polymer A-1 was obtained by the following method.
  • the following abbreviations represent the following compounds, respectively.
  • St Styrene (manufactured by Wako Pure Chemical Industries, Ltd.)
  • MAA Methacrylic acid (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.)
  • MMA Methyl methacrylate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.)
  • V-601 2,2'-azobis (isobutyric acid) dimethyl (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., polymerization initiator)
  • PGMEA Propylene Glycol Monomethyl Ether Acetate
  • PGMEA 116.5 parts by mass was placed in a three-necked flask, and the temperature was raised to 90 ° C. under a nitrogen atmosphere.
  • St 52.0 parts by mass
  • MMA (19.0 parts by mass)
  • MAA 29.0 parts by mass
  • V-601 3 parts by mass
  • a mixed solution of 4.0 parts by mass) and PGMEA 116.5 parts by mass was added dropwise into a three-necked flask over 2 hours. After completion of the dropping, the mixture was stirred for 2 hours while maintaining the liquid temperature at 90 ° C. ⁇ 2 ° C. to obtain a composition containing 30% by mass of the polymer A-1.
  • the properties of polymer A-1 are shown in the table below.
  • a composition containing 30% by mass of the polymer A-2 was obtained by a method according to the method for synthesizing the polymer A-1, except that the amount of V-601 added was changed to 12.0 parts by mass.
  • the properties of polymer A-2 are shown in the table below.
  • B-1 NK Ester BPE-500 (2,2-bis (4- (methacryloxypentethoxy) phenyl) propane, manufactured by Shin Nakamura Chemical Industry Co., Ltd.)
  • B-2 Aronix M-270 (polypropylene glycol diacrylate, manufactured by Toagosei Co., Ltd.)
  • B-3 Sartomer SR-454 (epoxidized trimethylolpropane triacrylate, manufactured by Arkema)
  • composition for intermediate layer ⁇ Preparation of composition for intermediate layer>
  • the components shown in the table below were mixed and filtered through a polytetrafluoroethylene filter having a pore size of 5.0 ⁇ m to prepare a composition for an intermediate layer.
  • the unit of the blending amount of the component is a mass part.
  • Snowtex O water-dispersed silica sol, solid content 20% by mass, manufactured by Nissan Chemical Industries, Ltd.
  • Example 1> (Preparation of transfer material)
  • the composition for intermediate layer C-1 was applied onto the polyethylene layer of the temporary support S-2 so that the dry film thickness was 1.0 ⁇ m, and dried in an oven at 100 ° C. for 2 minutes to prepare an intermediate layer.
  • the photosensitive resin composition P-1 is applied onto the intermediate layer using a slit-shaped nozzle so that the dry film thickness is 3.0 ⁇ m, and dried in an oven at 100 ° C. for 2 minutes to prepare a photosensitive layer. did.
  • a polypropylene film (Trefan # 30-2500H, 26 ⁇ m thick, manufactured by Toray Industries, Inc.) was laminated on the photosensitive layer as a protective film to prepare a transfer material.
  • a copper layer having a thickness of 200 nm was prepared by sputtering on a polyethylene terephthalate (PET) film having a thickness of 100 ⁇ m, and a PET substrate with a copper layer was prepared.
  • PET polyethylene terephthalate
  • the transfer material was laminated on a PET substrate with a copper layer under laminating conditions of a linear pressure of 0.6 MPa and a linear velocity (laminating rate) of 3.6 m / min.
  • the temporary support was peeled off.
  • the exposed intermediate layer and a glass mask having a line-and-space pattern (duty ratio 1: 1) with a line width of 3 ⁇ m to 20 ⁇ m are brought into contact with each other while adjusting the exposure position (alignment), and an ultra-high pressure mercury lamp is passed through the mask.
  • the photosensitive layer was exposed, it was allowed to stand for 30 minutes and then developed to form a resin pattern. Development was carried out by shower development for 40 seconds using a 1.0 mass% sodium carbonate aqueous solution at 28 ° C.
  • Examples 2 to 10 and Comparative Examples 1 to 2> With the transfer material and copper layer by the method according to the method of Example 1 except that the type of the temporary support, the type of the composition for the intermediate layer and the type of the photosensitive resin composition were appropriately changed according to the description in Table 5. A PET substrate, a resin pattern, and a circuit wiring pattern were produced.
  • the transfer material was laminated on a PET substrate with a copper layer under laminating conditions of a linear pressure of 0.6 MPa and a linear velocity (laminating speed) of 0.5 m / min.
  • laminating speed 0.5 m / min.
  • the transfer material was laminated on a PET substrate with a copper layer under laminating conditions of a linear pressure of 0.6 MPa and a linear velocity (laminating rate) of 0.5 m / min.
  • An ultrahigh pressure mercury lamp is used to irradiate light including g-line (436 nm), h-line (405 nm) and i-line (365 nm) with an exposure amount such that the line width after development of a 10 ⁇ m line-and-space pattern is 10 ⁇ m.
  • the photosensitive layer was exposed through a mask. After allowing to stand for 30 minutes, it was developed.
  • a resin pattern was prepared by using a 1.0 mass% sodium carbonate aqueous solution at 28 ° C. and performing shower development for 40 seconds. Wiring is performed by etching the laminate containing the resin pattern at 23 ° C.
  • Table 5 shows that the slipperiness (static friction) in Examples 1 to 10 is superior to the slipperiness (static friction) in Comparative Examples 1 and 2.
  • Table 5 shows that the slipperiness (dynamic friction) in Examples 1 to 10 is superior to the slipperiness (dynamic friction) in Comparative Examples 1 and 2.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • Architecture (AREA)
  • Structural Engineering (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Materials For Photolithography (AREA)
  • Laminated Bodies (AREA)

Abstract

L'invention concerne un matériau de transfert et un procédé de fabrication de stratifié mettant en œuvre ce matériau de transfert. Le matériau de transfert contient dans l'ordre un support temporaire, une couche intermédiaire en contact avec ledit support temporaire, et une couche photosensible. La rugosité (Ra) de la surface de ladite couche intermédiaire exposée lorsque ledit support temporaire est pelé vis-à-vis de ladite couche intermédiaire, est supérieure ou égale à 2nm.
PCT/JP2021/046631 2020-12-25 2021-12-16 Matériau de transfert, et procédé de fabrication de stratifié WO2022138468A1 (fr)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017208849A1 (fr) * 2016-05-31 2017-12-07 富士フイルム株式会社 Composition de résine photosensible, film de transfert, motif décoratif, écran tactile et procédé permettant de produire un motif
JP2018116255A (ja) * 2017-01-17 2018-07-26 太陽インキ製造株式会社 感光性フィルム積層体およびそれを用いて形成された硬化物
WO2020116068A1 (fr) * 2018-12-04 2020-06-11 富士フイルム株式会社 Matériau de transfert, procédé de production d'un motif en résine, procédé de production d'un câblage de circuit, et procédé de fabrication d'un panneau tactile
WO2020158316A1 (fr) * 2019-01-29 2020-08-06 富士フイルム株式会社 Matériau de transfert photosensible, procédé de production de motif en résine, procédé de production de câblage de circuit, procédé de production d'écran tactile, et film et procédé de production associés
JP2021128178A (ja) * 2020-02-10 2021-09-02 富士フイルム株式会社 樹脂パターンの製造方法、回路配線の製造方法、タッチパネルの製造方法、及び、感光性転写部材

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017208849A1 (fr) * 2016-05-31 2017-12-07 富士フイルム株式会社 Composition de résine photosensible, film de transfert, motif décoratif, écran tactile et procédé permettant de produire un motif
JP2018116255A (ja) * 2017-01-17 2018-07-26 太陽インキ製造株式会社 感光性フィルム積層体およびそれを用いて形成された硬化物
WO2020116068A1 (fr) * 2018-12-04 2020-06-11 富士フイルム株式会社 Matériau de transfert, procédé de production d'un motif en résine, procédé de production d'un câblage de circuit, et procédé de fabrication d'un panneau tactile
WO2020158316A1 (fr) * 2019-01-29 2020-08-06 富士フイルム株式会社 Matériau de transfert photosensible, procédé de production de motif en résine, procédé de production de câblage de circuit, procédé de production d'écran tactile, et film et procédé de production associés
JP2021128178A (ja) * 2020-02-10 2021-09-02 富士フイルム株式会社 樹脂パターンの製造方法、回路配線の製造方法、タッチパネルの製造方法、及び、感光性転写部材

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