WO2022181485A1 - Method for manufacturing laminate and method for manufacturing circuit wiring - Google Patents

Method for manufacturing laminate and method for manufacturing circuit wiring Download PDF

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Publication number
WO2022181485A1
WO2022181485A1 PCT/JP2022/006659 JP2022006659W WO2022181485A1 WO 2022181485 A1 WO2022181485 A1 WO 2022181485A1 JP 2022006659 W JP2022006659 W JP 2022006659W WO 2022181485 A1 WO2022181485 A1 WO 2022181485A1
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WO
WIPO (PCT)
Prior art keywords
photosensitive composition
composition layer
layer
substrate
temporary support
Prior art date
Application number
PCT/JP2022/006659
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French (fr)
Japanese (ja)
Inventor
悠 鬼塚
壮二 石坂
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富士フイルム株式会社
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Application filed by 富士フイルム株式会社 filed Critical 富士フイルム株式会社
Priority to JP2023502355A priority Critical patent/JPWO2022181485A1/ja
Priority to CN202280015875.1A priority patent/CN116868125A/en
Publication of WO2022181485A1 publication Critical patent/WO2022181485A1/en

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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • G03F7/033—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
    • G03F7/11—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having cover layers or intermediate layers, e.g. subbing layers
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/20—Exposure; Apparatus therefor
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/26—Processing photosensitive materials; Apparatus therefor
    • G03F7/40—Treatment after imagewise removal, e.g. baking
    • G—PHYSICS
    • G06—COMPUTING; CALCULATING OR COUNTING
    • G06F—ELECTRIC DIGITAL DATA PROCESSING
    • G06F3/00—Input arrangements for transferring data to be processed into a form capable of being handled by the computer; Output arrangements for transferring data from processing unit to output unit, e.g. interface arrangements
    • G06F3/01—Input arrangements or combined input and output arrangements for interaction between user and computer
    • G06F3/03—Arrangements for converting the position or the displacement of a member into a coded form
    • G06F3/041—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/02—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding
    • H05K3/06—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding the conductive material being removed chemically or electrolytically, e.g. by photo-etch process
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/10—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern
    • H05K3/18—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using precipitation techniques to apply the conductive material

Definitions

  • the present invention relates to a laminate manufacturing method and a circuit wiring manufacturing method.
  • a photosensitive composition layer was placed on an arbitrary substrate using a transfer film, and the photosensitive composition layer was exposed through a photomask. Post-development methods are widely used.
  • Patent Document 1 discloses a photosensitive transfer material having a temporary support, a thermoplastic resin layer, an intermediate layer, and a negative photosensitive layer in this order.
  • the inventors of the present invention have studied a laminate manufacturing method using a conventional transfer film or the like as described in Patent Document 1, and have found that the shape of the resulting pattern tends to be defective.
  • the transfer film is attached to the object to be transferred, pattern-exposed, and developed to obtain a desired pattern.
  • the pattern shape tended to widen at the bottom as the width of the pattern increased as it approached the substrate side from the side opposite to the substrate side.
  • the flared bottom shape means a pattern shape in which the length of the lower base (on the side of the substrate) is longer than the length of the upper base (on the side opposite to the substrate) in the resulting pattern shape. More specifically, as shown in FIG.
  • Measurement Y The surface of the photosensitive composition layer of the transfer film opposite to the temporary support side is brought into contact with the substrate, the transfer film and the substrate are bonded together, and the obtained laminate is The temporary support is peeled off, and the entire surface of the photosensitive composition layer in the laminate from which the temporary support is peeled off is exposed under the same exposure conditions as in the exposure step, and then the resulting cured film.
  • the glass transition temperature is measured and defined as the glass transition temperature Y.
  • the intermediate layer contains at least one selected from the group consisting of water-soluble cellulose derivatives, polyhydric alcohols, oxide adducts of polyhydric alcohols, polyether resins, phenol derivatives and amide compounds [10] Or the manufacturing method of the laminated body as described in [11]. [13] between the bonding step and the exposure step, further comprising a peeling step of peeling the temporary support from the laminate of the transfer film and the substrate;
  • the exposure step is an exposure step of pattern-exposing the photosensitive composition layer of the laminate from which the temporary support obtained in the peeling step is peeled through a photomask, [1] to [ 12].
  • Measurement Y The surface of the photosensitive composition layer of the transfer film opposite to the temporary support side is brought into contact with the substrate, the transfer film and the substrate are bonded together, and the obtained laminate is The temporary support is peeled off, and the entire surface of the photosensitive composition layer in the laminate from which the temporary support is peeled off is exposed under the same exposure conditions as in the exposure step, and then the resulting cured film.
  • the glass transition temperature is measured and defined as the glass transition temperature Y.
  • a method for manufacturing a laminate including a pattern which is excellent in pattern shape. Further, according to the present invention, a method for manufacturing circuit wiring can also be provided.
  • FIG. 4 is a schematic diagram showing a method for evaluating line width variation
  • a numerical range represented using “to” means a range including the numerical values described before and after “to” as lower and upper limits.
  • the upper limit or lower limit described in a certain numerical range may be replaced with the upper limit or lower limit of another numerical range described stepwise.
  • the upper or lower limits described in a certain numerical range may be replaced with the values shown in the examples.
  • the term "process” includes not only an independent process, but also a process that is indistinguishable from other processes, as long as the intended purpose of the process is achieved.
  • Transparent means that the average transmittance of visible light with a wavelength of 400 to 700 nm is 80% or more, preferably 90% or more, unless otherwise specified.
  • the average transmittance of visible light is a value measured using a spectrophotometer, and can be measured using, for example, a spectrophotometer U-3310 manufactured by Hitachi, Ltd.
  • a refractive index is a value measured using an ellipsometer at a wavelength of 550 nm unless otherwise specified.
  • the hue is a value measured using a color difference meter (CR-221, manufactured by Minolta) unless otherwise specified.
  • the weight average molecular weight (Mw) and number average molecular weight (Mn) were measured using TSKgel GMHxL, TSKgel G4000HxL, TSKgel G2000HxL (all trade names manufactured by Tosoh Corporation) as a column, and THF (tetrahydrofuran) as an eluent. ), using a differential refractometer as a detector and polystyrene as a standard substance, it is a value converted using polystyrene as a standard substance measured by a gel permeation chromatography (GPC) analyzer.
  • the molecular weights of compounds having a molecular weight distribution are weight average molecular weights (Mw) unless otherwise specified.
  • the content of metal elements is a value measured using an inductively coupled plasma (ICP) spectroscopic analyzer unless otherwise specified.
  • (Meth)acryl is a concept that includes both acryl and methacryl
  • (meth)acryloxy group” is a concept that includes both acryloxy and methacryloxy.
  • Alkali-soluble means that the solubility in 100 g of a 1 mass % aqueous solution of sodium carbonate at 22° C. is 0.1 g or more.
  • the "alkali-soluble resin” means a resin that satisfies the above solubility.
  • water-soluble means that the solubility in 100 g of water at pH 7.0 at a liquid temperature of 22° C. is 0.1 g or more.
  • the "water-soluble resin” means a resin that satisfies the above solubility.
  • the "solid content" of the composition means a component that forms a composition layer (e.g., a photosensitive composition layer, an intermediate layer and a thermoplastic resin layer) formed using the composition, and the composition is a solvent.
  • a solvent for example, organic solvent and water, etc.
  • it means all components except the solvent.
  • a liquid component is also regarded as a solid content.
  • the surface of the photosensitive composition layer of the transfer film having the temporary support and the photosensitive composition layer on the side opposite to the temporary support side is brought into contact with the substrate, and the transfer film and the substrate are separated.
  • a laminating step of laminating An exposure step of pattern-exposing the photosensitive composition layer; a developing step of developing the exposed photosensitive composition layer with a developer to form a pattern;
  • the glass transition temperature X (hereinafter also referred to as “TgX”) of the photosensitive composition layer is 110° C. or lower, and the glass transition temperature Y (hereinafter also referred to as “TgY”) obtained by measurement Y is 125° C. or higher.
  • Measurement Y The surface of the photosensitive composition layer of the transfer film opposite to the temporary support side is brought into contact with the substrate, the transfer film and the substrate are laminated, and the temporary support is peeled off from the resulting laminate. , the entire surface of the photosensitive composition layer in the laminate from which the temporary support is peeled off is exposed under the same exposure conditions as the exposure step, and then the glass transition temperature of the resulting cured film is measured, and the glass transition temperature Let Y.
  • a suitable aspect of the method for producing a laminate includes, for example, an aspect in which the lamination step, the exposure step, and the development step are performed in this order.
  • a characteristic point of the method for producing a laminate of the present invention is that TgX is 110° C. or less and TgY obtained by measurement Y is 125° C. or more.
  • the cross-linking density of the pattern (cured film) obtained by exposing the photosensitive composition layer is low, and when developed with a developer, the pattern swells and The present inventors have found that the obtained pattern (cured film) has a wide bottom shape because it is easily dissolved.
  • the method for manufacturing the laminate of the present invention is excellent in pattern shape by adjusting each to predetermined TgX and predetermined TgY.
  • being superior to the pattern shape is also referred to as being more superior in the effects of the present invention.
  • TgX is 110° C. or lower, preferably 105° C. or lower, and more preferably 100° C. or lower.
  • the lower limit is preferably 70°C or higher, more preferably 80°C or higher, and even more preferably 90°C or higher.
  • TgX As a method for measuring TgX, for example, it can be measured by the following method.
  • a measurement sample apparatus: DSC2500 manufactured by T.A. Instruments. Tzero aluminum pans are used for sample containment.
  • TgX As a method for measuring TgX, the following measurement X may be used.
  • the surface of the photosensitive composition layer of the transfer film opposite to the temporary support side is brought into contact with the substrate, the transfer film and the substrate are bonded together, and the temporary support and the photosensitive composition are separated from the resulting laminate.
  • the glass transition temperature of the exposed photosensitive composition layer is measured, and the obtained glass transition temperature is defined as the glass transition temperature X.
  • TgX is the glass transition temperature of a photosensitive composition layer that has not been subjected to exposure treatment, unlike TgY described later. That is, TgX is the glass transition temperature of the photosensitive composition layer in the unexposed area.
  • the substrate used in the measurement X is synonymous with the substrate described later, and the preferred embodiments are also the same.
  • Examples of the peeling method of the temporary support include known peeling methods, and a method of peeling by the same method as the peeling step described later is preferable.
  • the substrate used in the measurement X is the same as the substrate used in the method for manufacturing a laminate, which will be described later.
  • the measurement X is performed after peeling the protective film from the transfer film.
  • TgY is 125° C. or higher, preferably 130° C. or higher, more preferably 135° C. or higher, and even more preferably 140° C. or higher.
  • the upper limit is preferably 160°C or lower, more preferably 150°C or lower, and even more preferably 145°C or lower.
  • TgY is a value obtained by measurement Y below.
  • measurement Y the surface of the photosensitive composition layer of the transfer film opposite to the temporary support side is brought into contact with the substrate, the transfer film and the substrate are bonded together, and the temporary support is peeled off from the resulting laminate. Then, the entire surface of the photosensitive composition layer in the laminate from which the temporary support was removed was exposed under the same exposure conditions as the exposure step, and then the glass transition temperature of the resulting cured film was measured. Let the temperature be Y.
  • the exposure conditions for example, the type of light source, the amount of exposure, etc.
  • for the entire surface exposure are the same as those used in the exposure step described later.
  • the overall exposure performed in the measurement Y corresponds to the exposure in which the exposure range of the pattern exposure performed in the exposure step described later is changed to cover the entire surface of the photosensitive composition layer.
  • TgY is the glass transition temperature of a cured film formed by exposing the photosensitive composition layer.
  • the method for measuring the glass transition temperature, the method for peeling the temporary support, and the substrate used in measurement Y are synonymous with the above-mentioned measurement method and substrate for TgX, and the preferred embodiments are also the same.
  • the measurement Y is performed after the protective film is peeled off from the transfer film.
  • the difference between TgX and TgY is preferably 35-50°C, more preferably 40-50°C.
  • the "difference" is a numerical value obtained by subtracting the smaller one from the larger one of TgX and TgY. For example, if TgY is greater than TgX, the difference is a numerical value given by "TgY-TgX". In addition, when TgX and TgY are the same numerical value, let the difference be zero.
  • Methods for adjusting TgX and TgY include, for example, changing the types and contents of a resin and a polymerizable compound, which will be described later, contained in the photosensitive composition layer of the transfer film.
  • the Tg of the resin, the method of adjusting the type and content of the monomer that can constitute the structural unit of the resin to each preferred embodiment described later, the number of types of the polymerizable compound, the polymerizability of the polymerizable compound The group content, the type and content of a predetermined functional group (eg, ethyleneoxy group) in the polymerizable compound can be adjusted to the respective preferred embodiments described below, and a combination of these methods can be mentioned.
  • a predetermined functional group eg, ethyleneoxy group
  • the lamination step the surface of the photosensitive composition layer of the transfer film having the temporary support and the photosensitive composition layer on the side opposite to the temporary support side is brought into contact with the substrate, and the transfer film and the substrate are laminated. It is a process to do.
  • the transfer film has a protective film which will be described later, it is preferable to carry out the bonding step after peeling off the protective film.
  • the surface of the photosensitive composition layer of the transfer film opposite to the temporary support side is brought into contact with the substrate and pressed.
  • the pressure bonding method include known transfer methods and lamination methods, in which the surface of the photosensitive composition layer of the transfer film opposite to the temporary support side is superimposed on the substrate, and a method of pressing and heating with a roll or the like. is preferred.
  • the lamination method include a method using a known laminator such as a vacuum laminator and an autocut laminator.
  • the lamination temperature is preferably 70 to 130°C.
  • the substrate is preferably a conductive substrate having a supporting substrate and a conductive layer disposed on the supporting substrate.
  • the conductive substrate any layer other than the above-described conductive layer may be formed on the supporting substrate, if necessary. That is, the substrate is preferably a conductive substrate having at least a supporting substrate and a conductive layer arranged on the supporting substrate.
  • the support substrate include resin substrates, glass substrates, and semiconductor substrates, and the support substrate described in paragraph [0140] of WO2018/155193 is preferable.
  • a cycloolefin polymer or polyimide is preferable as a material for the resin substrate.
  • the thickness of the resin substrate is preferably 5-200 ⁇ m, more preferably 10-100 ⁇ m.
  • transparent substrate when using a photomask including light shielding portions arranged in a mesh pattern in the exposure step, it is preferable to use a transparent substrate as the substrate.
  • transparent as used herein means that the transmittance of the exposure wavelength is 50% or more.
  • the total light transmittance is preferably 80% or more, more preferably 90% or more, and even more preferably 95% or more.
  • the upper limit is preferably less than 100%.
  • transparent substrates include resin substrates (for example, resin films) and glass substrates.
  • the resin substrate is preferably a resin substrate that transmits visible light.
  • Preferred components of the resin substrate that transmits visible light include, for example, polyamide-based resins, polyethylene terephthalate-based resins, polyethylene naphthalate-based resins, cycloolefin-based resins, polyimide-based resins, and polycarbonate-based resins.
  • Preferred components of the resin substrate that transmit visible light include, for example, polyamide, polyethylene terephthalate (PET), cycloolefin polymer (COP), polyethylene naphthalate (PEN), polyimide, and polycarbonate.
  • the thickness of the transparent substrate is not limited.
  • the thickness of the transparent substrate is preferably 10 to 200 ⁇ m, more preferably 20 to 120 ⁇ m, even more preferably 20 to 100 ⁇ m.
  • the thickness of the transparent substrate is measured by the following method. A scanning electron microscope (SEM) is used to observe a cross section in a direction (that is, thickness direction) perpendicular to the main surface of the transparent substrate. Based on the observed image obtained, the thickness of the transparent substrate is measured at ten points. By arithmetically averaging the measured values, the average thickness of the transparent substrate is obtained.
  • the substrate when using a photomask including light shielding portions arranged in circular dots or openings arranged in circular dots, the substrate may be a silicon substrate, a glass substrate, or FR4 (Flame Retardant Type 4). ) is preferred. In that case, the thickness of the substrate is not particularly limited. Moreover, a wiring pattern may be formed on the surface of the substrate, and wiring layers may be laminated. A photomask including light shielding portions arranged in circular dots or openings arranged in circular dots will be described later.
  • the conductive layer is preferably 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, from the viewpoint of conductivity and fine wire formation.
  • One or more conductive layers may be arranged on the support substrate. When two or more conductive layers are arranged, the two or more conductive layers may be the same or different, and are preferably made of different materials.
  • Conductive layers include, for example, paragraph [0141] of WO2018/155193, the contents of which are incorporated herein.
  • a substrate having at least one of a transparent electrode and a lead wiring is preferable, and the above substrate can be used as a touch panel substrate.
  • the transparent electrode can function as a touch panel electrode.
  • the transparent electrodes are preferably composed of metal oxide films such as ITO (indium tin oxide) and IZO (indium zinc oxide), and fine metal wires such as metal mesh and metal nanowires. Examples of fine metal wires include fine metal wires of silver and copper, and silver conductive materials such as silver mesh and silver nanowires are preferred.
  • a metal is preferable as the material of the routing wiring.
  • the metal include gold, silver, copper, molybdenum, aluminum, titanium, chromium, zinc and manganese, and alloys thereof in combination, preferably copper, molybdenum, aluminum or titanium, more preferably copper. .
  • the method for producing a laminate preferably includes a peeling step from the viewpoint of excellent resolution. Between the bonding step and the exposure step, or between the exposure step and the developing step, peeling It is more preferable to have a step.
  • a peeling process is a process of peeling a temporary support body from the laminated body of a transfer film and a board
  • the exposure step is a step of patternwise exposing the photosensitive composition layer.
  • “Pattern exposure” is a form of exposure in a pattern, and means an exposure form in which an exposed portion and a non-exposed portion are present. The positional relationship between the exposed portion (exposed region) and the non-exposed portion (non-exposed region) in the pattern exposure can be adjusted as appropriate.
  • the exposure may be performed from the side of the photosensitive composition layer or the side (substrate side) opposite to the side of the photosensitive composition layer.
  • the exposure step it is also preferable to pattern-expose the photosensitive composition layer of the laminate from which the temporary support obtained in the peeling step was peeled off, through a photomask.
  • the exposure step since a high-definition pattern can be obtained, the surface of the layered product from which the temporary support has been peeled off in the peeling step, which is opposite to the substrate side, is brought into contact with the photomask. Therefore, the exposure step of patternwise exposing the photosensitive composition layer is preferable. In other words, the exposure step of exposing the photosensitive composition layer in a pattern by bringing the surface exposed by peeling the temporary support of the laminated body from which the temporary support has been peeled off into contact with a photomask is preferred.
  • the transfer film has a two-layer structure of the temporary support and the photosensitive composition layer
  • the exposed surface corresponds to the surface of the photosensitive composition layer
  • the transfer film is the temporary support and the intermediate layer.
  • a photosensitive composition layer the surface of the intermediate layer is applicable.
  • a curing reaction of the components contained in the photosensitive composition layer may occur in the exposed regions of the photosensitive composition layer (regions corresponding to the openings of the photomask).
  • the method for manufacturing the laminate has a photomask peeling step of peeling off the photomask used in the exposure step between the exposure step and the development treatment.
  • the photomask peeling process includes, for example, a known peeling process.
  • the light source for pattern exposure should be one capable of irradiating at least light in a wavelength range capable of curing the photosensitive composition layer (for example, 365 nm and 405 nm), preferably 365 nm.
  • a wavelength range capable of curing the photosensitive composition layer for example, 365 nm and 405 nm, preferably 365 nm.
  • dominant wavelength is meant the wavelength with the highest intensity.
  • Examples of light sources include various lasers, light emitting diodes (LEDs), ultrahigh pressure mercury lamps, high pressure mercury lamps, and metal halide lamps.
  • the exposure amount is preferably 5 to 200 mJ/cm 2 , more preferably 10 to 200 mJ/cm 2 .
  • Light sources, exposure doses and exposure methods include, for example, paragraphs [0146] to [0147] of WO2018/155193, the contents of which are incorporated herein.
  • the exposure target has a substrate on which a cushioning material is arranged.
  • the object to be exposed has a cushioning material
  • the intermediate layer include an intermediate layer that the transfer film may have.
  • the cushioning material may be arranged on the supporting substrate before the bonding process, or may be arranged on the supporting substrate after the bonding process.
  • a known method can be used as a method of arranging the cushion material.
  • the surface of the transfer film having a temporary support and a photosensitive composition layer opposite to the temporary support side of the photosensitive composition layer is the cushioning material of the substrate having a cushioning material.
  • a bonding step of bonding the transfer film and the substrate by bringing them into contact with opposite surfaces and an exposure step of pattern-exposing the photosensitive composition layer.
  • the surface of the transfer film having the temporary support and the photosensitive composition layer on the side opposite to the temporary support side of the photosensitive composition layer is brought into contact with the substrate, and the transfer film and the substrate are separated.
  • a lamination step of laminating, a forming step of forming a cushion material on the surface of the substrate opposite to the photosensitive composition layer, and an exposure step of pattern-exposing the photosensitive composition layer preferable.
  • the cushioning material include those made of silicon, urethane, nitrile, chloroprene, or the like.
  • the shape of the cushion material may be a sheet shape.
  • the hardness of the cushion material is preferably 30 or higher, more preferably 50 or higher, and even more preferably 70 or higher.
  • the upper limit is preferably 100 or less, more preferably 90 or less.
  • the above hardness is type A durometer hardness.
  • the development step is a step of developing the exposed photosensitive composition layer with a developer to form a pattern.
  • a developer By developing with a developer, the non-exposed regions of the photosensitive composition layer are removed to form a pattern having projections corresponding to the openings of the photomask.
  • Alkaline compounds contained in the alkaline aqueous solution include, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, tetramethylammonium hydroxide. , tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide and choline (2-hydroxyethyltrimethylammonium hydroxide).
  • Examples of the developing method include known developing methods. Specific examples include puddle development, shower development, spin development and dip development. As the developing method, the developing method described in paragraph [0195] of WO 2015/093271 is preferable.
  • the pattern obtained by the developing step is further subjected to a step of exposing (hereinafter also referred to as a “post-exposure step”) and/or a step of heating (hereinafter also referred to as a “post-baking step”. ).
  • a post-exposure step a step of exposing
  • post-baking step a step of heating
  • the exposure amount in the post-exposure step is preferably 100-5000 mJ/cm 2 , more preferably 200-3000 mJ/cm 2 .
  • the post-baking temperature in the post-baking step is preferably 80 to 250°C, more preferably 90 to 160°C.
  • the post-baking time in the post-baking step is preferably 1 to 180 minutes, more preferably 10 to 60 minutes.
  • the pattern is preferably in the form of fine lines.
  • the line width of the pattern is preferably 20 ⁇ m or less, more preferably 15 ⁇ m or less, still more preferably 10 ⁇ m or less, and particularly preferably 5 ⁇ m or less.
  • the lower limit is preferably 1.0 ⁇ m or more.
  • a laminate manufactured by the method for manufacturing a laminate can be applied to various devices.
  • the device including the laminate include an input device, preferably a touch panel, and more preferably a capacitive touch panel.
  • the input device can be applied to, for example, display devices such as organic EL (organic electroluminescence) display devices and liquid crystal display devices.
  • the method for producing a laminate according to the present invention includes, for example, production of conductive films such as transparent heaters, transparent antennas, electromagnetic wave shielding materials, and light control films; production of printed wiring boards and semiconductor packages; production of semiconductor chips and packages.
  • conductive films such as transparent heaters, transparent antennas, electromagnetic wave shielding materials, and light control films
  • production of printed wiring boards and semiconductor packages production of semiconductor chips and packages.
  • Manufacture of pillars and pins for interconnection between them Manufacture of metal masks
  • Manufacture of tape substrates such as COF (Chip on Film) and TAB (Tape Automated Bonding);
  • the surface of the photosensitive composition layer of the transfer film having the temporary support and the photosensitive composition layer on the side opposite to the temporary support is brought into contact with the conductive substrate.
  • a bonding step of bonding the transfer film and the conductive substrate An exposure step of pattern-exposing the photosensitive composition layer;
  • a preferred aspect of the circuit wiring manufacturing method includes an aspect in which the lamination step, the exposure step, the development step, and the etching step are performed in this order.
  • the above TgX, the above TgY, the lamination step, the exposure step, and the development step are synonymous with the respective terms in the method for producing the laminate, and the preferred embodiments are also the same.
  • the etching step is a step of etching a conductive layer in a region where no pattern is arranged in a laminate having a pattern produced by the method for producing a laminate when a conductive substrate is used as the substrate. Specifically, in the etching step, the conductive layer is etched using the pattern obtained from the photosensitive composition layer in the developing step in the laminate manufacturing method as an etching resist.
  • the substrate has the same meaning as the substrate in the method for manufacturing the laminate, and the preferred embodiments are also the same.
  • Examples of the etching method include known etching methods. Specifically, the method described in paragraphs [0209] to [0210] of JP-A-2017-120435, the method described in paragraphs [0048] to [0054] of JP-A-2010-152155, and the etching solution Dry etching such as immersion wet etching and plasma etching are included.
  • an acidic or alkaline etchant can be appropriately selected according to the object to be etched.
  • the acidic etchant include an acidic aqueous solution containing at least one acidic compound, and an acidic compound and at least one selected from the group consisting of ferric chloride, ammonium fluoride, and potassium permanganate.
  • alkaline etchant examples include an alkaline aqueous solution containing at least one alkaline compound and an alkaline mixed aqueous solution of an alkaline compound and a salt (eg, potassium permanganate).
  • Alkaline compounds contained in the alkaline aqueous solution include, for example, sodium hydroxide, potassium hydroxide, ammonia, organic amines, and salts of organic amines (e.g., tetramethylammonium hydroxide, etc.). At least one selected from the group consisting of is preferred.
  • the circuit wiring manufacturing method may have a removing step of removing the remaining pattern.
  • the removing step is preferably performed after the etching step.
  • a method for removing the remaining pattern for example, there is a method of removing by chemical treatment, and a method of removing using a removing liquid is preferable.
  • the method for removing the remaining pattern include a method of removing by known methods such as a spray method, a shower method and a paddle method using a removing liquid.
  • Examples of the remover include a remover in which an alkaline compound is dissolved in at least one selected from the group consisting of water, dimethylsulfoxide and N-methylpyrrolidone.
  • Examples of alkaline compounds include alkaline inorganic compounds such as sodium hydroxide and potassium hydroxide, primary amine compounds, secondary amine compounds, and tertiary amine compounds. and alkaline organic compounds such as quaternary ammonium salt compounds.
  • the liquid temperature of the removing liquid is preferably 30 to 80.degree. C., more preferably 50 to 80.degree.
  • a preferred embodiment of the removal method includes a method of immersing a substrate having a pattern to be removed in a stirring removing liquid having a liquid temperature of 50 to 80° C. for 1 to 30 minutes.
  • the first embodiment of the circuit wiring manufacturing method may further include a peeling step, a post-exposure step and/or a post-baking step in the laminate manufacturing method.
  • the surface of the photosensitive composition layer opposite to the temporary support side is brought into contact with the seed layer of the substrate with the seed layer, and the transfer film and the substrate with the seed layer are laminated to form the substrate, the seed layer, and the photosensitive composition.
  • the seed layer forming step is a step of forming a seed layer on the substrate.
  • the substrate include the substrates described above in the bonding step of the method for manufacturing the laminate.
  • the seed layer may contain metal.
  • the metal include known metals.
  • Main component metals contained in the seed layer include, for example, copper, chromium, lead, nickel, gold, silver, tin and zinc.
  • the “main component” means the metal with the highest content among the metals contained in the seed layer.
  • the thickness of the seed layer is preferably 50 nm or more, more preferably 100 nm or more.
  • the upper limit is preferably 2 ⁇ m or less.
  • Examples of methods for forming the seed layer include known methods such as a method of applying a dispersion liquid in which fine metal particles are dispersed and sintering the coating film, a sputtering method, and a vapor deposition method.
  • the metal plating layer forming step is a step of forming a metal plating layer by plating on the seed layer in the region where the pattern is not arranged.
  • Examples of the plating method include electrolytic plating and electroless plating, with electrolytic plating being preferred from the viewpoint of productivity.
  • the metal contained in the metal plating layer examples include known metals. Specific examples include metals such as copper, chromium, lead, nickel, gold, silver, tin and zinc, and alloys of these metals. Among them, the metal plating layer preferably contains copper or an alloy thereof from the viewpoint of better electrical conductivity of the conductive thin wires. In addition, the metal plating layer preferably contains copper as a main component in order to improve the electrical conductivity of the conductive fine wires.
  • the thickness of the metal plating layer is preferably 0.1 ⁇ m or more, more preferably 1 ⁇ m or more.
  • the upper limit is preferably 20 ⁇ m or less.
  • the protective layer forming step is a step of forming a protective layer on the metal plating layer.
  • a material for the protective layer a material having resistance to a removing liquid or an etchant in the removing process or the conductive fine line forming process is preferable. Examples include metals such as nickel, chromium, tin, zinc, magnesium, gold and silver, alloys thereof, and resins, with nickel or chromium being preferred.
  • Examples of methods for forming the protective layer include electroless plating and electroplating, with electroplating being preferred.
  • the thickness of the protective layer is preferably 0.3 ⁇ m or more, more preferably 0.5 ⁇ m or more.
  • the upper limit is preferably 3.0 ⁇ m or less, more preferably 2.0 ⁇ m or less.
  • the seed layer removing step is a step of removing the exposed seed layer to obtain a conductive thin line.
  • the metal plating layer formed in the metal plating layer forming step is used as an etching resist to etch the seed layer located in the non-pattern forming region (the region not protected by the metal plating layer). .
  • etchants include, for example, ferric chloride solutions, cupric chloride solutions, ammonia alkali solutions, mixtures of sulfuric acid and hydrogen peroxide, and mixtures of phosphoric acid and hydrogen peroxide.
  • the line width of the conductive thin line to be formed is preferably 8 ⁇ m or less, more preferably 6 ⁇ m or less.
  • the lower limit is preferably 1 ⁇ m or more.
  • the method for manufacturing the circuit wiring may have other steps in addition to the steps described above.
  • Other steps include, for example, a post-exposure step, a post-baking step, a step of reducing visible light reflectance described in paragraph [0172] of WO2019/022089 and paragraph [0172] of WO2019/022089. ], a step of forming a new conductive layer on the surface of the insulating film described in 1. above.
  • the circuit wiring manufacturing method may include a step of performing a process for reducing the visible light reflectance of a part or all of the plurality of conductive layers of the substrate.
  • the treatment for reducing the visible light reflectance includes, for example, oxidation treatment.
  • the visible light reflectance of the conductive layer can be reduced by oxidizing the copper to form copper oxide and blackening the conductive layer.
  • Examples of the treatment for reducing the visible light reflectance include paragraphs [0017] to [0025] of JP-A-2014-150118, and paragraphs [0041], [0042], and [0042] of JP-A-2013-206315 [0048] and [0058], the contents of which are incorporated herein.
  • the circuit wiring manufacturing method may include the steps of forming an insulating film on the surface of the circuit wiring and forming a new conductive layer on the surface of the insulating film. Through the above steps, the first electrode pattern and the insulated second electrode pattern can be formed.
  • the process of forming the insulating film includes, for example, a method of forming a known permanent film.
  • an insulating film having a desired pattern may be formed by photolithography using an insulating photosensitive composition.
  • a conductive photosensitive composition may be used to form a new conductive layer in a desired pattern by photolithography.
  • the method of manufacturing the circuit wiring may use a substrate having a plurality of conductive layers on both surfaces of the substrate, and sequentially or simultaneously form circuit wiring on the conductive layers formed on both surfaces of the substrate.
  • a substrate having a plurality of conductive layers on both surfaces of the substrate and sequentially or simultaneously form circuit wiring on the conductive layers formed on both surfaces of the substrate.
  • the circuit wiring manufactured by the circuit wiring manufacturing method can be applied to various devices.
  • the device having the circuit wiring include an input device, preferably a touch panel, and more preferably a capacitive touch panel.
  • the input device can be applied to display devices such as an organic EL display device and a liquid crystal display device, for example.
  • One aspect of the circuit wiring manufacturing method of the present invention includes, for example, an aspect in which a photomask including a light shielding portion arranged in a mesh pattern is used in the exposure.
  • the manufacturing method described above is suitable as a method for manufacturing a mesh-like metal wiring pattern.
  • a wiring circuit obtained by the above manufacturing method can be used, for example, as a transparent conductive film.
  • the sheet resistance value of the mesh pattern area is preferably as low as possible. Specifically, it is preferably 100 ⁇ / ⁇ or less, more preferably 20 ⁇ / ⁇ or less, and particularly preferably 5 ⁇ / ⁇ or less. The lower limit is preferably greater than 0 ⁇ / ⁇ .
  • the manufacturing method described above can be suitably used as a method for manufacturing vias, a method for manufacturing semiconductor chips, and a method for manufacturing pillars and pins for interconnects between packages.
  • the diameter of the pillars and pins is preferably 1-20 ⁇ m, more preferably 2-10 ⁇ m, even more preferably 3-8 ⁇ m.
  • the length of the pillars and pins is preferably 1 to 20 ⁇ m, more preferably 3 to 10 ⁇ m.
  • the manufacturing method described above is suitable as a method for manufacturing through holes and the like.
  • the diameter of the through-hole is preferably 1-20 ⁇ m, more preferably 2-10 ⁇ m, and even more preferably 3-8 ⁇ m.
  • the depth of the through-hole is preferably 1 to 20 ⁇ m, more preferably 3 to 10 ⁇ m.
  • the above-described manufacturing method using a photomask including light-shielding portions arranged in circular dots is also suitable as a manufacturing method for through-holes and the like.
  • the diameter of the through-hole is preferably 1-20 ⁇ m, more preferably 2-10 ⁇ m, and even more preferably 3-8 ⁇ m.
  • the depth of the through-hole is preferably 1 to 20 ⁇ m, more preferably 3 to 10 ⁇ m or less.
  • the manufacturing method of the circuit wiring of the present invention has been described above, the manufacturing method of the laminate of the present invention may be applied to the above.
  • the above-mentioned "circular shape” may be either a perfect circle or an approximate circle.
  • the diameter means the longest diameter in the substantially circle.
  • a photomask including a light shielding portion arranged in a circular dot shape may be a photomask in which one circular dot light shielding portion is arranged, or a photomask having two circular dot light shielding portions.
  • a photomask arranged as described above may be used.
  • the “photomask including openings arranged in circular dot shape” may be a photomask in which one circular dot-shaped opening is arranged, or a photomask in which two circular dot-shaped openings are arranged.
  • a photomask arranged as described above may be used.
  • the photomask including the light shielding portions arranged in a mesh pattern may include the light shielding portions arranged in a pattern different from the light shielding portions arranged in the mesh pattern.
  • a photomask including light shielding portions arranged in circular dots may include light shielding portions arranged in a pattern different from the light shielding portions arranged in circular dots.
  • the transfer film has a temporary support and a photosensitive composition layer, and is a transfer film to which an exposure step of pattern-exposing the photosensitive composition layer is performed, and has a TgX of 110° C. or less and a TgY of , above 125°C.
  • the above TgX and the above TgY have the same meanings as those described in the manufacturing method of the laminate, and the preferred embodiments are also the same.
  • the transfer film may have other layers in addition to the photosensitive composition layer described below.
  • Other layers include, for example, an intermediate layer to be described later and a thermoplastic resin layer to be described later.
  • the transfer film may have other members (for example, a protective film) which will be described later.
  • Embodiments of the transfer film include, for example, the following configurations (1) to (3). Above all, the transfer film preferably has an intermediate layer, and the following configuration (2) or configuration (3) is more preferred, and configuration (2) is even more preferred.
  • a negative photosensitive composition layer described later or a colored resin layer described later is preferable.
  • the maximum width of the undulation of the transfer film is preferably 300 ⁇ m or less, more preferably 200 ⁇ m or less, and even more preferably 60 ⁇ m or less.
  • the lower limit is preferably 0 ⁇ m or more, more preferably 0.1 ⁇ m or more, and even more preferably 1 ⁇ m or more.
  • the maximum width of waviness of the transfer film is a value measured by the following procedure. A test sample is prepared by cutting the transfer film in a direction perpendicular to the main surface so as to have a size of 20 cm long by 20 cm wide. In addition, when a transfer film has a protective film, a protective film is peeled from a transfer film.
  • test sample is placed on a flat and horizontal stage so that the surface of the temporary support faces the stage.
  • surface of the sample sample is scanned with a laser microscope (for example, VK-9700SP manufactured by Keyence Corporation) for the center 10 cm square range of the test sample to acquire a three-dimensional surface image, and the obtained three-dimensional surface image.
  • a laser microscope for example, VK-9700SP manufactured by Keyence Corporation
  • Subtract the minimum concave height from the maximum convex height observed in is performed for 10 test samples, and the arithmetic average value is taken as the maximum waviness width of the transfer film.
  • the photosensitive composition layer of the transfer film another composition layer (for example, a photosensitive composition layer, an intermediate layer, a thermoplastic resin layer, etc.) is further provided on the side opposite to the temporary support side of the photosensitive composition layer.
  • another composition layer for example, a photosensitive composition layer, an intermediate layer, a thermoplastic resin layer, etc.
  • the total thickness of the other composition layers is preferably 0.1 to 30%, more preferably 0.1 to 20%, of the thickness of the photosensitive composition layer.
  • the transmittance of light with a wavelength of 365 nm of the photosensitive composition layer is preferably 10% or more, more preferably 30% or more, and even more preferably 50% or more, from the viewpoint of better adhesion.
  • the upper limit is preferably 99.9% or less, more preferably 99.0% or less.
  • the transfer film 10 shown in FIG. 1 has a temporary support 11, a composition layer 17 including an intermediate layer 13 and a photosensitive composition layer 15, and a protective film 19 in this order.
  • the transfer film 10 shown in FIG. 1 has the intermediate layer 13 and the protective film 19, the intermediate layer 13 and the protective film 19 may be omitted.
  • each layer for example, a photosensitive composition layer, an intermediate layer and a thermoplastic resin layer
  • the transfer film may further have a thermoplastic resin layer in addition to the above layers.
  • the thermoplastic resin layer is preferably arranged between the temporary support 11 and the intermediate layer 13 .
  • the transfer film has a temporary support.
  • a temporary support is a member that supports the photosensitive composition layer, and is finally removed by a peeling treatment.
  • the temporary support may have either a single layer structure or a multilayer structure.
  • the temporary support is preferably a film, more preferably a resin film.
  • a film that has flexibility and does not undergo significant deformation, shrinkage, or elongation under pressure or under pressure and heat is also preferable, and a film that is free from deformation such as wrinkles and scratches is also preferable.
  • the film include polyethylene terephthalate film (eg, biaxially stretched polyethylene terephthalate film), polymethyl methacrylate film, cellulose triacetate film, polystyrene film, polyimide film and polycarbonate film, with polyethylene terephthalate film being preferred.
  • the temporary support preferably has high transparency from the viewpoint that pattern exposure can be performed through the temporary support.
  • the transmittance of the temporary support at a wavelength of 365 nm is preferably 60% or more, more preferably 70% or more.
  • the upper limit is preferably less than 100%.
  • the haze of the temporary support is preferably as small as possible.
  • the haze of the temporary support is preferably 2% or less, more preferably 0.5% or less, and even more preferably 0.1% or less.
  • the lower limit is preferably 0% or more.
  • the number of fine particles, foreign matter and defects in the temporary support is preferably as small as possible.
  • the number of fine particles (for example, fine particles with a diameter of 1 ⁇ m), foreign matter and defects 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 less than 1/10 mm 2 is particularly preferable.
  • the lower limit is preferably 0 pieces/10 mm 2 or more.
  • the thickness of the temporary support is preferably 5 to 200 ⁇ m, more preferably 5 to 150 ⁇ m, still more preferably 5 to 50 ⁇ m, particularly preferably 5 to 25 ⁇ m, from the viewpoint of ease of handling and versatility.
  • the thickness of the temporary support is calculated as an average value of arbitrary five points measured by cross-sectional observation with a SEM (Scanning Electron Microscope).
  • the temporary support may have a layer containing fine particles (lubricant layer) on one side or both sides of the temporary support from the viewpoint of handling.
  • the fine particles contained in the lubricant layer preferably have a diameter of 0.05 to 0.8 ⁇ m.
  • the thickness of the lubricant layer is preferably 0.05 to 1.0 ⁇ m.
  • the surface of the temporary support in contact with the photosensitive composition layer may be subjected to a surface modification treatment.
  • surface modification treatment include treatments using UV irradiation, corona discharge, plasma, and the like.
  • the exposure amount in UV irradiation is preferably 10-2000 mJ/cm 2 , more preferably 50-1000 mJ/cm 2 .
  • the lamp output and illuminance are not particularly limited.
  • Light sources for UV irradiation include, for example, low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, carbon arc lamps, metal halide lamps, xenon lamps, chemical lamps, electrodeless discharge lamps, and light-emitting diodes that emit light in the wavelength band of 150 to 450 nm. (LED).
  • LED light-emitting diodes
  • Examples of the temporary support include a 16 ⁇ m thick biaxially stretched polyethylene terephthalate film, a 12 ⁇ m thick biaxially stretched polyethylene terephthalate film, and a 9 ⁇ m thick biaxially stretched polyethylene terephthalate film.
  • the temporary support for example, paragraphs [0017] to [0018] of JP-A-2014-085643, paragraphs [0019] to [0026] of JP-A-2016-027363, International Publication No. 2012/081680 and paragraphs [0029] to [0040] of WO2018/179370, the contents of which are incorporated herein.
  • Examples of commercially available temporary supports include Lumirror 16KS40 (registered trademark) and Lumirror 16FB40 (registered trademark) (manufactured by Toray Industries, Inc.); Cosmoshine A4100, Cosmoshine A4300 and Cosmoshine A8300 (manufactured by Toyobo Co., Ltd.).
  • the transfer film has a photosensitive composition layer.
  • a display device having a touch panel such as a capacitive input device (for example, an organic EL display device, a liquid crystal display device, etc.), an electrode pattern corresponding to a sensor in the visual recognition part, wiring of the peripheral wiring part and the lead-out wiring part, etc.
  • a conductive layer pattern is provided inside the touch panel.
  • a photosensitive composition layer is provided on a substrate using a transfer film or the like, and the photosensitive composition layer is exposed through a photomask having a desired pattern. After that, the method of developing is widely adopted. Therefore, the photosensitive composition layer is preferably a negative photosensitive composition layer. When the photosensitive composition layer is a negative photosensitive composition layer, the formed pattern corresponds to a cured film.
  • the photosensitive composition layer preferably contains a resin to be described later and a polymerizable compound to be described later, and more preferably contains a resin to be described later, a polymerizable compound to be described later and a polymerization initiator to be described later. Moreover, it is also preferable that the photosensitive composition layer contains an alkali-soluble resin as the resin described later. That is, the photosensitive composition layer preferably contains a resin containing an alkali-soluble resin and a polymerizable compound.
  • the photosensitive composition layer contains 10.0 to 90.0% by weight of the resin, 5.0 to 70.0% by weight of the polymerizable compound, and 0 of the polymerization initiator with respect to the total weight of the photosensitive composition layer. 0.01 to 20.0% by mass is preferably contained. Each component that the photosensitive composition layer may contain will be described below.
  • the photosensitive composition layer may contain a resin.
  • a resin an alkali-soluble resin is preferable.
  • an alkali-soluble resin contained in the thermoplastic resin layer which will be described later, may be used.
  • the resin preferably contains a structural unit derived from a monomer having an aromatic hydrocarbon group from the viewpoint of suppressing thickening of the line width and deterioration of resolution when the focus position shifts during exposure.
  • the aromatic hydrocarbon group include an optionally substituted phenyl group and an optionally substituted aralkyl group.
  • the content of structural units derived from a monomer having an aromatic hydrocarbon group is preferably 10.0% by mass or more, more preferably 20.0% by mass or more, more preferably 30.0% by mass, based on the total mass of the resin. More than % by mass is more preferable.
  • the upper limit is preferably 80.0% by mass or less, more preferably 60.0% by mass or less, and even more preferably 55.0% by mass or less, relative to the total mass of the resin.
  • the weight average value of the content of structural units derived from the monomer having an aromatic hydrocarbon group is preferably within the above range.
  • monomers having an aromatic hydrocarbon group examples include monomers having an aralkyl group, styrene and polymerizable styrene derivatives (e.g., methylstyrene, vinyltoluene, tert-butoxystyrene, acetoxystyrene, 4-vinyl benzoic acid, styrene dimer, styrene trimer, etc.), preferably an aralkyl group-containing monomer or styrene, more preferably styrene.
  • styrene and polymerizable styrene derivatives e.g., methylstyrene, vinyltoluene, tert-butoxystyrene, acetoxystyrene, 4-vinyl benzoic acid, styrene dimer, styrene trimer, etc.
  • the content of structural units derived from styrene is preferably 10.0 to 80.0% by mass, preferably 20.0%, based on the total mass of the resin. ⁇ 60.0% by mass is more preferable, and 30.0 to 55.0% by mass is even more preferable.
  • the photosensitive composition layer contains a plurality of resins, it is preferable that the weight average value of the content of structural units having an aromatic hydrocarbon group is within the above range.
  • aralkyl group examples include a phenylalkyl group optionally having a substituent (excluding a benzyl group) and a benzyl group optionally having a substituent.
  • a benzyl group with a higher molecular weight is preferred.
  • Examples of monomers having a phenylalkyl group include phenylethyl (meth)acrylate.
  • Examples of monomers having a benzyl group include (meth)acrylates having a benzyl group such as benzyl (meth)acrylate and chlorobenzyl (meth)acrylate; vinyl monomers having a benzyl group such as vinylbenzyl chloride and vinylbenzyl alcohol.
  • a (meth)acrylate having a benzyl group is preferred, and a benzyl (meth)acrylate is more preferred.
  • the monomer having an aromatic hydrocarbon group is benzyl (meth)acrylate
  • the content of structural units derived from benzyl (meth)acrylate is 10.0 to 90.0 with respect to the total mass of the resin. % by mass is preferable, 20.0 to 80.0% by mass is more preferable, and 30.0 to 70.0% by mass is even more preferable.
  • the resin containing a structural unit derived from a monomer having an aromatic hydrocarbon group includes a monomer having an aromatic hydrocarbon group and at least one first monomer described later and/or a first monomer described later. It is preferably obtained by polymerizing 2 monomers with at least one.
  • the resin that does not contain a structural unit derived from a monomer having an aromatic hydrocarbon group is preferably obtained by polymerizing at least one of the first monomers described later, and the first monomer and at least one of the second monomers to be described later are more preferably obtained by polymerizing.
  • a 1st monomer is a monomer which has a carboxy group in a molecule
  • the first monomer include (meth)acrylic acid, fumaric acid, cinnamic acid, crotonic acid, itaconic acid, 4-vinylbenzoic acid, maleic anhydride and maleic acid half ester, ( Meth)acrylic acid is preferred.
  • the content of the structural unit derived from the first monomer is preferably 5.0 to 50.0% by mass, more preferably 10.0 to 40.0% by mass, based on the total mass of the resin. 0 to 30.0% by mass is more preferable. When the content is 5.0% by mass or more, excellent developability and control of edge fuse properties can be achieved. When the content is 50.0% by mass or less, high resolution of the resist pattern, control of the groove shape, and high chemical resistance of the resist pattern can be realized.
  • the second monomer is a monomer that is non-acidic (has no acidic group) and has a polymerizable group in its molecule.
  • the polymerizable group has the same meaning as the polymerizable group possessed by the polymerizable compound described later, and the preferred embodiments are also the same.
  • 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.
  • tert-butyl (meth)acrylate 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, cyclohexyl (meth)acrylate and 2-ethylhexyl (meth)acrylate; vinyl acetate vinyl alcohol esters such as; (meth)acrylonitrile; Among them, methyl (meth)acrylate, ethyl (meth)acrylate, 2-ethylhexyl (meth)acrylate and n-butyl (meth)acrylate are preferred, and methyl (meth)acrylate and ethyl (meth)acrylate are more preferred.
  • the content of the structural unit derived from the second monomer is preferably 1.0 to 80.0% by mass, more preferably 1.0 to 60.0% by mass, based on the total mass of the resin. 0 to 50.0% by mass is more preferable.
  • the resin may have any one of a linear structure, a branched structure and an alicyclic structure in the side chain.
  • a monomer containing a group having a branched structure in its side chain or a monomer containing a group having an alicyclic structure in its side chain a branched structure or alicyclic structure can be introduced into the side chain of the resin.
  • a group having an alicyclic structure may be either monocyclic or polycyclic.
  • “Side chain” means an atomic group branched off from the main chain.
  • the “main chain” means the relatively longest linking chain in the molecule of the polymer compound that constitutes the resin.
  • Examples of the monomer containing a group having a branched structure in the side chain include isopropyl (meth)acrylate, isobutyl (meth)acrylate, sec-butyl (meth)acrylate, tert-butyl (meth)acrylate, Isoamyl (meth)acrylate, tert-amyl (meth)acrylate, sec-amyl (meth)acrylate, 2-octyl (meth)acrylate, 3-octyl (meth)acrylate and tert- (meth)acrylate octyl.
  • the monomer containing a group having an alicyclic structure in its side chain includes, for example, a monomer having a monocyclic aliphatic hydrocarbon group and a monomer having a polycyclic aliphatic hydrocarbon group.
  • (Meth)acrylates having an alicyclic hydrocarbon group with 5 to 20 carbon atoms are also included.
  • (meth) acrylic acid (bicyclo[2.2.1] heptyl-2), (meth) acrylic acid-1-adamantyl, (meth) acrylic acid-2-adamantyl, (meth) acrylic acid- 3-methyl-1-adamantyl, (meth)acrylate-3,5-dimethyl-1-adamantyl, (meth)acrylate-3-ethyladamantyl, (meth)acrylate-3-methyl-5-ethyl-1 -adamantyl, (meth)acrylate-3,5,8-triethyl-1-adamantyl, (meth)acrylate-3,5-dimethyl-8-ethyl-1-adamantyl, (meth)acrylate 2-methyl- 2-adamantyl, 2-ethyl-2-adamantyl (meth) acrylate, 3-hydroxy-1-adamantyl (meth) acrylate, octahydro-4,7-menthanoinden-5-yl
  • cyclohexyl (meth)acrylate, (nor)bornyl (meth)acrylate, isobornyl (meth)acrylate, 1-adamantyl (meth)acrylate, 2-adamantyl (meth)acrylate, (meth)acrylate Fentyl acrylate, 1-menthyl (meth)acrylate or tricyclodecane (meth)acrylate is preferred, cyclohexyl (meth)acrylate, (nor)bornyl (meth)acrylate, isobornyl (meth)acrylate, (meth) ) 2-adamantyl acrylate or tricyclodecane (meth)acrylate is more preferred.
  • the resin preferably has a polymerizable group, more preferably contains a structural unit having a polymerizable group, and contains a structural unit having an ethylenically unsaturated group in the side chain, from the viewpoint that the effects of the present invention are more excellent. is more preferred.
  • the polymerizable group include a polymerizable group possessed by a polymerizable compound to be described later, preferably an ethylenically unsaturated group, and more preferably an acryloyl group or a methacryloyl group.
  • the polymerizable group is preferably a polymerizable group capable of undergoing a polymerization reaction with the polymerizable group of the polymerizable compound.
  • the resin containing a structural unit having a polymerizable group is preferably obtained by reacting a resin containing a structural unit derived from the first monomer with the third monomer.
  • the third monomer is a monomer having two or more polymerizable groups in the molecule, preferably a monomer having two polymerizable groups in the molecule.
  • the polymerizable group include a polymerizable group possessed by a polymerizable compound to be described later.
  • the third monomer preferably has two types of polymerizable groups, more preferably has an ethylenically unsaturated group and a cationic polymerizable group, an acryloyl group or a methacryloyl group and an epoxy It is more preferred to have a group.
  • Examples of the third monomer include glycidyl (meth)acrylate.
  • a structural unit represented by formula (P) is preferable.
  • R P represents a hydrogen atom or a methyl group.
  • LP represents a divalent linking group.
  • P represents a polymerizable group.
  • R P represents a hydrogen atom or a methyl group.
  • R 2 P is preferably a hydrogen atom.
  • LP represents a divalent linking group.
  • the divalent linking group include -CO-, -O-, -S-, -SO-, -SO 2 -, -NR N -, hydrocarbon groups, and combinations thereof.
  • RN represents a substituent.
  • the hydrocarbon group include an alkylene group, a cycloalkylene group and an arylene group.
  • the alkylene group may be linear or branched.
  • the alkylene group preferably has 1 to 10 carbon atoms, more preferably 2 to 8 carbon atoms, and still more preferably 3 to 5 carbon atoms.
  • the alkylene group may have a heteroatom, and the methylene group in the alkylene group may be replaced with a heteroatom.
  • the heteroatom is preferably an oxygen atom, a sulfur atom or a nitrogen atom, more preferably an oxygen atom.
  • the cycloalkylene group may be either monocyclic or polycyclic.
  • the cycloalkylene group preferably has 3 to 20 carbon atoms, more preferably 5 to 10 carbon atoms, and still more preferably 6 to 8 carbon atoms.
  • the arylene group may be monocyclic or polycyclic.
  • the arylene group preferably has 6 to 20 carbon atoms, more preferably 6 to 15 carbon atoms, and even more preferably 6 to 10 carbon atoms.
  • a phenylene group is preferable as the arylene group.
  • the cycloalkylene group and the arylene group may have a heteroatom as a ring member atom.
  • the heteroatom is preferably an oxygen atom, a sulfur atom or a nitrogen atom, more preferably an oxygen atom.
  • the hydrocarbon group may further have a substituent. Examples of the substituent include halogen atoms (eg, fluorine atoms), hydroxy groups, nitro groups, cyano groups, alkyl groups, alkoxy groups, alkoxycarbonyl groups and alkenyl groups, with hydroxy groups being preferred.
  • L P an alkylene group optionally having a heteroatom is preferable.
  • P represents a polymerizable group.
  • the polymerizable group is as described above.
  • Examples of structural units having a polymerizable group include the following structural units.
  • the content of the structural unit having a polymerizable group is preferably 5.0 to 70.0% by mass, preferably 10.0 to 50%, based on the total mass of the resin. 0% by mass is more preferable, 15.0 to 40.0% by mass is more preferable, and 20.0 to 40.0% by mass is particularly preferable because the effects of the present invention are more excellent.
  • a method for introducing a polymerizable group into a resin for example, an epoxy compound
  • a method of reacting a blocked isocyanate compound, an isocyanate compound, a vinyl sulfone compound, an aldehyde compound, a methylol compound and a carboxylic acid anhydride can be mentioned.
  • a preferred embodiment of the method of introducing a polymerizable group into a resin for example, after synthesizing a first monomer by a polymerization reaction, a carboxy group of a structural unit derived from the first monomer of the obtained resin is introduced.
  • a third monomer preferably glycidyl (meth)acrylate
  • a polymerizable group preferably (meth)acryloxy group
  • the reaction temperature for the polymer reaction is preferably 80 to 110.degree.
  • the polymer reaction preferably uses a catalyst, more preferably an ammonium salt (tetraethylammonium bromide).
  • the reaction temperature of the polymerization reaction is preferably 70 to 100°C, more preferably 80 to 90°C.
  • the polymerization reaction preferably uses a polymerization initiator, more preferably an azo initiator as the polymerization initiator, V-601 (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) or V-65 ( Fuji Film Wako Pure Chemical Industries, Ltd.) is more preferable.
  • a polymerization initiator more preferably an azo initiator as the polymerization initiator
  • V-601 manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.
  • V-65 Fuji Film Wako Pure Chemical Industries, Ltd.
  • a resin containing a structural unit derived from methacrylic acid, a structural unit derived from methyl methacrylate, a structural unit derived from styrene or a structural unit derived from benzyl methacrylate, and a structural unit derived from methacrylic acid and a structural unit derived from styrene A resin containing a structural unit having a polymerizable group is preferable, and a resin containing a structural unit having a polymerizable group is more preferable. In the above, it is also preferable to set the content of each structural unit to the above-mentioned suitable aspect.
  • the Tg of the resin is preferably 60 to 135°C, more preferably 70 to 115°C, even more preferably 75 to 105°C, and particularly preferably 80 to 100°C.
  • the acid value of the resin is preferably 220 mgKOH/g or less, more preferably less than 200 mgKOH/g, still more preferably less than 190 mgKOH/g, and particularly preferably less than 170 mgKOH/g, from the viewpoint that the effects of the present invention are more excellent.
  • the lower limit is preferably 10 mgKOH/g or more, more preferably 50 mgKOH/g or more, still more preferably 70 mgKOH/g or more, and particularly preferably 90 mgKOH/g or more, from the viewpoint that the effect of the present invention is more excellent.
  • “Acid number (mg KOH/g)" means the mass (mg) of potassium hydroxide required to neutralize 1 g of sample.
  • the acid value can be determined, for example, according to JIS K0070:1992.
  • the acid value of the resin can be adjusted by the type of structural unit contained in the resin and/or the content of the structural unit containing an acid group.
  • the weight average molecular weight of the resin is preferably 5,000 to 500,000, more preferably 10,000 to 100,000, even more preferably 10,000 to 60,000, and particularly preferably 20,000 to 50,000. .
  • weight average molecular weight is 500,000 or less, resolution and developability can be improved.
  • weight-average molecular weight is 5,000 or more, properties of development aggregates and properties of unexposed films such as edge-fuse properties and cut-chip properties of transfer films can be controlled.
  • edge-fusibility means the extent to which the photosensitive composition layer easily protrudes from the end face of the roll when the transfer film is wound into a roll.
  • Cut chip resistance means the degree of easiness of chip flying when an unexposed film is cut with a cutter.
  • the dispersity of the resin is preferably 1.0 to 6.0, more preferably 1.0 to 5.0, even more preferably 1.0 to 4.0, and particularly preferably 1.0 to 3.0.
  • the photosensitive composition layer may contain other resins in addition to the above resins.
  • Other resins include, for example, acrylic resins, styrene-acrylic copolymers, polyurethane resins, polyvinyl alcohol, polyvinyl formal, polyamide resins, polyester resins, polyamide resins, epoxy resins, polyacetal resins, polyhydroxystyrene resins, polyimide resins, Polybenzoxazole resins, polysiloxane resins, polyethyleneimines, polyallylamines and polyalkylene glycols are included.
  • One type of resin may be used alone, or two or more types may be used.
  • a mixture of two types of resins containing structural units derived from monomers having aromatic hydrocarbon groups or a structure derived from monomers having aromatic hydrocarbon groups It is preferable to use a mixture of a resin containing the unit and a resin not containing a structural unit derived from a monomer having an aromatic hydrocarbon group.
  • the content of the resin containing a structural unit derived from a monomer having an aromatic hydrocarbon group is preferably 50.0% by mass or more, preferably 70.0% by mass, based on the total mass of the resin.
  • the above is more preferable, 80.0% by mass or more is still more preferable, and 90.0% by mass or more is particularly preferable.
  • 100.0 mass % or less is preferable with respect to the total mass of resin.
  • the resin content is preferably 10.0 to 90.0% by mass, more preferably 20.0 to 80.0% by mass, and 30.0 to 70.0% by mass, based on the total mass of the photosensitive composition layer. % by mass is more preferred, and 40.0 to 60.0% by mass is particularly preferred.
  • the developing time can be controlled.
  • the content of the resin is 10.0% by mass or more with respect to the total mass of the photosensitive composition layer, the edge fuse resistance can be improved.
  • a suitable amount of a radical polymerization initiator such as benzoyl peroxide and azoisobutyronitrile is added to a solution obtained by diluting the above-mentioned monomer with a solvent such as acetone, methyl ethyl ketone and isopropanol, A method of heating and stirring can be used. You may synthesize
  • examples of resin synthesizing methods include bulk polymerization, suspension polymerization, and emulsion polymerization.
  • the photosensitive composition layer may contain a polymerizable compound having a polymerizable group.
  • Polymerizable compound means a compound that polymerizes under the action of a polymerization initiator described later and that is different from the above resin.
  • the polymerizable group possessed by the polymerizable compound may be any group that participates in the polymerization reaction. and groups having cationic polymerizable groups such as oxetane groups. Among them, as the polymerizable group, a group having an ethylenically unsaturated group is preferable, and an acryloyl group or a methacryloyl group is more preferable.
  • a compound having one or more ethylenically unsaturated groups (hereinafter also referred to as “ethylenically unsaturated compound”) is preferable, since the photosensitive composition layer has better photosensitivity.
  • Compounds having two or more ethylenically unsaturated groups therein (hereinafter also referred to as “polyfunctional ethylenically unsaturated compounds”) are more preferred.
  • the number of ethylenically unsaturated groups that the ethylenically unsaturated compound has in the molecule is preferably 1 to 6, more preferably 1 to 3, and 2 to 3. More preferred, 3 being particularly preferred.
  • the polymerizable compound may have an alkyleneoxy group.
  • an ethyleneoxy group or a propyleneoxy group is preferable, and an ethyleneoxy group is more preferable from the viewpoint that the effects of the present invention are more excellent.
  • the number of alkyleneoxy groups added to the polymerizable compound is preferably 2 to 30, more preferably 2 to 20 per molecule.
  • the polymerizable compound is a bifunctional or trifunctional ethylenic compound having two or three ethylenically unsaturated groups in the molecule from the viewpoint of better balance between photosensitivity, resolution, and releasability of the photosensitive composition layer. It preferably contains an unsaturated compound, and more preferably contains a trifunctional ethylenically unsaturated compound having three ethylenically unsaturated groups in one molecule.
  • the content of the bifunctional ethylenically unsaturated compound is preferably 20.0% by mass or more, more preferably more than 40.0% by mass, based on the total mass of the polymerizable compound, from the viewpoint of excellent peelability. 0% by mass or more is more preferable, and 90.0% by mass or more is particularly preferable.
  • the upper limit is preferably 100.0% by mass or less, more preferably 80.0% by mass or less. That is, all polymerizable compounds contained in the photosensitive composition layer may be bifunctional ethylenically unsaturated compounds.
  • the content of the trifunctional ethylenically unsaturated compound is preferably 10.0% by mass or more, more preferably 20.0% by mass or more, relative to the total mass of the polymerizable compound.
  • the upper limit is preferably 100.0% by mass or less, more preferably 80.0% by mass or less, and even more preferably 50.0% by mass or less. That is, all polymerizable compounds contained in the photosensitive composition layer may be trifunctional ethylenically unsaturated compounds.
  • a (meth)acrylate compound having a (meth)acryloyl group as a polymerizable group is preferable.
  • the photosensitive composition layer also preferably contains a polymerizable compound B1 having an aromatic ring and two ethylenically unsaturated groups.
  • the polymerizable compound B1 is a bifunctional ethylenically unsaturated compound having one or more aromatic rings in the molecule among the above polymerizable compounds.
  • aromatic ring of the polymerizable compound B1 examples include aromatic hydrocarbon rings such as benzene ring, naphthalene ring and anthracene ring; aromatic rings such as thiophene ring, furan ring, pyrrole ring, imidazole ring, triazole ring and pyridine ring Heterocycle; condensed rings thereof are mentioned, preferably an aromatic hydrocarbon ring, more preferably a benzene ring.
  • the aromatic ring may have a substituent.
  • Polymerizable compound B1 may have one or more aromatic rings.
  • the polymerizable compound B1 preferably has a bisphenol structure from the viewpoint of improving the resolution by suppressing swelling of the photosensitive composition layer due to the developer.
  • the bisphenol structure includes, for example, a bisphenol A structure derived from bisphenol A (2,2-bis(4-hydroxyphenyl)propane) and a bisphenol derived from bisphenol F (2,2-bis(4-hydroxyphenyl)methane).
  • Bisphenol B structures derived from F structures and bisphenol B (2,2-bis(4-hydroxyphenyl)butane) are included, with bisphenol A structures being preferred.
  • Examples of the polymerizable compound B1 having a bisphenol structure include compounds 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 bonded via one or more alkyleneoxy groups.
  • the alkyleneoxy group added to both ends of the bisphenol structure is preferably an ethyleneoxy group or a propyleneoxy group, more preferably an ethyleneoxy group.
  • polymerizable 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 includes, for example, 2,2-bis(4-(methacryloxydiethoxy)phenyl)propane (FA-324M, Hitachi Chemical Co., Ltd.) ), ethoxylated bisphenol A dimethacrylates (BPE series, Shin-Nakamura Chemical Co., Ltd.), 2,2-bis (4-(methacryloxide decaethoxytetrapropoxy) phenyl) propane (FA-3200MY, manufactured by Hitachi Chemical Co., Ltd.), and ethoxylated (10) bisphenol A diacrylate ( NK Ester A-BPE-10, manufactured by Shin-Nakamura Chemical Co., Ltd.).
  • a compound represented by the formula (B1) is also preferable as the polymerizable compound B1.
  • R 1 and R 2 each independently represent a hydrogen atom or a methyl group.
  • A represents an ethylene group.
  • B represents a propylene group.
  • n1 and n3 each independently represent an integer of 1 to 39; n1+n3 represents an integer of 2-40.
  • n2 and n4 each independently represent an integer of 0 to 29; n2+n4 represents an integer of 0-30.
  • the arrangement of -(AO)- and -(B-O)- constitutional units may be either random or block. In the case of a block, either -(AO)- or -(B-O)- may be on the side of the biphenyl group.
  • n1+n2+n3+n4 is preferably 2 to 20, more preferably 2 to 16, and even more preferably 4 to 12. Further, n2+n4 is preferably 0 to 10, more preferably 0 to 4, still more preferably 0 to 2, and particularly preferably 0.
  • the content of the polymerizable compound B1 is preferably 10.0% by mass or more, more preferably 20.0% by mass or more, with respect to the total mass of the photosensitive composition layer from the viewpoint of better resolution. 0% by mass or more is more preferable.
  • the upper limit is preferably 70.0% by mass or less, more preferably 60.0% by mass or less, from the viewpoint of transferability and edge fusion (phenomenon in which the photosensitive composition exudes from the edge of the transfer member).
  • the content of the polymerizable compound B1 is preferably 40.0% by mass or more, more preferably 50.0% by mass or more, more preferably 55.0% by mass, based on the total mass of the polymerizable compound, from the viewpoint of better resolution. % by mass or more is more preferable, and 60.0% by mass or more is particularly preferable.
  • the upper limit is preferably 100.0% by mass or less, more preferably 99.0% by mass or less, still more preferably 95.0% by mass or less, from the viewpoint of peelability, relative to the total mass of the polymerizable compound, and 90 0% by mass or less is particularly preferred, and 85.0% by mass or less is most preferred.
  • the photosensitive composition layer may contain other polymerizable compounds in addition to the above.
  • Other polymerizable compounds include, for example, known polymerizable compounds. Specifically, a compound having one ethylenically unsaturated group in the molecule (monofunctional ethylenically unsaturated compound), a bifunctional ethylenically unsaturated compound having no aromatic ring, and a trifunctional or higher ethylenically unsaturated compound compound.
  • Examples of monofunctional ethylenically unsaturated compounds include ethyl (meth)acrylate, ethylhexyl (meth)acrylate, 2-(meth)acryloyloxyethyl succinate, polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate. and phenoxyethyl (meth)acrylate.
  • Bifunctional ethylenically unsaturated compounds having no aromatic ring include, for example, alkylene glycol di(meth)acrylate, polyalkylene glycol di(meth)acrylate, urethane di(meth)acrylate and trimethylolpropane diacrylate.
  • Alkylene glycol di(meth)acrylates include, for example, tricyclodecanedimethanol diacrylate (A-DCP, manufactured by Shin-Nakamura Chemical Co., Ltd.), tricyclodecanedimethanol dimethacrylate (DCP, manufactured by Shin-Nakamura Chemical Co., Ltd.), 1,9-nonanediol diacrylate (A-NOD-N, manufactured by Shin-Nakamura Chemical Co., Ltd.), 1,6-hexanediol diacrylate (A-HD-N, manufactured by Shin-Nakamura Chemical Co., Ltd.), ethylene glycol dimethacrylate , 1,10-decanediol diacrylate and neopentyl glycol di(meth)acrylate.
  • A-DCP tricyclodecanedimethanol diacrylate
  • DCP tricyclodecanedimethanol dimethacrylate
  • A-NOD-N 1,9-nonanediol di
  • Polyalkylene glycol di(meth)acrylates include, for example, polyethylene glycol di(meth)acrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate and polypropylene glycol di(meth)acrylate.
  • Urethane di(meth)acrylates include, for example, propylene oxide-modified urethane di(meth)acrylates, and ethylene oxide and propylene oxide-modified urethane di(meth)acrylates.
  • urethane di(meth)acrylate Commercially available products of urethane di(meth)acrylate include, for example, 8UX-015A (manufactured by Taisei Fine Chemical Co., Ltd.), UA-32P (manufactured by Shin-Nakamura Chemical Co., Ltd.) and UA-1100H (manufactured by Shin-Nakamura Chemical Co., Ltd.). be done.
  • trifunctional or higher ethylenically unsaturated compounds include dipentaerythritol (tri/tetra/penta/hexa) (meth) acrylate, pentaerythritol (tri/tetra) (meth) acrylate, trimethylolpropane tri(meth) Acrylate, ditrimethylolpropane tetra(meth)acrylate, trimethylolethane tri(meth)acrylate, isocyanuric acid tri(meth)acrylate, glycerin tri(meth)acrylate 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 including tri(meth)acrylate and tetra(meth)acrylate.
  • alkylene oxide-modified tri- or higher ethylenically unsaturated compounds include, for example, caprolactone-modified (meth)acrylate compounds (KAYARAD (registered trademark) DPCA-20 manufactured by Nippon Kayaku Co., Ltd. and A-9300 manufactured by Shin-Nakamura Chemical Co., Ltd. -1CL, etc.), alkylene oxide-modified (meth)acrylate compounds (KAYARAD RP-1040 manufactured by Nippon Kayaku Co., Ltd., ATM-35E and A-9300 manufactured by Shin-Nakamura Chemical Co., Ltd., EBECRYL (registered trademark) 135 manufactured by Daicel Allnex Co., Ltd., etc.
  • ethoxylated glycerin triacrylate Shin-Nakamura Chemical Co., Ltd. A-GLY-9E, etc.
  • Aronix registered trademark
  • TO-2349 manufactured by Toagosei Co., Ltd.
  • Aronix M-520 manufactured by Toagosei Co., Ltd.
  • Aronix M -510 manufactured by Toagosei Co., Ltd.
  • the polymerizable compound may be a polymerizable compound having an acid group (eg, carboxyl group, etc.).
  • the acid group may form an acid anhydride group.
  • Examples of the polymerizable compound having an acid group include Aronix (registered trademark) TO-2349 (manufactured by Toagosei Co., Ltd.), Aronix (registered trademark) M-520 (manufactured by Toagosei Co., Ltd.) and Aronix (registered trademark) M-510. (manufactured by Toagosei Co., Ltd.).
  • Examples of the polymerizable compound having an acid group include polymerizable compounds having an acid group described in paragraphs [0025] to [0030] of JP-A-2004-239942.
  • the molecular weight of the polymerizable compound is preferably from 200 to 3,000, more preferably from 280 to 2,200, even more preferably from 300 to 2,200.
  • the viscosity of the polymerizable compound at 25° C. is preferably 1 to 10,000 mPa ⁇ s, more preferably 5 to 3,000 mPa ⁇ s, and even more preferably 10 to 1,500 mPa ⁇ s. Further, when two or more polymerizable compounds are used, among the two or more polymerizable compounds, the viscosity at 25 ° C. of the polymerizable compound A having the highest viscosity and the viscosity at 25 ° C. of the polymerizable compound B having the lowest viscosity is preferably 250 to 5000 mPa ⁇ s, more preferably 500 to 2500 Pa ⁇ s, and even more preferably 900 to 1000 Pa ⁇ s. Examples of the method for measuring the viscosity include the following methods.
  • the polymerizable compound (20 mL) is transferred to a container and allowed to stand at room temperature (25 ⁇ 2° C.) for 30 minutes. After that, after inserting the detection terminal into the container of the polymerizable compound and turning on the power, read the value of the viscosity 30 seconds later.
  • V-10A vibrating viscometer
  • the content of the polymerizable group possessed by the polymerizable compound is preferably 1.0 mmol/g or more, more preferably 2.0 mmol/g or more, and further preferably 2.4 mmol/g or more from the viewpoint that the effect of the present invention is more excellent. preferable.
  • the upper limit is preferably 10.0 mmol/g or less. Moreover, you may interpret by replacing the said polymerizable content with the content of a double bond.
  • the photosensitive composition layer contains a plurality of polymerizable compounds, it is preferable that the content of the polymerizable groups possessed by all the polymerizable compounds contained is in the preferred embodiment described above. For example, all polymerizable compounds preferably have 2.4 mmol/g or more of polymerizable groups.
  • Polymerizable group content means the equivalent amount (mol) of polymerizable groups contained per 1 g of the polymerizable compound.
  • the polymerizable compound may be used alone or in combination of two or more.
  • the polymerizable compound is preferably used in three or more types, and more preferably in three types, from the viewpoint that the effects of the present invention are more excellent.
  • at least one of the three types is preferably polymerizable compound B1
  • at least two of the three types are more preferably polymerizable compound B1.
  • the content of the polymerizable compound is preferably 10.0 to 70.0% by mass, more preferably 15.0 to 70.0% by mass, and 20.0 to 70% by mass, based on the total mass of the photosensitive composition layer. 0 mass % is more preferred.
  • the mass ratio of the polymerizable compound content to the resin content is preferably 0.10 to 2.00, more preferably 0.50 to 1.50, 0.70 to 1.10 is more preferable because the effect of the present invention is more excellent.
  • the photosensitive composition layer preferably contains the polymerizable compound B1 and a tri- or higher functional ethylenically unsaturated compound.
  • the mass ratio of the content of the polymerizable compound B1 to the content of the trifunctional or higher ethylenically unsaturated compound is 1.0. ⁇ 5.0 is preferred, 1.2 to 4.0 is more preferred, and 1.5 to 3.0 is even more preferred.
  • the photosensitive composition layer may contain a polymerization initiator.
  • the polymerization initiator include known polymerization initiators depending on the type of polymerization reaction. Specific examples include thermal polymerization initiators and photopolymerization initiators.
  • the polymerization initiator may be either a radical polymerization initiator or a cationic polymerization initiator.
  • the photosensitive composition layer preferably contains a photopolymerization initiator.
  • a photopolymerization initiator is a compound that initiates polymerization of a polymerizable compound upon exposure to actinic rays such as ultraviolet rays, visible rays, and X-rays. Examples of photopolymerization initiators include known photopolymerization initiators. Examples of photopolymerization initiators include radical photopolymerization initiators and cationic photopolymerization initiators, and radical photopolymerization initiators are preferred.
  • photoradical polymerization initiators examples include photopolymerization initiators having an oxime ester structure, photopolymerization initiators having an ⁇ -aminoalkylphenone structure, photopolymerization initiators having an ⁇ -hydroxyalkylphenone structure, and acylphosphine oxide.
  • a photopolymerization initiator having a structure and a photopolymerization initiator having an N-phenylglycine structure are included.
  • the photoradical polymerization initiator is at least selected from the group consisting of 2,4,5-triarylimidazole dimers and derivatives thereof, from the viewpoint of photosensitivity, visibility of exposed and unexposed areas, and resolution. It is preferred to include one.
  • the two 2,4,5-triarylimidazole structures in the 2,4,5-triarylimidazole dimer and its derivative may be the same or different.
  • 2,4,5-triarylimidazole dimer examples include, for example, 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer, 2-(o-chlorophenyl)-4,5-di (Methoxyphenyl)imidazole dimer, 2-(o-fluorophenyl)-4,5-diphenylimidazole dimer, 2-(o-methoxyphenyl)-4,5-diphenylimidazole dimer and 2-( p-Methoxyphenyl)-4,5-diphenylimidazole dimer.
  • photoradical polymerization initiator for example, the photoradical polymerization described in paragraphs [0031] to [0042] of JP-A-2011-095716 and paragraphs [0064] to [0081] of JP-A-2015-014783 initiators.
  • photoradical polymerization initiators examples include ethyl dimethylaminobenzoate (DBE), benzoin methyl ether, anisyl (p,p'-dimethoxybenzyl), TAZ-110 (manufactured by Midori Chemical Co., Ltd.), benzophenone, 4,4'.
  • DBE ethyl dimethylaminobenzoate
  • benzoin methyl ether anisyl
  • TAZ-110 manufactured by Midori Chemical Co., Ltd.
  • benzophenone 4,4'.
  • a photocationic polymerization initiator is a compound that generates an acid upon receiving an actinic ray.
  • the photocationic polymerization initiator is preferably a compound that responds to an actinic ray with a wavelength of 300 nm or more (preferably a wavelength of 300 to 450 nm) to generate an acid.
  • the sensitizer can be used for photocationic polymerization initiators that do not directly react to actinic rays with a wavelength of 300 nm or more.
  • the photocationic polymerization initiator is preferably a photocationic polymerization initiator that generates an acid with a pKa of 4 or less, more preferably a photocationic polymerization initiator that generates an acid with a pKa of 3 or less, and an acid with a pKa of 2 or less. Photocationic polymerization initiators that generate are more preferred.
  • the lower limit is preferably -10.0 or more.
  • photocationic polymerization initiators examples include ionic photocationic polymerization initiators and nonionic photocationic polymerization initiators.
  • Ionic photocationic polymerization initiators include, for example, onium salt compounds such as diaryliodonium salts and triarylsulfonium salts, and quaternary ammonium salts.
  • Examples of the ionic photocationic polymerization initiator include ionic photocationic polymerization initiators described in paragraphs [0114] to [0133] of JP-A-2014-085643.
  • Nonionic photocationic polymerization initiators include, for example, trichloromethyl-s-triazines, diazomethane compounds, imidosulfonate compounds and oximesulfonate compounds.
  • trichloromethyl-s-triazines, diazomethane compounds and imidosulfonate compounds include compounds described in paragraphs [0083] to [0088] of JP-A-2011-221494.
  • Oxime sulfonate compounds include, for example, compounds described in paragraphs [0084] to [0088] of WO2018/179640.
  • a polymerization initiator may be used individually by 1 type, and may be used in 2 or more types.
  • the content of the polymerization initiator (preferably photopolymerization initiator) is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, relative to the total mass of the photosensitive composition layer.
  • the upper limit is preferably 20% by mass or less, more preferably 15% by mass or less, and even more preferably 10% by mass or less, relative to the total mass of the photosensitive composition layer.
  • the photosensitive composition layer has a maximum absorption wavelength of 450 nm or more in a wavelength range of 400 to 780 nm during color development from the viewpoint of visibility of exposed and unexposed areas, and pattern visibility and resolution after development. And, it may contain a dye whose maximum absorption wavelength is changed by an acid, a base, or a radical (hereinafter also referred to as “dye N”).
  • a dye whose maximum absorption wavelength is changed by an acid, a base, or a radical hereinafter also referred to as “dye N”.
  • the dye N is contained, although the detailed mechanism is unknown, the adhesion to the adjacent layer (for example, the intermediate layer) is improved and the resolution is improved.
  • the dye "changes the maximum absorption wavelength by acid, base or radical” means that the dye in the colored state is decolored by acid, base or radical, and the dye in decolored state is colored by acid, base or radical. It may mean either one of the aspect in which the dye in the coloring state changes to the coloring state of another hue.
  • the dye N may be either a compound that changes from a decolored state to develop color upon exposure or a compound that changes from a colored state to decolor upon exposure. In the above case, it may be a dye whose coloring or decoloring state changes due to the action of an acid, a base, or a radical generated in the photosensitive composition layer by exposure, and is sensitized by an acid, a base, or a radical.
  • It may also be a dye that develops or decolors depending on the state (for example, pH) in the liquid composition layer. Further, it may be a dye that changes its coloring or decoloring state by being directly stimulated by an acid, a base, or a radical without being exposed to light.
  • the dye N is preferably a dye whose maximum absorption wavelength is changed by acid or radicals, more preferably a dye whose maximum absorption wavelength is changed by radicals.
  • the photosensitive composition layer preferably contains, as the dye N, both a dye whose maximum absorption wavelength is changed by radicals and a photoradical polymerization initiator.
  • the dye N is preferably a dye that develops color with an acid, a base, or a radical.
  • a photoradical polymerization initiator for example, a photoradical polymerization initiator, a photocationic polymerization initiator (photoacid generator) or a photobase generator is added to the photosensitive composition layer, and the photoradical polymerization initiator is added after exposure.
  • a radical-reactive dye, an acid-reactive dye, or a base-reactive dye develops color by radicals, acids, or bases generated from a photocationic polymerization initiator or a photobase generator.
  • the maximum absorption wavelength in the wavelength range of 400 to 780 nm during coloring of the dye N is preferably 550 nm or more, more preferably 550 to 700 nm, and even more preferably 550 to 650 nm.
  • the dye N may have one or more maximum absorption wavelengths in the wavelength range of 400 to 780 nm during color development.
  • the maximum absorption wavelength with the highest absorbance among the two or more maximum absorption wavelengths should be 450 nm or more.
  • the maximum absorption wavelength of Dye N is determined by measuring the transmission spectrum of a solution containing Dye N in the range of 400 to 780 nm (liquid temperature 25°C) using a spectrophotometer: UV3100 (manufactured by Shimadzu Corporation) in an air atmosphere. can be measured by detecting the wavelength (maximum absorption wavelength) at which the light intensity becomes minimum.
  • Examples of dyes that develop or decolorize upon exposure include leuco compounds.
  • Examples of dyes that are decolorized by exposure include leuco compounds, diarylmethane dyes, oxazine dyes, xanthene dyes, iminonaphthoquinone dyes, azomethine dyes, and anthraquinone dyes.
  • As the dye N a leuco compound is preferable from the viewpoint of the visibility of the exposed area and the non-exposed area.
  • leuco compounds include leuco compounds having a triarylmethane skeleton (triarylmethane dyes), leuco compounds having a spiropyran skeleton (spiropyran dyes), leuco compounds having a fluorane skeleton (fluoran dyes), and diarylmethane skeletons.
  • rhodamine lactam dye a leuco compound having an indolylphthalide skeleton
  • indolylphthalide dye indolylphthalide dye
  • leuco auramine dyes leuco auramine dyes
  • triarylmethane-based dyes or fluoran-based dyes are preferable, and leuco compounds having a triphenylmethane skeleton (triphenylmethane-based dyes) or fluoran-based dyes are more preferable.
  • the leuco compound preferably has a lactone ring, a sultine ring, or a sultone ring from the viewpoint of visibility in exposed and unexposed areas.
  • the lactone ring, sultine ring, or sultone ring of the leuco compound is reacted with a radical generated from a radical photopolymerization initiator or an acid generated from a photocationic polymerization initiator to change the leuco compound into a ring-closed state.
  • Color can be developed by decolorizing or by changing the leuco compound to a ring-opened state.
  • the leuco compound is preferably a compound that has a lactone ring, a sultine ring or a sultone ring and develops color by opening the lactone ring, sultine ring or sultone ring with a radical or an acid, and has a lactone ring and a radical or an acid.
  • a compound that develops color by opening the lactone ring is more preferred.
  • Dyes N include, for example, dyes and leuco compounds.
  • dyes include brilliant green, ethyl violet, methyl green, crystal violet, basic fuchsine, methyl violet 2B, quinaldine red, rose bengal, methanil yellow, thymolsulfophthalein, xylenol blue, methyl orange, and paramethyl red.
  • Congo Fred Benzopurpurin 4B, ⁇ -Naphthyl Red, Nile Blue 2B, Nile Blue A, Methyl Violet, Malachite Green, Parafuchsin, Victoria Pure Blue-Naphthalene Sulfonate, Victoria Pure Blue BOH (manufactured by Hodogaya Chemical Industry Co., Ltd.
  • oil blue #603 (manufactured by Orient Chemical Industry Co., Ltd.), oil pink #312 (manufactured by Orient Chemical Industry Co., Ltd.), oil red 5B (manufactured by Orient Chemical Industry Co., Ltd.), oil scarlet #308 (manufactured by Orient Chemical Industry Co., Ltd.), oil Red OG (manufactured by Orient Chemical Industry Co., Ltd.), Oil Red RR (manufactured by Orient Chemical Industry Co., Ltd.), Oil Green #502 (manufactured by Orient Chemical Industry Co., Ltd.), Spiron Red BEH Special (manufactured by Hodogaya Chemical Industry Co., Ltd.), m-cresol purple, cresol red, rhodamine B, rhodamine 6G, sulforhodamine B, auramine, 4-p-diethylaminophenyliminonaphthoquinone, 2-carboxanilino-4-p-dieth
  • Leuco compounds include, for example, p,p',p''-hexamethyltriaminotriphenylmethane (leuco crystal violet), Pergascript Blue SRB (manufactured by Ciba-Geigy), crystal violet lactone, malachite green lactone, benzoyl leuco methylene blue, 2-(N-phenyl-N-methylamino)-6-(Np-tolyl-N-ethyl)aminofluorane, 2-anilino-3-methyl-6-(N-ethyl-p-toluidino)fluorane , 3,6-dimethoxyfluorane, 3-(N,N-diethylamino)-5-methyl-7-(N,N-dibenzylamino)fluorane, 3-(N-cyclohexyl-N-methylamino)-6 -methyl-7-anilinofluorane, 3-(N,N-diethylamino
  • the dye N a dye whose maximum absorption wavelength is changed by radicals is preferable, and a dye that develops color by radicals is more preferable, from the viewpoint of excellent visibility in exposed and unexposed areas, pattern visibility and resolution after development.
  • Preferred dyes N are leuco crystal violet, crystal violet lactone, brilliant green or victoria pure blue-naphthalene sulfonate.
  • the dye N may be used alone or in combination of two or more.
  • the content of the dye N is 0.1 mass with respect to the total mass of the photosensitive composition layer from the viewpoint of visibility of the exposed area and non-exposed area, and excellent pattern visibility and resolution after development. % or more, more preferably 0.1 to 10% by mass, still more preferably 0.1 to 5% by mass, and particularly preferably 0.1 to 1% by mass.
  • the content of the dye N means the content of the dye when all the dyes N contained in the total weight of the photosensitive composition layer are in a colored state.
  • a method for quantifying the content of the dye N will be described using a dye that develops color by radicals as an example.
  • a solution of dye N (0.001 g) and a solution of dye N (0.01 g) in 100 mL of methyl ethyl ketone are prepared.
  • a photoradical polymerization initiator (Irgacure OXE01, manufactured by BASF Japan) is added to each of the obtained solutions, and radicals are generated by irradiation with light of 365 nm, and all dyes N are brought 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) in an air atmosphere to create a calibration curve.
  • the absorbance of the solution in which all the dyes are developed is measured in the same manner as described above except that instead of the dye N, the photosensitive composition layer (3 g) is dissolved in methyl ethyl ketone. From the absorbance of the obtained solution containing the photosensitive composition layer, the content of dye N contained in the photosensitive composition layer is calculated based on the calibration curve.
  • Photosensitive composition layer (3 g) is synonymous with 3 g of total solid content in the photosensitive composition.
  • the photosensitive composition layer may contain a thermally crosslinkable compound from the viewpoint of the strength of the resulting cured film and the adhesiveness of the resulting uncured film.
  • a thermally crosslinkable compound having an ethylenically unsaturated group, which will be described later, is not treated as a polymerizable compound, but as a thermally crosslinkable compound.
  • Examples of the thermally crosslinkable compound include methylol compounds and blocked isocyanate compounds, and blocked isocyanate compounds are preferred from the viewpoint of the strength of the resulting cured film and the adhesiveness of the resulting uncured film.
  • blocked isocyanate compound reacts with a hydroxy group and a carboxy group, for example, when the resin and/or the polymerizable compound has at least one of a hydroxy group and a carboxy group, the hydrophilicity of the formed film is lowered and the photosensitive composition The function tends to be enhanced when a film obtained by curing a material layer is used as a protective film.
  • a "blocked isocyanate compound” means a compound having a structure in which the isocyanate group of isocyanate is protected with a blocking agent.
  • the dissociation temperature of the blocked isocyanate compound is preferably 100 to 160°C, more preferably 130 to 150°C.
  • a method for measuring the dissociation temperature of the blocked isocyanate compound for example, DSC (Differential scanning calorimetry) analysis using a differential scanning calorimeter (e.g., DSC6200, manufactured by Seiko Instruments Inc.) is performed to determine the deprotection reaction of the blocked isocyanate compound.
  • DSC Different scanning calorimeter
  • blocking agents having a dissociation temperature of 100 to 160° C. include active methylene compounds such as malonic acid diesters and oxime compounds.
  • Malonic acid diesters include, for example, dimethyl malonate, diethyl malonate, di-n-butyl malonate and di-2-ethylhexyl malonate.
  • oxime compounds are preferable as blocking agents having a dissociation temperature of 100 to 160° C. from the viewpoint of storage stability.
  • the blocked isocyanate compound preferably has an isocyanurate structure from the viewpoint of improving the brittleness of the film and improving the adhesion to the transferred material.
  • a blocked isocyanate compound having an isocyanurate structure is obtained, for example, by isocyanurating hexamethylene diisocyanate and protecting it.
  • an oxime compound is used as a blocking agent because it is easier to adjust the dissociation temperature to a preferable range than a compound having no oxime structure and can reduce development residue.
  • Compounds having an oxime structure are preferred.
  • the blocked isocyanate compound may have a polymerizable group.
  • the polymerizable group has, for example, the same definition as the polymerizable group possessed by the polymerizable compound, and the preferred embodiments are also the same.
  • blocked isocyanate compounds examples include Karenz series (registered trademark) such as AOI-BM, MOI-BM and MOI-BP (manufactured by Showa Denko KK); ) (manufactured by Asahi Kasei Chemicals).
  • Karenz series registered trademark
  • MOI-BM MOI-BM
  • MOI-BP manufactured by Showa Denko KK
  • Asahi Kasei Chemicals the following compounds are preferred.
  • the thermally crosslinkable compound may be used singly or in combination of two or more.
  • the content of the thermally crosslinkable compound is preferably 1 to 50% by mass, more preferably 5 to 30% by mass, based on the total mass of the photosensitive composition layer.
  • the photosensitive composition layer may contain a pigment.
  • the photosensitive composition layer contains a pigment, it corresponds to the colored resin layer.
  • a colored resin layer may be used to form such a light shielding layer.
  • the pigment may be appropriately selected according to the desired hue. Examples thereof include black pigments, white pigments, and chromatic pigments other than black and white. As such, a black pigment is preferable.
  • black pigment examples include known black pigments (eg, organic pigments, inorganic pigments, etc.). Among them, carbon black, titanium oxide, titanium carbide, iron oxide, titanium oxide or graphite are preferable as the black pigment, and carbon black is more preferable, from the viewpoint of optical density. From the viewpoint of surface resistance, the carbon black is preferably surface-modified carbon black having at least a portion of the surface coated with a resin.
  • black pigments include known black pigments (eg, organic pigments, inorganic pigments, etc.).
  • carbon black, titanium oxide, titanium carbide, iron oxide, titanium oxide or graphite are preferable as the black pigment, and carbon black is more preferable, from the viewpoint of optical density.
  • the carbon black is preferably surface-modified carbon black having at least a portion of the surface coated with a resin.
  • the particle size (number average particle size) of the black pigment is preferably 0.001 to 0.1 ⁇ m, more preferably 0.01 to 0.08 ⁇ m, from the viewpoint of dispersion stability.
  • the term "particle size” means the diameter of a circle obtained by determining the area of a pigment particle from a photographic image of the pigment particle taken with an electron microscope and considering a circle having the same area as the area of the pigment particle. Further, the "number average particle size” means an average value obtained by determining the particle size of 100 arbitrary particles and averaging the obtained 100 particle sizes.
  • white pigments examples include inorganic pigments and white pigments described in paragraphs [0015] and [0114] of JP-A-2005-007765.
  • the inorganic pigment is preferably titanium oxide, zinc oxide, lithopone, light calcium carbonate, white carbon, aluminum oxide, aluminum hydroxide or barium sulfate, more preferably titanium oxide or zinc oxide, still more preferably titanium oxide, rutile type or Anatase-type titanium oxide is particularly preferred, and rutile-type titanium oxide is most preferred.
  • the surface of titanium oxide may be subjected to silica treatment, alumina treatment, titania treatment, zirconia treatment, organic substance treatment, or two or more of these treatments.
  • the surface treatment of the titanium oxide surface is preferably at least one of alumina treatment and zirconia treatment, and both alumina treatment and zirconia treatment are performed. is more preferable.
  • the photosensitive composition layer When the photosensitive composition layer is a colored resin layer, the photosensitive composition layer preferably contains a chromatic pigment other than the black pigment and the white pigment from the viewpoint of transferability.
  • the particle size (number average particle size) of the chromatic pigment is preferably 0.1 ⁇ m or less, more preferably 0.08 ⁇ m or less, from the viewpoint of better dispersibility. The lower limit is preferably 10 nm or more.
  • chromatic pigments include Victoria Pure Blue BO (Color Index (hereinafter also referred to as “CI”) 42595), Auramine (CI 41000), Fat Black HB (CI .26150), Monolite Yellow GT (C.I. Pigment Yellow 12), Permanent Yellow GR (C.I. Pigment Yellow 17), Permanent Yellow HR (C.I.
  • Pigment Yellow 83 Permanent Carmine FBB (C.I. Pigment Red 146), Hoster Balm Red ESB (C.I. Pigment Violet 19), Permanent Ruby FBH (C.I. Pigment Red 11), Fastel Pink B Splash (C.I. Pigment Red 81), Monastral Fast Blue (C.I. Pigment Blue 15), Monolite Fast Black B (C.I. 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.
  • the pigments may be used singly or in combination of two or more.
  • 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, and more than 5% by mass and 35% by mass or less with respect to the total mass of the photosensitive composition layer. More preferably, 10 to 35% by mass is particularly preferable.
  • the photosensitive composition layer contains pigments other than black pigments (e.g., white pigments, chromatic pigments, etc.), the content of pigments other than black pigments is 30% by mass or less with respect to the total mass of black pigments. is preferred, 1 to 20 mass % is more preferred, and 3 to 15 mass % is even more preferred.
  • pigments other than black pigments e.g., white pigments, chromatic pigments, etc.
  • the black pigment (preferably carbon black) is preferably introduced into the photosensitive 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 the mixture with a dispersing machine.
  • a pigment dispersant may be selected according to the pigment and solvent, and for example, a commercially available dispersant can be used.
  • vehicle is meant that portion of the medium in which the pigment is dispersed when made into a pigment dispersion.
  • the vehicle is liquid and contains a binder component that holds the black pigment in a dispersed state and a solvent component (organic solvent) that dissolves and dilutes the binder component.
  • dispersers examples include known dispersers such as kneaders, roll mills, attritors, super mills, dissolvers, homomixers and sand mills. Moreover, it may be finely pulverized using frictional force by mechanical grinding. Dispersers and fine pulverization are described, for example, in "Encyclopedia of Pigments" (Kunizo Asakura, 1st edition, Asakura Shoten, 2000, pp. 438, 310).
  • the photosensitive composition layer may contain other additives, if necessary, in addition to the above components.
  • Other additives include, for example, radical polymerization inhibitors, benzotriazoles, carboxybenzotriazoles, sensitizers, surfactants, plasticizers, heterocyclic compounds (e.g., triazole, etc.), pyridines (e.g., isonicotine amides, etc.) and purine bases (eg, adenine, etc.).
  • additives include, for example, metal oxide particles, chain transfer agents, antioxidants, dispersants, acid multipliers, development accelerators, conductive fibers, ultraviolet absorbers, thickeners, cross-linking agents, organic Or inorganic suspending agents and paragraphs [0165] to [0184] of JP-A-2014-085643, the contents of which are incorporated herein.
  • Other additives may be used singly or in combination of two or more.
  • radical polymerization inhibitors include thermal polymerization inhibitors described in paragraph [0018] of Japanese Patent No. 4502784, and phenothiazine, phenoxazine and 4-methoxyphenol are preferred.
  • the radical polymerization inhibitor includes, for example, naphthylamine, cuprous chloride, nitrosophenylhydroxyamine aluminum salt and diphenylnitrosamine. Nitrosophenylhydroxyamine aluminum salt is preferred from the viewpoint of not impairing the sensitivity of the photosensitive composition layer. .
  • the content of the radical polymerization inhibitor is preferably 0.001 to 5.0% by mass, more preferably 0.01 to 3.0% by mass, based on the total mass of the photosensitive composition layer, and 0.02 to 2.0% by mass is more preferred.
  • the content of the radical polymerization inhibitor is preferably 0.005 to 5.0% by mass, more preferably 0.01 to 3.0% by mass, more preferably 0.01 to 1.0% by mass, based on the total mass of the polymerizable compound. 0% by mass is more preferred.
  • benzotriazoles examples include 1,2,3-benzotriazole, 1-chloro-1,2,3-benzotriazole, bis(N-2-ethylhexyl)aminomethylene-1,2,3-benzotriazole, bis(N-2-ethylhexyl)aminomethylene-1,2,3-tolyltriazole and bis(N-2-hydroxyethyl)aminomethylene-1,2,3-benzotriazole.
  • Carboxybenzotriazoles include, for example, 4-carboxy-1,2,3-benzotriazole, 5-carboxy-1,2,3-benzotriazole, N-(N,N-di-2-ethylhexyl)aminomethylene Carboxybenzotriazole, N-(N,N-di-2-hydroxyethyl)aminomethylene carboxybenzotriazole and N-(N,N-di-2-ethylhexyl)aminoethylene carboxybenzotriazole.
  • Specific examples of carboxybenzotriazoles include CBT-1 (manufactured by Johoku Chemical Industry Co., Ltd.).
  • the total content of radical polymerization inhibitors, benzotriazoles and carboxybenzotriazoles is preferably 0.01 to 3% by mass, more preferably 0.05 to 1% by mass, based on the total mass of the photosensitive composition layer. preferable.
  • the content is 0.01% by mass or more, the storage stability of the photosensitive composition layer is more excellent.
  • the content is 3% by mass or less, the maintenance of sensitivity and suppression of decolorization of the dye are more excellent.
  • Sensitizers include, for example, known sensitizers, dyes and pigments. Sensitizers include, for example, dialkylaminobenzophenone compounds, pyrazoline compounds, anthracene compounds, coumarin compounds, xanthone compounds, thioxanthone compounds, acridone compounds, oxazole compounds, benzoxazole compounds, thiazole compounds, benzothiazole compounds, triazole compounds (e.g., 1,2,4-triazoles), stilbene compounds, triazine compounds, thiophene compounds, naphthalimide compounds, triarylamine compounds and aminoacridine compounds.
  • Sensitizers include, for example, known sensitizers, dyes and pigments. Sensitizers include, for example, dialkylaminobenzophenone compounds, pyrazoline compounds, anthracene compounds, coumarin compounds, xanthone compounds, thioxanthone compounds, acridone compounds,
  • the content of the sensitizer is 0.01 to 5% by mass with respect to the total mass of the photosensitive composition layer, from the viewpoint of improving the sensitivity to light sources and improving the curing speed due to the balance between polymerization speed and chain transfer.
  • surfactants examples include surfactants described in paragraph [0017] of Japanese Patent No. 4502784 and paragraphs [0060] to [0071] of JP-A-2009-237362.
  • a nonionic surfactant a fluorosurfactant or a silicone surfactant is preferred.
  • fluorosurfactants include Megafac F-171, F-172, F-173, F-176, F-177, F-141, F-142, F-143, F-144, F- 437, 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-578-2, EXP.
  • an acrylic compound having a molecular structure with a functional group containing a fluorine atom is also preferable, in which the portion of the functional group containing the fluorine atom is cleaved when heat is applied to volatilize the fluorine atom.
  • a fluorosurfactant include Megafac DS series manufactured by DIC (The Chemical Daily (February 22, 2016) and Nikkei Sangyo Shimbun (February 23, 2016)).
  • the fluorosurfactant it is also preferable to use a copolymer 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 fluorosurfactant.
  • the fluorosurfactant has 2 or more (preferably 5 or more) structural units derived from a (meth)acrylate compound having a fluorine atom and an alkyleneoxy group (preferably an ethyleneoxy group or a propyleneoxy group) (preferably 5 or more). ) and a structural unit derived from an acrylate compound.
  • fluorosurfactants also include fluoropolymers having ethylenically unsaturated groups in side chains, such as MEGAFACE RS-101, RS-102, RS-718K and RS-72-K (manufactured by DIC Corporation).
  • fluorine-based surfactants from the viewpoint of improving environmental suitability, compounds having linear perfluoroalkyl groups having 7 or more carbon atoms, such as perfluorooctanoic acid (PFOA) and perfluorooctane sulfonic acid (PFOS), are used.
  • PFOA perfluorooctanoic acid
  • PFOS perfluorooctane sulfonic acid
  • Surfactants derived from alternative materials are preferred.
  • nonionic surfactants include glycerol, trimethylolpropane, trimethylolethane, their ethoxylates and propoxylates (e.g., glycerol propoxylate and glycerol ethoxylate, etc.), polyoxyethylene lauryl ether, polyoxyethylene stearyl Ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, and sorbitan fatty acid ester; specific examples include Pluronic (registered trademark) L10, L31, L61, L62, 10R5, 17R2 and 25R2 (manufactured by BASF); Tetronic 304, 701, 704, 901, 904 and 150R1, HYDROPALAT WE 3323 (manufactured by BASF); Solsperse 20000 (manufactured by BASF) Japan
  • silicone-based surfactants include linear polymers composed of siloxane bonds, and modified siloxane polymers in which organic groups are introduced into side chains and/or terminals.
  • silicone-based surfactants include EXP. S-309-2, EXP. S-315, EXP. S-503-2, EXP. S-505-2 (manufactured by DIC Corporation), DOWSIL 8032 ADDITIVE, Toray Silicone DC3PA, Toray Silicone SH7PA, Toray Silicone DC11PA, Toray Silicone SH21PA, Toray Silicone SH28PA, Toray Silicone SH29PA, Toray Silicone SH30PA and Toray Silicone SH8400 ( Above, Dow Corning Toray Co., Ltd.); KF-643, X-22-6191, X-22-4515, KF-6004, KP-341, KF-6001, KF-6002, KP-101, KP-103, KP-104, KP-105, KP- 106, KP-109, KP-112, KP-120, KP-121, KP-124, KP-125, KP-301, KP-306, KP-310, KP-322, KP
  • the content of the surfactant is preferably 0.01 to 3.0% by mass, more preferably 0.01 to 1.0% by mass, and 0.05 to 0.0% by mass, based on the total mass of the photosensitive composition layer. 0.8% by weight is more preferred.
  • Plasticizers and heterocyclic compounds include, for example, compounds described in paragraphs [0097] to [0103] and paragraphs [0111] to [0118] of WO2018/179640.
  • the photosensitive composition layer may contain impurities.
  • Impurities include, for example, metal impurities or their ions, halide ions, residual organic solvents, residual monomers, and water.
  • Metal impurities and halide ions include, for example, sodium, potassium, magnesium, calcium, iron, manganese, copper, aluminum, titanium, chromium, cobalt, nickel, zinc, tin and ions thereof, and halide ions.
  • sodium ions, potassium ions and halide ions are preferably contained in the following amounts because they are easily mixed.
  • Metal impurities are compounds different from the particles (eg, metal oxide particles) that may be included in the transfer film.
  • the content of metal impurities is preferably 80 mass ppm or less, more preferably 10 mass ppm or less, and even more preferably 2 mass ppm or less, relative to the total mass of the photosensitive composition layer.
  • the lower limit is preferably 1 mass ppb or more, more preferably 0.1 mass ppm or more, relative to the total mass of the photosensitive composition layer.
  • Methods for adjusting the content of impurities include, for example, a method of selecting a material with a low impurity content as a raw material for the photosensitive composition layer, a method of preventing contamination of impurities during the formation of the photosensitive composition layer, and A method of removing by washing can be mentioned.
  • the content of impurities can be quantified by known methods such as ICP emission spectroscopy, atomic absorption spectroscopy and ion chromatography.
  • Residual organic solvents include, for example, benzene, formaldehyde, trichlorethylene, 1,3-butadiene, carbon tetrachloride, chloroform, N,N-dimethylformamide, N,N-dimethylacetamide and hexane.
  • the content of the residual organic solvent is preferably 100 ppm by mass or less, more preferably 20 ppm by mass or less, and even more preferably 4 ppm by mass or less, relative to the total mass of the photosensitive composition layer.
  • the lower limit is preferably 10 mass ppb or more, more preferably 100 mass ppb or more, relative to the total mass of the photosensitive composition layer.
  • a method for adjusting the content of the residual organic solvent there is a method for adjusting the drying treatment conditions in the transfer film manufacturing method described below. Also, the content of the residual organic solvent can be quantified by a known method such as gas chromatography analysis.
  • the photosensitive composition layer may contain residual monomers of the constituent units of the resin.
  • the content of the remaining monomer is preferably 5000 ppm by mass or less, more preferably 2000 ppm by mass or less, and even more preferably 500 ppm by mass or less relative to the total mass of the resin, from the viewpoint of patterning properties and reliability.
  • the lower limit is preferably 1 mass ppm or more, more preferably 10 mass ppm or more, relative to the total mass of the resin.
  • the residual monomer of each structural unit of the alkali-soluble resin is preferably 3000 ppm by mass or less, more preferably 600 ppm by mass or less, relative to the total mass of the photosensitive composition layer. , 100 ppm by mass or less is more preferable.
  • the lower limit is preferably 0.1 mass ppm or more, more preferably 1 mass ppm or more, relative to the total mass of the photosensitive composition layer.
  • the residual amount of the monomer when synthesizing the alkali-soluble resin by polymer reaction is also within the above range.
  • the content of glycidyl acrylate is preferably within the above range.
  • the method for adjusting the content of the remaining monomers include a method for adjusting the content of the impurities.
  • the amount of residual monomers can be measured by known methods such as liquid chromatography and gas chromatography.
  • the water content in the photosensitive composition layer is preferably 0.01 to 1.0% by mass, more preferably 0.05 to 0.5% by mass, from the viewpoint of improving reliability and laminating properties.
  • the thickness (film thickness) of the photosensitive composition layer is often 0.1 to 300 ⁇ m, preferably 0.2 to 100 ⁇ m, more preferably 0.5 to 50 ⁇ m, even more preferably 0.5 to 30 ⁇ m, 1 to 20 ⁇ m is particularly preferred. Thereby, the developability of the photosensitive composition layer can be improved, and the resolution can be improved.
  • the content of the polymerizable group contained in the photosensitive composition layer is preferably 1.0 mmol/g or more, more preferably 2.0 mmol/g or more, and 3.0 mmol/g from the viewpoint that the effects of the present invention are more excellent.
  • the above is more preferable.
  • the upper limit is preferably 10.0 mmol/g or less. Moreover, you may interpret by replacing the said polymerizable content with content of a double bond.
  • the acid value of the photosensitive composition layer is preferably 10 to 150 mgKOH/g, more preferably 40 to 120 mgKOH/g, still more preferably 50 to 120 mgKOH/g, particularly preferably 50 to 100 mgKOH/g, particularly preferably 60 to 100 mgKOH/g. is most preferred.
  • Examples of the method for measuring the acid value include a method for measuring the acid value in the resin and a method for calculating the acid value from the content of a resin whose acid value is known.
  • the transfer film may have an intermediate layer between the temporary support and the photosensitive composition layer.
  • the intermediate layer is between the temporary support and the photosensitive composition layer if it does not have a thermoplastic resin layer, or if it has a thermoplastic resin layer, the thermoplastic resin layer and the photosensitive composition layer is preferably placed between Examples of the intermediate layer include a water-soluble resin layer and an oxygen barrier layer having an oxygen barrier function described as a "separation layer" in JP-A-5-072724.
  • an oxygen-blocking layer is preferable from the viewpoint that the sensitivity at the time of exposure is improved, the time load of the exposure machine is reduced, and the productivity is improved. More preferred is an oxygen barrier layer dispersed or dissolved in a 1% by weight aqueous solution of sodium carbonate.
  • Each component that the intermediate layer may contain will be described below.
  • the intermediate layer may contain a water-soluble resin.
  • water-soluble resins include polyvinyl alcohol-based resins, polyvinylpyrrolidone-based resins, cellulose-based resins, polyether-based resins, gelatin, and polyamide resins.
  • Cellulose-based resins include, for example, water-soluble cellulose derivatives.
  • Water-soluble cellulose derivatives include, for example, hydroxyethylcellulose, hydroxypropylmethylcellulose, hydroxypropylcellulose, carboxymethylcellulose, methylcellulose and ethylcellulose.
  • polyether-based resins examples include polyethylene glycol, polypropylene glycol, alkylene oxide side adducts thereof, and vinyl ether-based resins.
  • Polyamide resins include, for example, acrylamide-based resins, vinylamide-based resins, and allylamide-based resins.
  • water-soluble resins examples include copolymers of (meth)acrylic acid/vinyl compounds, preferably copolymers of (meth)acrylic acid and allyl (meth)acrylate, and methacrylic acid and allyl methacrylate. and copolymers are more preferred.
  • each composition ratio (mol% of (meth)acrylic acid/mol% of vinyl compound) is 90/10 to 20/80. is preferred, and 80/20 to 30/70 is more preferred.
  • the weight average molecular weight of the water-soluble resin is preferably 5,000 or more, more preferably 7,000 or more, and even more preferably 10,000 or more.
  • the upper limit is preferably 200,000 or less, more preferably 100,000 or less, even more preferably 50,000 or less.
  • the dispersity of the water-soluble resin is preferably 1-10, more preferably 1-5, even more preferably 1-3.
  • One type of water-soluble resin may be used alone, or two or more types may be used.
  • the content of the water-soluble resin is preferably 50% by mass or more, more preferably 70% by mass or more, relative to the total mass of the intermediate layer.
  • the upper limit is preferably 100% by mass or less, more preferably 99.9% by mass or less, still more preferably 99.8% by mass or less, and particularly preferably 99% by mass or less, relative to the total mass of the intermediate layer.
  • the intermediate layer may contain other components in addition to the above resins.
  • polyhydric alcohols, alkylene oxide adducts of polyhydric alcohols, phenol derivatives or amide compounds are preferable, and polyhydric alcohols, phenol derivatives or amide compounds are more preferable.
  • Polyhydric alcohols include, for example, glycerin, diglycerin and diethylene glycol.
  • the number of hydroxy groups possessed by the polyhydric alcohol is preferably 2-10.
  • alkylene oxide adducts of polyhydric alcohols include compounds obtained by adding ethyleneoxy groups, propyleneoxy groups, and the like to the above polyhydric alcohols.
  • the average number of alkyleneoxy groups to be added is preferably 1-100, preferably 2-50, more preferably 2-20.
  • Phenol derivatives include, for example, bisphenol A and bisphenol S.
  • Amide compounds include, for example, N-methylpyrrolidone.
  • the intermediate layer preferably contains at least one selected from the group consisting of water-soluble cellulose derivatives, polyhydric alcohols, oxide adducts of polyhydric alcohols, polyether resins, phenol derivatives and amide compounds.
  • the molecular weight of other components is preferably less than 5,000, more preferably 4,000 or less, even more preferably 3,000 or less, particularly preferably 2,000 or less, and most preferably 1,500 or less.
  • the lower limit is preferably 60 or more.
  • the content of other components is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and even more preferably 1% by mass or more, relative to the total mass of the intermediate layer.
  • the upper limit is preferably less than 30% by mass, more preferably 10% by mass or less, and even more preferably 5% by mass or less.
  • the intermediate layer may contain impurities.
  • Impurities include, for example, impurities contained in the photosensitive composition layer.
  • the thickness of the intermediate layer is preferably 3.0 ⁇ m or less, more preferably 2.0 ⁇ m or less.
  • the lower limit is preferably 1.0 ⁇ m or more.
  • the transfer film may have a thermoplastic resin layer.
  • the thermoplastic resin layer is preferably arranged between the temporary support and the photosensitive composition layer when the intermediate layer is not provided, and between the temporary support and the intermediate layer when the intermediate layer is provided.
  • the transfer film has a thermoplastic resin layer, the followability to the transferred material in the step of laminating the transfer film and the transferred material is improved, and air bubbles are prevented from entering between the transfer film and the transferred material. can be suppressed.
  • adhesion with a layer (for example, temporary support) adjacent to the thermoplastic resin layer is improved.
  • Examples of the thermoplastic resin layer include paragraphs [0189] to [0193] of JP-A-2014-085643, the contents of which are incorporated herein. Each component that the thermoplastic resin layer may contain will be described below.
  • the thermoplastic resin layer may contain a thermoplastic resin.
  • an alkali-soluble resin is preferred.
  • alkali-soluble resins include acrylic resins, polystyrene resins, styrene-acrylic copolymers, polyurethane resins, polyvinyl alcohol, polyvinyl formal, polyamide resins, polyester resins, polyamide resins, epoxy resins, polyacetal resins, and polyhydroxystyrene resins. , polyimide resins, polybenzoxazole resins, polysiloxane resins, polyethyleneimines, polyallylamines and polyalkylene glycols.
  • the alkali-soluble resin the alkali-soluble resin contained in the photosensitive composition layer described above may be used.
  • an acrylic resin is preferable from the viewpoint of developability and adhesion to adjacent layers.
  • "Acrylic resin” means at least one selected from the group consisting of structural units derived from (meth)acrylic acid, structural units derived from (meth)acrylic acid esters, and structural units derived from (meth)acrylic acid amides. means a resin containing one constitutional unit.
  • the total content of structural units derived from (meth)acrylic acid, structural units derived from (meth)acrylic acid esters, and structural units derived from (meth)acrylic acid amides is equal to the total mass of the acrylic resin. On the other hand, 30% by mass or more is preferable, and 50% by mass or more is more preferable.
  • the upper limit is preferably 100% by mass or less with respect to the total mass of the acrylic resin.
  • the total content of structural units derived from (meth) acrylic acid and structural units derived from (meth) acrylic acid ester is preferably 30 to 100% by mass, based on the total mass of the acrylic resin, and 50 to 100% by mass is more preferred.
  • a resin having an acid group is preferable as the alkali-soluble resin.
  • the acid group includes, for example, a carboxy group, a sulfo group, a phosphoric acid group and a phosphonic acid group, with the carboxy group being preferred.
  • the alkali-soluble resin preferably contains a structural unit having an acid group, and more preferably contains a structural unit having a carboxy group. Acrylic resins having structural units derived from acrylic acid are more preferred.
  • the acid value of the alkali-soluble resin is preferably 60 mgKOH/g or more from the viewpoint of developability.
  • the upper limit is preferably 300 mgKOH/g or less, more preferably 250 mgKOH/g or less, still more preferably 200 mgKOH/g or less, and particularly preferably 150 mgKOH/g or less.
  • an alkali-soluble resin having an acid value of 60 mgKOH/g or more is preferable, and an acrylic resin having a carboxyl group having an acid value of 60 mgKOH/g or more is more preferable.
  • the acrylic resin having a carboxyl group with an acid value of 60 mgKOH/g or more for example, it can be appropriately selected from known resins and used. Specifically, paragraph [0025] of JP-A-2011-095716, paragraphs [0033] to [0052] of JP-A-2010-237589 and paragraphs [0053] to [0068 of JP-A-2016-224162 ] is mentioned.
  • the content of structural units having a carboxy group is preferably 5-50% by mass, more preferably 10-40% by mass, and even more preferably 12-30% by mass, relative to the total mass of the acrylic resin.
  • the alkali-soluble resin may have a polymerizable group.
  • the polymerizable group may be any group as long as it participates in the polymerization reaction, for example, 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; an epoxy group, an oxetane group, and the like. group having a cationic polymerizable group.
  • a group having an ethylenically unsaturated group is preferable, and an acryloyl group or a methacryloyl group is more preferable.
  • the weight average molecular weight of the alkali-soluble resin is preferably 1,000 or more, more preferably 10,000 to 100,000, and still more preferably 20,000 to 50,000.
  • the thermoplastic resin may be used alone or in combination of two or more.
  • the content of the thermoplastic resin is preferably 10 to 99% by mass, more preferably 20 to 90% by mass, based on the total mass of the thermoplastic resin layer, from the viewpoint of developability and adhesion to adjacent layers. 40 to 80 mass % is more preferred, and 50 to 75 mass % is particularly preferred.
  • the thermoplastic resin layer contains a dye having a maximum absorption wavelength of 450 nm or more in a wavelength range of 400 to 780 nm during color development, and the maximum absorption wavelength of which is changed by an acid, a base, or a radical (hereinafter simply referred to as "dye B"). may contain.
  • the preferred embodiments of the dye B are the same as those of the above dye N, and the preferred embodiments are also the same, except for the points described later.
  • the dye B is preferably a dye whose maximum absorption wavelength is changed by an acid or a radical, more preferably a dye whose maximum absorption wavelength is changed by an acid, from the viewpoints of visibility in exposed and unexposed areas and resolution.
  • the thermoplastic resin layer contains both a dye whose maximum absorption wavelength is changed by an acid as the dye B and a compound that generates an acid by light, which will be described later. is preferably included.
  • the dye B may be used singly or in combination of two or more.
  • the content of the dye B is preferably 0.2% by mass or more, and 0.2 to 6.0% by mass, based on the total mass of the thermoplastic resin layer, from the viewpoint of visibility of the exposed and unexposed areas. More preferably, 0.2 to 5.0% by mass is more preferable, and 0.25 to 3.0% by mass is particularly preferable.
  • the “content of dye B” means the content of the dye when all of the dye B contained in the thermoplastic resin layer is in a colored state. A method for quantifying the content of the dye B will be described below using a dye that develops color by radicals as an example.
  • a solution of dye B (0.001 g) and a solution of dye B (0.01 g) in 100 mL of methyl ethyl ketone are prepared.
  • a radical photopolymerization initiator (Irgacure OXE01, manufactured by BASF Japan) is added to each of the solutions obtained, and radicals are generated by irradiation with light of 365 nm, so that all the dyes B are colored.
  • the absorbance of each solution having a liquid temperature of 25° C. is measured using a spectrophotometer (UV3100, manufactured by Shimadzu Corporation) in an air atmosphere to create a calibration curve.
  • thermoplastic resin layer (3 g) is dissolved in methyl ethyl ketone instead of the dye B, the absorbance of the solution in which all the dyes are developed is measured. From the absorbance of the obtained solution containing the thermoplastic resin layer, the amount of dye B contained in the thermoplastic resin layer is calculated based on the calibration curve.
  • Thermoplastic resin layer (3 g) is synonymous with 3 g of the total solid content in the thermoplastic resin composition.
  • the thermoplastic resin layer may contain a compound that generates an acid, base, or radical upon exposure to light (hereinafter also simply referred to as "compound C").
  • Compound C is preferably a compound that generates an acid, a base, or a radical upon receiving actinic rays such as ultraviolet rays and visible rays.
  • Examples of the compound C include known photoacid generators, photobase generators and photoradical polymerization initiators (photoradical generators).
  • the thermoplastic resin layer may contain a photoacid generator.
  • the photoacid generator includes, for example, a photocationic polymerization initiator that can be contained in the photosensitive composition layer.
  • the photoacid generator preferably contains at least one compound selected from the group consisting of onium salt compounds and oxime sulfonate compounds. Therefore, it is more preferred to include an oxime sulfonate compound.
  • a photoacid generator having the following structure is also preferable.
  • thermoplastic resin layer may contain a radical photopolymerization initiator.
  • photoradical polymerization initiators include photoradical polymerization initiators that can be contained in the photosensitive composition layer, and preferred embodiments are also the same.
  • the thermoplastic resin composition may contain a photobase generator.
  • the photobase generator include known photobase generators. Specifically, 2-nitrobenzylcyclohexylcarbamate, triphenylmethanol, O-carbamoylhydroxylamide, O-carbamoyloxime, [[(2,6-dinitrobenzyl)oxy]carbonyl]cyclohexylamine, bis[[(2- nitrobenzyl)oxy]carbonyl]hexane 1,6-diamine, 4-(methylthiobenzoyl)-1-methyl-1-morpholinoethane, (4-morpholinobenzoyl)-1-benzyl-1-dimethylaminopropane, N-( 2-nitrobenzyloxycarbonyl)pyrrolidine, hexaamminecobalt (III) tris(triphenylmethylborate), 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone, 2,6-d
  • Compound C may be used alone or in combination of two or more.
  • the content of compound C is preferably 0.1 to 10% by mass, preferably 0.5%, based on the total mass of the thermoplastic resin layer, from the viewpoints of visibility in exposed and unexposed areas and resolution. ⁇ 5% by mass is more preferred.
  • the thermoplastic resin layer may contain a plasticizer from the viewpoint of resolution, adhesion to adjacent layers, and developability.
  • the plasticizer preferably has a smaller molecular weight (weight-average molecular weight if it is an oligomer or polymer and has a molecular weight distribution) than the thermoplastic resin (preferably alkali-soluble resin).
  • the molecular weight (weight average molecular weight) of the plasticizer is preferably 200 to 2,000.
  • the plasticizer is not particularly limited as long as it is a compound compatible with the alkali-soluble resin and exhibits plasticity.
  • the plasticizer preferably has an alkyleneoxy group in the molecule, and more preferably has a polyethyleneoxy structure or a polypropyleneoxy structure. Polyalkylene glycol compounds are preferred as plasticizers.
  • the plasticizer preferably contains a (meth)acrylate compound from the viewpoint of resolution and storage stability.
  • the alkali-soluble resin is an acrylic resin and the plasticizer contains a (meth)acrylate compound.
  • the (meth)acrylate compound includes, for example, a (meth)acrylate compound as a polymerizable compound that can be contained in the photosensitive composition layer.
  • both the thermoplastic resin layer and the photosensitive composition layer are the same (meta ) preferably contains an acrylate compound.
  • the (meth)acrylate compound may not be polymerized even in the exposed areas after exposure from the viewpoint of adhesion between the thermoplastic resin layer and adjacent layers.
  • the (meth)acrylate compound is a polyfunctional compound having two or more (meth)acryloyl groups in one molecule, from the viewpoint of the resolution of the thermoplastic resin layer, the adhesion to the adjacent layer, and the developability.
  • (Meth)acrylate compounds are preferred.
  • a (meth)acrylate compound or a urethane (meth)acrylate compound having an acid group is also preferable.
  • a plasticizer may be used individually by 1 type, and may be used in 2 or more types.
  • the content of the plasticizer is preferably from 1 to 70% by mass with respect to the total mass of the thermoplastic resin layer, from the viewpoints of resolution of the thermoplastic resin layer, adhesion to adjacent layers, and developability. ⁇ 60% by mass is more preferable, and 20 to 50% by mass is even more preferable.
  • the thermoplastic resin layer may contain a sensitizer.
  • Sensitizers include sensitizers that can be contained in the photosensitive composition layer.
  • the sensitizers may be used alone or in combination of two or more.
  • the content of the sensitizer is preferably 0.01 to 5% by mass based on the total mass of the thermoplastic resin layer, from the viewpoint of improving sensitivity to light sources and visibility of exposed and unexposed areas. 0.05 to 1% by mass is more preferable.
  • thermoplastic resin layer may contain other additives in addition to the above components.
  • Other additives include, for example, other additives that can be contained in the photosensitive composition layer.
  • the thermoplastic resin layer may contain impurities.
  • Impurities include, for example, impurities contained in the photosensitive composition layer.
  • the thickness (layer thickness) of the thermoplastic resin layer is preferably 1 ⁇ m or more, more preferably 2 ⁇ m or more, from the viewpoint of adhesion to adjacent layers.
  • the upper limit is preferably 20 ⁇ m or less, more preferably 10 ⁇ m or less, and even more preferably 8 ⁇ m or less, from the viewpoint of developability and resolution.
  • the transfer film may have other members in addition to the above members.
  • Other members include, for example, a protective film.
  • Protective films include, for example, resin films having heat resistance and solvent resistance. Specific examples include polyolefin films such as polypropylene films and polyethylene films, polyester films such as polyethylene terephthalate films, polycarbonate films, and polystyrene films. As the protective film, a resin film made of the same material as the temporary support may be used. Among them, the protective film is preferably a polyolefin film, more preferably a polypropylene film or a polyethylene film.
  • the thickness of the protective film is preferably 1 to 100 ⁇ m, more preferably 5 to 50 ⁇ m, even more preferably 5 to 40 ⁇ m, particularly preferably 15 to 30 ⁇ m.
  • the thickness of the protective film is preferably 1 ⁇ m or more from the viewpoint of excellent mechanical strength, and preferably 100 ⁇ m or less from the viewpoint of being relatively inexpensive.
  • the number of fisheyes with a diameter of 80 ⁇ m or more contained in the protective film is preferably 5/m 2 or less.
  • the lower limit is preferably 0/m 2 or more.
  • "Fish eye” means that when a film is produced by methods such as heat melting, kneading, extrusion, biaxial stretching, casting, etc., foreign substances, undissolved substances, and oxidation-degraded substances of the material are found in the film. It means what is taken.
  • the number of particles having a diameter of 3 ⁇ m or more contained in the protective film is preferably 30 particles/mm 2 or less, more preferably 10 particles/mm 2 or less, and even more preferably 5 particles/mm 2 or less.
  • the lower limit is preferably 0/mm 2 or more. When it is within the above range, it is possible to suppress defects caused by the unevenness caused by the particles contained in the protective film being transferred to the photosensitive composition layer or the conductive layer.
  • the surface of the protective film opposite to the surface in contact with the photosensitive composition layer or the surface in contact with the surface has an arithmetic mean roughness Ra of preferably 0.01 ⁇ m or more, more preferably 0.02 ⁇ m or more. It is preferably 0.03 ⁇ m or more, and more preferably 0.03 ⁇ m or more.
  • the upper limit is preferably less than 0.50 ⁇ m, more preferably 0.40 ⁇ m or less, even more preferably 0.30 ⁇ m or less.
  • a method for producing the transfer film 10 includes, for example, a step of applying an intermediate layer forming composition to the surface of the temporary support 11 to form a coating film, and drying the coating film to form the intermediate layer 13. , applying a photosensitive composition to the surface of the intermediate layer 13 to form a coating film, and further drying the coating film to form a photosensitive composition layer 15 .
  • the thermoplastic resin layer-forming composition is applied to the surface of the temporary support 11 to form a coating film, and the coating film is dried to form a thermoplastic resin.
  • a step of forming a layer may be included.
  • the transfer film 10 is manufactured by pressure-bonding the protective film 19 onto the photosensitive composition layer 15 of the laminate manufactured by the manufacturing method described above.
  • the method for producing the transfer film includes a step of providing a protective film 19 so as to be in contact with the surface of the photosensitive composition layer 15 opposite to the temporary support 11 side, whereby the temporary support 11, the intermediate layer 13, It is preferred to manufacture transfer film 10 comprising photosensitive composition layer 15 and protective film 19 .
  • the transfer film manufacturing method includes a step of providing a protective film 19 so as to be in contact with the surface of the photosensitive composition layer 15 opposite to the temporary support 11 side, so that the temporary support 11, the thermoplastic
  • a transfer film 10 comprising a resin layer, an intermediate layer 13, a photosensitive composition layer 15 and a protective film 19.
  • FIG. A roll-shaped transfer film may be produced and stored by winding the transfer film 10 produced by the above production method.
  • the transfer film in roll form can be provided as it is in the step of laminating with a substrate in a roll-to-roll system, which will be described later.
  • thermoplastic resin layer may be formed on the substrate.
  • Photosensitive composition and method for forming photosensitive composition layer there is a coating method in which a photosensitive composition containing components contained in the photosensitive composition layer (for example, a resin, a polymerizable compound, a polymerization initiator, etc.) and a solvent is used. preferable.
  • a photosensitive composition layer for example, a photosensitive composition is applied on the intermediate layer to form a coating film, and if necessary, the coating film is subjected to a drying treatment at a predetermined temperature to expose it. A method of forming a liquid composition layer is preferred. The amount of residual solvent is adjusted by the drying treatment of the coating film.
  • the photosensitive composition preferably contains components and a solvent contained in the photosensitive composition layer.
  • the content of each component contained in the photosensitive composition layer is as described above.
  • the solvent is not particularly limited as long as it can dissolve or disperse components other than the solvent contained in the photosensitive composition layer.
  • solvents include alkylene glycol ether solvents, alkylene glycol ether acetate solvents, alcohol solvents (e.g., methanol and ethanol), ketone solvents (e.g., acetone, methyl ethyl ketone, etc.), aromatic hydrocarbon solvents (e.g., toluene, etc.).
  • aprotic polar solvents e.g., N,N-dimethylformamide, etc.
  • cyclic ether solvents e.g., tetrahydrofuran, etc.
  • ester solvents e.g., n-propyl acetate, etc.
  • amide solvents lactone solvents, and combinations thereof and mixed solvents.
  • the solvent preferably contains at least one selected from the group consisting of alkylene glycol ether solvents and alkylene glycol ether acetate solvents.
  • a mixed solvent containing at least one selected from the group consisting of alkylene glycol ether solvents and alkylene glycol ether acetate solvents and at least one selected from the group consisting of ketone solvents and cyclic ether solvents is more preferable.
  • a mixed solvent containing at least one selected from the group consisting of an ether solvent and an alkylene glycol ether acetate solvent, a ketone solvent, and a cyclic ether solvent is more preferable.
  • Alkylene glycol ether solvents include, for example, ethylene glycol monoalkyl ether, ethylene glycol dialkyl ether, propylene glycol monoalkyl ether (eg, propylene glycol monomethyl ether acetate), propylene glycol dialkyl ether, diethylene glycol dialkyl ether, dipropylene glycol monoalkyl. Ethers and dipropylene glycol dialkyl ethers.
  • Alkylene glycol ether acetate solvents include, for example, ethylene glycol monoalkyl ether acetate, propylene glycol monoalkyl ether acetate, diethylene glycol monoalkyl ether acetate and dipropylene glycol monoalkyl ether acetate. Examples of the solvent include the solvents described in paragraphs [0092] to [0094] of International Publication No. 2018/179640 and the solvents described in paragraph [0014] of JP-A-2018-177889. the contents of which are incorporated herein.
  • a solvent may be used individually by 1 type, and may be used in 2 or more types.
  • the content of the solvent is preferably 50 to 1,900 parts by mass, more preferably 100 to 1,200 parts by mass, and even more preferably 100 to 900 parts by mass, based on 100 parts by mass of the total solid content of the photosensitive composition.
  • Examples of the coating method of the photosensitive composition include known coating methods. Specific examples include a printing method, a spray method, a roll coating method, a bar coating method, a curtain coating method, a spin coating method and a die coating method (slit coating method).
  • Heat drying or reduced pressure drying is preferable as a method for drying the coating film of the photosensitive composition.
  • the drying temperature is preferably 90° C. or higher, more preferably 100° C. or higher, and even more preferably 110° C. or higher.
  • the upper limit is preferably 130°C or lower, more preferably 120°C or lower.
  • a drying method a method of continuously changing the drying temperature may be used.
  • 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 preferably 600 seconds or less, more preferably 450 seconds or less, and even more preferably 300 seconds or less.
  • a transfer film may be produced by laminating a protective film to the photosensitive composition layer.
  • Examples of the method for bonding the protective film to the photosensitive composition layer include known methods.
  • Examples of the apparatus for laminating the protective film to the photosensitive composition layer include known laminators such as a vacuum laminator and an autocut laminator. As the laminator, it is preferable to have a heatable roller such as a rubber roller and to apply pressure and heat.
  • composition for Intermediate Layer Formation and Method for Forming Intermediate Layer As a method for forming the intermediate layer, a coating method in which a composition for forming an intermediate layer containing components contained in the intermediate layer (for example, a water-soluble resin, etc.) and a solvent is used for coating is preferable.
  • a method for forming the intermediate layer for example, the composition for forming an intermediate layer is applied onto a temporary support to form a coating film, and if necessary, the coating film is dried at a predetermined temperature to form an intermediate layer. A method of forming layers is preferred. The amount of residual solvent is adjusted by the drying treatment of the coating film.
  • the composition for forming the intermediate layer contains the components contained in the intermediate layer and the solvent.
  • the contents of the components contained in the intermediate layer are as described above.
  • the solvent is not particularly limited as long as it can dissolve or disperse the components contained in the intermediate layer.
  • the solvent is preferably at least one selected from the group consisting of water and water-miscible organic solvents, more preferably water or a mixed solvent of water and water-miscible organic solvents.
  • water-miscible organic solvents include alcohols having 1 to 3 carbon atoms, acetone, ethylene glycol, glycerin, and mixed solvents of these, preferably alcohols having 1 to 3 carbon atoms, and methanol or ethanol. more preferred.
  • a solvent may be used individually by 1 type, and may be used in 2 or more types.
  • the content of the solvent is preferably 50 to 2,500 parts by mass, more preferably 50 to 1,900 parts by mass, and even more preferably 100 to 900 parts by mass, based on 100 parts by mass of the total solid content of the intermediate layer-forming composition.
  • Examples of methods for forming the intermediate layer include known coating methods. Specific examples include slit coating, spin coating, curtain coating and inkjet coating.
  • Heat drying or reduced pressure drying is preferable as a method for drying the coating film of the intermediate layer forming composition.
  • the drying temperature is preferably 90° C. or higher, more preferably 100° C. or higher, and even more preferably 110° C. or higher.
  • the upper limit is preferably 130°C or lower, more preferably 120°C or lower.
  • a drying method a method of continuously changing the drying temperature may be used.
  • 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 preferably 600 seconds or less, more preferably 450 seconds or less, and even more preferably 300 seconds or less.
  • thermoplastic resin layer a coating method in which a thermoplastic resin layer-forming composition containing a component contained in the thermoplastic resin layer (for example, a thermoplastic resin, etc.) and a solvent is used for coating is preferred.
  • a method for forming a thermoplastic resin layer for example, the composition for forming an intermediate layer is applied onto a temporary support to form a coating film, and if necessary, the coating film is subjected to a drying treatment at a predetermined temperature.
  • a method of forming a thermoplastic resin layer by means of The amount of residual solvent is adjusted by the drying treatment of the coating film.
  • the composition for forming a thermoplastic resin layer preferably contains the components contained in the thermoplastic resin layer and a solvent.
  • the contents of the components contained in the thermoplastic resin layer are as described above.
  • the solvent is not particularly limited as long as it can dissolve or disperse the components contained in the thermoplastic resin layer.
  • the solvent is synonymous with the solvent contained in the photosensitive composition described above, and the preferred embodiments are also the same.
  • a solvent may be used individually by 1 type, and may be used in 2 or more types.
  • the content of the solvent is preferably 50 to 1,900 parts by mass, more preferably 100 to 900 parts by mass, based on 100 parts by mass of the total solid content of the composition for forming a thermoplastic resin layer.
  • thermoplastic resin layer examples include known coating methods. Specific examples include slit coating, spin coating, curtain coating and inkjet coating.
  • the drying temperature is preferably 90° C. or higher, more preferably 100° C. or higher, and even more preferably 110° C. or higher.
  • the upper limit is preferably 130°C or lower, more preferably 120°C or lower.
  • a method of continuously changing the drying temperature may be used.
  • 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 preferably 600 seconds or less, more preferably 450 seconds or less, and even more preferably 300 seconds or less.
  • the present invention will be described in more detail based on examples below.
  • the materials, amounts used, ratios, processing details, processing procedures, etc. shown in the following examples can be changed as appropriate without departing from the gist of the present invention. Therefore, the scope of the present invention should not be construed to be limited by the examples shown below.
  • Parts and “%” are based on mass unless otherwise specified.
  • the weight average molecular weight of the resin is the weight average molecular weight (Mw) obtained in terms of polystyrene by gel permeation chromatography (GPC). Also, the glass transition temperature was measured by the method described above.
  • V-601 (1.0 parts by mass) was added three times at intervals of one hour. After that, the reaction was further continued for 3 hours. Then, it was diluted with propylene glycol monomethyl ether acetate (60 parts by mass) and propylene glycol monomethyl ether (12 parts by mass). The temperature of the reaction solution was raised to 100° C. under an air stream, and tetraethylammonium bromide (0.7 parts by mass) and p-methoxyphenol (0.3 parts by mass) were added. Glycidyl methacrylate (Blenmer G manufactured by NOF Corporation) (32 parts by mass) was added dropwise over 20 minutes. This was reacted at 100° C. for 7 hours to obtain a solution containing resin A1. The solid content concentration of the obtained solution was 30.0% by mass. A solution containing any one of resins A2 to A4 was obtained with reference to the method for synthesizing resin A1. The solid content concentration of each obtained solution was 30.0% by mass.
  • Resins A1 to A6 are shown below.
  • GMA-MMA Structural units other than GMA-MMA represent monomers for forming each structural unit.
  • GMA-MAA indicates a structural unit in which glycidyl methacrylate is added to a structural unit derived from methacrylic acid.
  • Resins A1 to A6 correspond to alkali-soluble resins.
  • MAA methacrylic acid (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) St: Styrene (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.)
  • MMA Methyl methacrylate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.)
  • BzMA benzyl methacrylate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.)
  • GMA-MMA Structural unit in which glycidyl methacrylate is added to a structural unit derived from methacrylic acid
  • IBMA Isobornyl methacrylate (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.)
  • "A" in the "polymerizable group” column indicates that the resin has a polymerizable group.
  • Each photosensitive composition was prepared with the components and formulations shown in Table 2 below.
  • Table 2 the numerical value described in each component column represents the content (parts by mass) of each component.
  • the content shown in the table is the content of the resin itself, not the amount of the solution containing each resin added.
  • Resins A1 to A6 are as described above.
  • B1 BPE-900 (ethoxylated bisphenol A dimethacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd.)
  • B2 BPE-500 (ethoxylated bisphenol A dimethacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd.)
  • B3 BPE-100 (ethoxylated bisphenol A dimethacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd.)
  • B4 Aronix M-270 (polypropylene glycol diacrylate, manufactured by Toagosei Co., Ltd.)
  • B5 A-NOD-N (1,9-nonanediol diacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd.)
  • B6 A-DOD-N (1,10-decanediol diacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd.)
  • the properties of the polymerizable compounds are shown in the table below.
  • B-CIM 2,2′-bis(2-chlorophenyl)-4,4′,5,5′-tetraphenylbisimidazole (2-(2-chlorophenyl)-4,5-diphenylimidazole dimer) ( manufactured by Hampford)
  • SB-PI 701 4,4'-bis (diethylamino) benzophenone (manufactured by Sanyo Trading Co., Ltd.)
  • N-phenylcarbamoylmethyl-N-carboxymethylaniline manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.
  • TDP-G Phenothiazine (manufactured by Kawaguchi Chemical Industry Co., Ltd.)
  • CBT-1 Carboxybenzotriazole (manufactured by Johoku Chemical Industry Co., Ltd.) 4-hydroxymethyl-4-methyl-1-phenyl-3-pyrazolidone (manufactured by Fujifilm Wako Pure Chemical Industries) Megafac F-552 (manufactured by DIC)
  • PGMEA propylene glycol monomethyl ether acetate (manufactured by Showa Denko)
  • MEK methyl ethyl ketone (manufactured by Sankyo Chemical Co., Ltd.)
  • MFG propylene glycol monomethyl ether (manufactured by Nippon Emulsifier Co., Ltd.)
  • MeOH methanol (manufactured by Mitsubishi Gas Chemical Company)
  • An intermediate layer-forming composition 1 was prepared using the following components. Various components of the intermediate layer forming composition 1 are shown below.
  • PVA polyvinyl alcohol
  • PVP polypyrrolidone
  • HPMC hydroxypropyl methylcellulose
  • Product name "Metolose 60SH-03” manufactured by Shin-Etsu Chemical Co., Ltd.
  • a solvent solvent: ion-exchanged water and methanol (manufactured by Mitsubishi Gas Chemical Company) and was mixed so that the mixing ratio (mass ratio) was 40/60) to prepare an intermediate layer-forming composition 1.
  • a temporary support (16 ⁇ m thick polyethylene terephthalate film (registered trademark Lumirror 16KS40, manufactured by Toray Industries, Inc.)
  • Polyethylene terephthalate (Registered Trademark Lumirror 16KS40, manufactured by Toray Industries, Inc.) having a thickness of 16 ⁇ m was press-bonded onto the resulting negative photosensitive composition layer to prepare transfer films of Examples 1 to 11 and Comparative Examples 1 and 2.
  • Each transfer film composed of a temporary support, an intermediate layer and a photosensitive composition layer was produced so as to have the structure shown in Table 4. Specifically, it is as follows. First, on a temporary support (16 ⁇ m thick polyethylene terephthalate film (registered trademark Lumirror 16KS40, manufactured by Toray Industries, Inc.)), intermediate layer forming composition 1 for forming the intermediate layer was applied using a bar coater. It was applied so that the thickness after drying was 1.0 ⁇ m, and dried at 90° C. using an oven to form an intermediate layer.
  • a temporary support (16 ⁇ m thick polyethylene terephthalate film (registered trademark Lumirror 16KS40, manufactured by Toray Industries, Inc.)
  • intermediate layer forming composition 1 for forming the intermediate layer was applied using a bar coater. It was applied so that the thickness after drying was 1.0 ⁇ m, and dried at 90° C. using an oven to form an intermediate layer.
  • a photosensitive composition for forming a photosensitive composition layer shown in Table 4 was applied using a bar coater so that the thickness after drying was 3 ⁇ m, and was dried using an oven. It was dried at 80° C. to form a negative photosensitive composition layer.
  • Polyethylene terephthalate registered trademark 16KS40, manufactured by Toray Industries, Inc.
  • 16KS40 manufactured by Toray Industries, Inc.
  • ⁇ Pattern shape (flat bottom shape)> The protective film of the transfer film prepared above is peeled off, and the surface of the photosensitive composition layer opposite to the temporary support side is Ni-plated on glass (thickness 100 nm) on a substrate having a conductive layer, A laminate was obtained by lamination (laminating conditions: substrate temperature 80° C., rubber roller temperature 110° C., linear pressure 3 N/cm, conveying speed 2 m/min). Next, the temporary support is peeled off from the obtained laminate, and a photomask having a pattern with a line ( ⁇ m)/space ( ⁇ m) ratio of 1/1 is applied to the photosensitive composition layer in the obtained laminate. It was brought into close contact with the surface on the side opposite to the substrate side.
  • the photosensitive composition layer was exposed at 100 mJ/cm 2 by irradiating light using a high-pressure mercury lamp exposure machine (MAP-1200L, manufactured by Dainippon Kaken Co., Ltd., main wavelength: 365 nm). Thereafter, a pattern was formed by performing shower development for 30 seconds using an aqueous sodium carbonate solution having a liquid temperature of 25°C. The cross-sectional shape of the obtained pattern was observed with a scanning electron microscope. The pattern shape was evaluated according to the following evaluation criteria using the length as the tail length and using the longest tail length.
  • MAP-1200L manufactured by Dainippon Kaken Co., Ltd., main wavelength: 365 nm
  • the tail length is less than 0.20 ⁇ m
  • B The tail length is 0.20 ⁇ m or more and less than 0.30 ⁇ m
  • C The tail length is 0.30 ⁇ m or more and 0.40 ⁇ m or less
  • D The tail length is more than 0.40 ⁇ m
  • Table 4 shows the evaluation results. In Table 4, each description shows the following. If the "polymerizable group” column is “A”, the resin has a polymerizable group, and the content of the structural unit having a polymerizable group is 20.0% by mass with respect to the total mass of the resin. Indicates that In the case of "B”, the resin has a polymerizable group, and the content of the structural unit having a polymerizable group is more than 0% by mass and less than 20.0% by mass with respect to the total mass of the resin. indicate. "C” indicates that the resin does not have polymerizability.
  • the column "content of polymerizable group is 2.4 mmol/g or more" is "A"
  • “B” indicates that the content of the polymerizable group in the polymerizable compound is less than 2.4 mmol/g.
  • “A” is given only when all the polymerizable compounds are 2.4 mmol/g or more.
  • the "ethyleneoxy group” column is "A”, it indicates that the polymerizable compound has an ethyleneoxy group.
  • “B” indicates that the polymerizable compound does not have an ethyleneoxy group.
  • “A” is used only when all polymerizable compounds have an ethyleneoxy group.
  • the "TgY-TgX” column shows the value obtained by subtracting the TgX value (°C) from the TgY value (°C).
  • the “m/b” column shows the mass ratio of the polymerizable compound content to the resin content (polymerizable compound content/resin content). If the "intermediate layer” column is "A”, it indicates that the transfer film has an intermediate layer between the temporary support and the photosensitive composition layer. A “B” indicates that the transfer film does not have an intermediate layer between the temporary support and the photosensitive composition layer.
  • a PET substrate with a copper layer was obtained by forming a copper layer with a thickness of 500 nm on a PET film (polyethylene terephthalate film) with a thickness of 50 ⁇ m by a sputtering method.
  • the transfer film 1 prepared above was cut into 10 cm squares, the protective film was peeled off, and the exposed photosensitive composition layer was in contact with the copper layer on the surface of the PET substrate with the copper layer, and the roll temperature was 90 ° C. and the linear pressure was 0.
  • the transfer film 1 from which the protective film was removed was laminated on a PET substrate with a copper layer under lamination conditions of 8 MPa and a linear velocity of 3.0 m/min to obtain a laminate.
  • the laminate has each configuration in the order of "PET film--copper layer--photosensitive composition layer--intermediate layer--temporary support".
  • the temporary support was peeled off from the obtained laminate to expose the intermediate layer.
  • Line ( ⁇ m)/space ( ⁇ m) of 1/1, 2/2, 3/3, 4/4, 5/5, 6/6, 7/7, 8/8, 9/9 and 10/10 A photomask having any pattern on the entire surface was brought into close contact with the intermediate layer exposed on the surface.
  • the laminate has each configuration in the order of "PET film--copper layer--photosensitive composition layer--intermediate layer--photomask".
  • the resulting laminate was irradiated with light from the photomask side using a high-pressure mercury lamp exposure machine (MA-1200A, manufactured by Dainippon Kaken Co., Ltd., dominant wavelength: 365 nm, degree of vacuum during exposure: -50 kPa).
  • the amount of exposure was such that the resist pattern obtained after development reproduces the line-and-space shape of the photomask.
  • Example 101 the variation in line width was evaluated in the same manner as in Example 101, except that the exposure method of the laminate was changed as follows.
  • a laminate having each configuration in the order of "cushion material--PET film--copper layer--photosensitive composition layer--intermediate layer--temporary support" was prepared by referring to the procedure for preparing the pattern shape evaluation sample.
  • the temporary support was peeled off from the obtained laminate to expose the intermediate layer.
  • a photomask with either pattern over the entire surface was in intimate contact with the exposed intermediate layer.
  • the laminate has each configuration in the order of "cushion material--PET film--copper layer--photosensitive composition layer--intermediate layer--photomask". Then, light was irradiated from the photomask side using a high-pressure mercury lamp exposure machine (MA-1200A, manufactured by Dainippon Kaken Co., Ltd., dominant wavelength: 365 nm, degree of vacuum during exposure: -50 kPa).
  • MA-1200A manufactured by Dainippon Kaken Co., Ltd., dominant wavelength: 365 nm, degree of vacuum during exposure: -50 kPa
  • ⁇ Cushion material> ⁇ Cushion material 1: Silicon rubber sheet (thickness 1 mm) ⁇ Cushion material 2: Silicon rubber sheet (thickness 1 mm) ⁇ Cushion material 3: Urethane rubber sheet (thickness 1 mm) The hardness of each cushioning material indicates type A durometer hardness.
  • Table 5 shows the evaluation results.

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Abstract

The present invention provides a method for manufacturing a laminate including a pattern having an excellent pattern shape, and a method for manufacturing circuit wiring. This method for manufacturing a laminate comprises: a bonding step for bringing a surface of a photosensitive composition layer of a transfer film having a temporary support and the photosensitive composition layer, the surface being on the opposite side to the temporary support side, into contact with a substrate, and bonding the transfer film and the substrate; an exposure step for subjecting the photosensitive composition layer to pattern exposure; and a developing step for developing the exposed photosensitive composition layer using a developer and forming a pattern. A glass-transition temperature X of the photosensitive composition layer is 110°C or lower, and a glass-transition temperature Y obtained by measurement Y is 125°C or higher.

Description

積層体の製造方法、回路配線の製造方法Laminate manufacturing method, circuit wiring manufacturing method
　本発明は、積層体の製造方法及び回路配線の製造方法に関する。 The present invention relates to a laminate manufacturing method and a circuit wiring manufacturing method.
　所定のパターンを得るための工程数が少ないことから、転写フィルムを用いて任意の基板上に感光性組成物層を配置して、この感光性組成物層に対してフォトマスクを介して露光した後に現像する方法が広く使用されている。 Since the number of steps for obtaining a predetermined pattern is small, a photosensitive composition layer was placed on an arbitrary substrate using a transfer film, and the photosensitive composition layer was exposed through a photomask. Post-development methods are widely used.
　例えば、特許文献１では、仮支持体、熱可塑性樹脂層、中間層、及び、ネガ型感光性層をこの順に有する感光性転写材料が開示されている。 For example, Patent Document 1 discloses a photosensitive transfer material having a temporary support, a thermoplastic resin layer, an intermediate layer, and a negative photosensitive layer in this order.
国際公開第２０２０／２０３５０２号WO2020/203502
　本発明者らは、特許文献１に記載のような従来の転写フィルム等を用いる積層体の製造方法について検討したところ、得られるパターンの形状が不良になりやすいことを知見した。具体的には、転写フィルムを被転写体に貼り合わせ、パターン露光して、更に、現像して所望のパターンを得る。得られるパターンの断面形状を観察した際に、パターン形状が、基板側の反対側から基板側に近づくにつれて、パターンの幅が広がるような裾広がり形状になりやすいことを知見した。つまり、裾広がり形状とは、得られるパターン形状において、下底（基板側）の長さが上底（基板とは反対側）の長さよりも長いパターン形状をいう。より具体的には、図１に示すように、基板１上に配置されたパターン２において、破線部分に示すような裾広がり部分３が生じる問題があった。
　以下、得られるパターンが裾広がり形状になりにくいことを、パターン形状に優れるともいう。 The inventors of the present invention have studied a laminate manufacturing method using a conventional transfer film or the like as described in Patent Document 1, and have found that the shape of the resulting pattern tends to be defective. Specifically, the transfer film is attached to the object to be transferred, pattern-exposed, and developed to obtain a desired pattern. When observing the cross-sectional shape of the obtained pattern, it was found that the pattern shape tended to widen at the bottom as the width of the pattern increased as it approached the substrate side from the side opposite to the substrate side. In other words, the flared bottom shape means a pattern shape in which the length of the lower base (on the side of the substrate) is longer than the length of the upper base (on the side opposite to the substrate) in the resulting pattern shape. More specifically, as shown in FIG. 1, in the pattern 2 arranged on the substrate 1, there is a problem that the widening portion 3 as indicated by the dashed line occurs.
Hereinafter, the fact that the obtained pattern is less likely to have a flared bottom shape is also referred to as being excellent in pattern shape.
　そこで、本発明は、パターン形状に優れる、パターンを含む積層体の製造方法を提供することを課題とする。また、本発明は、回路配線の製造方法を提供することも課題とする。 Therefore, an object of the present invention is to provide a method for manufacturing a laminate including a pattern, which is excellent in pattern shape. Another object of the present invention is to provide a method for manufacturing circuit wiring.
　本発明者らは、上記課題について鋭意検討した結果、以下の構成により上記課題を解決できることを見出した。 As a result of earnestly examining the above problem, the inventors found that the above problem can be solved by the following configuration.
　〔１〕
　仮支持体と、感光性組成物層とを有する転写フィルムの上記感光性組成物層の上記仮支持体側とは反対側の表面を基板に接触させ、上記転写フィルムと上記基板とを貼合する貼合工程と、
　上記感光性組成物層をパターン露光する露光工程と、
　露光された上記感光性組成物層を、現像液を用いて現像してパターンを形成する現像工程とを有し、
　上記感光性組成物層のガラス転移温度Ｘが１１０℃以下であり、測定Ｙで求められるガラス転移温度Ｙが１２５℃以上である、積層体の製造方法。
　測定Ｙ：上記転写フィルムの上記感光性組成物層の上記仮支持体側とは反対側の表面を上記基板に接触させ、上記転写フィルムと上記基板とを貼り合わせて、得られた積層体から上記仮支持体を剥離して、上記仮支持体が剥離された積層体中の上記感光性組成物層を上記露光工程と同様の露光条件にて全面露光して、その後、得られた硬化膜のガラス転移温度を測定し、ガラス転移温度Ｙとする。
　〔２〕
　上記ガラス転移温度Ｘと上記ガラス転移温度Ｙとの差が、３５～５０℃である、〔１〕に記載の積層体の製造方法。
　〔３〕
　上記感光性組成物層が、樹脂及び重合性化合物を含む、〔１〕又は〔２〕に記載の積層体の製造方法。
　〔４〕
　上記樹脂のガラス転移温度が、７０～１１５℃である、〔３〕に記載の積層体の製造方法。
　〔５〕
　上記樹脂が、重合性基を有する、〔３〕又は〔４〕に記載の積層体の製造方法。
　〔６〕
　上記重合性化合物中の重合性基の含有量が、２．４ｍｍｏｌ／ｇ以上である、〔３〕～〔５〕のいずれか１つに記載の積層体の製造方法。
　〔７〕
　上記重合性化合物が、エチレンオキシ基を有する、〔３〕～〔６〕のいずれか１つに記載の積層体の製造方法。
　〔８〕
　上記感光性組成物層が、３種以上の重合性化合物を含む、〔３〕～〔７〕のいずれか１つに記載の積層体の製造方法。
　〔９〕
　上記樹脂の含有量に対する上記重合性化合物の含有量の質量比が、０．７０～１．１０である、〔３〕～〔８〕のいずれか１つに記載の積層体の製造方法。
　〔１０〕
　上記転写フィルムが、更に、上記仮支持体と上記感光性組成物層との間に中間層を有する、〔１〕～〔９〕のいずれか１つに記載の積層体の製造方法。
　〔１１〕
　上記中間層が、水溶性樹脂を含む、〔１０〕に記載の積層体の製造方法。
　〔１２〕
　上記中間層が、水溶性セルロース誘導体、多価アルコール類、多価アルコール類のオキサイド付加物、ポリエーテル系樹脂、フェノール誘導体及びアミド化合物からなる群から選択される少なくとも１つを含む、〔１０〕又は〔１１〕に記載の積層体の製造方法。
　〔１３〕
　上記貼合工程と上記露光工程との間に、上記転写フィルムと上記基板との積層体から上記仮支持体を剥離する剥離工程を更に有し、
　上記露光工程が、フォトマスクを介して、上記剥離工程にて得られた仮支持体が剥離された上記積層体の上記感光性組成物層をパターン露光する露光工程である、〔１〕～〔１２〕のいずれか１つに記載の積層体の製造方法。
　〔１４〕
　上記貼合工程と上記露光工程との間に、上記転写フィルムと上記基板との積層体から上記仮支持体を剥離する剥離工程を更に有し、
　上記露光工程が、上記剥離工程にて得られた仮支持体が剥離された上記積層体の上記基板側とは反対側の表面とフォトマスクとを接触させて、上記感光性組成物層にパターン露光する露光工程である、〔１〕～〔１２〕のいずれか１つに記載の積層体の製造方法。
　〔１５〕
　上記露光工程と上記現像工程との間に、上記転写フィルムと上記基板との積層体から上記仮支持体を剥離する剥離工程を更に有し、
　上記露光工程が、フォトマスクを介して、上記積層体の上記感光性組成物層をパターン露光する露光工程である、〔１〕～〔１２〕のいずれか１つに記載の積層体の製造方法。
　〔１６〕
　上記フォトマスクが、メッシュ状に配置された遮光部を含む、〔１３〕～〔１５〕のいずれか１つに記載の積層体の製造方法。
　〔１７〕
　上記フォトマスクが、円形ドット状に配置された遮光部を含む、〔１３〕～〔１５〕のいずれか１つに記載の積層体の製造方法。
　〔１８〕
　上記フォトマスクが、円形ドット状に配置された開口部を含む、〔１３〕～〔１５〕のいずれか１つに記載の積層体の製造方法。
　〔１９〕
　基板上にシード層を形成して、シード層付き基板を形成するシード層形成工程と、
　感光性組成物層の仮支持体側とは反対側の表面を上記シード層付き基板の上記シード層と接触させ、転写フィルムと上記シード層付き基板とを貼合して、上記基板、上記シード層、上記感光性組成物層及び上記仮支持体をこの順に有する感光性組成物層付き基板を得る貼合工程と、
　上記感光性組成物層付き基板から上記仮支持体を剥離する剥離工程と、
　上記仮支持体が剥離された感光性組成物層付き基板の上記基板側とは反対側の表面とフォトマスクとを接触させて、上記感光性組成物層をパターン露光する露光工程と、
　露光された上記感光性組成物層を、現像液を用いて現像してパターンを形成する現像工程と、
　上記パターンが配置されていない領域にある上記シード層上に、めっき処理によって金属めっき層を形成する金属めっき層形成工程と、
　上記金属めっき層上に保護層を形成する保護層形成工程と、
　上記パターンを除去する除去工程と、
　露出した上記シード層を除去して、導電性細線を得るシード層除去工程と、を有し、
　上記感光性組成物層のガラス転移温度Ｘが１１０℃以下であり、測定Ｙで求められるガラス転移温度Ｙが１２５℃以上である、回路配線の製造方法。
　測定Ｙ：上記転写フィルムの上記感光性組成物層の上記仮支持体側とは反対側の表面を上記基板に接触させ、上記転写フィルムと上記基板とを貼り合わせて、得られた積層体から上記仮支持体を剥離して、上記仮支持体が剥離された積層体中の上記感光性組成物層を上記露光工程と同様の露光条件にて全面露光して、その後、得られた硬化膜のガラス転移温度を測定し、ガラス転移温度Ｙとする。 [1]
The surface of the photosensitive composition layer of the transfer film having the temporary support and the photosensitive composition layer on the side opposite to the temporary support is brought into contact with the substrate, and the transfer film and the substrate are bonded together. a lamination process;
An exposure step of pattern-exposing the photosensitive composition layer;
and a developing step of developing the exposed photosensitive composition layer with a developer to form a pattern,
A method for producing a laminate, wherein the photosensitive composition layer has a glass transition temperature X of 110° C. or lower, and a glass transition temperature Y obtained by measurement Y of 125° C. or higher.
Measurement Y: The surface of the photosensitive composition layer of the transfer film opposite to the temporary support side is brought into contact with the substrate, the transfer film and the substrate are bonded together, and the obtained laminate is The temporary support is peeled off, and the entire surface of the photosensitive composition layer in the laminate from which the temporary support is peeled off is exposed under the same exposure conditions as in the exposure step, and then the resulting cured film. The glass transition temperature is measured and defined as the glass transition temperature Y.
[2]
The method for producing a laminate according to [1], wherein the difference between the glass transition temperature X and the glass transition temperature Y is 35 to 50°C.
[3]
The method for producing a laminate according to [1] or [2], wherein the photosensitive composition layer contains a resin and a polymerizable compound.
[4]
The method for producing a laminate according to [3], wherein the resin has a glass transition temperature of 70 to 115°C.
[5]
The method for producing a laminate according to [3] or [4], wherein the resin has a polymerizable group.
[6]
The method for producing a laminate according to any one of [3] to [5], wherein the content of polymerizable groups in the polymerizable compound is 2.4 mmol/g or more.
[7]
The method for producing a laminate according to any one of [3] to [6], wherein the polymerizable compound has an ethyleneoxy group.
[8]
The method for producing a laminate according to any one of [3] to [7], wherein the photosensitive composition layer contains three or more polymerizable compounds.
[9]
The method for producing a laminate according to any one of [3] to [8], wherein the mass ratio of the content of the polymerizable compound to the content of the resin is 0.70 to 1.10.
[10]
The method for producing a laminate according to any one of [1] to [9], wherein the transfer film further has an intermediate layer between the temporary support and the photosensitive composition layer.
[11]
The method for producing a laminate according to [10], wherein the intermediate layer contains a water-soluble resin.
[12]
The intermediate layer contains at least one selected from the group consisting of water-soluble cellulose derivatives, polyhydric alcohols, oxide adducts of polyhydric alcohols, polyether resins, phenol derivatives and amide compounds [10] Or the manufacturing method of the laminated body as described in [11].
[13]
between the bonding step and the exposure step, further comprising a peeling step of peeling the temporary support from the laminate of the transfer film and the substrate;
The exposure step is an exposure step of pattern-exposing the photosensitive composition layer of the laminate from which the temporary support obtained in the peeling step is peeled through a photomask, [1] to [ 12].
[14]
between the bonding step and the exposure step, further comprising a peeling step of peeling the temporary support from the laminate of the transfer film and the substrate;
In the exposure step, the surface of the laminate from which the temporary support obtained in the peeling step is peeled off is brought into contact with a photomask on the side opposite to the substrate side, and the photosensitive composition layer is patterned. The method for producing a laminate according to any one of [1] to [12], which is an exposure step of exposing.
[15]
between the exposure step and the development step, further comprising a peeling step of peeling the temporary support from the laminate of the transfer film and the substrate;
The method for producing a laminate according to any one of [1] to [12], wherein the exposure step is an exposure step of pattern-exposing the photosensitive composition layer of the laminate through a photomask. .
[16]
The method for producing a laminate according to any one of [13] to [15], wherein the photomask includes a light shielding portion arranged in a mesh pattern.
[17]
The method for producing a laminate according to any one of [13] to [15], wherein the photomask includes light shielding portions arranged in circular dots.
[18]
The method for producing a laminate according to any one of [13] to [15], wherein the photomask includes openings arranged in circular dots.
[19]
a seed layer forming step of forming a seed layer on a substrate to form a substrate with a seed layer;
The surface of the photosensitive composition layer opposite to the temporary support side is brought into contact with the seed layer of the substrate with the seed layer, and the transfer film and the substrate with the seed layer are bonded to form the substrate and the seed layer. , a bonding step of obtaining a substrate with a photosensitive composition layer having the photosensitive composition layer and the temporary support in this order;
A peeling step of peeling the temporary support from the substrate with the photosensitive composition layer;
An exposure step of pattern-exposing the photosensitive composition layer by bringing the surface of the substrate with the photosensitive composition layer from which the temporary support has been removed on the side opposite to the substrate side into contact with a photomask,
a developing step of developing the exposed photosensitive composition layer with a developer to form a pattern;
a metal plating layer forming step of forming a metal plating layer by plating on the seed layer in the region where the pattern is not arranged;
a protective layer forming step of forming a protective layer on the metal plating layer;
a removing step of removing the pattern;
a seed layer removing step of removing the exposed seed layer to obtain a conductive thin line;
A method for producing circuit wiring, wherein the photosensitive composition layer has a glass transition temperature X of 110° C. or lower, and a glass transition temperature Y determined by measurement Y of 125° C. or higher.
Measurement Y: The surface of the photosensitive composition layer of the transfer film opposite to the temporary support side is brought into contact with the substrate, the transfer film and the substrate are bonded together, and the obtained laminate is The temporary support is peeled off, and the entire surface of the photosensitive composition layer in the laminate from which the temporary support is peeled off is exposed under the same exposure conditions as in the exposure step, and then the resulting cured film. The glass transition temperature is measured and defined as the glass transition temperature Y.
　本発明によれば、パターン形状に優れる、パターンを含む積層体の製造方法を提供できる。また、本発明によれば、回路配線の製造方法も提供できる。 According to the present invention, it is possible to provide a method for manufacturing a laminate including a pattern, which is excellent in pattern shape. Further, according to the present invention, a method for manufacturing circuit wiring can also be provided.
裾広がり形状の一例を示す概略図である。It is the schematic which shows an example of a bottom-spreading shape. 転写フィルムの構成の一例を示す概略図である。It is the schematic which shows an example of a structure of a transfer film. 線幅のばらつきの評価方法を示す概略図である。FIG. 4 is a schematic diagram showing a method for evaluating line width variation;
　以下、本発明について詳細に説明する。
　本明細書における以下の各表記の意味を示す。
　「～」を用いて表される数値範囲は、「～」の前後に記載される数値を下限及び上限として含む範囲を意味する。
　段階的に記載されている数値範囲において、ある数値範囲で記載された上限又は下限は、他の段階的な記載の数値範囲の上限又は下限に置き換えてもよい。また、本明細書に記載されている数値範囲において、ある数値範囲で記載された上限又は下限は、実施例に示されている値に置き換えてもよい。
　「工程」とは、独立した工程だけではなく、他の工程と明確に区別できない場合であっても、その工程の所期の目的が達成されれば本用語に含まれる。
　「透明」とは、特段の断りがない限り、波長４００～７００ｎｍの可視光の平均透過率が、８０％以上であることを意味し、９０％以上であることが好ましい。
　可視光の平均透過率は、分光光度計を用いて測定される値であり、例えば、日立製作所社製の分光光度計Ｕ－３３１０を用いて測定できる。
　屈折率は、特段の断りがない限り、波長５５０ｎｍでエリプソメーターを用いて測定した値である。
　色相は、特段の断りがない限り、色差計（ＣＲ－２２１、ミノルタ社製）を用いて測定した値である。 The present invention will be described in detail below.
The meaning of each notation below in this specification is shown.
A numerical range represented using "to" means a range including the numerical values described before and after "to" as lower and upper limits.
In the numerical ranges described stepwise, the upper limit or lower limit described in a certain numerical range may be replaced with the upper limit or lower limit of another numerical range described stepwise. Moreover, in the numerical ranges described in this specification, the upper or lower limits described in a certain numerical range may be replaced with the values shown in the examples.
The term "process" includes not only an independent process, but also a process that is indistinguishable from other processes, as long as the intended purpose of the process is achieved.
“Transparent” means that the average transmittance of visible light with a wavelength of 400 to 700 nm is 80% or more, preferably 90% or more, unless otherwise specified.
The average transmittance of visible light is a value measured using a spectrophotometer, and can be measured using, for example, a spectrophotometer U-3310 manufactured by Hitachi, Ltd.
A refractive index is a value measured using an ellipsometer at a wavelength of 550 nm unless otherwise specified.
The hue is a value measured using a color difference meter (CR-221, manufactured by Minolta) unless otherwise specified.
　重量平均分子量（Ｍｗ）及び数平均分子量（Ｍｎ）は、特段の断りがない限り、カラムとして、ＴＳＫｇｅｌ　ＧＭＨｘＬ、ＴＳＫｇｅｌ　Ｇ４０００ＨｘＬ、ＴＳＫｇｅｌ　Ｇ２０００ＨｘＬ（いずれも東ソー社製の商品名）、溶離液としてＴＨＦ（テトラヒドロフラン）、検出器として示差屈折計及び標準物質としてポリスチレンを使用し、ゲルパーミエーションクロマトグラフィ（ＧＰＣ）分析装置により測定した標準物質のポリスチレンを用いて換算した値である。
　分子量分布がある化合物の分子量は、特段の断りがない限り、重量平均分子量（Ｍｗ）である。
　金属元素の含有量は、特段の断りがない限り、誘導結合プラズマ（ＩＣＰ：Ｉｎｄｕｃｔｉｖｅｌｙ　Ｃｏｕｐｌｅｄ　Ｐｌａｓｍａ）分光分析装置を用いて測定した値である。
　「（メタ）アクリル」とは、アクリル及びメタクリルの両方を包含する概念であり、「（メタ）アクリロキシ基」とは、アクリロキシ基及びメタアクリロキシ基の両方を包含する概念である。
　「アルカリ可溶性」とは、２２℃において炭酸ナトリウムの１質量％水溶液１００ｇへの溶解度が０．１ｇ以上であることを意味する。つまり、「アルカリ可溶性樹脂」とは、上記溶解度を満たす樹脂を意味する。
　「水溶性」とは、液温が２２℃であるｐＨ７．０の水１００ｇへの溶解度が０．１ｇ以上であることを意味する。つまり、「水溶性樹脂」とは、上記溶解度を満たす樹脂を意味する。 Unless otherwise specified, the weight average molecular weight (Mw) and number average molecular weight (Mn) were measured using TSKgel GMHxL, TSKgel G4000HxL, TSKgel G2000HxL (all trade names manufactured by Tosoh Corporation) as a column, and THF (tetrahydrofuran) as an eluent. ), using a differential refractometer as a detector and polystyrene as a standard substance, it is a value converted using polystyrene as a standard substance measured by a gel permeation chromatography (GPC) analyzer.
The molecular weights of compounds having a molecular weight distribution are weight average molecular weights (Mw) unless otherwise specified.
The content of metal elements is a value measured using an inductively coupled plasma (ICP) spectroscopic analyzer unless otherwise specified.
"(Meth)acryl" is a concept that includes both acryl and methacryl, and "(meth)acryloxy group" is a concept that includes both acryloxy and methacryloxy.
“Alkali-soluble” means that the solubility in 100 g of a 1 mass % aqueous solution of sodium carbonate at 22° C. is 0.1 g or more. In other words, the "alkali-soluble resin" means a resin that satisfies the above solubility.
The term “water-soluble” means that the solubility in 100 g of water at pH 7.0 at a liquid temperature of 22° C. is 0.1 g or more. In other words, the "water-soluble resin" means a resin that satisfies the above solubility.
　組成物の「固形分」とは、組成物を用いて形成される組成物層（例えば、感光性組成物層、中間層及び熱可塑性樹脂層）を形成する成分を意味し、組成物が溶剤（例えば、有機溶剤及び水等）を含む場合、溶剤を除いた全ての成分を意味する。また、組成物層を形成する成分であれば、液体状の成分も固形分とみなす。 The "solid content" of the composition means a component that forms a composition layer (e.g., a photosensitive composition layer, an intermediate layer and a thermoplastic resin layer) formed using the composition, and the composition is a solvent. When including (for example, organic solvent and water, etc.), it means all components except the solvent. In addition, as long as it is a component that forms a composition layer, a liquid component is also regarded as a solid content.
［積層体の製造方法］
　積層体の製造方法は、仮支持体と、感光性組成物層とを有する転写フィルムの感光性組成物層の仮支持体側とは反対側の表面を基板に接触させ、転写フィルムと基板とを貼合する貼合工程と、
　感光性組成物層をパターン露光する露光工程と、
　露光された感光性組成物層を、現像液を用いて現像してパターンを形成する現像工程とを有し、
　感光性組成物層のガラス転移温度Ｘ（以下、「ＴｇＸ」ともいう。）が１１０℃以下であり、測定Ｙで求められるガラス転移温度Ｙ（以下、「ＴｇＹ」ともいう。）が１２５℃以上である、積層体の製造方法。
　測定Ｙ：転写フィルムの感光性組成物層の仮支持体側とは反対側の表面を基板に接触させ、転写フィルムと基板とを貼り合わせて、得られた積層体から仮支持体を剥離して、仮支持体が剥離された積層体中の感光性組成物層を露光工程と同様の露光条件にて全面露光して、その後、得られた硬化膜のガラス転移温度を測定し、ガラス転移温度Ｙとする。
　積層体の製造方法の好適態様としては、例えば、上記貼合工程と、上記露光工程と、上記現像工程とをこの順に有する態様が挙げられる。 [Laminate production method]
In the method for producing a laminate, the surface of the photosensitive composition layer of the transfer film having the temporary support and the photosensitive composition layer on the side opposite to the temporary support side is brought into contact with the substrate, and the transfer film and the substrate are separated. a laminating step of laminating;
An exposure step of pattern-exposing the photosensitive composition layer;
a developing step of developing the exposed photosensitive composition layer with a developer to form a pattern;
The glass transition temperature X (hereinafter also referred to as “TgX”) of the photosensitive composition layer is 110° C. or lower, and the glass transition temperature Y (hereinafter also referred to as “TgY”) obtained by measurement Y is 125° C. or higher. A method for manufacturing a laminate.
Measurement Y: The surface of the photosensitive composition layer of the transfer film opposite to the temporary support side is brought into contact with the substrate, the transfer film and the substrate are laminated, and the temporary support is peeled off from the resulting laminate. , the entire surface of the photosensitive composition layer in the laminate from which the temporary support is peeled off is exposed under the same exposure conditions as the exposure step, and then the glass transition temperature of the resulting cured film is measured, and the glass transition temperature Let Y.
A suitable aspect of the method for producing a laminate includes, for example, an aspect in which the lamination step, the exposure step, and the development step are performed in this order.
　本発明の積層体の製造方法の特徴点としては、ＴｇＸが１１０℃以下であり、測定Ｙで求められるＴｇＹが１２５℃以上である点が挙げられる。
　本発明の積層体の製造方法が所望の効果を奏する作用機序の詳細は明らかではないが、本発明者らは以下のように推測している。
　ＴｇＸが１１０℃超である場合、感光性組成物層に対して露光処理の際に発生するラジカルの拡散が抑制されるため、得られるパターン（硬化膜）形状が裾広がり形状になりやすい。また、ＴｇＹが１２５℃未満である場合、感光性組成物層に対して露光して得られるパターン（硬化膜）の架橋密度等が低く、現像液を用いて現像した際に、パターンの膨潤及び溶解しやすいため、得られるパターン（硬化膜）形状が裾広がり形状になることを本発明者らは知見した。上記を鑑み、本発明の積層体の製造方法では、所定のＴｇＸ及び所定のＴｇＹにそれぞれを調整することで、パターン形状に優れると推測している。
　以下、パターン形状により優れることを、本発明の効果がより優れるともいう。 A characteristic point of the method for producing a laminate of the present invention is that TgX is 110° C. or less and TgY obtained by measurement Y is 125° C. or more.
Although the details of the action mechanism by which the method for producing a laminate of the present invention produces the desired effects are not clear, the present inventors presume as follows.
When TgX is higher than 110° C., the diffusion of radicals generated in the photosensitive composition layer during the exposure process is suppressed, so that the obtained pattern (cured film) tends to have a wide bottom shape. Further, when TgY is less than 125° C., the cross-linking density of the pattern (cured film) obtained by exposing the photosensitive composition layer is low, and when developed with a developer, the pattern swells and The present inventors have found that the obtained pattern (cured film) has a wide bottom shape because it is easily dissolved. In view of the above, it is presumed that the method for manufacturing the laminate of the present invention is excellent in pattern shape by adjusting each to predetermined TgX and predetermined TgY.
Hereinafter, being superior to the pattern shape is also referred to as being more superior in the effects of the present invention.
　以下、本発明の積層体の製造方法について、各工程を詳細に説明する。
　なお、以下に記載する構成要件の説明は、本発明の代表的な実施態様に基づいてなされることがあるが、本発明はそのような実施態様に限定されるものではない。 Each step of the method for manufacturing a laminate of the present invention will be described in detail below.
In addition, although description of the constituent elements described below may be made based on a representative embodiment of the present invention, the present invention is not limited to such an embodiment.
〔ガラス転移温度〕
＜ＴｇＸ＞
　ＴｇＸは、１１０℃以下であり、１０５℃以下が好ましく、１００℃以下がより好ましい。下限としては、７０℃以上が好ましく、８０℃以上がより好ましく、９０℃以上が更に好ましい。 〔Glass-transition temperature〕
<TgX>
TgX is 110° C. or lower, preferably 105° C. or lower, and more preferably 100° C. or lower. The lower limit is preferably 70°C or higher, more preferably 80°C or higher, and even more preferably 90°C or higher.
　ＴｇＸの測定方法としては、例えば、以下の方法で測定できる。
　まず、測定試料を５～６ｍｇを用いて、温度変調示差走査熱量測定を行う（装置：ティー　エイ　インスツルメント社製　ＤＳＣ２５００）。試料の封入には、Ｔｚｅｒｏアルミパンを使用する。なお、測定条件は、窒素雰囲気下、温度範囲－７０℃～２００℃（５℃／ｍｉｎ）、温度変調条件±１℃／　ｍｉｎ　（Ｎ＝２）とする。得られた測定データにおいて、リバーシングヒートフロー（Ｒｅｖ．　Ｈｅａｔ　Ｆｌｏｗ）においてベースラインがシフトする温度（中点）をガラス転移温度（Ｎ＝２の平均値）とする。 As a method for measuring TgX, for example, it can be measured by the following method.
First, temperature-modulated differential scanning calorimetry is performed using 5 to 6 mg of a measurement sample (apparatus: DSC2500 manufactured by T.A. Instruments). Tzero aluminum pans are used for sample containment. The measurement conditions are a nitrogen atmosphere, a temperature range of −70° C. to 200° C. (5° C./min), and a temperature modulation condition of ±1° C./min (N=2). In the obtained measurement data, the temperature (midpoint) at which the baseline shifts in the reversing heat flow (Rev. Heat Flow) is defined as the glass transition temperature (average value of N=2).
　ＴｇＸの測定方法としては、以下の測定Ｘであってもよい。
　測定Ｘは、転写フィルムの感光性組成物層の仮支持体側とは反対側の表面を基板に接触させ、転写フィルムと基板とを貼り合わせて、得られた積層体から仮支持体と感光性組成物層との間で仮支持体を剥離して、その後、露出した感光性組成物層のガラス転移温度を測定し、得られたガラス転移温度をガラス転移温度Ｘとする。
　ＴｇＸは、後述するＴｇＹとは異なり、露光処理を施していない感光性組成物層のガラス転移温度である。つまり、ＴｇＸは、未露光部の感光性組成物層のガラス転移温度である。
　測定Ｘで用いられる基板は、後述する基板と同義であり、好適態様も同じである。
　仮支持体の剥離方法としては、例えば、公知の剥離方法が挙げられ、後述する剥離工程と同じ方法で剥離する方法が好ましい。
　測定Ｘで用いられる基板は、後述する積層体の製造方法で用いられる基板と同じである。
　転写フィルムが後述する保護フィルムを有する場合、転写フィルムから保護フィルムを剥離した後に、測定Ｘを実施する。 As a method for measuring TgX, the following measurement X may be used.
In the measurement X, the surface of the photosensitive composition layer of the transfer film opposite to the temporary support side is brought into contact with the substrate, the transfer film and the substrate are bonded together, and the temporary support and the photosensitive composition are separated from the resulting laminate. After peeling the temporary support from the composition layer, the glass transition temperature of the exposed photosensitive composition layer is measured, and the obtained glass transition temperature is defined as the glass transition temperature X.
TgX is the glass transition temperature of a photosensitive composition layer that has not been subjected to exposure treatment, unlike TgY described later. That is, TgX is the glass transition temperature of the photosensitive composition layer in the unexposed area.
The substrate used in the measurement X is synonymous with the substrate described later, and the preferred embodiments are also the same.
Examples of the peeling method of the temporary support include known peeling methods, and a method of peeling by the same method as the peeling step described later is preferable.
The substrate used in the measurement X is the same as the substrate used in the method for manufacturing a laminate, which will be described later.
When the transfer film has a protective film, which will be described later, the measurement X is performed after peeling the protective film from the transfer film.
＜ＴｇＹ＞
　ＴｇＹは、１２５℃以上であり、１３０℃以上が好ましく、１３５℃以上がより好ましく、１４０℃以上が更に好ましい。上限としては、１６０℃以下が好ましく、１５０℃以下がより好ましく、１４５℃以下が更に好ましい。 <TgY>
TgY is 125° C. or higher, preferably 130° C. or higher, more preferably 135° C. or higher, and even more preferably 140° C. or higher. The upper limit is preferably 160°C or lower, more preferably 150°C or lower, and even more preferably 145°C or lower.
　ＴｇＹは、以下の測定Ｙで求められる値である。
　測定Ｙは、転写フィルムの感光性組成物層の仮支持体側とは反対側の表面を基板に接触させ、転写フィルムと基板とを貼り合わせて、得られた積層体から仮支持体を剥離して、仮支持体が剥離された積層体中の感光性組成物層を露光工程と同様の露光条件にて全面露光して、その後、得られた硬化膜のガラス転移温度を測定し、ガラス転移温度Ｙとする。
　なお、上記全面露光する際の露光条件（例えば、光源の種類及び露光量等）は、後述する露光工程にて実施する露光条件と同様の露光条件にて実施する。つまり、測定Ｙにて実施する全面露光は、後述する露光工程にて実施されるパターン露光の露光範囲を感光性組成物層全面に変更した露光に該当する。
　ＴｇＹは、感光性組成物層に対して露光処理が施されて形成される硬化膜のガラス転移温度である。
　ガラス転移温度の測定方法、仮支持体の剥離方法及び測定Ｙで用いられる基板は、上記ＴｇＸで挙げられる各測定方法及び基板と同義であり、好適態様も同じである。
　転写フィルムが後述する保護フィルムを有する場合、転写フィルムから保護フィルムを剥離した後に、測定Ｙを実施する。 TgY is a value obtained by measurement Y below.
In measurement Y, the surface of the photosensitive composition layer of the transfer film opposite to the temporary support side is brought into contact with the substrate, the transfer film and the substrate are bonded together, and the temporary support is peeled off from the resulting laminate. Then, the entire surface of the photosensitive composition layer in the laminate from which the temporary support was removed was exposed under the same exposure conditions as the exposure step, and then the glass transition temperature of the resulting cured film was measured. Let the temperature be Y.
The exposure conditions (for example, the type of light source, the amount of exposure, etc.) for the entire surface exposure are the same as those used in the exposure step described later. That is, the overall exposure performed in the measurement Y corresponds to the exposure in which the exposure range of the pattern exposure performed in the exposure step described later is changed to cover the entire surface of the photosensitive composition layer.
TgY is the glass transition temperature of a cured film formed by exposing the photosensitive composition layer.
The method for measuring the glass transition temperature, the method for peeling the temporary support, and the substrate used in measurement Y are synonymous with the above-mentioned measurement method and substrate for TgX, and the preferred embodiments are also the same.
When the transfer film has a protective film, which will be described later, the measurement Y is performed after the protective film is peeled off from the transfer film.
　ＴｇＸとＴｇＹとの差としては、３５～５０℃が好ましく、４０～５０℃がより好ましい。
　上記「差」とは、ＴｇＸとＴｇＹとのうち、より大きい方から小さい方を引くことにより得られる数値である。例えば、ＴｇＹがＴｇＸよりも大きい場合、上記差は「ＴｇＹ－ＴｇＸ」によって得られる数値である。なお、ＴｇＸとＴｇＹとが同じ数値である場合、差は０とする。 The difference between TgX and TgY is preferably 35-50°C, more preferably 40-50°C.
The "difference" is a numerical value obtained by subtracting the smaller one from the larger one of TgX and TgY. For example, if TgY is greater than TgX, the difference is a numerical value given by "TgY-TgX". In addition, when TgX and TgY are the same numerical value, let the difference be zero.
　ＴｇＸ及びＴｇＹを調整する方法としては、例えば、転写フィルムの感光性組成物層に含まれる、後述する樹脂及び後述する重合性化合物の種類及び含有量を変更することが挙げられる。
　具体的には、樹脂のＴｇ、樹脂の構成単位を構成し得る単量体の種類及び含有量を後述するそれぞれの好適態様に調整する方法、重合性化合物の種類数、重合性化合物の重合性基の含有量、重合性化合物中の所定の官能基（例えば、エチレンオキシ基）の種類及び含有量を後述するそれぞれの好適態様に調整する方法、並びに、これらを組み合わせた方法が挙げられる。 Methods for adjusting TgX and TgY include, for example, changing the types and contents of a resin and a polymerizable compound, which will be described later, contained in the photosensitive composition layer of the transfer film.
Specifically, the Tg of the resin, the method of adjusting the type and content of the monomer that can constitute the structural unit of the resin to each preferred embodiment described later, the number of types of the polymerizable compound, the polymerizability of the polymerizable compound The group content, the type and content of a predetermined functional group (eg, ethyleneoxy group) in the polymerizable compound can be adjusted to the respective preferred embodiments described below, and a combination of these methods can be mentioned.
〔貼合工程〕
　貼合工程は、仮支持体と、感光性組成物層とを有する転写フィルムの感光性組成物層の仮支持体側とは反対側の表面を基板に接触させ、転写フィルムと基板とを貼合する工程である。
　転写フィルムが後述する保護フィルムを有する場合、保護フィルムを剥離した後に貼合工程を実施することが好ましい。 [Lamination process]
In the lamination step, the surface of the photosensitive composition layer of the transfer film having the temporary support and the photosensitive composition layer on the side opposite to the temporary support side is brought into contact with the substrate, and the transfer film and the substrate are laminated. It is a process to do.
When the transfer film has a protective film which will be described later, it is preferable to carry out the bonding step after peeling off the protective film.
　転写フィルムの感光性組成物層の仮支持体側とは反対側の表面を、基板に接触させて圧着させる。
　圧着方法としては、例えば、公知の転写方法及びラミネート方法が挙げられ、転写フィルムの感光性組成物層の仮支持体側とは反対側の表面を基板に重ね、ロール等による加圧及び加熱する方法が好ましい。
　貼合方法としては、例えば、真空ラミネーター及びオートカットラミネーター等の公知のラミネーターを用いる方法が挙げられる。
　ラミネート温度としては、７０～１３０℃が好ましい。 The surface of the photosensitive composition layer of the transfer film opposite to the temporary support side is brought into contact with the substrate and pressed.
Examples of the pressure bonding method include known transfer methods and lamination methods, in which the surface of the photosensitive composition layer of the transfer film opposite to the temporary support side is superimposed on the substrate, and a method of pressing and heating with a roll or the like. is preferred.
Examples of the lamination method include a method using a known laminator such as a vacuum laminator and an autocut laminator.
The lamination temperature is preferably 70 to 130°C.
　基板としては、支持基板と、支持基板上に配置される導電層とを有する導電性基板が好ましい。
　導電性基板は、支持基板上に、必要に応じて上記導電層以外の任意の層が形成されていてもよい。つまり、基板は、支持基板と、支持基板上に配置される導電層とを少なくとも有する導電性基板であることが好ましい。
　支持基板としては、例えば、樹脂基板、ガラス基板及び半導体基板が挙げられ、国際公開第２０１８／１５５１９３号の段落［０１４０］に記載の支持基板が好ましい。
　樹脂基板の材料としては、シクロオレフィンポリマー又はポリイミドが好ましい。
　樹脂基板の厚みとしては、５～２００μｍが好ましく、１０～１００μｍがより好ましい。
　特に、露光工程において、メッシュ状に配置された遮光部を含むフォトマスクを使用する場合には、基板としては、透明基板を用いることが好ましい。
　なお、ここでいう「透明」とは、露光波長の透過率が５０％以上であることを意味する。透明基板の透過率は、全光線透過率が、８０％以上であることが好ましく、９０％以上であることがより好ましく、９５％以上であることが更に好ましい。上限は、１００％未満が好ましい。
　透明基板としては、例えば、樹脂基板（例えば、樹脂フィルム）、及び、ガラス基板が挙げられる。樹脂基板は、可視光を透過する樹脂基板であることが好ましい。可視光を透過する樹脂基板の好ましい成分としては、例えば、ポリアミド系樹脂、ポリエチレンテレフタレート系樹脂、ポリエチレンナフタレート系樹脂、シクロオレフィン系樹脂、ポリイミド系樹脂、及び、ポリカーボネート系樹脂が挙げられる。可視光を透過する樹脂基板のより好ましい成分としては、例えば、ポリアミド、ポリエチレンテレフタレート（ＰＥＴ）、シクロオレフィンポリマー（ＣＯＰ）、ポリエチレンナフタレート（ＰＥＮ）、ポリイミド、及び、ポリカーボネートが挙げられる。
　上記透明基板としては、なかでも、ポリアミドフィルム、ポリエチレンテレフタレートフィルム、シクロオレフィンポリマー、ポリエチレンナフタレートフィルム、ポリイミドフィルム、又は、ポリカーボネートフィルムが好ましく、ポリエチレンテレフタレートフィルムでがより好ましい。
　透明基板の厚さは、制限されない。透明基板の厚さは、１０～２００μｍであることが好ましく、２０～１２０μｍであることがより好ましく、２０～１００μｍであることが更に好ましい。
　上記透明基板の厚さは、以下の方法によって測定される。走査型電子顕微鏡（ＳＥＭ）を用いて、透明基板の主面に対して垂直な方向（すなわち、厚さ方向）の断面を観察する。得られた観察画像に基づいて、透明基板の厚さを１０点測定する。測定値を算術平均することで、透明基板の平均厚さを求める。 The substrate is preferably a conductive substrate having a supporting substrate and a conductive layer disposed on the supporting substrate.
As for the conductive substrate, any layer other than the above-described conductive layer may be formed on the supporting substrate, if necessary. That is, the substrate is preferably a conductive substrate having at least a supporting substrate and a conductive layer arranged on the supporting substrate.
Examples of the support substrate include resin substrates, glass substrates, and semiconductor substrates, and the support substrate described in paragraph [0140] of WO2018/155193 is preferable.
A cycloolefin polymer or polyimide is preferable as a material for the resin substrate.
The thickness of the resin substrate is preferably 5-200 μm, more preferably 10-100 μm.
In particular, when using a photomask including light shielding portions arranged in a mesh pattern in the exposure step, it is preferable to use a transparent substrate as the substrate.
The term "transparent" as used herein means that the transmittance of the exposure wavelength is 50% or more. As for the transmittance of the transparent substrate, the total light transmittance is preferably 80% or more, more preferably 90% or more, and even more preferably 95% or more. The upper limit is preferably less than 100%.
Examples of transparent substrates include resin substrates (for example, resin films) and glass substrates. The resin substrate is preferably a resin substrate that transmits visible light. Preferred components of the resin substrate that transmits visible light include, for example, polyamide-based resins, polyethylene terephthalate-based resins, polyethylene naphthalate-based resins, cycloolefin-based resins, polyimide-based resins, and polycarbonate-based resins. Preferred components of the resin substrate that transmit visible light include, for example, polyamide, polyethylene terephthalate (PET), cycloolefin polymer (COP), polyethylene naphthalate (PEN), polyimide, and polycarbonate.
Polyamide film, polyethylene terephthalate film, cycloolefin polymer, polyethylene naphthalate film, polyimide film, or polycarbonate film is preferable as the transparent substrate, and polyethylene terephthalate film is more preferable.
The thickness of the transparent substrate is not limited. The thickness of the transparent substrate is preferably 10 to 200 μm, more preferably 20 to 120 μm, even more preferably 20 to 100 μm.
The thickness of the transparent substrate is measured by the following method. A scanning electron microscope (SEM) is used to observe a cross section in a direction (that is, thickness direction) perpendicular to the main surface of the transparent substrate. Based on the observed image obtained, the thickness of the transparent substrate is measured at ten points. By arithmetically averaging the measured values, the average thickness of the transparent substrate is obtained.
　また、特に、円形ドット状に配置された遮光部又は円形ドット状に配置された開口部を含むフォトマスクを使用する場合、基板としては、シリコン基板、ガラス基板、又は、ＦＲ４（Flame Retardant Type 4）等の有機基板が好ましい。
　その場合、基板の厚みは特に限定されない。
　また、基板の表面上に配線パターンが形成されていてもよく、配線層が積層化されていてもよい。
　なお、円形ドット状に配置された遮光部又は円形ドット状に配置された開口部を含むフォトマスクについては、後段部にて説明する。 In particular, when using a photomask including light shielding portions arranged in circular dots or openings arranged in circular dots, the substrate may be a silicon substrate, a glass substrate, or FR4 (Flame Retardant Type 4). ) is preferred.
In that case, the thickness of the substrate is not particularly limited.
Moreover, a wiring pattern may be formed on the surface of the substrate, and wiring layers may be laminated.
A photomask including light shielding portions arranged in circular dots or openings arranged in circular dots will be described later.
　導電層としては、導電性及び細線形成性の点から、金属層、導電性金属酸化物層、グラフェン層、カーボンナノチューブ層及び導電ポリマー層からなる群から選択される少なくとも１つが好ましい。
　支持基板上には、導電層を１層又は２層以上配置してもよい。
　導電層を２層以上配置する場合、２層以上配置される導電層同士は、同一及び不同のいずれであってもよく、異なる材質の導電層であることが好ましい。
　導電層としては、例えば、国際公開第２０１８／１５５１９３号の段落［０１４１］が挙げられ、これらの内容は本明細書に組み込まれる。 The conductive layer is preferably 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, from the viewpoint of conductivity and fine wire formation.
One or more conductive layers may be arranged on the support substrate.
When two or more conductive layers are arranged, the two or more conductive layers may be the same or different, and are preferably made of different materials.
Conductive layers include, for example, paragraph [0141] of WO2018/155193, the contents of which are incorporated herein.
　導電性基板としては、透明電極及び引き回り配線の少なくとも一方を有する基板が好ましく、上記基板はタッチパネル用基板として使用できる。
　透明電極は、タッチパネル用電極として機能し得る。
　透明電極は、ＩＴＯ（酸化インジウムスズ）及びＩＺＯ（酸化インジウム亜鉛）等の金属酸化膜、並びに、金属メッシュ及び金属ナノワイヤー等の金属細線により構成されることが好ましい。
　金属細線としては、例えば、銀及び銅等の金属細線が挙げられ、銀メッシュ及び銀ナノワイヤー等の銀導電性材料が好ましい。 As the conductive substrate, a substrate having at least one of a transparent electrode and a lead wiring is preferable, and the above substrate can be used as a touch panel substrate.
The transparent electrode can function as a touch panel electrode.
The transparent electrodes are preferably composed of metal oxide films such as ITO (indium tin oxide) and IZO (indium zinc oxide), and fine metal wires such as metal mesh and metal nanowires.
Examples of fine metal wires include fine metal wires of silver and copper, and silver conductive materials such as silver mesh and silver nanowires are preferred.
　引き回し配線の材質としては、金属が好ましい。
　上記金属としては、例えば、金、銀、銅、モリブデン、アルミニウム、チタン、クロム、亜鉛及びマンガン、並びに、これらを組み合わせた合金が挙げられ、銅、モリブデン、アルミニウム又はチタンが好ましく、銅がより好ましい。 A metal is preferable as the material of the routing wiring.
Examples of the metal include gold, silver, copper, molybdenum, aluminum, titanium, chromium, zinc and manganese, and alloys thereof in combination, preferably copper, molybdenum, aluminum or titanium, more preferably copper. .
〔剥離工程〕
　積層体の製造方法は、解像性が優れる点から、剥離工程を有することが好ましく、上記貼合工程と上記露光工程との間、又は、上記露光工程と上記現像工程との間に、剥離工程を有することがより好ましい。
　剥離工程は、転写フィルムと基板との積層体から仮支持体を剥離する工程である。
　仮支持体の剥離方法としては、例えば、公知の剥離方法が挙げられる。具体的には、特開２０１０－０７２５８９号公報の段落［０１６１］～［０１６２］に記載されたカバーフィルム剥離機構が挙げられる。 [Peeling process]
The method for producing a laminate preferably includes a peeling step from the viewpoint of excellent resolution. Between the bonding step and the exposure step, or between the exposure step and the developing step, peeling It is more preferable to have a step.
A peeling process is a process of peeling a temporary support body from the laminated body of a transfer film and a board|substrate.
Examples of the peeling method of the temporary support include known peeling methods. Specifically, there is a cover film peeling mechanism described in paragraphs [0161] to [0162] of JP-A-2010-072589.
〔露光工程〕
　露光工程は、感光性組成物層をパターン露光する工程である。
　「パターン露光」とは、パターン状に露光する形態であり、露光部と非露光部とが存在する形態の露光を意味する。
　パターン露光における露光部（露光領域）と非露光部（非露光領域）との位置関係は、適宜調整できる。
　露光方向は、感光性組成物層側又は感光性組成物層側とは反対側（基板側）から露光してもよい。 [Exposure process]
The exposure step is a step of patternwise exposing the photosensitive composition layer.
“Pattern exposure” is a form of exposure in a pattern, and means an exposure form in which an exposed portion and a non-exposed portion are present.
The positional relationship between the exposed portion (exposed region) and the non-exposed portion (non-exposed region) in the pattern exposure can be adjusted as appropriate.
As for the exposure direction, the exposure may be performed from the side of the photosensitive composition layer or the side (substrate side) opposite to the side of the photosensitive composition layer.
　露光工程としては、フォトマスクを介して、上記剥離工程にて得られた仮支持体が剥離された積層体の感光性組成物層をパターン露光することも好ましい。
　また、露光工程としては、高精細なパターンが得られる点から、上記剥離工程にて得られた仮支持体が剥離された積層体の基板側とは反対側の表面とフォトマスクとを接触させて、感光性組成物層にパターン露光する露光工程が好ましい。言い換えれば、仮支持体が剥離された積層体の仮支持体が剥離されることにより露出した表面とフォトマスクとを接触させて、感光性組成物層にパターン露光する露光工程が好ましい。
　なお、上記露出した表面としては、転写フィルムが仮支持体と感光性組成物層との２層構成である場合、感光性組成物層の表面が該当し、転写フィルムが仮支持体と中間層と感光性組成物層との３層構成である場合、中間層の表面が該当する。
　上記パターン露光する露光工程である場合、感光性組成物層の露光領域（フォトマスクの開口部に相当する領域）において感光性組成物層に含まれる成分の硬化反応が生じ得る。露光後にアルカリ現像処理を実施することで感光性組成物層の非露光領域が除去されて、パターンが形成される。 As the exposure step, it is also preferable to pattern-expose the photosensitive composition layer of the laminate from which the temporary support obtained in the peeling step was peeled off, through a photomask.
In the exposure step, since a high-definition pattern can be obtained, the surface of the layered product from which the temporary support has been peeled off in the peeling step, which is opposite to the substrate side, is brought into contact with the photomask. Therefore, the exposure step of patternwise exposing the photosensitive composition layer is preferable. In other words, the exposure step of exposing the photosensitive composition layer in a pattern by bringing the surface exposed by peeling the temporary support of the laminated body from which the temporary support has been peeled off into contact with a photomask is preferred.
When the transfer film has a two-layer structure of the temporary support and the photosensitive composition layer, the exposed surface corresponds to the surface of the photosensitive composition layer, and the transfer film is the temporary support and the intermediate layer. and a photosensitive composition layer, the surface of the intermediate layer is applicable.
In the case of the pattern exposure step, a curing reaction of the components contained in the photosensitive composition layer may occur in the exposed regions of the photosensitive composition layer (regions corresponding to the openings of the photomask). By carrying out alkali development treatment after exposure, the non-exposed areas of the photosensitive composition layer are removed to form a pattern.
　上記フォトマスクとしては、後述する、メッシュ状に配置された遮光部を含むフォトマスク又は円形ドット状に配置された遮光部を含むフォトマスクが好ましい。 As the photomask, a photomask including a light shielding portion arranged in a mesh pattern or a photomask including a light shielding portion arranged in a circular dot shape, which will be described later, is preferable.
　積層体の製造方法は、露光工程と現像処理との間で、露光工程で用いたフォトマスクを剥離するフォトマスク剥離工程を有することが好ましい。
　フォトマスク剥離工程としては、例えば、公知の剥離工程が挙げられる。 It is preferable that the method for manufacturing the laminate has a photomask peeling step of peeling off the photomask used in the exposure step between the exposure step and the development treatment.
The photomask peeling process includes, for example, a known peeling process.
　パターン露光の光源としては、少なくとも感光性組成物層を硬化し得る波長域の光（例えば、３６５ｎｍ及び４０５ｎｍ）を照射できるものであればよく、３６５ｎｍが好ましい。「主波長」とは、最も強度が高い波長を意味する。 The light source for pattern exposure should be one capable of irradiating at least light in a wavelength range capable of curing the photosensitive composition layer (for example, 365 nm and 405 nm), preferably 365 nm. By "dominant wavelength" is meant the wavelength with the highest intensity.
　光源としては、例えば、各種レーザー、発光ダイオード（ＬＥＤ）、超高圧水銀灯、高圧水銀灯及びメタルハライドランプが挙げられる。
　露光量としては、５～２００ｍＪ／ｃｍ２が好ましく、１０～２００ｍＪ／ｃｍ２がより好ましい。
　光源、露光量及び露光方法としては、例えば、国際公開第２０１８／１５５１９３号の段落［０１４６］～［０１４７］が挙げられ、これらの内容は本明細書に組み込まれる。 Examples of light sources include various lasers, light emitting diodes (LEDs), ultrahigh pressure mercury lamps, high pressure mercury lamps, and metal halide lamps.
The exposure amount is preferably 5 to 200 mJ/cm 2 , more preferably 10 to 200 mJ/cm 2 .
Light sources, exposure doses and exposure methods include, for example, paragraphs [0146] to [0147] of WO2018/155193, the contents of which are incorporated herein.
　また、露光対象物は、支持基板上にクッション材が配置される基板を有することも好ましい。露光対象物がクッション材を有する場合、露光対象物は、更に中間層を有することが好ましい。上記中間層としては、例えば、転写フィルムが有し得る中間層が挙げられる。
　クッション材は、上記貼合工程前に支持基板上にクッション材を配置してもよく、上記貼合工程後に支持基板上にクッション材を配置してもよい。クッション材を配置する方法は、公知の方法を用いることができる。
　具体的には、仮支持体と、感光性組成物層とを有する転写フィルムの上記感光性組成物層の上記仮支持体側とは反対側の表面を、クッション材を有する基板のクッション材とは反対側の表面に接触させ、上記転写フィルムと上記基板とを貼合する貼合工程と、上記感光性組成物層をパターン露光する露光工程と、を含むことが好ましい。また、仮支持体と、感光性組成物層とを有する転写フィルムの上記感光性組成物層の上記仮支持体側とは反対側の表面を、基板に接触させ、上記転写フィルムと上記基板とを貼合する貼合工程と、上記基板の感光性組成物層とは反対側の表面にクッション材を形成する形成工程と、上記感光性組成物層をパターン露光する露光工程と、を含むことも好ましい。
　クッション材としては、例えば、シリコン、ウレタン、ニトリル及びクロロプレン等の材質を有するクッション材が挙げられる。
　クッション材の形状としては、シート状であってもよい。
　クッション材の硬度は、３０以上が好ましく、５０以上がより好ましく、７０以上が更に好ましい。上限は、１００以下が好ましく、９０以下がより好ましい。なお、上記硬度は、タイプＡデュロメーター硬度である。 It is also preferable that the exposure target has a substrate on which a cushioning material is arranged. When the object to be exposed has a cushioning material, it is preferable that the object to be exposed further has an intermediate layer. Examples of the intermediate layer include an intermediate layer that the transfer film may have.
The cushioning material may be arranged on the supporting substrate before the bonding process, or may be arranged on the supporting substrate after the bonding process. A known method can be used as a method of arranging the cushion material.
Specifically, the surface of the transfer film having a temporary support and a photosensitive composition layer opposite to the temporary support side of the photosensitive composition layer is the cushioning material of the substrate having a cushioning material. It is preferable to include a bonding step of bonding the transfer film and the substrate by bringing them into contact with opposite surfaces, and an exposure step of pattern-exposing the photosensitive composition layer. In addition, the surface of the transfer film having the temporary support and the photosensitive composition layer on the side opposite to the temporary support side of the photosensitive composition layer is brought into contact with the substrate, and the transfer film and the substrate are separated. A lamination step of laminating, a forming step of forming a cushion material on the surface of the substrate opposite to the photosensitive composition layer, and an exposure step of pattern-exposing the photosensitive composition layer. preferable.
Examples of the cushioning material include those made of silicon, urethane, nitrile, chloroprene, or the like.
The shape of the cushion material may be a sheet shape.
The hardness of the cushion material is preferably 30 or higher, more preferably 50 or higher, and even more preferably 70 or higher. The upper limit is preferably 100 or less, more preferably 90 or less. The above hardness is type A durometer hardness.
〔現像工程〕
　現像工程は、露光された感光性組成物層を現像液を用いて現像してパターンを形成する工程である。
　現像液を用いて現像することで、感光性組成物層の非露光領域が除去され、フォトマスクの開口部を凸部とするパターンが形成される。 [Development process]
The development step is a step of developing the exposed photosensitive composition layer with a developer to form a pattern.
By developing with a developer, the non-exposed regions of the photosensitive composition layer are removed to form a pattern having projections corresponding to the openings of the photomask.
　現像液としては、アルカリ性水溶液が好ましい。
　アルカリ性水溶液に含まれるアルカリ性化合物（水に溶解してアルカリ性を示す化合物）としては、例えば、水酸化ナトリウム、水酸化カリウム、炭酸ナトリウム、炭酸カリウム、炭酸水素ナトリウム、炭酸水素カリウム、テトラメチルアンモニウムヒドロキシド、テトラエチルアンモニウムヒドロキシド、テトラプロピルアンモニウムヒドロキシド、テトラブチルアンモニウムヒドロキシド及びコリン（２－ヒドロキシエチルトリメチルアンモニウムヒドロキシド）が挙げられる。 As the developer, an alkaline aqueous solution is preferred.
Alkaline compounds contained in the alkaline aqueous solution (compounds that dissolve in water and exhibit alkalinity) include, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, tetramethylammonium hydroxide. , tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide and choline (2-hydroxyethyltrimethylammonium hydroxide).
　現像方法としては、例えば、公知の現像方法が挙げられる。
　具体的には、パドル現像、シャワー現像、スピン現像及びディップ現像が挙げられる。
　現像方法としては、国際公開第２０１５／０９３２７１号の段落［０１９５］に記載の現像方法が好ましい。 Examples of the developing method include known developing methods.
Specific examples include puddle development, shower development, spin development and dip development.
As the developing method, the developing method described in paragraph [0195] of WO 2015/093271 is preferable.
〔ポスト露光工程及びポストベーク工程〕
　積層体の製造方法は、現像工程によって得られたパターンを、更に、露光する工程（以下、「ポスト露光工程」ともいう。）及び／又は加熱する工程（以下、「ポストベーク工程」ともいう。）を有していてもよい。
　積層体の製造方法がポスト露光工程及びポストベーク工程の両方を有する場合、ポスト露光工程を実施した後に、ポストベーク工程を実施することが好ましい。
　ポスト露光工程における露光量は、１００～５０００ｍＪ／ｃｍ２が好ましく、２００～３０００ｍＪ／ｃｍ２がより好ましい。
　ポストベーク工程におけるポストベークの温度は、８０～２５０℃が好ましく、９０～１６０℃がより好ましい。
　ポストベーク工程におけるポストベークの時間は、１～１８０分が好ましく、１０～６０分がより好ましい。 [Post-exposure process and post-bake process]
In the method for producing a laminate, the pattern obtained by the developing step is further subjected to a step of exposing (hereinafter also referred to as a “post-exposure step”) and/or a step of heating (hereinafter also referred to as a “post-baking step”. ).
When the method for manufacturing a laminate includes both a post-exposure step and a post-baking step, it is preferable to perform the post-baking step after performing the post-exposure step.
The exposure amount in the post-exposure step is preferably 100-5000 mJ/cm 2 , more preferably 200-3000 mJ/cm 2 .
The post-baking temperature in the post-baking step is preferably 80 to 250°C, more preferably 90 to 160°C.
The post-baking time in the post-baking step is preferably 1 to 180 minutes, more preferably 10 to 60 minutes.
　積層体の製造方法によって得られる基板上に形成されるパターンの位置及び大きさは特に制限されないが、細線状が好ましい。
　具体的には、パターンの線幅は、２０μｍ以下が好ましく、１５μｍ以下がより好ましく、１０μｍ以下が更に好ましく、５μｍ以下が特に好ましい。下限は、１．０μｍ以上が好ましい。 Although the position and size of the pattern formed on the substrate obtained by the laminate manufacturing method are not particularly limited, the pattern is preferably in the form of fine lines.
Specifically, the line width of the pattern is preferably 20 μm or less, more preferably 15 μm or less, still more preferably 10 μm or less, and particularly preferably 5 μm or less. The lower limit is preferably 1.0 μm or more.
［積層体の用途］
　積層体の製造方法によって製造される積層体は、種々の装置に適用することができる。上記積層体を備えた装置としては、例えば、入力装置が挙げられ、タッチパネルが好ましく、静電容量型タッチパネルがより好ましい。上記入力装置は、例えば、有機ＥＬ（有機エレクトロルミネッセンス）表示装置及び液晶表示装置等の表示装置に適用できる。 [Use of laminate]
A laminate manufactured by the method for manufacturing a laminate can be applied to various devices. Examples of the device including the laminate include an input device, preferably a touch panel, and more preferably a capacitive touch panel. The input device can be applied to, for example, display devices such as organic EL (organic electroluminescence) display devices and liquid crystal display devices.
　また、本発明に係る積層体の製造方法は、例えば、透明ヒーター、透明アンテナ、電磁波シールド材、及び、調光フィルム等の導電膜の製造；プリント配線板及び半導体パッケージの製造；半導体チップやパッケージ間のインターコネクト用のピラー及びピンの製造；メタルマスクの製造；ＣＯＦ（Chip on Film）及びＴＡＢ（Tape Automated Bonding）等のテープ基板の製造；等に適用できる。 In addition, the method for producing a laminate according to the present invention includes, for example, production of conductive films such as transparent heaters, transparent antennas, electromagnetic wave shielding materials, and light control films; production of printed wiring boards and semiconductor packages; production of semiconductor chips and packages. Manufacture of pillars and pins for interconnection between them; Manufacture of metal masks; Manufacture of tape substrates such as COF (Chip on Film) and TAB (Tape Automated Bonding);
［回路配線の製造方法］
＜＜第１実施形態＞＞
　回路配線の製造方法の第１実施形態は、仮支持体と、感光性組成物層とを有する転写フィルムの感光性組成物層の仮支持体とは反対側の表面を導電性基板に接触させ、転写フィルムと導電性基板とを貼合する貼合工程と、
　感光性組成物層をパターン露光する露光工程と、
　露光された感光性組成物層を、現像液を用いて現像してパターンを形成する現像工程と、
　パターンが配置されていない領域における導電層をエッチング処理するエッチング工程とを有し、
　ＴｇＸが１１０℃以下であり、ＴｇＹが１２５℃以上である。
　回路配線の製造方法の好適態様としては、上記貼合工程と、上記露光工程と、上記現像工程と、上記エッチング工程とをこの順に有する態様が挙げられる。
　上記ＴｇＸ、上記ＴｇＹ、上記貼合工程、上記露光工程及び上記現像工程は、上記積層体の製造方法における各用語と同義であり、好適態様も同じである。 [Method for producing circuit wiring]
<<First Embodiment>>
In the first embodiment of the method for producing circuit wiring, the surface of the photosensitive composition layer of the transfer film having the temporary support and the photosensitive composition layer on the side opposite to the temporary support is brought into contact with the conductive substrate. , a bonding step of bonding the transfer film and the conductive substrate;
An exposure step of pattern-exposing the photosensitive composition layer;
A developing step of developing the exposed photosensitive composition layer with a developer to form a pattern;
an etching step of etching the conductive layer in a region where the pattern is not arranged;
TgX is 110° C. or lower and TgY is 125° C. or higher.
A preferred aspect of the circuit wiring manufacturing method includes an aspect in which the lamination step, the exposure step, the development step, and the etching step are performed in this order.
The above TgX, the above TgY, the lamination step, the exposure step, and the development step are synonymous with the respective terms in the method for producing the laminate, and the preferred embodiments are also the same.
　以下、回路配線の製造方法の実施形態について、各工程を詳細に説明する。なお、回路配線の製造方法に含まれる工程のうち、既に上段で説明した工程と同じ工程は説明を省略する。具体的には、貼合工程、露光工程、及び、現像工程に関しては、説明を省略する。
　なお、以下に記載する構成要件の説明は、本発明の代表的な実施態様に基づいてなされることがあるが、本発明はそのような実施態様に限定されるものではない。 Each step of the embodiment of the circuit wiring manufacturing method will be described in detail below. In addition, among the steps included in the method of manufacturing the circuit wiring, the description of the same steps as the steps already described above will be omitted. Specifically, descriptions of the bonding process, the exposure process, and the development process are omitted.
In addition, although description of the constituent elements described below may be made based on a representative embodiment of the present invention, the present invention is not limited to such an embodiment.
〔エッチング工程〕
　エッチング工程は、基板として導電性基板を用いた際に、上記積層体の製造方法により製造されるパターンを有する積層体中のパターンが配置されていない領域における導電層をエッチング処理する工程である。
　具体的には、エッチング工程において、上記積層体の製造方法における現像工程により感光性組成物層から得られるパターンをエッチングレジストとして使用し、導電層をエッチング処理する工程である。
　基板としては、上記積層体の製造方法における基板と同義であり、好適態様も同じである。 [Etching process]
The etching step is a step of etching a conductive layer in a region where no pattern is arranged in a laminate having a pattern produced by the method for producing a laminate when a conductive substrate is used as the substrate.
Specifically, in the etching step, the conductive layer is etched using the pattern obtained from the photosensitive composition layer in the developing step in the laminate manufacturing method as an etching resist.
The substrate has the same meaning as the substrate in the method for manufacturing the laminate, and the preferred embodiments are also the same.
　エッチング処理の方法としては、例えば、公知のエッチング方法が挙げられる。
　具体的には、特開２０１７－１２０４３５号公報の段落［０２０９］～［０２１０］に記載の方法、特開２０１０－１５２１５５号公報の段落［００４８］～［００５４］に記載の方法、エッチング液に浸漬するウェットエッチング及びプラズマエッチング等のドライエッチングが挙げられる。 Examples of the etching method include known etching methods.
Specifically, the method described in paragraphs [0209] to [0210] of JP-A-2017-120435, the method described in paragraphs [0048] to [0054] of JP-A-2010-152155, and the etching solution Dry etching such as immersion wet etching and plasma etching are included.
　ウェットエッチングに用いられるエッチング液は、エッチングの対象に合わせて酸性又はアルカリ性のエッチング液を適宜選択できる。
　酸性のエッチング液としては、例えば、少なくとも１つの酸性化合物を含む酸性水溶液、並びに、酸性化合物と、塩化第２鉄、フッ化アンモニウム及び過マンガン酸カリウムからなる群から選択される少なくとも１つとの酸性の混合水溶液が挙げられる。
　酸性水溶液に含まれる酸性化合物（水に溶解して酸性を示す化合物）としては、塩酸、硫酸、硝酸、酢酸、フッ酸、シュウ酸及びリン酸からなる群から選択される少なくとも１つが好ましい。
　アルカリ性のエッチング液としては、例えば、少なくとも１つのアルカリ性化合物を含むアルカリ性水溶液及びアルカリ性化合物と塩（例えば、過マンガン酸カリウム等）とのアルカリ性の混合水溶液が挙げられる。
　アルカリ性水溶液に含まれるアルカリ性化合物（水に溶解してアルカリ性を示す化合物）としては、例えば、水酸化ナトリウム、水酸化カリウム、アンモニア、有機アミン及び有機アミンの塩（例えば、テトラメチルアンモニウムハイドロオキサイド等）からなる群から選択される少なくとも１つが好ましい。 As the etchant used for wet etching, an acidic or alkaline etchant can be appropriately selected according to the object to be etched.
Examples of the acidic etchant include an acidic aqueous solution containing at least one acidic compound, and an acidic compound and at least one selected from the group consisting of ferric chloride, ammonium fluoride, and potassium permanganate. A mixed aqueous solution of
As the acidic compound contained in the acidic aqueous solution (the compound exhibiting acidity when dissolved in water), at least one selected from the group consisting of hydrochloric acid, sulfuric acid, nitric acid, acetic acid, hydrofluoric acid, oxalic acid and phosphoric acid is preferable.
Examples of the alkaline etchant include an alkaline aqueous solution containing at least one alkaline compound and an alkaline mixed aqueous solution of an alkaline compound and a salt (eg, potassium permanganate).
Alkaline compounds contained in the alkaline aqueous solution (compounds exhibiting alkalinity when dissolved in water) include, for example, sodium hydroxide, potassium hydroxide, ammonia, organic amines, and salts of organic amines (e.g., tetramethylammonium hydroxide, etc.). At least one selected from the group consisting of is preferred.
〔除去工程〕
　回路配線の製造方法は、残存するパターンを除去する除去工程を有していてもよい。
　除去工程は、上記エッチング工程の後に実施することが好ましい。
　残存するパターンを除去する方法としては、例えば、薬品処理により除去する方法が挙げられ、除去液を用いて除去する方法が好ましい。
　残存するパターンを除去する方法としては、例えば、除去液を用いて、スプレー法、シャワー法及びパドル法等の公知の方法により除去する方法が挙げられる。 [Removal process]
The circuit wiring manufacturing method may have a removing step of removing the remaining pattern.
The removing step is preferably performed after the etching step.
As a method for removing the remaining pattern, for example, there is a method of removing by chemical treatment, and a method of removing using a removing liquid is preferable.
Examples of the method for removing the remaining pattern include a method of removing by known methods such as a spray method, a shower method and a paddle method using a removing liquid.
　除去液としては、例えば、アルカリ性化合物を、水、ジメチルスルホキシド及びＮ－メチルピロリドンからなる群から選択される少なくとも１つに溶解させた除去液が挙げられる。
　アルカリ性化合物（水に溶解してアルカリ性を示す化合物）としては、例えば、水酸化ナトリウム及び水酸化カリウム等のアルカリ性無機化合物、並びに、第１級アミン化合物、第２級アミン化合物、第３級アミン化合物及び第４級アンモニウム塩化合物等のアルカリ性有機化合物が挙げられる。
　除去液の液温としては、３０～８０℃が好ましく、５０～８０℃がより好ましい。
　除去方法の好適態様としては、液温が５０～８０℃である撹拌中の除去液に、除去対象のパターンを有する基板を１～３０分間浸漬する方法が挙げられる。 Examples of the remover include a remover in which an alkaline compound is dissolved in at least one selected from the group consisting of water, dimethylsulfoxide and N-methylpyrrolidone.
Examples of alkaline compounds (compounds that exhibit alkalinity when dissolved in water) include alkaline inorganic compounds such as sodium hydroxide and potassium hydroxide, primary amine compounds, secondary amine compounds, and tertiary amine compounds. and alkaline organic compounds such as quaternary ammonium salt compounds.
The liquid temperature of the removing liquid is preferably 30 to 80.degree. C., more preferably 50 to 80.degree.
A preferred embodiment of the removal method includes a method of immersing a substrate having a pattern to be removed in a stirring removing liquid having a liquid temperature of 50 to 80° C. for 1 to 30 minutes.
　回路配線の製造方法の第１実施形態は、積層体の製造方法における、剥離工程、ポスト露光工程及び／又はポストベーク工程を更に有していてもよい。 The first embodiment of the circuit wiring manufacturing method may further include a peeling step, a post-exposure step and/or a post-baking step in the laminate manufacturing method.
＜＜第２実施形態＞＞
　基板上にシード層を形成して、シード層付き基板を形成するシード層形成工程と、
　感光性組成物層の仮支持体側とは反対側の表面をシード層付き基板のシード層と接触させ、転写フィルムとシード層付き基板とを貼合して、基板、シード層、感光性組成物層及び仮支持体をこの順に有する感光性組成物層付き基板を得る貼合工程と、
　感光性組成物層付き基板から仮支持体を剥離する剥離工程と、
　仮支持体が剥離された感光性組成物層付き基板の基板側とは反対側の表面とフォトマスクとを接触させて、感光性組成物層をパターン露光する露光工程と、
　露光された感光性組成物層を、現像液を用いて現像してパターンを形成する現像工程と、
　パターンが配置されていない領域にあるシード層上に、めっき処理によって金属めっき層を形成する金属めっき層形成工程と、
　金属めっき層上に保護層を形成する保護層形成工程と、
　パターンを除去する除去工程と、
　露出したシード層を除去して、導電性細線を得るシード層除去工程と、を有し、
　感光性組成物層のガラス転移温度Ｘが１１０℃以下であり、測定Ｙで求められるガラス転移温度Ｙが１２５℃以上である、回路配線の製造方法。
　上記ＴｇＸ、上記ＴｇＹ、上記貼合工程、上記剥離工程、上記露光工程、上記現像工程及び上記除去工程において基板をシード層付き基板に変更した以外は、上記積層体の製造方法における各用語と同義であり、好適態様も同じである。 <<Second Embodiment>>
a seed layer forming step of forming a seed layer on a substrate to form a substrate with a seed layer;
The surface of the photosensitive composition layer opposite to the temporary support side is brought into contact with the seed layer of the substrate with the seed layer, and the transfer film and the substrate with the seed layer are laminated to form the substrate, the seed layer, and the photosensitive composition. A lamination step of obtaining a substrate with a photosensitive composition layer having a layer and a temporary support in this order;
A peeling step of peeling the temporary support from the substrate with the photosensitive composition layer;
The surface of the substrate with the photosensitive composition layer from which the temporary support has been removed is brought into contact with the surface of the substrate opposite to the substrate side with the photomask, and an exposure step of exposing the photosensitive composition layer in a pattern;
A developing step of developing the exposed photosensitive composition layer with a developer to form a pattern;
a metal plating layer forming step of forming a metal plating layer by plating on the seed layer in a region where no pattern is arranged;
a protective layer forming step of forming a protective layer on the metal plating layer;
a removing step of removing the pattern;
a seed layer removing step of removing the exposed seed layer to obtain a conductive thin line;
A method for producing circuit wiring, wherein the photosensitive composition layer has a glass transition temperature X of 110° C. or lower, and a glass transition temperature Y determined by measurement Y of 125° C. or higher.
Synonymous with each term in the method for producing a laminate except that the substrate is changed to a substrate with a seed layer in the above TgX, the above TgY, the bonding step, the peeling step, the exposure step, the development step, and the removal step. and the preferred embodiments are also the same.
〔シード層形成工程〕
　シード層形成工程は、基板上にシード層を形成する工程である。
　上記基板としては、例えば、上記積層体の製造方法の貼合工程にて上述した基板が挙げられる。 [Seed layer forming step]
The seed layer forming step is a step of forming a seed layer on the substrate.
Examples of the substrate include the substrates described above in the bonding step of the method for manufacturing the laminate.
　シード層は、金属を含んでいてもよい。
　上記金属としては、例えば、公知の金属が挙げられる。
　シード層に含まれる主成分の金属としては、例えば、銅、クロム、鉛、ニッケル、金、銀、すず及び亜鉛が挙げられる。「主成分」とは、シード層中に含まれる金属のうち、最も含有量が大きい金属を意味する。 The seed layer may contain metal.
Examples of the metal include known metals.
Main component metals contained in the seed layer include, for example, copper, chromium, lead, nickel, gold, silver, tin and zinc. The “main component” means the metal with the highest content among the metals contained in the seed layer.
　シード層の厚みとしては、５０ｎｍ以上が好ましく、１００ｎｍ以上がより好ましい。上限は、２μｍ以下が好ましい。 The thickness of the seed layer is preferably 50 nm or more, more preferably 100 nm or more. The upper limit is preferably 2 μm or less.
　シード層の形成方法としては、例えば、金属微粒子を分散した分散液を塗布して、塗膜を焼結する方法、スパッタリング法及び蒸着法等の公知の方法が挙げられる。 Examples of methods for forming the seed layer include known methods such as a method of applying a dispersion liquid in which fine metal particles are dispersed and sintering the coating film, a sputtering method, and a vapor deposition method.
〔金属めっき層形成工程〕
　金属めっき層形成工程は、パターンが配置されていない領域にあるシード層上に、めっき処理によって金属めっき層を形成する工程である。
　めっき処理の方法としては、例えば、電解めっき法及び無電解めっき法が挙げられ、生産性の点から、電解めっき法が好ましい。 [Metal Plating Layer Forming Step]
The metal plating layer forming step is a step of forming a metal plating layer by plating on the seed layer in the region where the pattern is not arranged.
Examples of the plating method include electrolytic plating and electroless plating, with electrolytic plating being preferred from the viewpoint of productivity.
　金属めっき層に含まれる金属としては、例えば、公知の金属が挙げられる。
　具体的には、銅、クロム、鉛、ニッケル、金、銀、すず及び亜鉛等の金属、並びに、これらの金属の合金が挙げられる。
　なかでも、金属めっき層は、導電性細線の導電性がより優れる点から、銅又はその合金を含むことが好ましい。また、導電性細線の導電性がより優れる点から、金属めっき層は、主成分として銅を含むことが好ましい。 Examples of the metal contained in the metal plating layer include known metals.
Specific examples include metals such as copper, chromium, lead, nickel, gold, silver, tin and zinc, and alloys of these metals.
Among them, the metal plating layer preferably contains copper or an alloy thereof from the viewpoint of better electrical conductivity of the conductive thin wires. In addition, the metal plating layer preferably contains copper as a main component in order to improve the electrical conductivity of the conductive fine wires.
　金属めっき層の厚みとしては、０．１μｍ以上が好ましく、１μｍ以上がより好ましい。上限は、２０μｍ以下が好ましい。 The thickness of the metal plating layer is preferably 0.1 μm or more, more preferably 1 μm or more. The upper limit is preferably 20 μm or less.
〔保護層形成工程〕
　保護層形成工程は、金属めっき層上に保護層を形成する工程である。
　保護層の材料としては、除去工程又は導電性細線形成工程において、除去液又はエッチング液に対する耐性を有する材料が好ましい。例えば、ニッケル、クロム、錫、亜鉛、マグネシウム、金及び銀等の金属、これらの合金、並びに、樹脂が挙げられ、ニッケル又はクロムが好ましい。 [Protective layer forming step]
The protective layer forming step is a step of forming a protective layer on the metal plating layer.
As a material for the protective layer, a material having resistance to a removing liquid or an etchant in the removing process or the conductive fine line forming process is preferable. Examples include metals such as nickel, chromium, tin, zinc, magnesium, gold and silver, alloys thereof, and resins, with nickel or chromium being preferred.
　保護層の形成方法としては、例えば、無電解めっき法及び電気めっき法が挙げられ、電気めっき法が好ましい。 Examples of methods for forming the protective layer include electroless plating and electroplating, with electroplating being preferred.
　保護層の厚みとしては、０．３μｍ以上が好ましく、０．５μｍ以上がより好ましい。上限は、３．０μｍ以下が好ましく、２．０μｍ以下がより好ましい。 The thickness of the protective layer is preferably 0.3 μm or more, more preferably 0.5 μm or more. The upper limit is preferably 3.0 μm or less, more preferably 2.0 μm or less.
〔シード層除去工程〕
　シード層除去工程は、露出したシード層を除去して、導電性細線を得る工程である。
　シード層除去工程では、金属めっき層形成工程によって形成された金属めっき層をエッチングレジストとして使用し、非パターン形成領域（金属めっき層で保護されていない領域）に位置するシード層のエッチング処理を行う。 [Seed layer removal step]
The seed layer removing step is a step of removing the exposed seed layer to obtain a conductive thin line.
In the seed layer removing step, the metal plating layer formed in the metal plating layer forming step is used as an etching resist to etch the seed layer located in the non-pattern forming region (the region not protected by the metal plating layer). .
　シード層の除去方法としては、例えば、公知のエッチング液を用いる方法が挙げられる。
　公知のエッチング液としては、例えば、塩化第二鉄溶液、塩化第二銅溶液、アンモニアアルカリ溶液、硫酸及び過酸化水素の混合液、並びに、リン酸及び過酸化水素の混合液が挙げられる。 As a method for removing the seed layer, for example, a method using a known etchant can be used.
Known etchants include, for example, ferric chloride solutions, cupric chloride solutions, ammonia alkali solutions, mixtures of sulfuric acid and hydrogen peroxide, and mixtures of phosphoric acid and hydrogen peroxide.
　形成される導電性細線の線幅としては、８μｍ以下が好ましく、６μｍ以下がより好ましい。下限は、１μｍ以上が好ましい。 The line width of the conductive thin line to be formed is preferably 8 μm or less, more preferably 6 μm or less. The lower limit is preferably 1 μm or more.
〔その他工程〕
　回路配線の製造方法は、上記各工程以外に、その他工程を有していてもよい。
　その他工程としては、例えば、ポスト露光工程、ポストベーク工程、国際公開第２０１９／０２２０８９号の段落［０１７２］に記載の可視光線反射率を低下させる工程及び国際公開第２０１９／０２２０８９号の段落［０１７２］に記載の絶縁膜の表面に新たな導電層を形成する工程が挙げられる。 [Other processes]
The method for manufacturing the circuit wiring may have other steps in addition to the steps described above.
Other steps include, for example, a post-exposure step, a post-baking step, a step of reducing visible light reflectance described in paragraph [0172] of WO2019/022089 and paragraph [0172] of WO2019/022089. ], a step of forming a new conductive layer on the surface of the insulating film described in 1. above.
＜可視光線反射率を低下させる工程＞
　回路配線の製造方法は、基板が有する複数の導電層の一部又は全ての可視光線反射率を低下させる処理を行う工程を有していてもよい。
　可視光線反射率を低下させる処理としては、例えば、酸化処理が挙げられる。基板が銅を含む導電層を有する場合、銅を酸化処理して酸化銅とし、導電層を黒化することにより、導電層の可視光線反射率を低下できる。
　可視光線反射率を低下させる処理としては、例えば、特開２０１４－１５０１１８号公報の段落［００１７］～［００２５］、並びに、特開２０１３－２０６３１５号公報の段落［００４１］、［００４２］、［００４８］及び［００５８］が挙げられ、これらの内容は本明細書に組み込まれる。 <Step of reducing visible light reflectance>
The circuit wiring manufacturing method may include a step of performing a process for reducing the visible light reflectance of a part or all of the plurality of conductive layers of the substrate.
The treatment for reducing the visible light reflectance includes, for example, oxidation treatment. When the substrate has a conductive layer containing copper, the visible light reflectance of the conductive layer can be reduced by oxidizing the copper to form copper oxide and blackening the conductive layer.
Examples of the treatment for reducing the visible light reflectance include paragraphs [0017] to [0025] of JP-A-2014-150118, and paragraphs [0041], [0042], and [0042] of JP-A-2013-206315 [0048] and [0058], the contents of which are incorporated herein.
＜絶縁膜を形成する工程、絶縁膜の表面に新たな導電層を形成する工程＞
　回路配線の製造方法は、回路配線の表面に絶縁膜を形成する工程と、絶縁膜の表面に新たな導電層を形成する工程とを有していてもよい。
　上記工程により、第１の電極パターンと、絶縁した第２の電極パターンとを形成できる。
　絶縁膜を形成する工程としては、例えば、公知の永久膜を形成する方法が挙げられる。また、絶縁性を有する感光性組成物を用いて、フォトリソグラフィにより所望のパターンの絶縁膜を形成してもよい。
　絶縁膜の表面に新たな導電層を形成する工程としては、例えば、導電性を有する感光性組成物を用いて、フォトリソグラフィにより所望のパターンの新たな導電層を形成してもよい。 <Step of Forming an Insulating Film, Step of Forming a New Conductive Layer on the Surface of the Insulating Film>
The circuit wiring manufacturing method may include the steps of forming an insulating film on the surface of the circuit wiring and forming a new conductive layer on the surface of the insulating film.
Through the above steps, the first electrode pattern and the insulated second electrode pattern can be formed.
The process of forming the insulating film includes, for example, a method of forming a known permanent film. Alternatively, an insulating film having a desired pattern may be formed by photolithography using an insulating photosensitive composition.
As the step of forming a new conductive layer on the surface of the insulating film, for example, a conductive photosensitive composition may be used to form a new conductive layer in a desired pattern by photolithography.
　回路配線の製造方法は、基板の両方の表面にそれぞれ複数の導電層を有する基板を用いて、基材の両方の表面に形成された導電層に対して逐次又は同時に回路配線を形成することも好ましい。
　上記構成により、一方の基板表面に第１の導電パターンを形成し、他方の基板表面に第２の導電パターンを形成したタッチパネル用回路配線を形成できる。また、上記構成のタッチパネル用回路配線を、ロールツーロールで基板の両面から形成することも好ましい。 The method of manufacturing the circuit wiring may use a substrate having a plurality of conductive layers on both surfaces of the substrate, and sequentially or simultaneously form circuit wiring on the conductive layers formed on both surfaces of the substrate. preferable.
With the above configuration, it is possible to form a touch panel circuit wiring in which the first conductive pattern is formed on one substrate surface and the second conductive pattern is formed on the other substrate surface. It is also preferable to form the touch panel circuit wiring having the above configuration from both sides of the substrate by roll-to-roll.
［回路配線の用途］
　回路配線の製造方法によって製造される回路配線は、種々の装置に適用することができる。上記回路配線を備えた装置としては、例えば、入力装置が挙げられ、タッチパネルが好ましく、静電容量型タッチパネルがより好ましい。上記入力装置は、例えば、有機ＥＬ表示装置及び液晶表示装置等の表示装置に適用できる。
　本発明の回路配線の製造方法の一態様として、例えば、露光する際に、メッシュ状に配置された遮光部を含むフォトマスクを使用する態様が挙げられる。上記製造方法は、メッシュ状の金属配線パターンの製造方法として好適である。上記製造方法により得られる配線回路は、例えば、透明導電膜として使用できる。具体的には、タッチパネル電極、透明ヒーター、透明アンテナ、電磁波シールド材、及び、調光フィルム等に使用できる。その場合、メッシュパターン領域のシート抵抗値は、低いほど好ましい。具体的には、１００Ω／□以下が好ましく、２０Ω／□以下がより好ましく、５Ω／□以下が特に好ましい。
下限は、０Ω／□超が好ましい。 [Use of circuit wiring]
The circuit wiring manufactured by the circuit wiring manufacturing method can be applied to various devices. Examples of the device having the circuit wiring include an input device, preferably a touch panel, and more preferably a capacitive touch panel. The input device can be applied to display devices such as an organic EL display device and a liquid crystal display device, for example.
One aspect of the circuit wiring manufacturing method of the present invention includes, for example, an aspect in which a photomask including a light shielding portion arranged in a mesh pattern is used in the exposure. The manufacturing method described above is suitable as a method for manufacturing a mesh-like metal wiring pattern. A wiring circuit obtained by the above manufacturing method can be used, for example, as a transparent conductive film. Specifically, it can be used for touch panel electrodes, transparent heaters, transparent antennas, electromagnetic wave shield materials, light control films, and the like. In that case, the sheet resistance value of the mesh pattern area is preferably as low as possible. Specifically, it is preferably 100Ω/□ or less, more preferably 20Ω/□ or less, and particularly preferably 5Ω/□ or less.
The lower limit is preferably greater than 0Ω/□.
　また、本発明の回路配線の製造の他の態様として、例えば、露光する際に、円形ドット状に配置された遮光部を含むフォトマスクを使用する態様が挙げられる。上記製造方法は、ビアの製造方法、半導体チップ、並びに、パッケージ間のインターコネクト用のピラー及びピンの製造方法として好適に使用され得る。ピラー及びピンの直径としては、１～２０μｍが好ましく、２～１０μｍがより好ましく、３～８μｍが更に好ましい。また、ピラー及びピンの長さとしては、１～２０μｍが好ましく、３～１０μｍがより好ましい。
　また、他の一例として、露光工程の際に、円形ドット状に配置された開口部を含むフォトマスクを使用する態様が挙げられる。上記製造方法は、スルーホール等の製造方法として好適である。スルーホールの直径としては、１～２０μｍが好ましく、２～１０μｍがより好ましく、３～８μｍが更に好ましい。また、スルーホールの深さとしては、１～２０μｍが好ましく、３～１０μｍがより好ましい。 Further, as another aspect of manufacturing the circuit wiring of the present invention, for example, there is an aspect in which a photomask including light shielding portions arranged in circular dots is used in the exposure. The manufacturing method described above can be suitably used as a method for manufacturing vias, a method for manufacturing semiconductor chips, and a method for manufacturing pillars and pins for interconnects between packages. The diameter of the pillars and pins is preferably 1-20 μm, more preferably 2-10 μm, even more preferably 3-8 μm. Also, the length of the pillars and pins is preferably 1 to 20 μm, more preferably 3 to 10 μm.
Further, as another example, there is a mode of using a photomask including openings arranged in the form of circular dots in the exposure process. The manufacturing method described above is suitable as a method for manufacturing through holes and the like. The diameter of the through-hole is preferably 1-20 μm, more preferably 2-10 μm, and even more preferably 3-8 μm. Also, the depth of the through-hole is preferably 1 to 20 μm, more preferably 3 to 10 μm.
　円形ドット状に配置された遮光部を含むフォトマスクを使用する上記の製造方法は、スルーホール等の製造方法としても好適である。スルーホールの直径としては、１～２０μｍが好ましく、２～１０μｍがより好ましく、３～８μｍが更に好ましい。また、スルーホールの深さとしては、１～２０μｍが好ましく、３～１０μｍ以下がより好ましい。
　なお、上記では本発明の回路配線の製造方法について述べたが、上記については本発明の積層体の製造方法であってもよい。 The above-described manufacturing method using a photomask including light-shielding portions arranged in circular dots is also suitable as a manufacturing method for through-holes and the like. The diameter of the through-hole is preferably 1-20 μm, more preferably 2-10 μm, and even more preferably 3-8 μm. Also, the depth of the through-hole is preferably 1 to 20 μm, more preferably 3 to 10 μm or less.
In addition, although the manufacturing method of the circuit wiring of the present invention has been described above, the manufacturing method of the laminate of the present invention may be applied to the above.
　上述の「円形」とは、真円及び略円のいずれであってもよい。上記円形が略円である場合、その直径とは、略円中で最も長い直径を意味する。
　また、「円形ドット状に配置された遮光部を含むフォトマスク」とは、円形ドット状の遮光部が１個配置されたフォトマスクであってもよいし、円形ドット状の遮光部が２個以上配置されたフォトマスクであってもよい。
　また、「円形ドット状に配置された開口部を含むフォトマスク」とは、円形ドット状の開口部が１個配置されたフォトマスクであってもよいし、円形ドット状の開口部が２個以上配置されたフォトマスクであってもよい。 The above-mentioned "circular shape" may be either a perfect circle or an approximate circle. When the circle is a substantially circle, the diameter means the longest diameter in the substantially circle.
Further, "a photomask including a light shielding portion arranged in a circular dot shape" may be a photomask in which one circular dot light shielding portion is arranged, or a photomask having two circular dot light shielding portions. A photomask arranged as described above may be used.
Further, the “photomask including openings arranged in circular dot shape” may be a photomask in which one circular dot-shaped opening is arranged, or a photomask in which two circular dot-shaped openings are arranged. A photomask arranged as described above may be used.
　なお、メッシュ状に配置された遮光部を含むフォトマスクは、メッシュ状に配置された遮光部とは異なるパターン状に配置された遮光部を含んでいてもよい。
　また、円形ドット状に配置された遮光部を含むフォトマスクは、円形ドット状に配置された遮光部とは異なるパターン状に配置された遮光部を含んでいてもよい。 The photomask including the light shielding portions arranged in a mesh pattern may include the light shielding portions arranged in a pattern different from the light shielding portions arranged in the mesh pattern.
A photomask including light shielding portions arranged in circular dots may include light shielding portions arranged in a pattern different from the light shielding portions arranged in circular dots.
［転写フィルム］
　転写フィルムは、仮支持体と、感光性組成物層とを有し、感光性組成物層をパターン露光する露光工程が施される転写フィルムであって、ＴｇＸが１１０℃以下であり、ＴｇＹが、１２５℃以上である。
　上記ＴｇＸ及び上記ＴｇＹは、上記積層体の製造方法における各記載と同義であり、好適態様も同じである。 [Transfer film]
The transfer film has a temporary support and a photosensitive composition layer, and is a transfer film to which an exposure step of pattern-exposing the photosensitive composition layer is performed, and has a TgX of 110° C. or less and a TgY of , above 125°C.
The above TgX and the above TgY have the same meanings as those described in the manufacturing method of the laminate, and the preferred embodiments are also the same.
　転写フィルムは、後述する感光性組成物層以外に、その他層を有していてもよい。
　その他層としては、例えば、後述する中間層及び後述する熱可塑性樹脂層が挙げられる。また、転写フィルムは、後述するその他部材（例えば、保護フィルム）を有していてもよい。 The transfer film may have other layers in addition to the photosensitive composition layer described below.
Other layers include, for example, an intermediate layer to be described later and a thermoplastic resin layer to be described later. Moreover, the transfer film may have other members (for example, a protective film) which will be described later.
　転写フィルムの実施態様としては、例えば、以下の構成（１）～（３）が挙げられる。
　なかでも、転写フィルムは中間層を有することが好ましく、以下の構成（２）又は構成（３）がより好ましく、構成（２）が更に好ましい。
（１）「仮支持体／感光性組成物層／保護フィルム」
（２）「仮支持体／中間層／感光性組成物層／保護フィルム」
（３）「仮支持体／熱可塑性樹脂層／中間層／感光性組成物層／保護フィルム」
　上記各構成における感光性組成物層としては、後述するネガ型感光性組成物層又は後述する着色樹脂層が好ましい。 Embodiments of the transfer film include, for example, the following configurations (1) to (3).
Above all, the transfer film preferably has an intermediate layer, and the following configuration (2) or configuration (3) is more preferred, and configuration (2) is even more preferred.
(1) "Temporary support/photosensitive composition layer/protective film"
(2) "Temporary support/intermediate layer/photosensitive composition layer/protective film"
(3) "Temporary support/thermoplastic resin layer/intermediate layer/photosensitive composition layer/protective film"
As the photosensitive composition layer in each of the above configurations, a negative photosensitive composition layer described later or a colored resin layer described later is preferable.
　上記貼合工程における気泡発生抑止の点から、転写フィルムのうねりの最大幅は、３００μｍ以下が好ましく、２００μｍ以下がより好ましく、６０μｍ以下が更に好ましい。下限は、０μｍ以上が好ましく、０．１μｍ以上がより好ましく、１μｍ以上が更に好ましい。
　転写フィルムのうねりの最大幅は、以下の手順により測定される値である。
　転写フィルムを縦２０ｃｍ×横２０ｃｍのサイズとなるように主面に垂直な方向に裁断し、試験サンプルを作製する。なお、転写フィルムが保護フィルムを有する場合、転写フィルムから保護フィルムを剥離する。次いで、表面が平滑かつ水平なステージ上に、上記試験サンプルを仮支持体の表面がステージに対向するように静置する。静置後、試験サンプルの中心１０ｃｍ角の範囲について、試料サンプルの表面をレーザー顕微鏡（例えば、キーエンス社製　ＶＫ－９７００ＳＰ）で走査して３次元表面画像を取得し、得られた３次元表面画像で観察される最大凸高さから最低凹高さを引き算する。上記操作を１０個の試験サンプルについて行い、その算術平均値を転写フィルムのうねり最大幅とする。 From the viewpoint of suppressing the generation of air bubbles in the bonding step, the maximum width of the undulation of the transfer film is preferably 300 μm or less, more preferably 200 μm or less, and even more preferably 60 μm or less. The lower limit is preferably 0 µm or more, more preferably 0.1 µm or more, and even more preferably 1 µm or more.
The maximum width of waviness of the transfer film is a value measured by the following procedure.
A test sample is prepared by cutting the transfer film in a direction perpendicular to the main surface so as to have a size of 20 cm long by 20 cm wide. In addition, when a transfer film has a protective film, a protective film is peeled from a transfer film. Next, the test sample is placed on a flat and horizontal stage so that the surface of the temporary support faces the stage. After standing still, the surface of the sample sample is scanned with a laser microscope (for example, VK-9700SP manufactured by Keyence Corporation) for the center 10 cm square range of the test sample to acquire a three-dimensional surface image, and the obtained three-dimensional surface image. Subtract the minimum concave height from the maximum convex height observed in . The above operation is performed for 10 test samples, and the arithmetic average value is taken as the maximum waviness width of the transfer film.
　転写フィルムの感光性組成物層において、感光性組成物層の仮支持体側とは反対側に、更に他の組成物層（例えば、感光性組成物層、中間層及び熱可塑性樹脂層等）を有する場合、他の組成物層の合計厚みとしては、感光性組成物層の厚みに対して、０．１～３０％が好ましく、０．１～２０％がより好ましい。 In the photosensitive composition layer of the transfer film, another composition layer (for example, a photosensitive composition layer, an intermediate layer, a thermoplastic resin layer, etc.) is further provided on the side opposite to the temporary support side of the photosensitive composition layer. When it is present, the total thickness of the other composition layers is preferably 0.1 to 30%, more preferably 0.1 to 20%, of the thickness of the photosensitive composition layer.
　密着性により優れる点から、感光性組成物層の波長３６５ｎｍの光の透過率は、１０％以上が好ましく、３０％以上がより好ましく、５０％以上が更に好ましい。上限は、９９．９％以下が好ましく、９９．０％以下がより好ましい。 The transmittance of light with a wavelength of 365 nm of the photosensitive composition layer is preferably 10% or more, more preferably 30% or more, and even more preferably 50% or more, from the viewpoint of better adhesion. The upper limit is preferably 99.9% or less, more preferably 99.0% or less.
　転写フィルムの実施形態の例について説明する。
　図１に示す転写フィルム１０は、仮支持体１１と、中間層１３及び感光性組成物層１５を含む組成物層１７と、保護フィルム１９とを、この順に有する。
　図１で示す転写フィルム１０は、中間層１３及び保護フィルム１９を有する形態であるが、中間層１３及び保護フィルム１９を有していなくてもよい。
　図１においては、仮支持体１１上に配置され得る保護フィルム１９を除く各層（例えば、感光性組成物層、中間層及び熱可塑性樹脂層）を、「組成物層」ともいう。
　転写フィルムは、上記層以外に、更に熱可塑性樹脂層を有していてもよい。熱可塑性樹脂層は、仮支持体１１と中間層１３と間に配置されることが好ましい。 Example embodiments of transfer films are described.
The transfer film 10 shown in FIG. 1 has a temporary support 11, a composition layer 17 including an intermediate layer 13 and a photosensitive composition layer 15, and a protective film 19 in this order.
Although the transfer film 10 shown in FIG. 1 has the intermediate layer 13 and the protective film 19, the intermediate layer 13 and the protective film 19 may be omitted.
In FIG. 1, each layer (for example, a photosensitive composition layer, an intermediate layer and a thermoplastic resin layer) other than the protective film 19 that can be placed on the temporary support 11 is also referred to as a "composition layer".
The transfer film may further have a thermoplastic resin layer in addition to the above layers. The thermoplastic resin layer is preferably arranged between the temporary support 11 and the intermediate layer 13 .
　以下、転写フィルムについて、各部材及び各成分を詳細に説明する。
　なお、以下に記載する構成要件の説明は、本発明の代表的な実施態様に基づいてなされることがあるが、本発明はそのような実施態様に限定されるものではない。 Each member and each component of the transfer film will be described in detail below.
In addition, although description of the constituent elements described below may be made based on a representative embodiment of the present invention, the present invention is not limited to such an embodiment.
〔仮支持体〕
　転写フィルムは、仮支持体を有する。
　仮支持体は、感光性組成物層を支持する部材であり、最終的には剥離処理により除去される。 [Temporary support]
The transfer film has a temporary support.
A temporary support is a member that supports the photosensitive composition layer, and is finally removed by a peeling treatment.
　仮支持体は、単層構造及び多層構造のいずれであってもよい。
　仮支持体としては、フィルムが好ましく、樹脂フィルムがより好ましい。また、仮支持体としては、可撓性を有し、かつ、加圧下又は加圧下及び加熱下において、著しい変形、収縮又は伸びを生じないフィルムも好ましく、シワ等の変形及び傷がないフィルムも好ましい。
　フィルムとしては、例えば、ポリエチレンテレフタレートフィルム（例えば、２軸延伸ポリエチレンテレフタレートフィルム）、ポリメチルメタクリレートフィルム、トリ酢酸セルロースフィルム、ポリスチレンフィルム、ポリイミドフィルム及びポリカーボネートフィルムが挙げられ、ポリエチレンテレフタレートフィルムが好ましい。 The temporary support may have either a single layer structure or a multilayer structure.
The temporary support is preferably a film, more preferably a resin film. In addition, as the temporary support, a film that has flexibility and does not undergo significant deformation, shrinkage, or elongation under pressure or under pressure and heat is also preferable, and a film that is free from deformation such as wrinkles and scratches is also preferable. preferable.
Examples of the film include polyethylene terephthalate film (eg, biaxially stretched polyethylene terephthalate film), polymethyl methacrylate film, cellulose triacetate film, polystyrene film, polyimide film and polycarbonate film, with polyethylene terephthalate film being preferred.
　仮支持体は、仮支持体を介してパターン露光できる点から、透明性が高いことが好ましい。具体的には、波長３６５ｎｍにおける仮支持体の透過率は、６０％以上が好ましく、７０％以上がより好ましい。上限は、１００％未満が好ましい。
　仮支持体を介するパターン露光時のパターン形成性及び仮支持体の透明性の点から、仮支持体のヘイズは小さい方が好ましい。具体的には、仮支持体のヘイズは、２％以下が好ましく、０．５％以下がより好ましく、０．１％以下が更に好ましい。下限は、０％以上が好ましい。 The temporary support preferably has high transparency from the viewpoint that pattern exposure can be performed through the temporary support. Specifically, the transmittance of the temporary support at a wavelength of 365 nm is preferably 60% or more, more preferably 70% or more. The upper limit is preferably less than 100%.
From the viewpoint of pattern formability during pattern exposure through the temporary support and transparency of the temporary support, the haze of the temporary support is preferably as small as possible. Specifically, the haze of the temporary support is preferably 2% or less, more preferably 0.5% or less, and even more preferably 0.1% or less. The lower limit is preferably 0% or more.
　仮支持体を介するパターン露光時のパターン形成性及び仮支持体の透明性の点から、仮支持体中の微粒子、異物及び欠陥の数は、少ない方が好ましい。具体的には、仮支持体中の微粒子（例えば、直径１μｍの微粒子）、異物及び欠陥の数は、５０個／１０ｍｍ２以下が好ましく、１０個／１０ｍｍ２以下がより好ましく、３個／１０ｍｍ２以下が更に好ましく、１個／１０ｍｍ２未満が特に好ましい。下限は、０個／１０ｍｍ２以上が好ましい。 From the viewpoint of pattern formability during pattern exposure through the temporary support and transparency of the temporary support, the number of fine particles, foreign matter and defects in the temporary support is preferably as small as possible. Specifically, the number of fine particles (for example, fine particles with a diameter of 1 μm), foreign matter and defects 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 less than 1/10 mm 2 is particularly preferable. The lower limit is preferably 0 pieces/10 mm 2 or more.
　仮支持体の厚みは、５～２００μｍが好ましく、取り扱いやすさ及び汎用性の点から、５～１５０μｍがより好ましく、５～５０μｍが更に好ましく、５～２５μｍが特に好ましい。
　仮支持体の厚みは、ＳＥＭ（走査型電子顕微鏡：Ｓｃａｎｎｉｎｇ　Ｅｌｅｃｔｒｏｎ　Ｍｉｃｒｏｓｃｏｐｅ）による断面観察により測定した任意の５点の平均値として算出される。 The thickness of the temporary support is preferably 5 to 200 μm, more preferably 5 to 150 μm, still more preferably 5 to 50 μm, particularly preferably 5 to 25 μm, from the viewpoint of ease of handling and versatility.
The thickness of the temporary support is calculated as an average value of arbitrary five points measured by cross-sectional observation with a SEM (Scanning Electron Microscope).
　仮支持体は、ハンドリング性の点から、仮支持体の片面又は両面に、微粒子を含む層（滑剤層）を有していてもよい。
　滑剤層に含まれる微粒子の直径は、０．０５～０．８μｍが好ましい。
　滑剤層の厚みは、０．０５～１．０μｍが好ましい。 The temporary support may have a layer containing fine particles (lubricant layer) on one side or both sides of the temporary support from the viewpoint of handling.
The fine particles contained in the lubricant layer preferably have a diameter of 0.05 to 0.8 μm.
The thickness of the lubricant layer is preferably 0.05 to 1.0 μm.
　仮支持体と感光性組成物層との密着性を向上させる点から、仮支持体の感光性組成物層と接する面は、表面改質処理されていてもよい。
　表面改質処理としては、例えば、ＵＶ照射、コロナ放電及びプラズマ等を用いる処理が挙げられる。
　ＵＶ照射における露光量は、１０～２０００ｍＪ／ｃｍ２が好ましく、５０～１０００ｍＪ／ｃｍ２がより好ましい。
　露光量が上記範囲であれば、ランプ出力及び照度は特に制限されない。
　ＵＶ照射における光源としては、例えば、１５０～４５０ｎｍ波長帯域の光を発する低圧水銀ランプ、高圧水銀ランプ、超高圧水銀灯、カーボンアーク灯、メタルハライドランプ、キセノンランプ、ケミカルランプ、無電極放電ランプ及び発光ダイオード（ＬＥＤ）が挙げられる。 From the viewpoint of improving the adhesion between the temporary support and the photosensitive composition layer, the surface of the temporary support in contact with the photosensitive composition layer may be subjected to a surface modification treatment.
Examples of surface modification treatment include treatments using UV irradiation, corona discharge, plasma, and the like.
The exposure amount in UV irradiation is preferably 10-2000 mJ/cm 2 , more preferably 50-1000 mJ/cm 2 .
As long as the exposure amount is within the above range, the lamp output and illuminance are not particularly limited.
Light sources for UV irradiation include, for example, low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, carbon arc lamps, metal halide lamps, xenon lamps, chemical lamps, electrodeless discharge lamps, and light-emitting diodes that emit light in the wavelength band of 150 to 450 nm. (LED).
　仮支持体としては、例えば、厚み１６μｍの２軸延伸ポリエチレンテレフタレートフィルム、厚み１２μｍの２軸延伸ポリエチレンテレフタレートフィルム及び厚み９μｍの２軸延伸ポリエチレンテレフタレートフィルムが挙げられる。
　また、仮支持体としては、例えば、特開２０１４－０８５６４３号公報の段落［００１７］～［００１８］、特開２０１６－０２７３６３号公報の段落［００１９］～［００２６］、国際公開第２０１２／０８１６８０号の段落［００４１］～［００５７］及び国際公開第２０１８／１７９３７０号の段落［００２９］～［００４０］も挙げられ、これらの内容は本明細書に組み込まれる。
　仮支持体の市販品としては、例えば、登録商標ルミラー１６ＫＳ４０及び登録商標ルミラー１６ＦＢ４０（以上、東レ社製)；コスモシャインＡ４１００、コスモシャインＡ４３００及びコスモシャインＡ８３００（以上、東洋紡社製）が挙げられる。 Examples of the temporary support include a 16 μm thick biaxially stretched polyethylene terephthalate film, a 12 μm thick biaxially stretched polyethylene terephthalate film, and a 9 μm thick biaxially stretched polyethylene terephthalate film.
Further, as the temporary support, for example, paragraphs [0017] to [0018] of JP-A-2014-085643, paragraphs [0019] to [0026] of JP-A-2016-027363, International Publication No. 2012/081680 and paragraphs [0029] to [0040] of WO2018/179370, the contents of which are incorporated herein.
Examples of commercially available temporary supports include Lumirror 16KS40 (registered trademark) and Lumirror 16FB40 (registered trademark) (manufactured by Toray Industries, Inc.); Cosmoshine A4100, Cosmoshine A4300 and Cosmoshine A8300 (manufactured by Toyobo Co., Ltd.).
〔感光性組成物層〕
　転写フィルムは、感光性組成物層を有する。
　静電容量型入力装置等のタッチパネルを備えた表示装置（例えば、有機ＥＬ表示装置及び液晶表示装置等）では、視認部のセンサーに相当する電極パターン、周辺配線部分及び取り出し配線部分の配線等の導電層パターンがタッチパネル内部に設けられている。一般的にパターン化した層の形成には、転写フィルム等を用いて基板上に感光性組成物層を設け、その感光性組成物層に対して所望のパターンを有するフォトマスクを介して露光した後、現像する方法が広く採用されている。したがって、感光性組成物層としては、ネガ型感光性組成物層が好ましい。感光性組成物層がネガ型感光性組成物層である場合、形成されるパターンは硬化膜に該当する。 [Photosensitive composition layer]
The transfer film has a photosensitive composition layer.
In a display device having a touch panel such as a capacitive input device (for example, an organic EL display device, a liquid crystal display device, etc.), an electrode pattern corresponding to a sensor in the visual recognition part, wiring of the peripheral wiring part and the lead-out wiring part, etc. A conductive layer pattern is provided inside the touch panel. Generally, for forming a patterned layer, a photosensitive composition layer is provided on a substrate using a transfer film or the like, and the photosensitive composition layer is exposed through a photomask having a desired pattern. After that, the method of developing is widely adopted. Therefore, the photosensitive composition layer is preferably a negative photosensitive composition layer. When the photosensitive composition layer is a negative photosensitive composition layer, the formed pattern corresponds to a cured film.
　感光性組成物層は、後述する樹脂及び後述する重合性化合物を含むことが好ましく、後述する樹脂、後述する重合性化合物及び後述する重合開始剤を含むことがより好ましい。また、感光性組成物層は、後述する樹脂がアルカリ可溶性樹脂を含むことも好ましい。つまり、感光性組成物層は、アルカリ可溶性樹脂を含む樹脂及び重合性化合物を含むことが好ましい。
　感光性組成物層は、感光性組成物層の全質量に対して、樹脂を１０．０～９０．０質量％、重合性化合物を５．０～７０．０質量％及び重合開始剤を０．０１～２０．０質量％含むことが好ましい。
　以下、感光性組成物層が含み得る各成分について説明する。 The photosensitive composition layer preferably contains a resin to be described later and a polymerizable compound to be described later, and more preferably contains a resin to be described later, a polymerizable compound to be described later and a polymerization initiator to be described later. Moreover, it is also preferable that the photosensitive composition layer contains an alkali-soluble resin as the resin described later. That is, the photosensitive composition layer preferably contains a resin containing an alkali-soluble resin and a polymerizable compound.
The photosensitive composition layer contains 10.0 to 90.0% by weight of the resin, 5.0 to 70.0% by weight of the polymerizable compound, and 0 of the polymerization initiator with respect to the total weight of the photosensitive composition layer. 0.01 to 20.0% by mass is preferably contained.
Each component that the photosensitive composition layer may contain will be described below.
＜樹脂＞
　感光性組成物層は、樹脂を含んでいてもよい。
　樹脂としては、アルカリ可溶性樹脂が好ましい。
　樹脂としては、後述する熱可塑性樹脂層に含まれるアルカリ可溶性樹脂を用いてもよい。 <Resin>
The photosensitive composition layer may contain a resin.
As the resin, an alkali-soluble resin is preferable.
As the resin, an alkali-soluble resin contained in the thermoplastic resin layer, which will be described later, may be used.
　露光時の焦点位置にずれが生じたときの線幅太り及び解像度の悪化を抑制する点から、樹脂は、芳香族炭化水素基を有する単量体に由来する構成単位を含むことが好ましい。
　上記芳香族炭化水素基としては、例えば、置換基を有していてもよいフェニル基及び置換基を有していてもよいアラルキル基が挙げられる。
　芳香族炭化水素基を有する単量体に由来する構成単位の含有量は、樹脂の全質量に対して、１０．０質量％以上が好ましく、２０．０質量％以上がより好ましく、３０．０質量％以上が更に好ましい。上限は、樹脂の全質量に対して、８０．０質量％以下が好ましく、６０．０質量％以下がより好ましく、５５．０質量％以下が更に好ましい。感光性組成物層が複数の樹脂を含む場合、芳香族炭化水素基を有する単量体に由来する構成単位の含有量の質量平均値が、上記範囲内であることが好ましい。 The resin preferably contains a structural unit derived from a monomer having an aromatic hydrocarbon group from the viewpoint of suppressing thickening of the line width and deterioration of resolution when the focus position shifts during exposure.
Examples of the aromatic hydrocarbon group include an optionally substituted phenyl group and an optionally substituted aralkyl group.
The content of structural units derived from a monomer having an aromatic hydrocarbon group is preferably 10.0% by mass or more, more preferably 20.0% by mass or more, more preferably 30.0% by mass, based on the total mass of the resin. More than % by mass is more preferable. The upper limit is preferably 80.0% by mass or less, more preferably 60.0% by mass or less, and even more preferably 55.0% by mass or less, relative to the total mass of the resin. When the photosensitive composition layer contains a plurality of resins, the weight average value of the content of structural units derived from the monomer having an aromatic hydrocarbon group is preferably within the above range.
　芳香族炭化水素基を有する単量体としては、例えば、アラルキル基を有する単量体、スチレン及び重合可能なスチレン誘導体（例えば、メチルスチレン、ビニルトルエン、ｔｅｒｔ－ブトキシスチレン、アセトキシスチレン、４－ビニル安息香酸、スチレンダイマー及びスチレントリマー等）が挙げられ、アラルキル基を有する単量体又はスチレンが好ましく、スチレンがより好ましい。
　芳香族炭化水素基を有する単量体がスチレンである場合、スチレンに由来する構成単位の含有量は、樹脂の全質量に対して、１０．０～８０．０質量％が好ましく、２０．０～６０．０質量％がより好ましく、３０．０～５５．０質量％が更に好ましい。感光性組成物層が複数の樹脂を含む場合、芳香族炭化水素基を有する構成単位の含有量の質量平均値が、上記範囲内であることが好ましい。 Examples of monomers having an aromatic hydrocarbon group include monomers having an aralkyl group, styrene and polymerizable styrene derivatives (e.g., methylstyrene, vinyltoluene, tert-butoxystyrene, acetoxystyrene, 4-vinyl benzoic acid, styrene dimer, styrene trimer, etc.), preferably an aralkyl group-containing monomer or styrene, more preferably styrene.
When the monomer having an aromatic hydrocarbon group is styrene, the content of structural units derived from styrene is preferably 10.0 to 80.0% by mass, preferably 20.0%, based on the total mass of the resin. ~60.0% by mass is more preferable, and 30.0 to 55.0% by mass is even more preferable. When the photosensitive composition layer contains a plurality of resins, it is preferable that the weight average value of the content of structural units having an aromatic hydrocarbon group is within the above range.
　アラルキル基としては、例えば、置換基を有していてもよいフェニルアルキル基（ただし、ベンジル基を除く）及び置換基を有していてもよいベンジル基が挙げられ、置換基を有していてもよいベンジル基が好ましい。 Examples of the aralkyl group include a phenylalkyl group optionally having a substituent (excluding a benzyl group) and a benzyl group optionally having a substituent. A benzyl group with a higher molecular weight is preferred.
　フェニルアルキル基を有する単量体としては、例えば、フェニルエチル（メタ）アクリレートが挙げられる。 Examples of monomers having a phenylalkyl group include phenylethyl (meth)acrylate.
　ベンジル基を有する単量体としては、例えば、ベンジル（メタ）アクリレート及びクロロベンジル（メタ）アクリレート等のベンジル基を有する（メタ）アクリレート；ビニルベンジルクロライド及びビニルベンジルアルコール等のベンジル基を有するビニルモノマーが挙げられ、ベンジル基を有する（メタ）アクリレートが好ましく、ベンジル（メタ）アクリレートがより好ましい。
　芳香族炭化水素基を有する単量体がベンジル（メタ）アクリレートである場合、ベンジル（メタ）アクリレートに由来する構成単位の含有量は、樹脂の全質量に対して、１０．０～９０．０質量％が好ましく、２０．０～８０．０質量％がより好ましく、３０．０～７０．０質量％が更に好ましい。 Examples of monomers having a benzyl group include (meth)acrylates having a benzyl group such as benzyl (meth)acrylate and chlorobenzyl (meth)acrylate; vinyl monomers having a benzyl group such as vinylbenzyl chloride and vinylbenzyl alcohol. A (meth)acrylate having a benzyl group is preferred, and a benzyl (meth)acrylate is more preferred.
When the monomer having an aromatic hydrocarbon group is benzyl (meth)acrylate, the content of structural units derived from benzyl (meth)acrylate is 10.0 to 90.0 with respect to the total mass of the resin. % by mass is preferable, 20.0 to 80.0% by mass is more preferable, and 30.0 to 70.0% by mass is even more preferable.
　芳香族炭化水素基を有する単量体に由来する構成単位を含む樹脂は、芳香族炭化水素基を有する単量体と、後述する第１の単量体を少なくとも１つ及び／又は後述する第２の単量体を少なくとも１つと、を重合することにより得られることが好ましい。 The resin containing a structural unit derived from a monomer having an aromatic hydrocarbon group includes a monomer having an aromatic hydrocarbon group and at least one first monomer described later and/or a first monomer described later. It is preferably obtained by polymerizing 2 monomers with at least one.
　芳香族炭化水素基を有する単量体に由来する構成単位を含まない樹脂は、後述する第１の単量体の少なくとも１つを重合することにより得られることが好ましく、第１の単量体の少なくとも１つと後述する第２の単量体の少なくとも１つとを重合することにより得られることがより好ましい。 The resin that does not contain a structural unit derived from a monomer having an aromatic hydrocarbon group is preferably obtained by polymerizing at least one of the first monomers described later, and the first monomer and at least one of the second monomers to be described later are more preferably obtained by polymerizing.
　第１の単量体は、分子中にカルボキシ基を有する単量体である。
　第１の単量体としては、例えば、（メタ）アクリル酸、フマル酸、ケイ皮酸、クロトン酸、イタコン酸、４－ビニル安息香酸、マレイン酸無水物及びマレイン酸半エステルが挙げられ、（メタ）アクリル酸が好ましい。
　第１の単量体に由来する構成単位の含有量は、樹脂の全質量に対して、５．０～５０．０質量％が好ましく、１０．０～４０．０質量％がより好ましく、１０．０～３０．０質量％が更に好ましい。
　上記含有量が５．０質量％以上である場合、優れる現像性及びエッジフューズ性の制御等を実現できる。上記含有量が５０．０質量％以下である場合、レジストパターンの高解像性、スソ形状の制御及びレジストパターンの高耐薬品性を実現できる。 A 1st monomer is a monomer which has a carboxy group in a molecule|numerator.
Examples of the first monomer include (meth)acrylic acid, fumaric acid, cinnamic acid, crotonic acid, itaconic acid, 4-vinylbenzoic acid, maleic anhydride and maleic acid half ester, ( Meth)acrylic acid is preferred.
The content of the structural unit derived from the first monomer is preferably 5.0 to 50.0% by mass, more preferably 10.0 to 40.0% by mass, based on the total mass of the resin. 0 to 30.0% by mass is more preferable.
When the content is 5.0% by mass or more, excellent developability and control of edge fuse properties can be achieved. When the content is 50.0% by mass or less, high resolution of the resist pattern, control of the groove shape, and high chemical resistance of the resist pattern can be realized.
　第２の単量体は、非酸性（酸性基を有さない）であり、かつ、分子中に重合性基を有する単量体である。
　重合性基は、後述する重合性化合物が有する重合性基と同義であり、好適態様も同じである。
　第２の単量体としては、例えば、メチル（メタ）アクリレート、エチル（メタ）アクリレート、ｎ－プロピル（メタ）アクリレート、イソプロピル（メタ）アクリレート、ｎ－ブチル（メタ）アクリレート、イソブチル（メタ）アクリレート、ｔｅｒｔ－ブチル（メタ）アクリレート、２－ヒドロキシエチル（メタ）アクリレート、２－ヒドロキシプロピル（メタ）アクリレート、シクロヘキシル（メタ）アクリレート及び２－エチルヘキシル（メタ）アクリレート等の（メタ）アクリレート類；酢酸ビニル等のビニルアルコールのエステル類；（メタ）アクリロニトリルが挙げられる。
　なかでも、メチル（メタ）アクリレート、エチル（メタ）アクリレート、２－エチルヘキシル（メタ）アクリレート又はｎ－ブチル（メタ）アクリレートが好ましく、メチル（メタ）アクリレート又はエチル（メタ）アクリレートがより好ましい。
　第２の単量体に由来する構成単位の含有量は、樹脂の全質量に対して、１．０～８０．０質量％が好ましく、１．０～６０．０質量％がより好ましく、１．０～５０．０質量％が更に好ましい。 The second monomer is a monomer that is non-acidic (has no acidic group) and has a polymerizable group in its molecule.
The polymerizable group has the same meaning as the polymerizable group possessed by the polymerizable compound described later, and the preferred embodiments are also the same.
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. , tert-butyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, cyclohexyl (meth)acrylate and 2-ethylhexyl (meth)acrylate; vinyl acetate vinyl alcohol esters such as; (meth)acrylonitrile;
Among them, methyl (meth)acrylate, ethyl (meth)acrylate, 2-ethylhexyl (meth)acrylate and n-butyl (meth)acrylate are preferred, and methyl (meth)acrylate and ethyl (meth)acrylate are more preferred.
The content of the structural unit derived from the second monomer is preferably 1.0 to 80.0% by mass, more preferably 1.0 to 60.0% by mass, based on the total mass of the resin. 0 to 50.0% by mass is more preferable.
　樹脂は、側鎖に、直鎖構造、分岐構造及び脂環構造のいずれかを有していてもよい。
　側鎖に分岐構造を有する基を含む単量体又は側鎖に脂環構造を有する基を含む単量体を使用することによって、樹脂の側鎖に分岐構造又は脂環構造を導入することができる。脂環構造を有する基は、単環及び多環のいずれであってもよい。
　「側鎖」とは、主鎖から枝分かれした原子団を意味する。「主鎖」とは、樹脂を構成する高分子化合物の分子中で相対的に最も長い結合鎖を意味する。
　側鎖に分岐構造を有する基を含む単量体としては、例えば、（メタ）アクリル酸イソプロピル、（メタ）アクリル酸イソブチル、（メタ）アクリル酸ｓｅｃ－ブチル、（メタ）アクリル酸ｔｅｒｔ－ブチル、（メタ）アクリル酸イソアミル、（メタ）アクリル酸ｔｅｒｔ－アミル、（メタ）アクリル酸ｓｅｃ－アミル、（メタ）アクリル酸２－オクチル、（メタ）アクリル酸３－オクチル及び（メタ）アクリル酸ｔｅｒｔ－オクチルが挙げられる。
　なかでも、（メタ）アクリル酸イソプロピル、（メタ）アクリル酸イソブチル又はメタクリル酸ｔｅｒｔ－ブチルが好ましく、メタクリル酸イソプロピル又はメタクリル酸ｔｅｒｔ－ブチルがより好ましい。
　側鎖に脂環構造を有する基を含む単量体としては、例えば、単環の脂肪族炭化水素基を有する単量体及び多環の脂肪族炭化水素基を有する単量体が挙げられる。また、炭素数５～２０の脂環式炭化水素基を有する（メタ）アクリレートが挙げられる。
　具体的には、（メタ）アクリル酸（ビシクロ〔２．２．１〕ヘプチル－２）、（メタ）アクリル酸－１－アダマンチル、（メタ）アクリル酸－２－アダマンチル、（メタ）アクリル酸－３－メチル－１－アダマンチル、（メタ）アクリル酸－３，５－ジメチル－１－アダマンチル、（メタ）アクリル酸－３－エチルアダマンチル、（メタ）アクリル酸－３－メチル－５－エチル－１－アダマンチル、（メタ）アクリル酸－３，５，８－トリエチル－１－アダマンチル、（メタ）アクリル酸－３，５－ジメチル－８－エチル－１－アダマンチル、（メタ）アクリル酸２－メチル－２－アダマンチル、（メタ）アクリル酸２－エチル－２－アダマンチル、（メタ）アクリル酸３－ヒドロキシ－１－アダマンチル、（メタ）アクリル酸オクタヒドロ－４，７－メンタノインデン－５－イル、（メタ）アクリル酸オクタヒドロ－４，７－メンタノインデン－１－イルメチル、（メタ）アクリル酸－１－メンチル、（メタ）アクリル酸トリシクロデカン、（メタ）アクリル酸－３－ヒドロキシ－２，６，６－トリメチル－ビシクロ〔３．１．１〕ヘプチル、（メタ）アクリル酸－３，７，７－トリメチル－４－ヒドロキシ－ビシクロ〔４．１．０〕ヘプチル、（メタ）アクリル酸（ノル）ボルニル、（メタ）アクリル酸イソボルニル、（メタ）アクリル酸フェンチル、（メタ）アクリル酸－２，２，５－トリメチルシクロヘキシル及び（メタ）アクリル酸シクロヘキシルが挙げられる。
　なかでも、（メタ）アクリル酸シクロヘキシル、（メタ）アクリル酸（ノル）ボルニル、（メタ）アクリル酸イソボルニル、（メタ）アクリル酸－１－アダマンチル、（メタ）アクリル酸－２－アダマンチル、（メタ）アクリル酸フェンチル、（メタ）アクリル酸１－メンチル又は（メタ）アクリル酸トリシクロデカンが好ましく、（メタ）アクリル酸シクロヘキシル、（メタ）アクリル酸（ノル）ボルニル、（メタ）アクリル酸イソボルニル、（メタ）アクリル酸－２－アダマンチル又は（メタ）アクリル酸トリシクロデカンがより好ましい。 The resin may have any one of a linear structure, a branched structure and an alicyclic structure in the side chain.
By using a monomer containing a group having a branched structure in its side chain or a monomer containing a group having an alicyclic structure in its side chain, a branched structure or alicyclic structure can be introduced into the side chain of the resin. can. A group having an alicyclic structure may be either monocyclic or polycyclic.
"Side chain" means an atomic group branched off from the main chain. The “main chain” means the relatively longest linking chain in the molecule of the polymer compound that constitutes the resin.
Examples of the monomer containing a group having a branched structure in the side chain include isopropyl (meth)acrylate, isobutyl (meth)acrylate, sec-butyl (meth)acrylate, tert-butyl (meth)acrylate, Isoamyl (meth)acrylate, tert-amyl (meth)acrylate, sec-amyl (meth)acrylate, 2-octyl (meth)acrylate, 3-octyl (meth)acrylate and tert- (meth)acrylate octyl.
Among them, isopropyl (meth)acrylate, isobutyl (meth)acrylate and tert-butyl methacrylate are preferred, and isopropyl methacrylate and tert-butyl methacrylate are more preferred.
The monomer containing a group having an alicyclic structure in its side chain includes, for example, a monomer having a monocyclic aliphatic hydrocarbon group and a monomer having a polycyclic aliphatic hydrocarbon group. (Meth)acrylates having an alicyclic hydrocarbon group with 5 to 20 carbon atoms are also included.
Specifically, (meth) acrylic acid (bicyclo[2.2.1] heptyl-2), (meth) acrylic acid-1-adamantyl, (meth) acrylic acid-2-adamantyl, (meth) acrylic acid- 3-methyl-1-adamantyl, (meth)acrylate-3,5-dimethyl-1-adamantyl, (meth)acrylate-3-ethyladamantyl, (meth)acrylate-3-methyl-5-ethyl-1 -adamantyl, (meth)acrylate-3,5,8-triethyl-1-adamantyl, (meth)acrylate-3,5-dimethyl-8-ethyl-1-adamantyl, (meth)acrylate 2-methyl- 2-adamantyl, 2-ethyl-2-adamantyl (meth) acrylate, 3-hydroxy-1-adamantyl (meth) acrylate, octahydro-4,7-menthanoinden-5-yl (meth) acrylate, ( Octahydro-4,7-menthanoinden-1-ylmethyl meth)acrylate, 1-menthyl (meth)acrylate, tricyclodecane (meth)acrylate, 3-hydroxy-2,6 (meth)acrylate ,6-trimethyl-bicyclo[3.1.1]heptyl, (meth)acrylic acid-3,7,7-trimethyl-4-hydroxy-bicyclo[4.1.0]heptyl, (meth)acrylic acid (nor ) bornyl, isobornyl (meth)acrylate, fenchyl (meth)acrylate, 2,2,5-trimethylcyclohexyl (meth)acrylate and cyclohexyl (meth)acrylate.
Among them, cyclohexyl (meth)acrylate, (nor)bornyl (meth)acrylate, isobornyl (meth)acrylate, 1-adamantyl (meth)acrylate, 2-adamantyl (meth)acrylate, (meth)acrylate Fentyl acrylate, 1-menthyl (meth)acrylate or tricyclodecane (meth)acrylate is preferred, cyclohexyl (meth)acrylate, (nor)bornyl (meth)acrylate, isobornyl (meth)acrylate, (meth) ) 2-adamantyl acrylate or tricyclodecane (meth)acrylate is more preferred.
　樹脂は、本発明の効果がより優れる点から、重合性基を有することが好ましく、重合性基を有する構成単位を含むことがより好ましく、側鎖にエチレン性不飽和基を有する構成単位を含むことが更に好ましい。
　上記重合性基としては、後述する重合性化合物が有する重合性基が挙げられ、エチレン性不飽和基が好ましく、アクリロイル基又はメタアクリロイル基がより好ましい。
　また、上記重合性基は、重合性化合物の重合性基と重合反応し得る重合性基も好ましい。 The resin preferably has a polymerizable group, more preferably contains a structural unit having a polymerizable group, and contains a structural unit having an ethylenically unsaturated group in the side chain, from the viewpoint that the effects of the present invention are more excellent. is more preferred.
Examples of the polymerizable group include a polymerizable group possessed by a polymerizable compound to be described later, preferably an ethylenically unsaturated group, and more preferably an acryloyl group or a methacryloyl group.
Further, the polymerizable group is preferably a polymerizable group capable of undergoing a polymerization reaction with the polymerizable group of the polymerizable compound.
　重合性基を有する構成単位を含む樹脂は、第１の単量体に由来する構成単位を含む樹脂と、第３の単量体とを反応することにより得られることが好ましい。 The resin containing a structural unit having a polymerizable group is preferably obtained by reacting a resin containing a structural unit derived from the first monomer with the third monomer.
　第３の単量体は、分子中に２つ以上の重合性基を有する単量体であり、分子中に２つの重合性基を有する単量体であることが好ましい。
　上記重合性基としては、例えば、後述する重合性化合物が有する重合性基が挙げられる。なかでも、第３の単量体は、２種の重合性基を有することが好ましく、エチレン性不飽和基とカチオン性重合性基とを有することがより好ましく、アクリロイル基又はメタアクリロイル基とエポキシ基とを有することが更に好ましい。 The third monomer is a monomer having two or more polymerizable groups in the molecule, preferably a monomer having two polymerizable groups in the molecule.
Examples of the polymerizable group include a polymerizable group possessed by a polymerizable compound to be described later. Among them, the third monomer preferably has two types of polymerizable groups, more preferably has an ethylenically unsaturated group and a cationic polymerizable group, an acryloyl group or a methacryloyl group and an epoxy It is more preferred to have a group.
　第３の単量体としては、例えば、（メタ）アクリル酸グリシジルが挙げられる。 Examples of the third monomer include glycidyl (meth)acrylate.
　重合性基を有する構成単位としては、式（Ｐ）で表される構成単位が好ましい。 As the structural unit having a polymerizable group, a structural unit represented by formula (P) is preferable.
Figure JPOXMLDOC01-appb-C000001
Figure JPOXMLDOC01-appb-C000001
　式（Ｐ）中、ＲＰは、水素原子又はメチル基を表す。ＬＰは、２価の連結基を表す。Ｐは、重合性基を表す。 In formula (P), R P represents a hydrogen atom or a methyl group. LP represents a divalent linking group. P represents a polymerizable group.
　ＲＰは、水素原子又はメチル基を表す。
　ＲＰとしては、水素原子が好ましい。 R P represents a hydrogen atom or a methyl group.
R 2 P is preferably a hydrogen atom.
　ＬＰは、２価の連結基を表す。
　上記２価の連結基としては、例えば、－ＣＯ－、－Ｏ－、－Ｓ－、－ＳＯ－、－ＳＯ２－、－ＮＲＮ－、炭化水素基及びそれらを組み合わせた基が挙げられる。ＲＮは、置換基を表す。
　上記炭化水素基としては、例えば、アルキレン基、シクロアルキレン基及びアリーレン基が挙げられる。
　上記アルキレン基は、直鎖状及び分岐鎖状のいずれであってもよい。上記アルキレン基の炭素数は、１～１０が好ましく、２～８がより好ましく、３～５が更に好ましい。上記アルキレン基は、ヘテロ原子を有していてもよく、上記アルキレン基中のメチレン基がヘテロ原子に置き換わってもよい。上記ヘテロ原子としては、酸素原子、硫黄原子又は窒素原子が好ましく、酸素原子がより好ましい。
　上記シクロアルキレン基は、単環及び多環のいずれであってもよい。上記シクロアルキレン基の炭素数は、３～２０が好ましく、５～１０がより好ましく、６～８が更に好ましい。
　上記アリーレン基は、単環及び多環のいずれであってもよい。上記アリーレン基の炭素数は、６～２０が好ましく、６～１５がより好ましく、６～１０が更に好ましい。上記アリーレン基としては、フェニレン基が好ましい。
　上記シクロアルキレン基及び上記アリーレン基は、環員原子としてヘテロ原子を有していてもよい。上記ヘテロ原子としては、酸素原子、硫黄原子又は窒素原子が好ましく、酸素原子がより好ましい。
　上記炭化水素基は、更に置換基を有していてもよい。
　上記置換基としては、例えば、ハロゲン原子（例えば、フッ素原子等）、ヒドロキシ基、ニトロ基、シアノ基、アルキル基、アルコキシ基、アルコキシカルボニル基及びアルケニル基が挙げられ、ヒドロキシ基が好ましい。
　ＬＰとしては、ヘテロ原子を有していてもよいアルキレン基が好ましい。 LP represents a divalent linking group.
Examples of the divalent linking group include -CO-, -O-, -S-, -SO-, -SO 2 -, -NR N -, hydrocarbon groups, and combinations thereof. RN represents a substituent.
Examples of the hydrocarbon group include an alkylene group, a cycloalkylene group and an arylene group.
The alkylene group may be linear or branched. The alkylene group preferably has 1 to 10 carbon atoms, more preferably 2 to 8 carbon atoms, and still more preferably 3 to 5 carbon atoms. The alkylene group may have a heteroatom, and the methylene group in the alkylene group may be replaced with a heteroatom. The heteroatom is preferably an oxygen atom, a sulfur atom or a nitrogen atom, more preferably an oxygen atom.
The cycloalkylene group may be either monocyclic or polycyclic. The cycloalkylene group preferably has 3 to 20 carbon atoms, more preferably 5 to 10 carbon atoms, and still more preferably 6 to 8 carbon atoms.
The arylene group may be monocyclic or polycyclic. The arylene group preferably has 6 to 20 carbon atoms, more preferably 6 to 15 carbon atoms, and even more preferably 6 to 10 carbon atoms. A phenylene group is preferable as the arylene group.
The cycloalkylene group and the arylene group may have a heteroatom as a ring member atom. The heteroatom is preferably an oxygen atom, a sulfur atom or a nitrogen atom, more preferably an oxygen atom.
The hydrocarbon group may further have a substituent.
Examples of the substituent include halogen atoms (eg, fluorine atoms), hydroxy groups, nitro groups, cyano groups, alkyl groups, alkoxy groups, alkoxycarbonyl groups and alkenyl groups, with hydroxy groups being preferred.
As L P , an alkylene group optionally having a heteroatom is preferable.
　Ｐは、重合性基を表す。
　上記重合性基は、上述したとおりである。 P represents a polymerizable group.
The polymerizable group is as described above.
　重合性基を有する構成単位としては、例えば、以下の構成単位が挙げられる。 Examples of structural units having a polymerizable group include the following structural units.
Figure JPOXMLDOC01-appb-C000002
Figure JPOXMLDOC01-appb-C000002
　樹脂が重合性基を有する構成単位を含む場合、重合性基を有する構成単位の含有量は、樹脂の全質量に対して、５．０～７０．０質量％が好ましく、１０．０～５０．０質量％がより好ましく、１５．０～４０．０質量％が更に好ましく、本発明の効果がより優れる点から、２０．０～４０．０質量％が特に好ましい。 When the resin contains a structural unit having a polymerizable group, the content of the structural unit having a polymerizable group is preferably 5.0 to 70.0% by mass, preferably 10.0 to 50%, based on the total mass of the resin. 0% by mass is more preferable, 15.0 to 40.0% by mass is more preferable, and 20.0 to 40.0% by mass is particularly preferable because the effects of the present invention are more excellent.
　重合性基を樹脂に導入する方法としては、例えば、樹脂が有する、ヒドロキシ基、カルボキシ基、第１級アミノ基、第２級アミノ基、アセトアセチル基及びスルホ基等の基に、エポキシ化合物、ブロックイソシアネート化合物、イソシアネート化合物、ビニルスルホン化合物、アルデヒド化合物、メチロール化合物及びカルボン酸無水物を反応させる方法が挙げられる。
　重合性基を樹脂に導入する方法の好適態様としては、例えば、第１の単量体を重合反応により合成した後、得られた樹脂の第１の単量体に由来する構成単位のカルボキシ基の一部に第３の単量体（好ましくは、グリシジル（メタ）アクリレート）を高分子反応させて、樹脂に重合性基（好ましくは、（メタ）アクリロキシ基）を導入する方法が挙げられる。上記高分子反応の反応温度は、８０～１１０℃が好ましい。上記高分子反応は、触媒を用いることが好ましく、アンモニウム塩（テトラエチルアンモニウムブロミド）を用いることがより好ましい。
　上記重合反応の反応温度は、７０～１００℃が好ましく、８０～９０℃がより好ましい。上記重合反応は、重合開始剤を用いることが好ましく、重合開始剤としてアゾ系開始剤を用いることがより好ましく、重合開始剤としてＶ－６０１（富士フイルム和光純薬社製）又はＶ－６５（富士フイルム和光純薬社製）が更に好ましい。 As a method for introducing a polymerizable group into a resin, for example, an epoxy compound, A method of reacting a blocked isocyanate compound, an isocyanate compound, a vinyl sulfone compound, an aldehyde compound, a methylol compound and a carboxylic acid anhydride can be mentioned.
As a preferred embodiment of the method of introducing a polymerizable group into a resin, for example, after synthesizing a first monomer by a polymerization reaction, a carboxy group of a structural unit derived from the first monomer of the obtained resin is introduced. A third monomer (preferably glycidyl (meth)acrylate) is subjected to a polymer reaction in a part of to introduce a polymerizable group (preferably (meth)acryloxy group) into the resin. The reaction temperature for the polymer reaction is preferably 80 to 110.degree. The polymer reaction preferably uses a catalyst, more preferably an ammonium salt (tetraethylammonium bromide).
The reaction temperature of the polymerization reaction is preferably 70 to 100°C, more preferably 80 to 90°C. The polymerization reaction preferably uses a polymerization initiator, more preferably an azo initiator as the polymerization initiator, V-601 (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) or V-65 ( Fuji Film Wako Pure Chemical Industries, Ltd.) is more preferable.
　樹脂としては、メタクリル酸に由来する構成単位とメチルメタクリレートに由来する構成単位とスチレンに由来する構成単位又はベンジルメタクリレートに由来する構成単位とを含む樹脂及びメタクリル酸に由来する構成単位とスチレンに由来する構成単位とを含む樹脂が好ましく、更に重合性基を有する構成単位を含む樹脂がより好ましい。
　上記において、各構成単位の含有量を、上述したそれぞれの好適態様にすることも好ましい。 As the resin, a resin containing a structural unit derived from methacrylic acid, a structural unit derived from methyl methacrylate, a structural unit derived from styrene or a structural unit derived from benzyl methacrylate, and a structural unit derived from methacrylic acid and a structural unit derived from styrene A resin containing a structural unit having a polymerizable group is preferable, and a resin containing a structural unit having a polymerizable group is more preferable.
In the above, it is also preferable to set the content of each structural unit to the above-mentioned suitable aspect.
　樹脂のＴｇは、６０～１３５℃が好ましく、７０～１１５℃がより好ましく、７５～１０５℃が更に好ましく、８０～１００℃が特に好ましい。 The Tg of the resin is preferably 60 to 135°C, more preferably 70 to 115°C, even more preferably 75 to 105°C, and particularly preferably 80 to 100°C.
　樹脂の酸価は、本発明の効果がより優れる点から、２２０ｍｇＫＯＨ／ｇ以下が好ましく、２００ｍｇＫＯＨ／ｇ未満がより好ましく、１９０ｍｇＫＯＨ／ｇ未満が更に好ましく、１７０ｍｇＫＯＨ／ｇ未満が特に好ましい。下限は、本発明の効果がより優れる点から、１０ｍｇＫＯＨ／ｇ以上が好ましく、５０ｍｇＫＯＨ／ｇ以上がより好ましく、７０ｍｇＫＯＨ／ｇ以上が更に好ましく、９０ｍｇＫＯＨ／ｇ以上が特に好ましい。
　「酸価（ｍｇＫＯＨ／ｇ）」とは、試料１ｇを中和するのに必要な水酸化カリウムの質量（ｍｇ）を意味する。酸価は、例えば、ＪＩＳ　Ｋ００７０：１９９２に準拠して求めることができる。
　樹脂の酸価は、樹脂が有する構成単位の種類及び／又は酸基を含む構成単位の含有量によって調整できる。 The acid value of the resin is preferably 220 mgKOH/g or less, more preferably less than 200 mgKOH/g, still more preferably less than 190 mgKOH/g, and particularly preferably less than 170 mgKOH/g, from the viewpoint that the effects of the present invention are more excellent. The lower limit is preferably 10 mgKOH/g or more, more preferably 50 mgKOH/g or more, still more preferably 70 mgKOH/g or more, and particularly preferably 90 mgKOH/g or more, from the viewpoint that the effect of the present invention is more excellent.
"Acid number (mg KOH/g)" means the mass (mg) of potassium hydroxide required to neutralize 1 g of sample. The acid value can be determined, for example, according to JIS K0070:1992.
The acid value of the resin can be adjusted by the type of structural unit contained in the resin and/or the content of the structural unit containing an acid group.
　樹脂の重量平均分子量としては、５，０００～５００，０００が好ましく、１０，０００～１００，０００がより好ましく、１０，０００～６０，０００が更に好ましく、２０，０００～５０，０００が特に好ましい。
　重量平均分子量が５００，０００以下である場合、解像性及び現像性を向上できる。また。重量平均分子量が５，０００以上である場合、現像凝集物の性状、並びに、転写フィルムのエッジフューズ性及びカットチップ性等の未露光膜の性状を制御できる。「エッジフューズ性」とは、転写フィルムをロール状に巻き取った場合に、ロールの端面からの、感光性組成物層のはみ出し易さの程度を意味する。「カットチップ性」とは、未露光膜をカッターで切断した場合に、チップの飛び易さの程度を意味する。このチップが転写フィルムの上面等に付着すると、後の露光工程等でフォトマスクに転写して不良品の原因となる。
　樹脂の分散度は、１．０～６．０が好ましく、１．０～５．０がより好ましく、１．０～４．０が更に好ましく、１．０～３．０が特に好ましい。 The weight average molecular weight of the resin is preferably 5,000 to 500,000, more preferably 10,000 to 100,000, even more preferably 10,000 to 60,000, and particularly preferably 20,000 to 50,000. .
When the weight average molecular weight is 500,000 or less, resolution and developability can be improved. Also. When the weight-average molecular weight is 5,000 or more, properties of development aggregates and properties of unexposed films such as edge-fuse properties and cut-chip properties of transfer films can be controlled. The term “edge-fusibility” means the extent to which the photosensitive composition layer easily protrudes from the end face of the roll when the transfer film is wound into a roll. “Cut chip resistance” means the degree of easiness of chip flying when an unexposed film is cut with a cutter. If this chip adheres to the upper surface of the transfer film, etc., it will be transferred to the photomask in the subsequent exposure process, etc., resulting in defective products.
The dispersity of the resin is preferably 1.0 to 6.0, more preferably 1.0 to 5.0, even more preferably 1.0 to 4.0, and particularly preferably 1.0 to 3.0.
　感光性組成物層は、上記樹脂以外に、その他樹脂を含んでいてもよい。
　その他樹脂としては、例えば、アクリル樹脂、スチレン－アクリル系共重合体、ポリウレタン樹脂、ポリビニルアルコール、ポリビニルホルマール、ポリアミド樹脂、ポリエステル樹脂、ポリアミド樹脂、エポキシ樹脂、ポリアセタール樹脂、ポリヒドロキシスチレン樹脂、ポリイミド樹脂、ポリベンゾオキサゾール樹脂、ポリシロキサン樹脂、ポリエチレンイミン、ポリアリルアミン及びポリアルキレングリコールが挙げられる。 The photosensitive composition layer may contain other resins in addition to the above resins.
Other resins include, for example, acrylic resins, styrene-acrylic copolymers, polyurethane resins, polyvinyl alcohol, polyvinyl formal, polyamide resins, polyester resins, polyamide resins, epoxy resins, polyacetal resins, polyhydroxystyrene resins, polyimide resins, Polybenzoxazole resins, polysiloxane resins, polyethyleneimines, polyallylamines and polyalkylene glycols are included.
　樹脂は、１種単独で用いてもよく、２種以上で用いてもよい。
　２種以上の樹脂を使用する場合、芳香族炭化水素基を有する単量体に由来する構成単位を含む樹脂を２種類混合使用すること又は芳香族炭化水素基を有する単量体に由来する構成単位を含む樹脂と芳香族炭化水素基を有する単量体に由来する構成単位を含まない樹脂とを混合使用することが好ましい。後者である場合、芳香族炭化水素基を有する単量体に由来する構成単位を含む樹脂の含有量は、樹脂の全質量に対して、５０．０質量％以上が好ましく、７０．０質量％以上がより好ましく、８０．０質量％以上が更に好ましく、９０．０質量％以上が特に好ましい。上限としては、樹脂の全質量に対して、１００．０質量％以下が好ましい。 One type of resin may be used alone, or two or more types may be used.
When two or more resins are used, a mixture of two types of resins containing structural units derived from monomers having aromatic hydrocarbon groups or a structure derived from monomers having aromatic hydrocarbon groups It is preferable to use a mixture of a resin containing the unit and a resin not containing a structural unit derived from a monomer having an aromatic hydrocarbon group. In the latter case, the content of the resin containing a structural unit derived from a monomer having an aromatic hydrocarbon group is preferably 50.0% by mass or more, preferably 70.0% by mass, based on the total mass of the resin. The above is more preferable, 80.0% by mass or more is still more preferable, and 90.0% by mass or more is particularly preferable. As an upper limit, 100.0 mass % or less is preferable with respect to the total mass of resin.
　樹脂の含有量は、感光性組成物層の全質量に対して、１０．０～９０．０質量％が好ましく、２０．０～８０．０質量％がより好ましく、３０．０～７０．０質量％が更に好ましく、４０．０～６０．０質量％が特に好ましい。樹脂の含有量が、感光性組成物層の全質量に対して、９０．０質量％以下である場合、現像時間を制御できる。また、樹脂の含有量が、感光性組成物層の全質量に対して、１０．０質量％以上である場合、耐エッジフューズ性を向上できる。 The resin content is preferably 10.0 to 90.0% by mass, more preferably 20.0 to 80.0% by mass, and 30.0 to 70.0% by mass, based on the total mass of the photosensitive composition layer. % by mass is more preferred, and 40.0 to 60.0% by mass is particularly preferred. When the resin content is 90.0% by mass or less with respect to the total mass of the photosensitive composition layer, the developing time can be controlled. Moreover, when the content of the resin is 10.0% by mass or more with respect to the total mass of the photosensitive composition layer, the edge fuse resistance can be improved.
　樹脂の合成方法としては、例えば、上述した単量体を、アセトン、メチルエチルケトン及びイソプロパノール等の溶剤で希釈した溶液に、過酸化ベンゾイル及びアゾイソブチロニトリル等のラジカル重合開始剤を適量添加し、加熱撹拌する方法が挙げられる。混合物の一部を反応液に滴下しながら合成してもよい。また、反応終了後、更に溶剤を加えて、所望の濃度に調整してもよい。
　樹脂の合成方法としては、上記以外に、例えば、塊状重合、懸濁重合及び乳化重合が挙げられる。 As a method for synthesizing the resin, for example, a suitable amount of a radical polymerization initiator such as benzoyl peroxide and azoisobutyronitrile is added to a solution obtained by diluting the above-mentioned monomer with a solvent such as acetone, methyl ethyl ketone and isopropanol, A method of heating and stirring can be used. You may synthesize|combine, dripping a part of mixture to a reaction liquid. Further, after the completion of the reaction, a solvent may be further added to adjust the desired concentration.
In addition to the methods described above, examples of resin synthesizing methods include bulk polymerization, suspension polymerization, and emulsion polymerization.
＜重合性化合物＞
　感光性組成物層は、重合性基を有する重合性化合物を含んでいてもよい。
　「重合性化合物」とは、後述する重合開始剤の作用で重合する化合物であって、上記樹脂とは異なる化合物を意味する。 <Polymerizable compound>
The photosensitive composition layer may contain a polymerizable compound having a polymerizable group.
"Polymerizable compound" means a compound that polymerizes under the action of a polymerization initiator described later and that is different from the above resin.
　重合性化合物が有する重合性基としては、重合反応に関与する基であればよく、例えば、ビニル基、アクリロイル基、メタクリロイル基、スチリル基及びマレイミド基等のエチレン性不飽和基を有する基；エポキシ基及びオキセタン基等のカチオン性重合性基を有する基が挙げられる。
　なかでも、重合性基としては、エチレン性不飽和基を有する基が好ましく、アクリロイル基又はメタアクリロイル基がより好ましい。 The polymerizable group possessed by the polymerizable compound may be any group that participates in the polymerization reaction. and groups having cationic polymerizable groups such as oxetane groups.
Among them, as the polymerizable group, a group having an ethylenically unsaturated group is preferable, and an acryloyl group or a methacryloyl group is more preferable.
　重合性化合物としては、感光性組成物層の感光性がより優れる点から、１つ以上のエチレン性不飽和基を有する化合物（以下、「エチレン性不飽和化合物」ともいう。）が好ましく、分子中に２つ以上のエチレン性不飽和基を有する化合物（以下、「多官能エチレン性不飽和化合物」ともいう。）がより好ましい。
　また、解像性及び剥離性がより優れる点で、エチレン性不飽和化合物が分子中に有するエチレン性不飽和基の数は、１～６が好ましく、１～３がより好ましく、２～３が更に好ましく、３が特に好ましい。 As the polymerizable compound, a compound having one or more ethylenically unsaturated groups (hereinafter also referred to as "ethylenically unsaturated compound") is preferable, since the photosensitive composition layer has better photosensitivity. Compounds having two or more ethylenically unsaturated groups therein (hereinafter also referred to as "polyfunctional ethylenically unsaturated compounds") are more preferred.
Further, from the viewpoint of better resolution and peelability, the number of ethylenically unsaturated groups that the ethylenically unsaturated compound has in the molecule is preferably 1 to 6, more preferably 1 to 3, and 2 to 3. More preferred, 3 being particularly preferred.
　重合性化合物は、アルキレンオキシ基を有していてもよい。
　上記アルキレン基としては、エチレンオキシ基又はプロピレンオキシ基が好ましく、本発明の効果がより優れる点から、エチレンオキシ基がより好ましい。重合性化合物に付加するアルキレンオキシ基の付加数は、１分子当たり２～３０が好ましく、２～２０がより好ましい。 The polymerizable compound may have an alkyleneoxy group.
As the alkylene group, an ethyleneoxy group or a propyleneoxy group is preferable, and an ethyleneoxy group is more preferable from the viewpoint that the effects of the present invention are more excellent. The number of alkyleneoxy groups added to the polymerizable compound is preferably 2 to 30, more preferably 2 to 20 per molecule.
　感光性組成物層の感光性と解像性及び剥離性とのバランスがより優れる点から、重合性化合物は、分子中に２又は３つのエチレン性不飽和基を有する２官能又は３官能エチレン性不飽和化合物を含むことが好ましく、１分子中に３つのエチレン性不飽和基を有する３官能エチレン性不飽和化合物を含むことがより好ましい。 The polymerizable compound is a bifunctional or trifunctional ethylenic compound having two or three ethylenically unsaturated groups in the molecule from the viewpoint of better balance between photosensitivity, resolution, and releasability of the photosensitive composition layer. It preferably contains an unsaturated compound, and more preferably contains a trifunctional ethylenically unsaturated compound having three ethylenically unsaturated groups in one molecule.
　２官能エチレン性不飽和化合物の含有量は、重合性化合物の全質量に対して、剥離性に優れる点から、２０．０質量％以上が好ましく、４０．０質量％超がより好ましく、５５．０質量％以上が更に好ましく、９０．０質量％以上が特に好ましい。上限は、１００．０質量％以下が好ましく、８０．０質量％以下がより好ましい。つまり、感光性組成物層に含まれる全ての重合性化合物が２官能エチレン性不飽和化合物であってもよい。
　３官能エチレン性不飽和化合物の含有量は、重合性化合物の全質量に対して、１０．０質量％以上が好ましく、２０．０質量％以上がより好ましい。上限は、１００．０質量％以下が好ましく、８０．０質量％以下がより好ましく、５０．０質量％以下が更に好ましい。つまり、感光性組成物層に含まれる全ての重合性化合物が３官能エチレン性不飽和化合物であってもよい。
　また、エチレン性不飽和化合物としては、重合性基として（メタ）アクリロイル基を有する（メタ）アクリレート化合物が好ましい。 The content of the bifunctional ethylenically unsaturated compound is preferably 20.0% by mass or more, more preferably more than 40.0% by mass, based on the total mass of the polymerizable compound, from the viewpoint of excellent peelability. 0% by mass or more is more preferable, and 90.0% by mass or more is particularly preferable. The upper limit is preferably 100.0% by mass or less, more preferably 80.0% by mass or less. That is, all polymerizable compounds contained in the photosensitive composition layer may be bifunctional ethylenically unsaturated compounds.
The content of the trifunctional ethylenically unsaturated compound is preferably 10.0% by mass or more, more preferably 20.0% by mass or more, relative to the total mass of the polymerizable compound. The upper limit is preferably 100.0% by mass or less, more preferably 80.0% by mass or less, and even more preferably 50.0% by mass or less. That is, all polymerizable compounds contained in the photosensitive composition layer may be trifunctional ethylenically unsaturated compounds.
Moreover, as the ethylenically unsaturated compound, a (meth)acrylate compound having a (meth)acryloyl group as a polymerizable group is preferable.
（重合性化合物Ｂ１）
　感光性組成物層は、芳香環及び２つのエチレン性不飽和基を有する重合性化合物Ｂ１を含むことも好ましい。
　重合性化合物Ｂ１は、上記重合性化合物のうち、分子中に１つ以上の芳香環を有する２官能エチレン性不飽和化合物である。 (Polymerizable compound B1)
The photosensitive composition layer also preferably contains a polymerizable compound B1 having an aromatic ring and two ethylenically unsaturated groups.
The polymerizable compound B1 is a bifunctional ethylenically unsaturated compound having one or more aromatic rings in the molecule among the above polymerizable compounds.
　重合性化合物Ｂ１が有する芳香環としては、例えば、ベンゼン環、ナフタレン環及びアントラセン環等の芳香族炭化水素環；チオフェン環、フラン環、ピロール環、イミダゾール環、トリアゾール環及びピリジン環等の芳香族複素環；これらの縮合環が挙げられ、芳香族炭化水素環が好ましく、ベンゼン環がより好ましい。上記芳香環は、置換基を有してもよい。
　重合性化合物Ｂ１は、１又は２つ以上の芳香環を有していてもよい。 Examples of the aromatic ring of the polymerizable compound B1 include aromatic hydrocarbon rings such as benzene ring, naphthalene ring and anthracene ring; aromatic rings such as thiophene ring, furan ring, pyrrole ring, imidazole ring, triazole ring and pyridine ring Heterocycle; condensed rings thereof are mentioned, preferably an aromatic hydrocarbon ring, more preferably a benzene ring. The aromatic ring may have a substituent.
Polymerizable compound B1 may have one or more aromatic rings.
　重合性化合物Ｂ１は、現像液による感光性組成物層の膨潤を抑制することにより、解像性が向上する点から、ビスフェノール構造を有することが好ましい。
　ビスフェノール構造としては、例えば、ビスフェノールＡ（２，２－ビス（４－ヒドロキシフェニル）プロパン）に由来するビスフェノールＡ構造、ビスフェノールＦ（２，２－ビス（４－ヒドロキシフェニル）メタン）に由来するビスフェノールＦ構造及びビスフェノールＢ（２，２－ビス（４－ヒドロキシフェニル）ブタン）に由来するビスフェノールＢ構造が挙げられ、ビスフェノールＡ構造が好ましい。 The polymerizable compound B1 preferably has a bisphenol structure from the viewpoint of improving the resolution by suppressing swelling of the photosensitive composition layer due to the developer.
The bisphenol structure includes, for example, a bisphenol A structure derived from bisphenol A (2,2-bis(4-hydroxyphenyl)propane) and a bisphenol derived from bisphenol F (2,2-bis(4-hydroxyphenyl)methane). Bisphenol B structures derived from F structures and bisphenol B (2,2-bis(4-hydroxyphenyl)butane) are included, with bisphenol A structures being preferred.
　ビスフェノール構造を有する重合性化合物Ｂ１としては、例えば、ビスフェノール構造と、そのビスフェノール構造の両端に結合した２つの重合性基（好ましくは（メタ）アクリロイル基）とを有する化合物が挙げられる。
　ビスフェノール構造の両端と２つの重合性基とは、直接結合してもいてもよく、１つ以上のアルキレンオキシ基を介して結合してもよい。ビスフェノール構造の両端に付加するアルキレンオキシ基としては、エチレンオキシ基又はプロピレンオキシ基が好ましく、エチレンオキシ基がより好ましい。ビスフェノール構造に付加するアルキレンオキシ基（好ましくは、エチレンオキシ基）の付加数は、１分子当たり２～３０が好ましく、２～２０がより好ましい。
　ビスフェノール構造を有する重合性化合物Ｂ１としては、例えば、特開２０１６－２２４１６２号公報の段落［００７２］～［００８０］が挙げられ、これらの内容は本明細書に組み込まれる。 Examples of the polymerizable compound B1 having a bisphenol structure include compounds 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 bonded via one or more alkyleneoxy groups. The alkyleneoxy group added to both ends of the bisphenol structure is preferably an ethyleneoxy group or a propyleneoxy group, more preferably an ethyleneoxy group. The number of alkyleneoxy groups (preferably ethyleneoxy groups) added to the bisphenol structure is preferably 2 to 30, more preferably 2 to 20 per molecule.
Examples of the polymerizable compound B1 having a bisphenol structure include paragraphs [0072] to [0080] of JP-A-2016-224162, the contents of which are incorporated herein.
　重合性化合物Ｂ１としては、ビスフェノールＡ構造を有する２官能エチレン性不飽和化合物が好ましく、２，２－ビス（４－（（メタ）アクリロキシポリアルコキシ）フェニル）プロパンがより好ましい。
　２，２－ビス（４－（（メタ）アクリロキシポリアルコキシ）フェニル）プロパンとしては、例えば、２，２－ビス（４－（メタクリロキシジエトキシ）フェニル）プロパン（ＦＡ－３２４Ｍ、日立化成社製）、２，２－ビス（４－（メタクリロキシエトキシプロポキシ）フェニル）プロパン及び２，２－ビス（４－（メタクリロキシペンタエトキシ）フェニル）プロパン等のエトキシ化ビスフェノールＡジメタクリレート（ＢＰＥシリーズ、新中村化学工業社製）、２，２－ビス（４－（メタクリロキシドデカエトキシテトラプロポキシ）フェニル）プロパン（ＦＡ－３２００ＭＹ、日立化成社製）、並びに、エトキシ化（１０）ビスフェノールＡジアクリレート（ＮＫエステルＡ－ＢＰＥ－１０、新中村化学工業社製）が挙げられる。 As the polymerizable 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 includes, for example, 2,2-bis(4-(methacryloxydiethoxy)phenyl)propane (FA-324M, Hitachi Chemical Co., Ltd.) ), ethoxylated bisphenol A dimethacrylates (BPE series, Shin-Nakamura Chemical Co., Ltd.), 2,2-bis (4-(methacryloxide decaethoxytetrapropoxy) phenyl) propane (FA-3200MY, manufactured by Hitachi Chemical Co., Ltd.), and ethoxylated (10) bisphenol A diacrylate ( NK Ester A-BPE-10, manufactured by Shin-Nakamura Chemical Co., Ltd.).
　重合性化合物Ｂ１としては、式（Ｂ１）で表される化合物も好ましい。 A compound represented by the formula (B1) is also preferable as the polymerizable compound B1.
Figure JPOXMLDOC01-appb-C000003
Figure JPOXMLDOC01-appb-C000003
　式（Ｂ１）中、Ｒ１及びＲ２は、それぞれ独立に、水素原子又はメチル基を表す。Ａはエチレン基を表す。Ｂはプロピレン基を表す。ｎ１及びｎ３は、それぞれ独立に、１～３９の整数を表す。ｎ１＋ｎ３は、２～４０の整数を表す。ｎ２及びｎ４は、それぞれ独立に、０～２９の整数を表す。ｎ２＋ｎ４は、０～３０の整数を表す。
　－（Ａ－Ｏ）－及び－（Ｂ－Ｏ）－の構成単位の配列は、ランダム及びブロックのいずれであってもよい。ブロックである場合、－（Ａ－Ｏ）－及び－（Ｂ－Ｏ）－のいずれがビスフェニル基側であってもよい。
　ｎ１＋ｎ２＋ｎ３＋ｎ４としては、２～２０が好ましく、２～１６がより好ましく、４～１２が更に好ましい。また、ｎ２＋ｎ４は、０～１０が好ましく、０～４がより好ましく、０～２が更に好ましく、０が特に好ましい。 In formula (B1), R 1 and R 2 each independently represent a hydrogen atom or a methyl group. A represents an ethylene group. B represents a propylene group. n1 and n3 each independently represent an integer of 1 to 39; n1+n3 represents an integer of 2-40. n2 and n4 each independently represent an integer of 0 to 29; n2+n4 represents an integer of 0-30.
The arrangement of -(AO)- and -(B-O)- constitutional units may be either random or block. In the case of a block, either -(AO)- or -(B-O)- may be on the side of the biphenyl group.
n1+n2+n3+n4 is preferably 2 to 20, more preferably 2 to 16, and even more preferably 4 to 12. Further, n2+n4 is preferably 0 to 10, more preferably 0 to 4, still more preferably 0 to 2, and particularly preferably 0.
　重合性化合物Ｂ１の含有量は、解像性がより優れる点から、感光性組成物層の全質量に対して、１０．０質量％以上が好ましく、２０．０質量％以上がより好ましく、２５．０質量％以上が更に好ましい。上限は、転写性及びエッジフュージョン（転写部材の端部から感光性組成物が滲み出す現象）の点から、７０．０質量％以下が好ましく、６０．０質量％以下がより好ましい。 The content of the polymerizable compound B1 is preferably 10.0% by mass or more, more preferably 20.0% by mass or more, with respect to the total mass of the photosensitive composition layer from the viewpoint of better resolution. 0% by mass or more is more preferable. The upper limit is preferably 70.0% by mass or less, more preferably 60.0% by mass or less, from the viewpoint of transferability and edge fusion (phenomenon in which the photosensitive composition exudes from the edge of the transfer member).
　重合性化合物Ｂ１の含有量は、重合性化合物の全質量に対して、解像性がより優れる点から、４０．０質量％以上が好ましく、５０．０質量％以上がより好ましく、５５．０質量％以上が更に好ましく、６０．０質量％以上が特に好ましい。上限としては、重合性化合物の全質量に対して、剥離性の点から、１００．０質量％以下が好ましく、９９．０質量％以下がより好ましく、９５．０質量％以下が更に好ましく、９０．０質量％以下が特に好ましく、８５．０質量％以下が最も好ましい。 The content of the polymerizable compound B1 is preferably 40.0% by mass or more, more preferably 50.0% by mass or more, more preferably 55.0% by mass, based on the total mass of the polymerizable compound, from the viewpoint of better resolution. % by mass or more is more preferable, and 60.0% by mass or more is particularly preferable. The upper limit is preferably 100.0% by mass or less, more preferably 99.0% by mass or less, still more preferably 95.0% by mass or less, from the viewpoint of peelability, relative to the total mass of the polymerizable compound, and 90 0% by mass or less is particularly preferred, and 85.0% by mass or less is most preferred.
（その他重合性化合物）
　感光性組成物層は、上記以外に、その他重合性化合物を含んでいてもよい。
　その他重合性化合物としては、例えば、公知の重合性化合物が挙げられる。
　具体的には、分子中に１つのエチレン性不飽和基を有する化合物（単官能エチレン性不飽和化合物）、芳香環を有さない２官能エチレン性不飽和化合物及び３官能以上のエチレン性不飽和化合物が挙げられる。 (Other polymerizable compounds)
The photosensitive composition layer may contain other polymerizable compounds in addition to the above.
Other polymerizable compounds include, for example, known polymerizable compounds.
Specifically, a compound having one ethylenically unsaturated group in the molecule (monofunctional ethylenically unsaturated compound), a bifunctional ethylenically unsaturated compound having no aromatic ring, and a trifunctional or higher ethylenically unsaturated compound compound.
　単官能エチレン性不飽和化合物としては、例えば、エチル（メタ）アクリレート、エチルヘキシル（メタ）アクリレート、２－（メタ）アクリロイルオキシエチルサクシネート、ポリエチレングリコールモノ（メタ）アクリレート、ポリプロピレングリコールモノ（メタ）アクリレート及びフェノキシエチル（メタ）アクリレートが挙げられる。 Examples of monofunctional ethylenically unsaturated compounds include ethyl (meth)acrylate, ethylhexyl (meth)acrylate, 2-(meth)acryloyloxyethyl succinate, polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate. and phenoxyethyl (meth)acrylate.
　芳香環を有さない２官能エチレン性不飽和化合物としては、例えば、アルキレングリコールジ（メタ）アクリレート、ポリアルキレングリコールジ（メタ）アクリレート、ウレタンジ（メタ）アクリレート及びトリメチロールプロパンジアクリレートが挙げられる。
　アルキレングリコールジ（メタ）アクリレートとしては、例えば、トリシクロデカンジメタノールジアクリレート（Ａ－ＤＣＰ、新中村化学工業社製）、トリシクロデカンジメタノールジメタクリレート（ＤＣＰ、新中村化学工業社製）、１，９－ノナンジオールジアクリレート（Ａ－ＮＯＤ－Ｎ、新中村化学工業社製）、１，６－ヘキサンジオールジアクリレート（Ａ－ＨＤ－Ｎ、新中村化学工業社製）、エチレングリコールジメタクリレート、１，１０－デカンジオールジアクリレート及びネオペンチルグリコールジ（メタ）アクリレートが挙げられる。
　ポリアルキレングリコールジ（メタ）アクリレートとしては、例えば、ポリエチレングリコールジ（メタ）アクリレート、ジプロピレングリコールジアクリレート、トリプロピレングリコールジアクリレート及びポリプロピレングリコールジ（メタ）アクリレートが挙げられる。
　ウレタンジ（メタ）アクリレートとしては、例えば、プロピレンオキサイド変性ウレタンジ（メタ）アクリレート、並びに、エチレンオキサイド及びプロピレンオキサイド変性ウレタンジ（メタ）アクリレートが挙げられる。また、ウレタンジ（メタ）アクリレートの市販品としては、例えば、８ＵＸ－０１５Ａ（大成ファインケミカル社製）、ＵＡ－３２Ｐ（新中村化学工業社製）及びＵＡ－１１００Ｈ（新中村化学工業社製）が挙げられる。 Bifunctional ethylenically unsaturated compounds having no aromatic ring include, for example, alkylene glycol di(meth)acrylate, polyalkylene glycol di(meth)acrylate, urethane di(meth)acrylate and trimethylolpropane diacrylate.
Alkylene glycol di(meth)acrylates include, for example, tricyclodecanedimethanol diacrylate (A-DCP, manufactured by Shin-Nakamura Chemical Co., Ltd.), tricyclodecanedimethanol dimethacrylate (DCP, manufactured by Shin-Nakamura Chemical Co., Ltd.), 1,9-nonanediol diacrylate (A-NOD-N, manufactured by Shin-Nakamura Chemical Co., Ltd.), 1,6-hexanediol diacrylate (A-HD-N, manufactured by Shin-Nakamura Chemical Co., Ltd.), ethylene glycol dimethacrylate , 1,10-decanediol diacrylate and neopentyl glycol di(meth)acrylate.
Polyalkylene glycol di(meth)acrylates include, for example, polyethylene glycol di(meth)acrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate and polypropylene glycol di(meth)acrylate.
Urethane di(meth)acrylates include, for example, propylene oxide-modified urethane di(meth)acrylates, and ethylene oxide and propylene oxide-modified urethane di(meth)acrylates. Commercially available products of urethane di(meth)acrylate include, for example, 8UX-015A (manufactured by Taisei Fine Chemical Co., Ltd.), UA-32P (manufactured by Shin-Nakamura Chemical Co., Ltd.) and UA-1100H (manufactured by Shin-Nakamura Chemical Co., Ltd.). be done.
　３官能以上のエチレン性不飽和化合物としては、例えば、ジペンタエリスリトール（トリ／テトラ／ペンタ／ヘキサ）（メタ）アクリレート、ペンタエリスリトール（トリ／テトラ）（メタ）アクリレート、トリメチロールプロパントリ（メタ）アクリレート、ジトリメチロールプロパンテトラ（メタ）アクリレート、トリメチロールエタントリ（メタ）アクリレート、イソシアヌル酸トリ（メタ）アクリレート、グリセリントリ（メタ）アクリレート及びこれらのアルキレンオキサイド変性物が挙げられる。
　「（トリ／テトラ／ペンタ／ヘキサ）（メタ）アクリレート」とは、トリ（メタ）アクリレート、テトラ（メタ）アクリレート、ペンタ（メタ）アクリレート及びヘキサ（メタ）アクリレートを包含する概念である。また、「（トリ／テトラ）（メタ）アクリレート」とは、トリ（メタ）アクリレート及びテトラ（メタ）アクリレートを包含する概念である。 Examples of trifunctional or higher ethylenically unsaturated compounds include dipentaerythritol (tri/tetra/penta/hexa) (meth) acrylate, pentaerythritol (tri/tetra) (meth) acrylate, trimethylolpropane tri(meth) Acrylate, ditrimethylolpropane tetra(meth)acrylate, trimethylolethane tri(meth)acrylate, isocyanuric acid tri(meth)acrylate, glycerin tri(meth)acrylate 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. Moreover, "(tri/tetra)(meth)acrylate" is a concept including tri(meth)acrylate and tetra(meth)acrylate.
　３官能以上のエチレン性不飽和化合物のアルキレンオキサイド変性物としては、例えば、カプロラクトン変性（メタ）アクリレート化合物（日本化薬社製ＫＡＹＡＲＡＤ（登録商標）ＤＰＣＡ－２０及び新中村化学工業社製Ａ－９３００－１ＣＬ等）、アルキレンオキサイド変性（メタ）アクリレート化合物（日本化薬社製ＫＡＹＡＲＡＤ　ＲＰ－１０４０、新中村化学工業社製ＡＴＭ－３５Ｅ及びＡ－９３００、ダイセル・オルネクス社製ＥＢＥＣＲＹＬ（登録商標）　１３５等）、エトキシル化グリセリントリアクリレート（新中村化学工業社製Ａ－ＧＬＹ－９Ｅ等）、アロニックス（登録商標）ＴＯ－２３４９（東亞合成社製）、アロニックスＭ－５２０（東亞合成社製）及びアロニックスＭ－５１０（東亞合成社製）が挙げられる。 Examples of alkylene oxide-modified tri- or higher ethylenically unsaturated compounds include, for example, caprolactone-modified (meth)acrylate compounds (KAYARAD (registered trademark) DPCA-20 manufactured by Nippon Kayaku Co., Ltd. and A-9300 manufactured by Shin-Nakamura Chemical Co., Ltd. -1CL, etc.), alkylene oxide-modified (meth)acrylate compounds (KAYARAD RP-1040 manufactured by Nippon Kayaku Co., Ltd., ATM-35E and A-9300 manufactured by Shin-Nakamura Chemical Co., Ltd., EBECRYL (registered trademark) 135 manufactured by Daicel Allnex Co., Ltd., etc. ), ethoxylated glycerin triacrylate (Shin-Nakamura Chemical Co., Ltd. A-GLY-9E, etc.), Aronix (registered trademark) TO-2349 (manufactured by Toagosei Co., Ltd.), Aronix M-520 (manufactured by Toagosei Co., Ltd.) and Aronix M -510 (manufactured by Toagosei Co., Ltd.).
　重合性化合物は、酸基（例えば、カルボキシ基等）を有する重合性化合物であってもよい。上記酸基は酸無水物基を形成していてもよい。
　酸基を有する重合性化合物としては、例えば、アロニックス（登録商標）ＴＯ－２３４９（東亞合成社製）、アロニックス（登録商標）Ｍ－５２０（東亞合成社製）及びアロニックス（登録商標）Ｍ－５１０（東亞合成社製）が挙げられる。
　酸基を有する重合性化合物として、例えば、特開２００４－２３９９４２号公報の段落［００２５］～［００３０］に記載の酸基を有する重合性化合物が挙げられる。 The polymerizable compound may be a polymerizable compound having an acid group (eg, carboxyl group, etc.). The acid group may form an acid anhydride group.
Examples of the polymerizable compound having an acid group include Aronix (registered trademark) TO-2349 (manufactured by Toagosei Co., Ltd.), Aronix (registered trademark) M-520 (manufactured by Toagosei Co., Ltd.) and Aronix (registered trademark) M-510. (manufactured by Toagosei Co., Ltd.).
Examples of the polymerizable compound having an acid group include polymerizable compounds having an acid group described in paragraphs [0025] to [0030] of JP-A-2004-239942.
　重合性化合物の分子量としては、２００～３，０００が好ましく、２８０～２，２００がより好ましく、３００～２，２００が更に好ましい。 The molecular weight of the polymerizable compound is preferably from 200 to 3,000, more preferably from 280 to 2,200, even more preferably from 300 to 2,200.
　重合性化合物の２５℃における粘度としては、１～１００００ｍＰａ・ｓが好ましく、５～３０００ｍＰａ・ｓがより好ましく、１０～１５００ｍＰａ・ｓが更に好ましい。
　また、重合性化合物を２種以上用いる場合、２種以上の重合性化合物のうち、最も粘度の高い重合性化合物Ａの２５℃における粘度と、最も粘度の低い重合性化合物Ｂの２５℃における粘度との差（絶対値）としては、２５０～５０００ｍＰａ・ｓが好ましく、５００～２５００Ｐａ・ｓがより好ましく、９００～１０００Ｐａ・ｓが更に好ましい。
　上記粘度の測定方法としては、例えば、以下の方法が挙げられる。
　振動式粘度計（ＳＥＫＯＮＩＣ社製、ＶＭ－１０Ａ）を用いて測定する。具体的には、重合性化合物（２０ｍＬ）を容器に移し、室温（２５±２℃）で３０分静置する。その後、重合性化合物の容器へ検出端子を挿入してから電源を入れ３０秒後の粘度の値を読み取る。 The viscosity of the polymerizable compound at 25° C. is preferably 1 to 10,000 mPa·s, more preferably 5 to 3,000 mPa·s, and even more preferably 10 to 1,500 mPa·s.
Further, when two or more polymerizable compounds are used, among the two or more polymerizable compounds, the viscosity at 25 ° C. of the polymerizable compound A having the highest viscosity and the viscosity at 25 ° C. of the polymerizable compound B having the lowest viscosity is preferably 250 to 5000 mPa·s, more preferably 500 to 2500 Pa·s, and even more preferably 900 to 1000 Pa·s.
Examples of the method for measuring the viscosity include the following methods.
It is measured using a vibrating viscometer (VM-10A manufactured by SEKONIC). Specifically, the polymerizable compound (20 mL) is transferred to a container and allowed to stand at room temperature (25±2° C.) for 30 minutes. After that, after inserting the detection terminal into the container of the polymerizable compound and turning on the power, read the value of the viscosity 30 seconds later.
　重合性化合物が有する重合性基の含有量は、１．０ｍｍｏｌ／ｇ以上が好ましく、２．０ｍｍｏｌ／ｇ以上がより好ましく、本発明の効果がより優れる点から、２．４ｍｍｏｌ／ｇ以上が更に好ましい。上限としては、１０．０ｍｍｏｌ／ｇ以下が好ましい。また、上記重合性の含有量を二重結合の含有量に置き換えて解釈してもよい。
　感光性組成物層が、複数の重合性化合物を含む場合、含まれる全ての重合性化合物が有する重合性基の含有量は、上記好適態様であることが好ましい。例えば、全ての重合性化合物は、重合性基を２．４ｍｍｏｌ／ｇ以上有することが好ましい。
　「重合性基の含有量」とは、重合性化合物１ｇ当たりに含まれる重合性基の当量（ｍｏｌ）を意味する。 The content of the polymerizable group possessed by the polymerizable compound is preferably 1.0 mmol/g or more, more preferably 2.0 mmol/g or more, and further preferably 2.4 mmol/g or more from the viewpoint that the effect of the present invention is more excellent. preferable. The upper limit is preferably 10.0 mmol/g or less. Moreover, you may interpret by replacing the said polymerizable content with the content of a double bond.
When the photosensitive composition layer contains a plurality of polymerizable compounds, it is preferable that the content of the polymerizable groups possessed by all the polymerizable compounds contained is in the preferred embodiment described above. For example, all polymerizable compounds preferably have 2.4 mmol/g or more of polymerizable groups.
"Polymerizable group content" means the equivalent amount (mol) of polymerizable groups contained per 1 g of the polymerizable compound.
　重合性化合物は、１種単独で用いてもよく、２種以上で用いてもよい。
　なかでも、重合性化合物は、本発明の効果がより優れる点から、３種以上で用いることが好ましく、３種で用いることがより好ましい。
　３種の重合性化合物を用いる場合、３種のうち少なくとも１つは重合性化合物Ｂ１であることが好ましく、３種のうち少なくとも２つは重合性化合物Ｂ１であることがより好ましい。
　重合性化合物の含有量は、感光性組成物層の全質量に対して、１０．０～７０．０質量％が好ましく、１５．０～７０．０質量％がより好ましく、２０．０～７０．０質量％が更に好ましい。 The polymerizable compound may be used alone or in combination of two or more.
Among them, the polymerizable compound is preferably used in three or more types, and more preferably in three types, from the viewpoint that the effects of the present invention are more excellent.
When three types of polymerizable compounds are used, at least one of the three types is preferably polymerizable compound B1, and at least two of the three types are more preferably polymerizable compound B1.
The content of the polymerizable compound is preferably 10.0 to 70.0% by mass, more preferably 15.0 to 70.0% by mass, and 20.0 to 70% by mass, based on the total mass of the photosensitive composition layer. 0 mass % is more preferred.
　樹脂の含有量に対する重合性化合物の含有量の質量比（重合性化合物の含有量／樹脂の含有量）が、０．１０～２．００が好ましく、０．５０～１．５０がより好ましく、本発明の効果がより優れる点から、０．７０～１．１０が更に好ましい。 The mass ratio of the polymerizable compound content to the resin content (polymerizable compound content/resin content) is preferably 0.10 to 2.00, more preferably 0.50 to 1.50, 0.70 to 1.10 is more preferable because the effect of the present invention is more excellent.
　感光性組成物層は、上記重合性化合物Ｂ１及び３官能以上のエチレン性不飽和化合物を含むことも好ましい。
　３官能以上のエチレン性不飽和化合物の含有量に対する重合性化合物Ｂ１の含有量の質量比（重合性化合物Ｂ１の含有量／３官能以上のエチレン性不飽和化合物の含有量）は、１．０～５．０が好ましく、１．２～４．０がより好ましく、１．５～３．０が更に好ましい。 The photosensitive composition layer preferably contains the polymerizable compound B1 and a tri- or higher functional ethylenically unsaturated compound.
The mass ratio of the content of the polymerizable compound B1 to the content of the trifunctional or higher ethylenically unsaturated compound (content of the polymerizable compound B1/content of the trifunctional or higher ethylenically unsaturated compound) is 1.0. ~5.0 is preferred, 1.2 to 4.0 is more preferred, and 1.5 to 3.0 is even more preferred.
＜重合開始剤＞
　感光性組成物層は、重合開始剤を含んでいてもよい。
　重合開始剤としては、例えば、重合反応の形式に応じて公知の重合開始剤が挙げられる。具体的には、熱重合開始剤及び光重合開始剤が挙げられる。
　重合開始剤は、ラジカル重合開始剤及びカチオン重合開始剤のいずれであってもよい。 <Polymerization initiator>
The photosensitive composition layer may contain a polymerization initiator.
Examples of the polymerization initiator include known polymerization initiators depending on the type of polymerization reaction. Specific examples include thermal polymerization initiators and photopolymerization initiators.
The polymerization initiator may be either a radical polymerization initiator or a cationic polymerization initiator.
　感光性組成物層は、光重合開始剤を含むことが好ましい。
　光重合開始剤は、紫外線、可視光線及びＸ線等の活性光線を受けて、重合性化合物の重合を開始する化合物である。光重合開始剤としては、例えば、公知の光重合開始剤が挙げられる。
　光重合開始剤としては、例えば、光ラジカル重合開始剤及び光カチオン重合開始剤が挙げられ、光ラジカル重合開始剤が好ましい。 The photosensitive composition layer preferably contains a photopolymerization initiator.
A photopolymerization initiator is a compound that initiates polymerization of a polymerizable compound upon exposure to actinic rays such as ultraviolet rays, visible rays, and X-rays. Examples of photopolymerization initiators include known photopolymerization initiators.
Examples of photopolymerization initiators include radical photopolymerization initiators and cationic photopolymerization initiators, and radical photopolymerization initiators are preferred.
　光ラジカル重合開始剤としては、例えば、オキシムエステル構造を有する光重合開始剤、α－アミノアルキルフェノン構造を有する光重合開始剤、α－ヒドロキシアルキルフェノン構造を有する光重合開始剤、アシルフォスフィンオキサイド構造を有する光重合開始剤及びＮ－フェニルグリシン構造を有する光重合開始剤が挙げられる。 Examples of photoradical polymerization initiators include photopolymerization initiators having an oxime ester structure, photopolymerization initiators having an α-aminoalkylphenone structure, photopolymerization initiators having an α-hydroxyalkylphenone structure, and acylphosphine oxide. A photopolymerization initiator having a structure and a photopolymerization initiator having an N-phenylglycine structure are included.
　光ラジカル重合開始剤は、感光性、露光部及び非露光部の視認性及び解像性の点から、２，４，５－トリアリールイミダゾール二量体及びその誘導体からなる群から選択される少なくとも１つを含むことが好ましい。なお、２，４，５－トリアリールイミダゾール二量体及びその誘導体における２つの２，４，５－トリアリールイミダゾール構造は、同一であっても異なっていてもよい。
　２，４，５－トリアリールイミダゾール二量体の誘導体としては、例えば、２－（ｏ－クロロフェニル）－４，５－ジフェニルイミダゾール二量体、２－（ｏ－クロロフェニル）－４，５－ジ（メトキシフェニル）イミダゾール二量体、２－（ｏ－フルオロフェニル）－４，５－ジフェニルイミダゾール二量体、２－（ｏ－メトキシフェニル）－４，５－ジフェニルイミダゾール二量体及び２－（ｐ－メトキシフェニル）－４，５－ジフェニルイミダゾール二量体が挙げられる。 The photoradical polymerization initiator is at least selected from the group consisting of 2,4,5-triarylimidazole dimers and derivatives thereof, from the viewpoint of photosensitivity, visibility of exposed and unexposed areas, and resolution. It is preferred to include one. The two 2,4,5-triarylimidazole structures in the 2,4,5-triarylimidazole dimer and its derivative may be the same or different.
Derivatives of 2,4,5-triarylimidazole dimer include, for example, 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer, 2-(o-chlorophenyl)-4,5-di (Methoxyphenyl)imidazole dimer, 2-(o-fluorophenyl)-4,5-diphenylimidazole dimer, 2-(o-methoxyphenyl)-4,5-diphenylimidazole dimer and 2-( p-Methoxyphenyl)-4,5-diphenylimidazole dimer.
　光ラジカル重合開始剤としては、例えば、特開２０１１－０９５７１６号公報の段落［００３１］～［００４２］及び特開２０１５－０１４７８３号公報の段落［００６４］～［００８１］に記載される光ラジカル重合開始剤が挙げられる。 As the photoradical polymerization initiator, for example, the photoradical polymerization described in paragraphs [0031] to [0042] of JP-A-2011-095716 and paragraphs [0064] to [0081] of JP-A-2015-014783 initiators.
　光ラジカル重合開始剤としては、例えば、ジメチルアミノ安息香酸エチル（ＤＢＥ）、ベンゾインメチルエーテル、アニシル（ｐ，ｐ’－ジメトキシベンジル）、ＴＡＺ－１１０（みどり化学社製）、ベンゾフェノン、４，４’－ビス（ジエチルアミノ）ベンゾフェノン、ＴＡＺ－１１１（みどり化学社製）、１－［４－（フェニルチオ）］－１，２－オクタンジオン－２－（Ｏ－ベンゾイルオキシム）（ＩＲＧＡＣＵＲＥ（登録商標）　ＯＸＥ－０１、ＢＡＳＦ社製）、１－［９－エチル－６－（２－メチルベンゾイル）－９Ｈ－カルバゾール－３－イル］エタノン－１－（Ｏ－アセチルオキシム）（ＩＲＧＡＣＵＲＥ　ＯＸＥ－０２、ＢＡＳＦ社製）、ＩＲＧＡＣＵＲＥ　ＯＸＥ－０３（ＢＡＳＦ社製）、ＩＲＧＡＣＵＲＥ　ＯＸＥ－０４（ＢＡＳＦ社製）、２－（ジメチルアミノ）－２－［（４－メチルフェニル）メチル］－１－［４－（４－モルフォリニル）フェニル］－１－ブタノン（Ｏｍｎｉｒａｄ　３７９ＥＧ、ＩＧＭ　Ｒｅｓｉｎｓ　Ｂ．Ｖ．社製）、２－メチル－１－（４－メチルチオフェニル）－２－モルフォリノプロパン－１－オン（Ｏｍｎｉｒａｄ　９０７、ＩＧＭ　Ｒｅｓｉｎｓ　Ｂ．Ｖ．社製）、２－ヒドロキシ－１－｛４－［４－（２－ヒドロキシ－２－メチルプロピオニル）ベンジル］フェニル｝－２－メチルプロパン－１－オン（Ｏｍｎｉｒａｄ　１２７、ＩＧＭ　Ｒｅｓｉｎｓ　Ｂ．Ｖ．社製）、２－ベンジル－２－ジメチルアミノ－１－（４－モルフォリノフェニル）ブタノン－１（Ｏｍｎｉｒａｄ　３６９、ＩＧＭ　Ｒｅｓｉｎｓ　Ｂ．Ｖ．社製）、２－ヒドロキシ－２－メチル－１－フェニルプロパン－１－オン（Ｏｍｎｉｒａｄ　１１７３、ＩＧＭ　Ｒｅｓｉｎｓ　Ｂ．Ｖ．社製）、１－ヒドロキシシクロヘキシルフェニルケトン（Ｏｍｎｉｒａｄ　１８４、ＩＧＭ　Ｒｅｓｉｎｓ　Ｂ．Ｖ．社製）、２，２－ジメトキシ－１，２－ジフェニルエタン－１－オン（Ｏｍｎｉｒａｄ　６５１、ＩＧＭ　Ｒｅｓｉｎｓ　Ｂ．Ｖ．社製）、２，４，６－トリメチルベンゾリル－ジフェニルフォスフィンオキサイド（Ｏｍｎｉｒａｄ　ＴＰＯ　Ｈ、ＩＧＭ　Ｒｅｓｉｎｓ　Ｂ．Ｖ．社製）、ビス（２，４，６－トリメチルベンゾリル）フェニルフォスフィンオキサイド（Ｏｍｎｉｒａｄ　８１９、ＩＧＭ　Ｒｅｓｉｎｓ　Ｂ．Ｖ．社製）、オキシムエステル系の光重合開始剤（Ｌｕｎａｒ　６、ＤＫＳＨジャパン社製）、２，２’－ビス（２－クロロフェニル）－４，４’，５，５’－テトラフェニルビスイミダゾール（２－（２－クロロフェニル）－４，５－ジフェニルイミダゾール二量体）（Ｂ－ＣＩＭ、Ｈａｍｐｆｏｒｄ社製）、２－（ｏ－クロロフェニル）－４，５－ジフェニルイミダゾール二量体（ＢＣＴＢ、東京化成工業社製）、１－［４－（フェニルチオ）フェニル］－３－シクロペンチルプロパン－１，２－ジオン－２－（Ｏ－ベンゾイルオキシム）（ＴＲ－ＰＢＧ－３０５、常州強力電子新材料社製）、１，２－プロパンジオン，３－シクロヘキシル－１－［９－エチル－６－（２－フラニルカルボニル）－９Ｈ－カルバゾール－３－イル］－，２－（Ｏ－アセチルオキシム）（ＴＲ－ＰＢＧ－３２６、常州強力電子新材料社製）及び３－シクロヘキシル－１－（６－（２－（ベンゾイルオキシイミノ）ヘキサノイル）－９－エチル－９Ｈ－カルバゾール－３－イル）－プロパン－１，２－ジオン－２－（Ｏ－ベンゾイルオキシム）（ＴＲ－ＰＢＧ－３９１、常州強力電子新材料社製）が挙げられる。 Examples of photoradical polymerization initiators include ethyl dimethylaminobenzoate (DBE), benzoin methyl ether, anisyl (p,p'-dimethoxybenzyl), TAZ-110 (manufactured by Midori Chemical Co., Ltd.), benzophenone, 4,4'. -Bis(diethylamino)benzophenone, TAZ-111 (manufactured by Midori Chemical Co., Ltd.), 1-[4-(phenylthio)]-1,2-octanedione-2-(O-benzoyloxime) (IRGACURE (registered trademark) OXE- 01, manufactured by BASF), 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone-1-(O-acetyloxime) (IRGACURE OXE-02, manufactured by BASF) ), IRGACURE OXE-03 (manufactured by BASF), IRGACURE OXE-04 (manufactured by BASF), 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl ) Phenyl]-1-butanone (Omnirad 379EG, IGM Resins B.V.), 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one (Omnirad 907, IGM Resins B V. Co.), 2-hydroxy-1-{4-[4-(2-hydroxy-2-methylpropionyl)benzyl]phenyl}-2-methylpropan-1-one (Omnirad 127, IGM Resins B.I. V.), 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butanone-1 (Omnirad 369, manufactured by IGM Resins B.V.), 2-hydroxy-2-methyl-1 -Phenylpropan-1-one (Omnirad 1173, manufactured by IGM Resins B.V.), 1-hydroxycyclohexylphenyl ketone (Omnirad 184, manufactured by IGM Resins B.V.), 2,2-dimethoxy-1,2 -diphenylethan-1-one (Omnirad 651, manufactured by IGM Resins B.V.), 2,4,6-trimethylbenzoyl-diphenylphosphine oxide (Omnirad TPO H, manufactured by IGM Resins B.V.), Bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide (Omnirad 819, manufactured by IGM Resins B.V.), oxime ester photopolymerization initiator (Lu nar 6, manufactured by DKSH Japan), 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbisimidazole (2-(2-chlorophenyl)-4,5-diphenylimidazole dimer) (B-CIM, manufactured by Hampford), 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer (BCTB, manufactured by Tokyo Chemical Industry Co., Ltd.), 1-[4-(phenylthio)phenyl ]-3-Cyclopentylpropane-1,2-dione-2-(O-benzoyloxime) (TR-PBG-305, manufactured by Changzhou Strong Electronic New Materials Co., Ltd.), 1,2-propanedione, 3-cyclohexyl-1- [9-ethyl-6-(2-furanylcarbonyl)-9H-carbazol-3-yl]-,2-(O-acetyloxime) (TR-PBG-326, manufactured by Changzhou Tenryu Electric New Materials Co., Ltd.) and 3 -cyclohexyl-1-(6-(2-(benzoyloximino)hexanoyl)-9-ethyl-9H-carbazol-3-yl)-propane-1,2-dione-2-(O-benzoyloxime) (TR -PBG-391, manufactured by Changzhou Strong Electronic New Materials Co., Ltd.).
　光カチオン重合開始剤（光酸発生剤）は、活性光線を受けて酸を発生する化合物である。光カチオン重合開始剤としては、波長３００ｎｍ以上（好ましくは波長３００～４５０ｎｍ）の活性光線に感応し、酸を発生する化合物が好ましい。また、波長３００ｎｍ以上の活性光線に直接感応しない光カチオン重合開始剤についても、増感剤と併用することによって波長３００ｎｍ以上の活性光線に感応し、酸を発生する化合物であれば、増感剤と組み合わせて好ましく使用できる。
　光カチオン重合開始剤としては、ｐＫａが４以下の酸を発生する光カチオン重合開始剤が好ましく、ｐＫａが３以下の酸を発生する光カチオン重合開始剤がより好ましく、ｐＫａが２以下の酸を発生する光カチオン重合開始剤が更に好ましい。下限は、－１０．０以上が好ましい。 A photocationic polymerization initiator (photoacid generator) is a compound that generates an acid upon receiving an actinic ray. The photocationic polymerization initiator is preferably a compound that responds to an actinic ray with a wavelength of 300 nm or more (preferably a wavelength of 300 to 450 nm) to generate an acid. In addition, for photocationic polymerization initiators that do not directly react to actinic rays with a wavelength of 300 nm or more, if they are compounds that react to actinic rays with a wavelength of 300 nm or more and generate an acid by using them in combination with a sensitizer, the sensitizer can be used. It can be preferably used in combination with
The photocationic polymerization initiator is preferably a photocationic polymerization initiator that generates an acid with a pKa of 4 or less, more preferably a photocationic polymerization initiator that generates an acid with a pKa of 3 or less, and an acid with a pKa of 2 or less. Photocationic polymerization initiators that generate are more preferred. The lower limit is preferably -10.0 or more.
　光カチオン重合開始剤としては、例えば、イオン性光カチオン重合開始剤及び非イオン性光カチオン重合開始剤が挙げられる。
　イオン性光カチオン重合開始剤として、例えば、ジアリールヨードニウム塩類及びトリアリールスルホニウム塩類等のオニウム塩化合物、並びに、第４級アンモニウム塩類が挙げられる。
　イオン性光カチオン重合開始剤としては、例えば、特開２０１４－０８５６４３号公報の段落［０１１４］～［０１３３］に記載のイオン性光カチオン重合開始剤が挙げられる。 Examples of photocationic polymerization initiators include ionic photocationic polymerization initiators and nonionic photocationic polymerization initiators.
Ionic photocationic polymerization initiators include, for example, onium salt compounds such as diaryliodonium salts and triarylsulfonium salts, and quaternary ammonium salts.
Examples of the ionic photocationic polymerization initiator include ionic photocationic polymerization initiators described in paragraphs [0114] to [0133] of JP-A-2014-085643.
　非イオン性光カチオン重合開始剤としては、例えば、トリクロロメチル－ｓ－トリアジン類、ジアゾメタン化合物、イミドスルホネート化合物及びオキシムスルホネート化合物が挙げられる。
　トリクロロメチル－ｓ－トリアジン類、ジアゾメタン化合物及びイミドスルホネート化合物としては、例えば、特開２０１１－２２１４９４号公報の段落［００８３］～［００８８］に記載の化合物が挙げられる。
　オキシムスルホネート化合物としては、例えば、国際公開第２０１８／１７９６４０号の段落［００８４］～［００８８］に記載された化合物が挙げられる。 Nonionic photocationic polymerization initiators include, for example, trichloromethyl-s-triazines, diazomethane compounds, imidosulfonate compounds and oximesulfonate compounds.
Examples of trichloromethyl-s-triazines, diazomethane compounds and imidosulfonate compounds include compounds described in paragraphs [0083] to [0088] of JP-A-2011-221494.
Oxime sulfonate compounds include, for example, compounds described in paragraphs [0084] to [0088] of WO2018/179640.
　重合開始剤は、１種単独で用いてもよく、２種以上で用いてもよい。
　重合開始剤（好ましくは光重合開始剤）の含有量は、感光性組成物層の全質量に対して、０．１質量％以上が好ましく、０．５質量％以上がより好ましい。上限は、感光性組成物層の全質量に対して、２０質量％以下が好ましく、１５質量％以下がより好ましく、１０質量％以下が更に好ましい。 A polymerization initiator may be used individually by 1 type, and may be used in 2 or more types.
The content of the polymerization initiator (preferably photopolymerization initiator) is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, relative to the total mass of the photosensitive composition layer. The upper limit is preferably 20% by mass or less, more preferably 15% by mass or less, and even more preferably 10% by mass or less, relative to the total mass of the photosensitive composition layer.
＜色素＞
　感光性組成物層は、露光部及び非露光部の視認性、並びに、現像後のパターン視認性及び解像性の点から、発色時の波長範囲４００～７８０ｎｍにおける最大吸収波長が４５０ｎｍ以上であり、かつ、酸、塩基又はラジカルにより最大吸収波長が変化する色素（以下、「色素Ｎ」ともいう。）を含んでいてもよい。
　色素Ｎを含む場合、詳細なメカニズムは不明であるが、隣接する層（例えば、中間層）との密着性が向上して解像性により優れる。 <Pigment>
The photosensitive composition layer has a maximum absorption wavelength of 450 nm or more in a wavelength range of 400 to 780 nm during color development from the viewpoint of visibility of exposed and unexposed areas, and pattern visibility and resolution after development. And, it may contain a dye whose maximum absorption wavelength is changed by an acid, a base, or a radical (hereinafter also referred to as “dye N”).
When the dye N is contained, although the detailed mechanism is unknown, the adhesion to the adjacent layer (for example, the intermediate layer) is improved and the resolution is improved.
　色素が「酸、塩基又はラジカルにより極大吸収波長が変化する」とは、発色状態にある色素が酸、塩基又はラジカルにより消色する態様、消色状態にある色素が酸、塩基又はラジカルにより発色する態様及び発色状態にある色素が他の色相の発色状態に変化する態様のいずれの態様を意味してもよい。
　具体的には、色素Ｎは、露光により消色状態から変化して発色する化合物及び露光により発色状態から変化して消色する化合物のいずれであってもよい。上記である場合、露光により酸、塩基又はラジカルが感光性組成物層内において発生し作用することにより、発色又は消色の状態が変化する色素であってもよく、酸、塩基又はラジカルにより感光性組成物層内の状態（例えば、ｐＨ）が変化することで発色又は消色の状態が変化する色素であってもよい。また、露光を介さずに、酸、塩基又はラジカルを刺激として直接受けて発色又は消色の状態が変化する色素であってもよい。 The dye "changes the maximum absorption wavelength by acid, base or radical" means that the dye in the colored state is decolored by acid, base or radical, and the dye in decolored state is colored by acid, base or radical. It may mean either one of the aspect in which the dye in the coloring state changes to the coloring state of another hue.
Specifically, the dye N may be either a compound that changes from a decolored state to develop color upon exposure or a compound that changes from a colored state to decolor upon exposure. In the above case, it may be a dye whose coloring or decoloring state changes due to the action of an acid, a base, or a radical generated in the photosensitive composition layer by exposure, and is sensitized by an acid, a base, or a radical. It may also be a dye that develops or decolors depending on the state (for example, pH) in the liquid composition layer. Further, it may be a dye that changes its coloring or decoloring state by being directly stimulated by an acid, a base, or a radical without being exposed to light.
　なかでも、露光部及び非露光部の視認性及び解像性の点から、色素Ｎは、酸又はラジカルにより最大吸収波長が変化する色素が好ましく、ラジカルにより最大吸収波長が変化する色素がより好ましい。
　感光性組成物層は、露光部及び非露光部の視認性及び解像性の点から、色素Ｎとしてラジカルにより最大吸収波長が変化する色素及び光ラジカル重合開始剤の両者を含むことが好ましい。また、露光部及び非露光部の視認性の点から、色素Ｎは、酸、塩基又はラジカルにより発色する色素であることが好ましい。 Among them, from the viewpoint of the visibility and resolution of the exposed and unexposed areas, the dye N is preferably a dye whose maximum absorption wavelength is changed by acid or radicals, more preferably a dye whose maximum absorption wavelength is changed by radicals. .
From the viewpoint of visibility and resolution of exposed and unexposed areas, the photosensitive composition layer preferably contains, as the dye N, both a dye whose maximum absorption wavelength is changed by radicals and a photoradical polymerization initiator. From the viewpoint of the visibility of the exposed and unexposed areas, the dye N is preferably a dye that develops color with an acid, a base, or a radical.
　色素Ｎの発色機構としては、例えば、感光性組成物層に光ラジカル重合開始剤、光カチオン重合開始剤（光酸発生剤）又は光塩基発生剤を添加して、露光後に光ラジカル重合開始剤、光カチオン重合開始剤又は光塩基発生剤から発生するラジカル、酸又は塩基によって、ラジカル反応性色素、酸反応性色素又は塩基反応性色素（例えば、ロイコ色素）が発色する態様が挙げられる。 As the coloring mechanism of the dye N, for example, a photoradical polymerization initiator, a photocationic polymerization initiator (photoacid generator) or a photobase generator is added to the photosensitive composition layer, and the 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) develops color by radicals, acids, or bases generated from a photocationic polymerization initiator or a photobase generator.
　露光部及び非露光部の視認性の点から、色素Ｎの発色時の波長範囲４００～７８０ｎｍにおける極大吸収波長としては、５５０ｎｍ以上が好ましく、５５０～７００ｎｍがより好ましく、５５０～６５０ｎｍが更に好ましい。
　また、色素Ｎは、発色時の波長範囲４００～７８０ｎｍにおける極大吸収波長を１つ又は２つ以上有していてもよい。色素Ｎが発色時の波長範囲４００～７８０ｎｍにおける極大吸収波長を２つ以上有する場合、２つ以上の極大吸収波長のうち吸光度が最も高い極大吸収波長が４５０ｎｍ以上であればよい。 From the viewpoint of the visibility of the exposed and unexposed areas, the maximum absorption wavelength in the wavelength range of 400 to 780 nm during coloring of the dye N is preferably 550 nm or more, more preferably 550 to 700 nm, and even more preferably 550 to 650 nm.
In addition, the dye N may have one or more maximum absorption wavelengths in the wavelength range of 400 to 780 nm during color development. When the dye N has two or more maximum absorption wavelengths in the wavelength range of 400 to 780 nm during color development, the maximum absorption wavelength with the highest absorbance among the two or more maximum absorption wavelengths should be 450 nm or more.
　色素Ｎの極大吸収波長は、大気雰囲気下で、分光光度計：ＵＶ３１００（島津製作所社製）を用いて、４００～７８０ｎｍの範囲で色素Ｎを含む溶液（液温２５℃）の透過スペクトルを測定し、光の強度が極小となる波長（極大吸収波長）を検出することによって測定できる。 The maximum absorption wavelength of Dye N is determined by measuring the transmission spectrum of a solution containing Dye N in the range of 400 to 780 nm (liquid temperature 25°C) using a spectrophotometer: UV3100 (manufactured by Shimadzu Corporation) in an air atmosphere. can be measured by detecting the wavelength (maximum absorption wavelength) at which the light intensity becomes minimum.
　露光により発色又は消色する色素としては、例えば、ロイコ化合物が挙げられる。
　露光により消色する色素としては、例えば、ロイコ化合物、ジアリールメタン系色素、オキザジン系色素、キサンテン系色素、イミノナフトキノン系色素、アゾメチン系色素及びアントラキノン系色素が挙げられる。
　色素Ｎとしては、露光部及び非露光部の視認性の点から、ロイコ化合物が好ましい。 Examples of dyes that develop or decolorize upon exposure include leuco compounds.
Examples of dyes that are decolorized by exposure include leuco compounds, diarylmethane dyes, oxazine dyes, xanthene dyes, iminonaphthoquinone dyes, azomethine dyes, and anthraquinone dyes.
As the dye N, a leuco compound is preferable from the viewpoint of the visibility of the exposed area and the non-exposed area.
　ロイコ化合物としては、例えば、トリアリールメタン骨格を有するロイコ化合物（トリアリールメタン系色素）、スピロピラン骨格を有するロイコ化合物（スピロピラン系色素）、フルオラン骨格を有するロイコ化合物（フルオラン系色素）、ジアリールメタン骨格を有するロイコ化合物（ジアリールメタン系色素）、ローダミンラクタム骨格を有するロイコ化合物（ローダミンラクタム系色素）、インドリルフタリド骨格を有するロイコ化合物（インドリルフタリド系色素）及びロイコオーラミン骨格を有するロイコ化合物（ロイコオーラミン系色素）が挙げられる。
　なかでも、トリアリールメタン系色素又はフルオラン系色素が好ましく、トリフェニルメタン骨格を有するロイコ化合物（トリフェニルメタン系色素）又はフルオラン系色素がより好ましい。 Examples of leuco compounds include leuco compounds having a triarylmethane skeleton (triarylmethane dyes), leuco compounds having a spiropyran skeleton (spiropyran dyes), leuco compounds having a fluorane skeleton (fluoran dyes), and diarylmethane skeletons. a leuco compound having a rhodamine lactam skeleton (rhodamine lactam dye), a leuco compound having an indolylphthalide skeleton (indolylphthalide dye), and a leuco having a leuco auramine skeleton compounds (leuco auramine dyes).
Among them, triarylmethane-based dyes or fluoran-based dyes are preferable, and leuco compounds having a triphenylmethane skeleton (triphenylmethane-based dyes) or fluoran-based dyes are more preferable.
　ロイコ化合物は、露光部及び非露光部の視認性の点から、ラクトン環、スルチン環又はスルトン環を有することが好ましい。これにより、ロイコ化合物が有するラクトン環、スルチン環又はスルトン環を、光ラジカル重合開始剤から発生するラジカル又は光カチオン重合開始剤から発生する酸と反応させて、ロイコ化合物を閉環状態に変化させて消色させるか又はロイコ化合物を開環状態に変化させて発色させることができる。ロイコ化合物としては、ラクトン環、スルチン環又はスルトン環を有し、ラジカル又は酸により、ラクトン環、スルチン環又はスルトン環が開環して発色する化合物が好ましく、ラクトン環を有し、ラジカル又は酸によりラクトン環が開環して発色する化合物がより好ましい。 The leuco compound preferably has a lactone ring, a sultine ring, or a sultone ring from the viewpoint of visibility in exposed and unexposed areas. As a result, the lactone ring, sultine ring, or sultone ring of the leuco compound is reacted with a radical generated from a radical photopolymerization initiator or an acid generated from a photocationic polymerization initiator to change the leuco compound into a ring-closed state. Color can be developed by decolorizing or by changing the leuco compound to a ring-opened state. The leuco compound is preferably a compound that has a lactone ring, a sultine ring or a sultone ring and develops color by opening the lactone ring, sultine ring or sultone ring with a radical or an acid, and has a lactone ring and a radical or an acid. A compound that develops color by opening the lactone ring is more preferred.
　色素Ｎとしては、例えば、染料及びロイコ化合物が挙げられる。
　染料としては、例えば、ブリリアントグリーン、エチルバイオレット、メチルグリーン、クリスタルバイオレット、ベイシックフクシン、メチルバイオレット２Ｂ、キナルジンレッド、ローズベンガル、メタニルイエロー、チモールスルホフタレイン、キシレノールブルー、メチルオレンジ、パラメチルレッド、コンゴーフレッド、ベンゾプルプリン４Ｂ、α－ナフチルレッド、ナイルブルー２Ｂ、ナイルブルーＡ、メチルバイオレット、マラカイトグリーン、パラフクシン、ビクトリアピュアブルー－ナフタレンスルホン酸塩、ビクトリアピュアブルーＢＯＨ（保土谷化学工業社製）、オイルブルー＃６０３（オリヱント化学工業社製）、オイルピンク＃３１２（オリヱント化学工業社製）、オイルレッド５Ｂ（オリヱント化学工業社製）、オイルスカーレット＃３０８（オリヱント化学工業社製）、オイルレッドＯＧ（オリヱント化学工業社製）、オイルレッドＲＲ（オリヱント化学工業社製）、オイルグリーン＃５０２（オリヱント化学工業社製）、スピロンレッドＢＥＨスペシャル（保土谷化学工業社製）、ｍ－クレゾールパープル、クレゾールレッド、ローダミンＢ、ローダミン６Ｇ、スルホローダミンＢ、オーラミン、４－ｐ－ジエチルアミノフェニルイミノナフトキノン、２－カルボキシアニリノ－４－ｐ－ジエチアミノフェニルイミノナフトキノン、２－カルボキシステアリルアミノ－４－ｐ－Ｎ，Ｎ－ビス（ヒドロキシエチル）アミノ－フェニルイミノナフトキノン、１－フェニル－３－メチル－４－ｐ－ジエチルアミノフェニルイミノ－５－ピラゾロン及び１－β－ナフチル－４－ｐ－ジエチルアミノフェニルイミノ－５－ピラゾロンが挙げられる。 Dyes N include, for example, dyes and leuco compounds.
Examples of dyes include brilliant green, ethyl violet, methyl green, crystal violet, basic fuchsine, methyl violet 2B, quinaldine red, rose bengal, methanil yellow, thymolsulfophthalein, xylenol blue, methyl orange, and paramethyl red. , Congo Fred, Benzopurpurin 4B, α-Naphthyl Red, Nile Blue 2B, Nile Blue A, Methyl Violet, Malachite Green, Parafuchsin, Victoria Pure Blue-Naphthalene Sulfonate, Victoria Pure Blue BOH (manufactured by Hodogaya Chemical Industry Co., Ltd. ), oil blue #603 (manufactured by Orient Chemical Industry Co., Ltd.), oil pink #312 (manufactured by Orient Chemical Industry Co., Ltd.), oil red 5B (manufactured by Orient Chemical Industry Co., Ltd.), oil scarlet #308 (manufactured by Orient Chemical Industry Co., Ltd.), oil Red OG (manufactured by Orient Chemical Industry Co., Ltd.), Oil Red RR (manufactured by Orient Chemical Industry Co., Ltd.), Oil Green #502 (manufactured by Orient Chemical Industry Co., Ltd.), Spiron Red BEH Special (manufactured by Hodogaya Chemical Industry Co., Ltd.), m-cresol purple, cresol red, rhodamine B, rhodamine 6G, sulforhodamine B, auramine, 4-p-diethylaminophenyliminonaphthoquinone, 2-carboxanilino-4-p-diethyaminophenyliminonaphthoquinone, 2-carboxystearylamino-4-p -N,N-bis(hydroxyethyl)amino-phenyliminonaphthoquinone, 1-phenyl-3-methyl-4-p-diethylaminophenylimino-5-pyrazolone and 1-β-naphthyl-4-p-diethylaminophenylimino- 5-pyrazolones.
　ロイコ化合物としては、例えば、ｐ，ｐ’，ｐ’’－ヘキサメチルトリアミノトリフェニルメタン（ロイコクリスタルバイオレット）、Ｐｅｒｇａｓｃｒｉｐｔ　Ｂｌｕｅ　ＳＲＢ（チバガイギー社製）、クリスタルバイオレットラクトン、マラカイトグリーンラクトン、ベンゾイルロイコメチレンブルー、２－（Ｎ－フェニル－Ｎ－メチルアミノ）－６－（Ｎ－ｐ－トリル－Ｎ－エチル）アミノフルオラン、２－アニリノ－３－メチル－６－（Ｎ－エチル－ｐ－トルイジノ）フルオラン、３，６－ジメトキシフルオラン、３－（Ｎ，Ｎ－ジエチルアミノ）－５－メチル－７－（Ｎ，Ｎ－ジベンジルアミノ）フルオラン、３－（Ｎ－シクロヘキシル－Ｎ－メチルアミノ）－６－メチル－７－アニリノフルオラン、３－（Ｎ，Ｎ－ジエチルアミノ）－６－メチル－７－アニリノフルオラン、３－（Ｎ，Ｎ－ジエチルアミノ）－６－メチル－７－キシリジノフルオラン、３－（Ｎ，Ｎ－ジエチルアミノ）－６－メチル－７－クロロフルオラン、３－（Ｎ，Ｎ－ジエチルアミノ）－６－メトキシ－７－アミノフルオラン、３－（Ｎ，Ｎ－ジエチルアミノ）－７－（４－クロロアニリノ）フルオラン、３－（Ｎ，Ｎ－ジエチルアミノ）－７－クロロフルオラン、３－（Ｎ，Ｎ－ジエチルアミノ）－７－ベンジルアミノフルオラン、３－（Ｎ，Ｎ－ジエチルアミノ）－７，８－ベンゾフロオラン、３－（Ｎ，Ｎ－ジブチルアミノ）－６－メチル－７－アニリノフルオラン、３－（Ｎ，Ｎ－ジブチルアミノ）－６－メチル－７－キシリジノフルオラン、３－ピペリジノ－６－メチル－７－アニリノフルオラン、３－ピロリジノ－６－メチル－７－アニリノフルオラン、３，３－ビス（１－エチル－２－メチルインドール－３－イル）フタリド、３，３－ビス（１－ｎ－ブチル－２－メチルインドール－３－イル）フタリド、３，３－ビス（ｐ－ジメチルアミノフェニル）－６－ジメチルアミノフタリド、３－（４－ジエチルアミノ－２－エトキシフェニル）－３－（１－エチル－２－メチルインドール－３－イル）－４－ザフタリド、３－（４－ジエチルアミノフェニル）－３－（１－エチル－２－メチルインドール－３－イル）フタリド及び３’，６’－ビス（ジフェニルアミノ）スピロイソベンゾフラン－１（３Ｈ），９’－［９Ｈ］キサンテン－３－オンが挙げられる。 Leuco compounds include, for example, p,p',p''-hexamethyltriaminotriphenylmethane (leuco crystal violet), Pergascript Blue SRB (manufactured by Ciba-Geigy), crystal violet lactone, malachite green lactone, benzoyl leuco methylene blue, 2-(N-phenyl-N-methylamino)-6-(Np-tolyl-N-ethyl)aminofluorane, 2-anilino-3-methyl-6-(N-ethyl-p-toluidino)fluorane , 3,6-dimethoxyfluorane, 3-(N,N-diethylamino)-5-methyl-7-(N,N-dibenzylamino)fluorane, 3-(N-cyclohexyl-N-methylamino)-6 -methyl-7-anilinofluorane, 3-(N,N-diethylamino)-6-methyl-7-anilinofluorane, 3-(N,N-diethylamino)-6-methyl-7-xylidinofluor Olan, 3-(N,N-diethylamino)-6-methyl-7-chlorofluorane, 3-(N,N-diethylamino)-6-methoxy-7-aminofluorane, 3-(N,N-diethylamino )-7-(4-chloroanilino)fluorane, 3-(N,N-diethylamino)-7-chlorofluorane, 3-(N,N-diethylamino)-7-benzylaminofluorane, 3-(N,N -diethylamino)-7,8-benzofluorane, 3-(N,N-dibutylamino)-6-methyl-7-anilinofluorane, 3-(N,N-dibutylamino)-6-methyl-7 -xyridinofluorane, 3-piperidino-6-methyl-7-anilinofluorane, 3-pyrrolidino-6-methyl-7-anilinofluorane, 3,3-bis(1-ethyl-2-methylindole -3-yl)phthalide, 3,3-bis(1-n-butyl-2-methylindol-3-yl)phthalide, 3,3-bis(p-dimethylaminophenyl)-6-dimethylaminophthalide, 3-(4-diethylamino-2-ethoxyphenyl)-3-(1-ethyl-2-methylindol-3-yl)-4-zaphthalide, 3-(4-diethylaminophenyl)-3-(1-ethyl- 2-methylindol-3-yl)phthalide and 3′,6′-bis(diphenylamino)spiroisobenzofuran-1(3H),9′-[9H]xanthen-3-one.
　色素Ｎとしては、露光部及び非露光部の視認性、現像後のパターン視認性及び解像性が優れる点から、ラジカルにより最大吸収波長が変化する色素が好ましく、ラジカルにより発色する色素がより好ましい。
　色素Ｎとしては、ロイコクリスタルバイオレット、クリスタルバイオレットラクトン、ブリリアントグリーン又はビクトリアピュアブルー－ナフタレンスルホン酸塩が好ましい。 As the dye N, a dye whose maximum absorption wavelength is changed by radicals is preferable, and a dye that develops color by radicals is more preferable, from the viewpoint of excellent visibility in exposed and unexposed areas, pattern visibility and resolution after development. .
Preferred dyes N are leuco crystal violet, crystal violet lactone, brilliant green or victoria pure blue-naphthalene sulfonate.
　色素Ｎは、１種単独で用いてもよく、２種以上で用いてもよい。
　色素Ｎの含有量は、露光部及び非露光部の視認性、並びに、現像後のパターン視認性及び解像性が優れる点から、感光性組成物層の全質量に対して、０．１質量％以上が好ましく、０．１～１０質量％がより好ましく、０．１～５質量％が更に好ましく、０．１～１質量％が特に好ましい。 The dye N may be used alone or in combination of two or more.
The content of the dye N is 0.1 mass with respect to the total mass of the photosensitive composition layer from the viewpoint of visibility of the exposed area and non-exposed area, and excellent pattern visibility and resolution after development. % or more, more preferably 0.1 to 10% by mass, still more preferably 0.1 to 5% by mass, and particularly preferably 0.1 to 1% by mass.
　色素Ｎの含有量は、感光性組成物層の全質量中に含まれる色素Ｎの全てを発色状態にした場合の色素の含有量を意味する。以下、ラジカルにより発色する色素を例に、色素Ｎの含有量の定量方法を説明する。
　メチルエチルケトン１００ｍＬに、色素Ｎ（０．００１ｇ）を溶かした溶液及び色素Ｎ（０．０１ｇ）を溶かした溶液を調製する。得られた各溶液に、光ラジカル重合開始剤（Ｉｒｇａｃｕｒｅ　ＯＸＥ０１、ＢＡＳＦジャパン社製）を加え、３６５ｎｍの光を照射することによりラジカルを発生させ、全ての色素Ｎを発色状態にする。その後、大気雰囲気下で、分光光度計（ＵＶ３１００、島津製作所社製）を用いて、液温が２５℃である各溶液の吸光度を測定し、検量線を作成する。
　次に、色素Ｎに代えて感光性組成物層（３ｇ）をメチルエチルケトンに溶かすこと以外は上記と同様の方法で、色素を全て発色させた溶液の吸光度を測定する。得られた感光性組成物層を含む溶液の吸光度から、検量線に基づいて感光性組成物層に含まれる色素Ｎの含有量を算出する。「感光性組成物層（３ｇ）」とは、感光性組成物中の全固形分３ｇと同義である。 The content of the dye N means the content of the dye when all the dyes N contained in the total weight of the photosensitive composition layer are in a colored state. Hereinafter, a method for quantifying the content of the dye N will be described using a dye that develops color by radicals as an example.
A solution of dye N (0.001 g) and a solution of dye N (0.01 g) in 100 mL of methyl ethyl ketone are prepared. A photoradical polymerization initiator (Irgacure OXE01, manufactured by BASF Japan) is added to each of the obtained solutions, and radicals are generated by irradiation with light of 365 nm, and all dyes N are brought into a colored state. After that, the absorbance of each solution having a liquid temperature of 25° C. is measured using a spectrophotometer (UV3100, manufactured by Shimadzu Corporation) in an air atmosphere to create a calibration curve.
Next, the absorbance of the solution in which all the dyes are developed is measured in the same manner as described above except that instead of the dye N, the photosensitive composition layer (3 g) is dissolved in methyl ethyl ketone. From the absorbance of the obtained solution containing the photosensitive composition layer, the content of dye N contained in the photosensitive composition layer is calculated based on the calibration curve. "Photosensitive composition layer (3 g)" is synonymous with 3 g of total solid content in the photosensitive composition.
＜熱架橋性化合物＞
　感光性組成物層は、得られる硬化膜の強度及び得られる未硬化膜の粘着性の点から、熱架橋性化合物を含んでいてもよい。
　後述するエチレン性不飽和基を有する熱架橋性化合物は、重合性化合物としては扱わず、熱架橋性化合物として扱うものとする。
　熱架橋性化合物としては、例えば、メチロール化合物及びブロックイソシアネート化合物が挙げられ、得られる硬化膜の強度及び得られる未硬化膜の粘着性の点から、ブロックイソシアネート化合物が好ましい。
　ブロックイソシアネート化合物は、ヒドロキシ基及びカルボキシ基と反応するため、例えば、樹脂及び／又は重合性化合物がヒドロキシ基及びカルボキシ基の少なくとも一方を有する場合、形成される膜の親水性が下がり、感光性組成物層を硬化した膜を保護膜として使用する場合の機能が強化される傾向がある。
　「ブロックイソシアネート化合物」とは、イソシアネートのイソシアネート基をブロック剤で保護した構造を有する化合物を意味する。 <Thermal crosslinkable compound>
The photosensitive composition layer may contain a thermally crosslinkable compound from the viewpoint of the strength of the resulting cured film and the adhesiveness of the resulting uncured film.
A thermally crosslinkable compound having an ethylenically unsaturated group, which will be described later, is not treated as a polymerizable compound, but as a thermally crosslinkable compound.
Examples of the thermally crosslinkable compound include methylol compounds and blocked isocyanate compounds, and blocked isocyanate compounds are preferred from the viewpoint of the strength of the resulting cured film and the adhesiveness of the resulting uncured film.
Since the blocked isocyanate compound reacts with a hydroxy group and a carboxy group, for example, when the resin and/or the polymerizable compound has at least one of a hydroxy group and a carboxy group, the hydrophilicity of the formed film is lowered and the photosensitive composition The function tends to be enhanced when a film obtained by curing a material layer is used as a protective film.
A "blocked isocyanate compound" means a compound having a structure in which the isocyanate group of isocyanate is protected with a blocking agent.
　ブロックイソシアネート化合物の解離温度としては、１００～１６０℃が好ましく、１３０～１５０℃がより好ましい。
　ブロックイソシアネート化合物の解離温度の測定方法としては、例えば、示差走査熱量計（例えば、ＤＳＣ６２００、セイコーインスツルメンツ社製）を用いてＤＳＣ（Ｄｉｆｆｅｒｅｎｔｉａｌ　ｓｃａｎｎｉｎｇ　ｃａｌｏｒｉｍｅｔｒｙ）分析にて、ブロックイソシアネート化合物の脱保護反応に伴う吸熱ピークの温度を解離度とする測定する方法が挙げられる。 The dissociation temperature of the blocked isocyanate compound is preferably 100 to 160°C, more preferably 130 to 150°C.
As a method for measuring the dissociation temperature of the blocked isocyanate compound, for example, DSC (Differential scanning calorimetry) analysis using a differential scanning calorimeter (e.g., DSC6200, manufactured by Seiko Instruments Inc.) is performed to determine the deprotection reaction of the blocked isocyanate compound. A method of measuring the temperature of the endothermic peak as the degree of dissociation can be mentioned.
　解離温度が１００～１６０℃であるブロック剤としては、例えば、マロン酸ジエステル等の活性メチレン化合物及びオキシム化合物が挙げられる。
　マロン酸ジエステルとしては、例えば、マロン酸ジメチル、マロン酸ジエチル、マロン酸ジｎ－ブチル及びマロン酸ジ２－エチルヘキシルが挙げられる。
　オキシム化合物としては、例えば、ホルムアルドオキシム、アセトアルドオキシム、アセトオキシム、メチルエチルケトオキシム及びシクロヘキサノンオキシム等の分子中に－Ｃ（＝Ｎ－ＯＨ）－で表される構造を有する化合物が挙げられる。
　なかでも、解離温度が１００～１６０℃であるブロック剤としては、保存安定性の点から、オキシム化合物が好ましい。 Examples of blocking agents having a dissociation temperature of 100 to 160° C. include active methylene compounds such as malonic acid diesters and oxime compounds.
Malonic acid diesters include, for example, dimethyl malonate, diethyl malonate, di-n-butyl malonate and di-2-ethylhexyl malonate.
Examples of oxime compounds include compounds having a structure represented by -C(=N-OH)- in the molecule such as formaldoxime, acetaldoxime, acetoxime, methylethylketoxime and cyclohexanone oxime.
Among them, oxime compounds are preferable as blocking agents having a dissociation temperature of 100 to 160° C. from the viewpoint of storage stability.
　ブロックイソシアネート化合物は、膜の脆性改良及び被転写体との密着力向上の点から、イソシアヌレート構造を有することが好ましい。
　イソシアヌレート構造を有するブロックイソシアネート化合物は、例えば、ヘキサメチレンジイソシアネートをイソシアヌレート化して保護することにより得られる。
　なかでも、オキシム構造を有さない化合物よりも解離温度を好ましい範囲に調整しやすく、かつ、現像残渣を低減できる点から、イソシアヌレート構造を有するブロックイソシアネート化合物としては、オキシム化合物をブロック剤として用いたオキシム構造を有する化合物が好ましい。 The blocked isocyanate compound preferably has an isocyanurate structure from the viewpoint of improving the brittleness of the film and improving the adhesion to the transferred material.
A blocked isocyanate compound having an isocyanurate structure is obtained, for example, by isocyanurating hexamethylene diisocyanate and protecting it.
Among them, as a blocked isocyanate compound having an isocyanurate structure, an oxime compound is used as a blocking agent because it is easier to adjust the dissociation temperature to a preferable range than a compound having no oxime structure and can reduce development residue. Compounds having an oxime structure are preferred.
　ブロックイソシアネート化合物は、重合性基を有していてもよい。
　重合性基としては、例えば、上記重合性化合物が有する重合性基と同義であり、好適態様も同じである。 The blocked isocyanate compound may have a polymerizable group.
The polymerizable group has, for example, the same definition as the polymerizable group possessed by the polymerizable compound, and the preferred embodiments are also the same.
　ブロックイソシアネート化合物としては、例えば、ＡＯＩ－ＢＭ、ＭＯＩ－ＢＭ及びＭＯＩ－ＢＰ等カレンズシリーズ（登録商標）（昭和電工社製）；ＴＰＡ－Ｂ８０Ｅ及びＷＴ３２－Ｂ７５Ｐ等ブロック型のデュラネートシリーズ（登録商標）（旭化成ケミカルズ社製）が挙げられる。
　ブロックイソシアネート化合物として、下記の化合物が好ましい。 Examples of blocked isocyanate compounds include Karenz series (registered trademark) such as AOI-BM, MOI-BM and MOI-BP (manufactured by Showa Denko KK); ) (manufactured by Asahi Kasei Chemicals).
As the blocked isocyanate compound, the following compounds are preferred.
Figure JPOXMLDOC01-appb-C000004
Figure JPOXMLDOC01-appb-C000004
　熱架橋性化合物は、１種単独で用いてもよく、２種以上で用いてもよい。
　熱架橋性化合物の含有量は、感光性組成物層の全質量に対して、１～５０質量％が好ましく、５～３０質量％がより好ましい。 The thermally crosslinkable compound may be used singly or in combination of two or more.
The content of the thermally crosslinkable compound is preferably 1 to 50% by mass, more preferably 5 to 30% by mass, based on the total mass of the photosensitive composition layer.
＜顔料＞
　感光性組成物層は、顔料を含んでいてもよい。
　感光性組成物層が顔料を含む場合、着色樹脂層に該当する。
　近年の電子機器が有する液晶表示窓には、液晶表示窓を保護するために、透明なガラス基板等の裏面周縁部に黒色の枠状遮光層が形成されたカバーガラスが取り付けられている場合がある。このような遮光層を形成するために着色樹脂層が使用され得る。
　顔料としては、所望とする色相に合わせて適宜選択すればよく、例えば、黒色顔料、白色顔料、並びに、黒色及び白色以外の有彩色の顔料が挙げられ、黒色系のパターンを形成する場合、顔料としては、黒色顔料が好ましい。 <Pigment>
The photosensitive composition layer may contain a pigment.
When the photosensitive composition layer contains a pigment, it corresponds to the colored resin layer.
In order to protect the liquid crystal display window of electronic equipment in recent years, there are cases where a cover glass with a black frame-shaped light-shielding layer formed on the periphery of the back surface of a transparent glass substrate or the like is attached to the liquid crystal display window. be. A colored resin layer may be used to form such a light shielding layer.
The pigment may be appropriately selected according to the desired hue. Examples thereof include black pigments, white pigments, and chromatic pigments other than black and white. As such, a black pigment is preferable.
（黒色顔料）
　黒色顔料としては、例えば、公知の黒色顔料（例えば、有機顔料及び無機顔料等）が挙げられる。
　なかでも、光学濃度の点から、黒色顔料としては、カーボンブラック、酸化チタン、チタンカーバイド、酸化鉄、酸化チタン又は黒鉛が好ましく、カーボンブラックがより好ましい。カーボンブラックとしては、表面抵抗の点から、表面の少なくとも一部が樹脂で被覆された表面修飾カーボンブラックが好ましい。 (black pigment)
Examples of black pigments include known black pigments (eg, organic pigments, inorganic pigments, etc.).
Among them, carbon black, titanium oxide, titanium carbide, iron oxide, titanium oxide or graphite are preferable as the black pigment, and carbon black is more preferable, from the viewpoint of optical density. From the viewpoint of surface resistance, the carbon black is preferably surface-modified carbon black having at least a portion of the surface coated with a resin.
　黒色顔料の粒径（数平均粒径）は、分散安定性の点から、０．００１～０．１μｍが好ましく、０．０１～０．０８μｍがより好ましい。
　「粒径」とは、電子顕微鏡で撮影した顔料粒子の写真像から顔料粒子の面積を求め、顔料粒子の面積と同面積の円を考えた場合の円の直径を意味する。また、「数平均粒径」とは、任意の１００個の粒子について上記粒径を求め、求められた１００個の粒径を平均して得られる平均値を意味する。 The particle size (number average particle size) of the black pigment is preferably 0.001 to 0.1 μm, more preferably 0.01 to 0.08 μm, from the viewpoint of dispersion stability.
The term "particle size" means the diameter of a circle obtained by determining the area of a pigment particle from a photographic image of the pigment particle taken with an electron microscope and considering a circle having the same area as the area of the pigment particle. Further, the "number average particle size" means an average value obtained by determining the particle size of 100 arbitrary particles and averaging the obtained 100 particle sizes.
　白色顔料としては、例えば、無機顔料、特開２００５－００７７６５号公報の段落［００１５］及び［０１１４］に記載の白色顔料が挙げられる。
　無機顔料としては、酸化チタン、酸化亜鉛、リトポン、軽質炭酸カルシウム、ホワイトカーボン、酸化アルミニウム、水酸化アルミニウム又は硫酸バリウムが好ましく、酸化チタン又は酸化亜鉛がより好ましく、酸化チタンが更に好ましく、ルチル型又はアナターゼ型の酸化チタンが特に好ましく、ルチル型の酸化チタンが最も好ましい。
　また、酸化チタンの表面は、シリカ処理、アルミナ処理、チタニア処理、ジルコニア処理又は有機物処理が施されていてもよく、これらの２つ以上の処理が施されてもよい。これにより、酸化チタンの触媒活性が抑制され、耐熱性及び褪光性が改善できる。
　加熱後の感光性組成物層の厚みを薄くする点から、酸化チタンの表面への表面処理としては、アルミナ処理及びジルコニア処理の少なくとも一方を施すことが好ましく、アルミナ処理及びジルコニア処理の両方を施すことがより好ましい。 Examples of white pigments include inorganic pigments and white pigments described in paragraphs [0015] and [0114] of JP-A-2005-007765.
The inorganic pigment is preferably titanium oxide, zinc oxide, lithopone, light calcium carbonate, white carbon, aluminum oxide, aluminum hydroxide or barium sulfate, more preferably titanium oxide or zinc oxide, still more preferably titanium oxide, rutile type or Anatase-type titanium oxide is particularly preferred, and rutile-type titanium oxide is most preferred.
In addition, the surface of titanium oxide may be subjected to silica treatment, alumina treatment, titania treatment, zirconia treatment, organic substance treatment, or two or more of these treatments. Thereby, the catalytic activity of titanium oxide is suppressed, and the heat resistance and fade resistance can be improved.
From the viewpoint of reducing the thickness of the photosensitive composition layer after heating, the surface treatment of the titanium oxide surface is preferably at least one of alumina treatment and zirconia treatment, and both alumina treatment and zirconia treatment are performed. is more preferable.
　感光性組成物層が着色樹脂層である場合、転写性の点から、感光性組成物層は、黒色顔料及び白色顔料以外の有彩色の顔料を含むことも好ましい。
　有彩色の顔料の粒径（数平均粒径）としては、分散性がより優れる点から、０．１μｍ以下が好ましく、０．０８μｍ以下がより好ましい。下限は、１０ｎｍ以上が好ましい。
　有彩色の顔料としては、例えば、ビクトリア・ピュアーブルーＢＯ（Ｃｏｌｏｒ　Ｉｎｄｅｘ（以下、「Ｃ．Ｉ．」ともいう。）４２５９５）、オーラミン（Ｃ．Ｉ．４１０００）、ファット・ブラックＨＢ（Ｃ．Ｉ．２６１５０）、モノライト・エローＧＴ（Ｃ．Ｉ．ピグメント・エロー１２）、パーマネント・エローＧＲ（Ｃ．Ｉ．ピグメント・エロー１７）、パーマネント・エローＨＲ（Ｃ．Ｉ．ピグメント・エロー８３）、パーマネント・カーミンＦＢＢ（Ｃ．Ｉ．ピグメント・レッド１４６）、ホスターバームレッドＥＳＢ（Ｃ．Ｉ．ピグメント・バイオレット１９）、パーマネント・ルビーＦＢＨ（Ｃ．Ｉ．ピグメント・レッド１１）、ファステル・ピンクＢスプラ（Ｃ．Ｉ．ピグメント・レッド８１）、モナストラル・ファースト・ブルー（Ｃ．Ｉ．ピグメント・ブルー１５）、モノライト・ファースト・ブラックＢ（Ｃ．Ｉ．ピグメント・ブラック１）及びカーボン、Ｃ．Ｉ．ピグメント・レッド９７、Ｃ．Ｉ．ピグメント・レッド１２２、Ｃ．Ｉ．ピグメント・レッド１４９、Ｃ．Ｉ．ピグメント・レッド１６８、Ｃ．Ｉ．ピグメント・レッド１７７、Ｃ．Ｉ．ピグメント・レッド１８０、Ｃ．Ｉ．ピグメント・レッド１９２、Ｃ．Ｉ．ピグメント・レッド２１５、Ｃ．Ｉ．ピグメント・グリーン７、Ｃ．Ｉ．ピグメント・ブルー１５：１、Ｃ．Ｉ．ピグメント・ブルー１５：４、Ｃ．Ｉ．ピグメント・ブルー２２、Ｃ．Ｉ．ピグメント・ブルー６０、Ｃ．Ｉ．ピグメント・ブルー６４及びＣ．Ｉ．ピグメント・バイオレット２３が挙げられ、Ｃ．Ｉ．ピグメント・レッド１７７が好ましい。 When the photosensitive composition layer is a colored resin layer, the photosensitive composition layer preferably contains a chromatic pigment other than the black pigment and the white pigment from the viewpoint of transferability.
The particle size (number average particle size) of the chromatic pigment is preferably 0.1 μm or less, more preferably 0.08 μm or less, from the viewpoint of better dispersibility. The lower limit is preferably 10 nm or more.
Examples of chromatic pigments include Victoria Pure Blue BO (Color Index (hereinafter also referred to as “CI”) 42595), Auramine (CI 41000), Fat Black HB (CI .26150), Monolite Yellow GT (C.I. Pigment Yellow 12), Permanent Yellow GR (C.I. Pigment Yellow 17), Permanent Yellow HR (C.I. Pigment Yellow 83), Permanent Carmine FBB (C.I. Pigment Red 146), Hoster Balm Red ESB (C.I. Pigment Violet 19), Permanent Ruby FBH (C.I. Pigment Red 11), Fastel Pink B Splash (C.I. Pigment Red 81), Monastral Fast Blue (C.I. Pigment Blue 15), Monolite Fast Black B (C.I. 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, C.I. I. Pigment Red 177 is preferred.
　顔料は、１種単独で用いてもよく、２種以上で用いてもよい。
　顔料の含有量は、感光性組成物層の全質量に対して、３質量％超４０質量％以下が好ましく、３質量％超３５質量％以下がより好ましく、５質量％超３５質量％以下が更に好ましく、１０～３５質量％が特に好ましい。 The pigments may be used singly or in combination of two or more.
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, and more than 5% by mass and 35% by mass or less with respect to the total mass of the photosensitive composition layer. More preferably, 10 to 35% by mass is particularly preferable.
　感光性組成物層が黒色顔料以外の顔料（例えば、白色顔料及び有彩色の顔料等）を含む場合、黒色顔料以外の顔料の含有量は、黒色顔料の全質量に対して、３０質量％以下が好ましく、１～２０質量％がより好ましく、３～１５質量％が更に好ましい。 When the photosensitive composition layer contains pigments other than black pigments (e.g., white pigments, chromatic pigments, etc.), the content of pigments other than black pigments is 30% by mass or less with respect to the total mass of black pigments. is preferred, 1 to 20 mass % is more preferred, and 3 to 15 mass % is even more preferred.
　感光性組成物層が黒色顔料を含む場合、黒色顔料（好ましくはカーボンブラック）は、顔料分散液の形態で感光性組成物に導入されることが好ましい。
　分散液は、黒色顔料と顔料分散剤とを事前に混合して得られる混合物を、有機溶剤（又はビヒクル）に加えて分散機で分散させることによって調製されるものであってもよい。顔料分散剤は、顔料及び溶剤に応じて選択すればよく、例えば、市販の分散剤を使用することができる。
　「ビヒクル」とは、顔料分散液とした場合に顔料を分散させている媒質の部分を意味する。上記ビヒクルは、液状であり、黒色顔料を分散状態で保持するバインダー成分と、バインダー成分を溶解及び希釈する溶剤成分（有機溶剤）とを含む。 When the photosensitive composition layer contains a black pigment, the black pigment (preferably carbon black) is preferably introduced into the photosensitive 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 the mixture with a dispersing machine. A pigment dispersant may be selected according to the pigment and solvent, and for example, a commercially available dispersant can be used.
By "vehicle" is meant that portion of the medium in which the pigment is dispersed when made into a pigment dispersion. The vehicle is liquid and contains a binder component that holds the black pigment in a dispersed state and a solvent component (organic solvent) that dissolves and dilutes the binder component.
　分散機としては、例えば、ニーダー、ロールミル、アトライター、スーパーミル、ディゾルバ、ホモミキサー及びサンドミル等の公知の分散機が挙げられる。
　また、機械的摩砕により摩擦力を利用して微粉砕してもよい。分散機及び微粉砕としては、例えば、「顔料の事典」（朝倉邦造著、第一版、朝倉書店、２０００年、４３８頁、３１０頁）の記載が挙げられる。 Examples of dispersers include known dispersers such as kneaders, roll mills, attritors, super mills, dissolvers, homomixers and sand mills.
Moreover, it may be finely pulverized using frictional force by mechanical grinding. Dispersers and fine pulverization are described, for example, in "Encyclopedia of Pigments" (Kunizo Asakura, 1st edition, Asakura Shoten, 2000, pp. 438, 310).
＜その他添加剤＞
　感光性組成物層は、上記成分以外に、必要に応じてその他添加剤を含んでいてもよい。
　その他添加剤としては、例えば、ラジカル重合禁止剤、ベンゾトリアゾール類、カルボキシベンゾトリアゾール類、増感剤、界面活性剤、可塑剤、ヘテロ環状化合物（例えば、トリアゾール等）、ピリジン類（例えば、イソニコチンアミド等）及びプリン塩基（例えば、アデニン等）が挙げられる。
　また、その他添加剤としては、例えば、金属酸化物粒子、連鎖移動剤、酸化防止剤、分散剤、酸増殖剤、現像促進剤、導電性繊維、紫外線吸収剤、増粘剤、架橋剤、有機又は無機の沈殿防止剤及び特開２０１４－０８５６４３号公報の段落［０１６５］～［０１８４］が挙げられ、これらの内容は本明細書に組み込まれる。
　その他添加剤は、１種単独で用いてもよく、２種以上で用いてもよい。 <Other additives>
The photosensitive composition layer may contain other additives, if necessary, in addition to the above components.
Other additives include, for example, radical polymerization inhibitors, benzotriazoles, carboxybenzotriazoles, sensitizers, surfactants, plasticizers, heterocyclic compounds (e.g., triazole, etc.), pyridines (e.g., isonicotine amides, etc.) and purine bases (eg, adenine, etc.).
Other additives include, for example, metal oxide particles, chain transfer agents, antioxidants, dispersants, acid multipliers, development accelerators, conductive fibers, ultraviolet absorbers, thickeners, cross-linking agents, organic Or inorganic suspending agents and paragraphs [0165] to [0184] of JP-A-2014-085643, the contents of which are incorporated herein.
Other additives may be used singly or in combination of two or more.
（ラジカル重合禁止剤）
　ラジカル重合禁止剤としては、例えば、特許第４５０２７８４号公報の段落［００１８］に記載された熱重合防止剤が挙げられ、フェノチアジン、フェノキサジン又は４－メトキシフェノールが好ましい。
　ラジカル重合禁止剤としては、例えば、ナフチルアミン、塩化第一銅、ニトロソフェニルヒドロキシアミンアルミニウム塩及びジフェニルニトロソアミンが挙げられ、感光性組成物層の感度を損なわない点から、ニトロソフェニルヒドロキシアミンアルミニウム塩が好ましい。
　ラジカル重合禁止剤の含有量は、感光性組成物層の全質量に対して、０．００１～５．０質量％が好ましく、０．０１～３．０質量％がより好ましく、０．０２～２．０質量％が更に好ましい。
　ラジカル重合禁止剤の含有量は、重合性化合物の全質量に対して、０．００５～５．０質量％が好ましく、０．０１～３．０質量％がより好ましく、０．０１～１．０質量％が更に好ましい。 (Radical polymerization inhibitor)
Examples of radical polymerization inhibitors include thermal polymerization inhibitors described in paragraph [0018] of Japanese Patent No. 4502784, and phenothiazine, phenoxazine and 4-methoxyphenol are preferred.
The radical polymerization inhibitor includes, for example, naphthylamine, cuprous chloride, nitrosophenylhydroxyamine aluminum salt and diphenylnitrosamine. Nitrosophenylhydroxyamine aluminum salt is preferred from the viewpoint of not impairing the sensitivity of the photosensitive composition layer. .
The content of the radical polymerization inhibitor is preferably 0.001 to 5.0% by mass, more preferably 0.01 to 3.0% by mass, based on the total mass of the photosensitive composition layer, and 0.02 to 2.0% by mass is more preferred.
The content of the radical polymerization inhibitor is preferably 0.005 to 5.0% by mass, more preferably 0.01 to 3.0% by mass, more preferably 0.01 to 1.0% by mass, based on the total mass of the polymerizable compound. 0% by mass is more preferred.
（ベンゾトリアゾール類）
　ベンゾトリアゾール類としては、例えば、１，２，３－ベンゾトリアゾール、１－クロロ－１，２，３－ベンゾトリアゾール、ビス（Ｎ－２－エチルヘキシル）アミノメチレン－１，２，３－ベンゾトリアゾール、ビス（Ｎ－２－エチルヘキシル）アミノメチレン－１，２，３－トリルトリアゾール及びビス（Ｎ－２－ヒドロキシエチル）アミノメチレン－１，２，３－ベンゾトリアゾールが挙げられる。 (Benzotriazoles)
Examples of benzotriazoles include 1,2,3-benzotriazole, 1-chloro-1,2,3-benzotriazole, bis(N-2-ethylhexyl)aminomethylene-1,2,3-benzotriazole, bis(N-2-ethylhexyl)aminomethylene-1,2,3-tolyltriazole and bis(N-2-hydroxyethyl)aminomethylene-1,2,3-benzotriazole.
（カルボキシベンゾトリアゾール類）
　カルボキシベンゾトリアゾール類としては、例えば、４－カルボキシ－１，２，３－ベンゾトリアゾール、５－カルボキシ－１，２，３－ベンゾトリアゾール、Ｎ－（Ｎ，Ｎ－ジ－２－エチルヘキシル）アミノメチレンカルボキシベンゾトリアゾール、Ｎ－（Ｎ，Ｎ－ジ－２－ヒドロキシエチル）アミノメチレンカルボキシベンゾトリアゾール及びＮ－（Ｎ，Ｎ－ジ－２－エチルヘキシル）アミノエチレンカルボキシベンゾトリアゾールが挙げられる。
　カルボキシベンゾトリアゾール類としては、具体的に、ＣＢＴ－１（城北化学工業社製）が挙げられる。 (Carboxybenzotriazoles)
Carboxybenzotriazoles include, for example, 4-carboxy-1,2,3-benzotriazole, 5-carboxy-1,2,3-benzotriazole, N-(N,N-di-2-ethylhexyl)aminomethylene Carboxybenzotriazole, N-(N,N-di-2-hydroxyethyl)aminomethylene carboxybenzotriazole and N-(N,N-di-2-ethylhexyl)aminoethylene carboxybenzotriazole.
Specific examples of carboxybenzotriazoles include CBT-1 (manufactured by Johoku Chemical Industry Co., Ltd.).
　ラジカル重合禁止剤、ベンゾトリアゾール類及びカルボキシベンゾトリアゾール類の合計含有量は、感光性組成物層の全質量に対して、０．０１～３質量％が好ましく、０．０５～１質量％がより好ましい。上記含有量が０．０１質量％以上である場合、感光性組成物層の保存安定性がより優れる。一方、上記含有量が３質量％以下である場合、感度の維持及び染料の脱色を抑制がより優れる。 The total content of radical polymerization inhibitors, benzotriazoles and carboxybenzotriazoles is preferably 0.01 to 3% by mass, more preferably 0.05 to 1% by mass, based on the total mass of the photosensitive composition layer. preferable. When the content is 0.01% by mass or more, the storage stability of the photosensitive composition layer is more excellent. On the other hand, when the content is 3% by mass or less, the maintenance of sensitivity and suppression of decolorization of the dye are more excellent.
（増感剤）
　増感剤としては、例えば、公知の増感剤、染料及び顔料が挙げられる。
　増感剤としては、例えば、ジアルキルアミノベンゾフェノン化合物、ピラゾリン化合物、アントラセン化合物、クマリン化合物、キサントン化合物、チオキサントン化合物、アクリドン化合物、オキサゾール化合物、ベンゾオキサゾール化合物、チアゾール化合物、ベンゾチアゾール化合物、トリアゾール化合物（例えば、１，２，４－トリアゾール）、スチルベン化合物、トリアジン化合物、チオフェン化合物、ナフタルイミド化合物、トリアリールアミン化合物及びアミノアクリジン化合物が挙げられる。 (sensitizer)
Sensitizers include, for example, known sensitizers, dyes and pigments.
Sensitizers include, for example, dialkylaminobenzophenone compounds, pyrazoline compounds, anthracene compounds, coumarin compounds, xanthone compounds, thioxanthone compounds, acridone compounds, oxazole compounds, benzoxazole compounds, thiazole compounds, benzothiazole compounds, triazole compounds (e.g., 1,2,4-triazoles), stilbene compounds, triazine compounds, thiophene compounds, naphthalimide compounds, triarylamine compounds and aminoacridine compounds.
　増感剤の含有量は、光源に対する感度の向上及び重合速度と連鎖移動のバランスによる硬化速度の向上の点から、感光性組成物層の全質量に対して、０．０１～５質量％が好ましく、０．０５～１質量％がより好ましい。 The content of the sensitizer is 0.01 to 5% by mass with respect to the total mass of the photosensitive composition layer, from the viewpoint of improving the sensitivity to light sources and improving the curing speed due to the balance between polymerization speed and chain transfer. Preferably, 0.05 to 1% by mass is more preferable.
（界面活性剤）
　界面活性剤としては、例えば、特許第４５０２７８４号公報の段落［００１７］及び特開２００９－２３７３６２号公報の段落［００６０］～［００７１］に記載の界面活性剤が挙げられる。 (Surfactant)
Examples of surfactants include surfactants described in paragraph [0017] of Japanese Patent No. 4502784 and paragraphs [0060] to [0071] of JP-A-2009-237362.
　界面活性剤としては、ノニオン系界面活性剤、フッ素系界面活性剤又はシリコーン系界面活性剤が好ましい。
　フッ素系界面活性剤としては、例えば、メガファック　Ｆ－１７１、Ｆ－１７２、Ｆ－１７３、Ｆ－１７６、Ｆ－１７７、Ｆ－１４１、Ｆ－１４２、Ｆ－１４３、Ｆ－１４４、Ｆ－４３７、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－５７８－２、ＥＸＰ．ＭＦＳ－５７９、ＥＸＰ．ＭＦＳ－５８６、ＥＸＰ．ＭＦＳ－５８７、ＥＸＰ．ＭＦＳ－６２８、ＥＸＰ．ＭＦＳ－６３１、ＥＸＰ．ＭＦＳ－６０３、Ｒ－４１、Ｒ－４１－ＬＭ、Ｒ－０１、Ｒ－４０、Ｒ－４０－ＬＭ、ＲＳ－４３、ＴＦ－１９５６、ＲＳ－９０、Ｒ－９４及びＤＳ－２１（以上、ＤＩＣ社製）；フロラード　ＦＣ４３０、ＦＣ４３１及びＦＣ１７１（以上、住友スリーエム社製）；サーフロンＳ－３８２、ＳＣ－１０１、ＳＣ－１０３、ＳＣ－１０４、ＳＣ－１０５、ＳＣ－１０６８、ＳＣ－３８１、ＳＣ－３８３、Ｓ－３９３及びＫＨ－４０（以上、ＡＧＣ社製）；ＰｏｌｙＦｏｘ　ＰＦ６３６、ＰＦ６５６、ＰＦ６３２０、ＰＦ６５２０及びＰＦ７００２（以上、ＯＭＮＯＶＡ社製）；フタージェント　７１０ＦＬ、７１０ＦＭ、６１０ＦＭ、６０１ＡＤ、６０１ＡＤＨ２、６０２Ａ、２１５Ｍ、２４５Ｆ、２５１、２１２Ｍ、２５０、２０９Ｆ、２２２Ｆ、２０８Ｇ、７１０ＬＡ、７１０ＦＳ、７３０ＬＭ、６５０ＡＣ、６８１及び６８３（以上、ＮＥＯＳ社製）、Ｕ－１２０Ｅ（ユニケム株式会社）が挙げられる。 As the surfactant, a nonionic surfactant, a fluorosurfactant or a silicone surfactant is preferred.
Examples of fluorosurfactants include Megafac F-171, F-172, F-173, F-176, F-177, F-141, F-142, F-143, F-144, F- 437, 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-578-2, EXP. MFS-579, EXP. MFS-586, EXP. MFS-587, EXP. MFS-628, EXP. MFS-631, EXP. MFS-603, R-41, R-41-LM, R-01, R-40, R-40-LM, RS-43, TF-1956, RS-90, R-94 and DS-21 (above, DIC); Florard FC430, FC431 and FC171 (manufactured by Sumitomo 3M); Surflon S-382, SC-101, SC-103, SC-104, SC-105, SC-1068, SC-381, SC -383, S-393 and KH-40 (manufactured by AGC); PolyFox PF636, PF656, PF6320, PF6520 and PF7002 (manufactured by OMNOVA); 215M, 245F, 251, 212M, 250, 209F, 222F, 208G, 710LA, 710FS, 730LM, 650AC, 681 and 683 (manufactured by NEOS), and U-120E (Unichem Co., Ltd.).
　また、フッ素系界面活性剤としては、フッ素原子を含む官能基を持つ分子構造を有し、熱を加えるとフッ素原子を含む官能基の部分が切断されてフッ素原子が揮発するアクリル系化合物も好ましい。
　このようなフッ素系界面活性剤としては、例えば、ＤＩＣ社製のメガファック　ＤＳシリーズ（化学工業日報（２０１６年２月２２日）及び日経産業新聞（２０１６年２月２３日））が挙げられる。
　また、フッ素系界面活性剤としては、フッ素化アルキル基又はフッ素化アルキレンエーテル基を有するフッ素原子含有ビニルエーテル化合物と、親水性のビニルエーテル化合物との共重合体を用いることも好ましい。
　フッ素系界面活性剤としては、ブロックポリマーも使用できる。
　フッ素系界面活性剤としては、フッ素原子を有する（メタ）アクリレート化合物に由来する構成単位と、アルキレンオキシ基（好ましくはエチレンオキシ基、プロピレンオキシ基）を２以上（好ましくは５以上）有する（メタ）アクリレート化合物に由来する構成単位と、を含む含フッ素高分子化合物も好ましい。
　また、フッ素系界面活性剤としては、例えば、側鎖にエチレン性不飽和基を有する含フッ素重合体も挙げられ、メガファック　ＲＳ－１０１、ＲＳ－１０２、ＲＳ－７１８Ｋ及びＲＳ－７２－Ｋ（以上、ＤＩＣ社製）が挙げられる。 Further, as the fluorosurfactant, an acrylic compound having a molecular structure with a functional group containing a fluorine atom is also preferable, in which the portion of the functional group containing the fluorine atom is cleaved when heat is applied to volatilize the fluorine atom. .
Examples of such a fluorosurfactant include Megafac DS series manufactured by DIC (The Chemical Daily (February 22, 2016) and Nikkei Sangyo Shimbun (February 23, 2016)).
As the fluorosurfactant, it is also preferable to use a copolymer 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 fluorosurfactant.
The fluorosurfactant has 2 or more (preferably 5 or more) structural units derived from a (meth)acrylate compound having a fluorine atom and an alkyleneoxy group (preferably an ethyleneoxy group or a propyleneoxy group) (preferably 5 or more). ) and a structural unit derived from an acrylate compound.
Examples of fluorosurfactants also include fluoropolymers having ethylenically unsaturated groups in side chains, such as MEGAFACE RS-101, RS-102, RS-718K and RS-72-K ( (manufactured by DIC Corporation).
　フッ素系界面活性剤としては、環境適性向上の点から、パーフルオロオクタン酸（ＰＦＯＡ）及びパーフルオロオクタンスルホン酸（ＰＦＯＳ）等の炭素数が７以上の直鎖状パーフルオロアルキル基を有する化合物の代替材料に由来する界面活性剤が好ましい。 As fluorine-based surfactants, from the viewpoint of improving environmental suitability, compounds having linear perfluoroalkyl groups having 7 or more carbon atoms, such as perfluorooctanoic acid (PFOA) and perfluorooctane sulfonic acid (PFOS), are used. Surfactants derived from alternative materials are preferred.
　ノニオン系界面活性剤としては、例えば、グリセロール、トリメチロールプロパン、トリメチロールエタン、それらのエトキシレート及びプロポキシレート（例えば、グリセロールプロポキシレート及びグリセロールエトキシレート等）、ポリオキシエチレンラウリルエーテル、ポリオキシエチレンステアリルエーテル、ポリオキシエチレンオレイルエーテル、ポリオキシエチレンオクチルフェニルエーテル、ポリオキシエチレンノニルフェニルエーテル、ポリエチレングリコールジラウレート、ポリエチレングリコールジステアレート、並びに、ソルビタン脂肪酸エステル；具体例としては、プルロニック（登録商標）　Ｌ１０、Ｌ３１、Ｌ６１、Ｌ６２、１０Ｒ５、１７Ｒ２及び２５Ｒ２（以上、ＢＡＳＦ社製）；テトロニック　３０４、７０１、７０４、９０１、９０４、及び１５０Ｒ１、ＨＹＤＲＯＰＡＬＡＴ　ＷＥ　３３２３（以上、ＢＡＳＦ社製）；ソルスパース　２００００（以上、日本ルーブリゾール社製）；ＮＣＷ－１０１、ＮＣＷ－１００１及びＮＣＷ－１００２（以上、富士フイルム和光純薬社製）；パイオニン　Ｄ－１１０５、Ｄ－６１１２、Ｄ－６１１２－Ｗ及びＤ－６３１５（以上、竹本油脂社製）；オルフィンＥ１０１０、サーフィノール１０４、４００及び４４０（以上、日信化学工業社製）が挙げられる。 Examples of nonionic surfactants include glycerol, trimethylolpropane, trimethylolethane, their ethoxylates and propoxylates (e.g., glycerol propoxylate and glycerol ethoxylate, etc.), polyoxyethylene lauryl ether, polyoxyethylene stearyl Ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, and sorbitan fatty acid ester; specific examples include Pluronic (registered trademark) L10, L31, L61, L62, 10R5, 17R2 and 25R2 (manufactured by BASF); Tetronic 304, 701, 704, 901, 904 and 150R1, HYDROPALAT WE 3323 (manufactured by BASF); Solsperse 20000 (manufactured by BASF) Japan Lubrizol Co., Ltd.); NCW-101, NCW-1001 and NCW-1002 (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.); Pionein D-1105, D-6112, D-6112-W and D-6315 , manufactured by Takemoto Oil & Fat Co., Ltd.); Olfine E1010, Surfynol 104, 400 and 440 (manufactured by Nissin Chemical Industry Co., Ltd.).
　シリコーン系界面活性剤としては、例えば、シロキサン結合からなる直鎖状ポリマー、並びに、側鎖及び／又は末端に有機基を導入した変性シロキサンポリマーが挙げられる。 Examples of silicone-based surfactants include linear polymers composed of siloxane bonds, and modified siloxane polymers in which organic groups are introduced into side chains and/or terminals.
　シリコーン系界面活性剤としては、具体的には、ＥＸＰ．Ｓ－３０９－２、ＥＸＰ．Ｓ－３１５、ＥＸＰ．Ｓ－５０３－２、ＥＸＰ．Ｓ－５０５－２（以上、ＤＩＣ株式会社製）、ＤＯＷＳＩＬ　８０３２　ＡＤＤＩＴＩＶＥ、トーレシリコーンＤＣ３ＰＡ、トーレシリコーンＳＨ７ＰＡ、トーレシリコーンＤＣ１１ＰＡ、トーレシリコーンＳＨ２１ＰＡ、トーレシリコーンＳＨ２８ＰＡ、トーレシリコーンＳＨ２９ＰＡ、トーレシリコーンＳＨ３０ＰＡ及びトーレシリコーンＳＨ８４００（以上、東レ・ダウコーニング社製）；Ｘ－２２－４９５２、Ｘ－２２－４２７２、Ｘ－２２－６２６６、ＫＦ－３５１Ａ、Ｋ３５４Ｌ、ＫＦ－３５５Ａ、ＫＦ－９４５、ＫＦ－６４０、ＫＦ－６４２、ＫＦ－６４３、Ｘ－２２－６１９１、Ｘ－２２－４５１５、ＫＦ－６００４、ＫＰ－３４１、ＫＦ－６００１、ＫＦ－６００２、ＫＰ－１０１、ＫＰ－１０３、ＫＰ－１０４、ＫＰ－１０５、ＫＰ－１０６、ＫＰ－１０９、ＫＰ－１１２、ＫＰ－１２０、ＫＰ－１２１、ＫＰ－１２４、ＫＰ－１２５、ＫＰ－３０１、ＫＰ－３０６、ＫＰ－３１０、ＫＰ－３２２、ＫＰ－３２３、ＫＰ－３２７、ＫＰ－３４１、ＫＰ－３６８、ＫＰ－３６９、ＫＰ－６１１、ＫＰ－６２０、ＫＰ－６２１、ＫＰ－６２６、ＫＰ－６５２（以上、信越シリコーン社製）；Ｆ－４４４０、ＴＳＦ－４３００、ＴＳＦ－４４４５、ＴＳＦ－４４６０及びＴＳＦ－４４５２（以上、モメンティブ・パフォーマンス・マテリアルズ社製）；ＢＹＫ３００、ＢＹＫ３０６、ＢＹＫ３０７、ＢＹＫ３１０、ＢＹＫ３２０、ＢＹＫ３２３、ＢＹＫ３２５、ＢＹＫ３３０、ＢＹＫ３１３、ＢＹＫ３１５Ｎ、ＢＹＫ３３１、ＢＹＫ３３３、ＢＹＫ３４５、ＢＹＫ３４７、ＢＹＫ３４８、ＢＹＫ３４９、ＢＹＫ３７０、ＢＹＫ３７７、ＢＹＫ３７８、ＢＹＫ３２３（以上、ビックケミー社製）が挙げられる。 Specific examples of silicone-based surfactants include EXP. S-309-2, EXP. S-315, EXP. S-503-2, EXP. S-505-2 (manufactured by DIC Corporation), DOWSIL 8032 ADDITIVE, Toray Silicone DC3PA, Toray Silicone SH7PA, Toray Silicone DC11PA, Toray Silicone SH21PA, Toray Silicone SH28PA, Toray Silicone SH29PA, Toray Silicone SH30PA and Toray Silicone SH8400 ( Above, Dow Corning Toray Co., Ltd.); KF-643, X-22-6191, X-22-4515, KF-6004, KP-341, KF-6001, KF-6002, KP-101, KP-103, KP-104, KP-105, KP- 106, KP-109, KP-112, KP-120, KP-121, KP-124, KP-125, KP-301, KP-306, KP-310, KP-322, KP-323, KP-327, KP-341, KP-368, KP-369, KP-611, KP-620, KP-621, KP-626, KP-652 (manufactured by Shin-Etsu Silicone Co., Ltd.); F-4440, TSF-4300, TSF- 4445, TSF-4460 and TSF-4452 (manufactured by Momentive Performance Materials); BYK348, BYK349, BYK370, BYK377, BYK378, and BYK323 (manufactured by BYK-Chemie).
　界面活性剤の含有量は、感光性組成物層の全質量に対して、０．０１～３．０質量％が好ましく、０．０１～１．０質量％がより好ましく、０．０５～０．８質量％が更に好ましい。 The content of the surfactant is preferably 0.01 to 3.0% by mass, more preferably 0.01 to 1.0% by mass, and 0.05 to 0.0% by mass, based on the total mass of the photosensitive composition layer. 0.8% by weight is more preferred.
　可塑剤及びヘテロ環状化合物としては、例えば、国際公開第２０１８／１７９６４０号の段落［００９７］～［０１０３］及び段落［０１１１］～［０１１８］に記載された化合物が挙げられる。 Plasticizers and heterocyclic compounds include, for example, compounds described in paragraphs [0097] to [0103] and paragraphs [0111] to [0118] of WO2018/179640.
＜不純物＞
　感光性組成物層は、不純物を含んでいてもよい。
　不純物としては、例えば、金属不純物又はそのイオン、ハロゲン化物イオン、残存有機溶剤、残存モノマー及び水が挙げられる。 <Impurities>
The photosensitive composition layer may contain impurities.
Impurities include, for example, metal impurities or their ions, halide ions, residual organic solvents, residual monomers, and water.
（金属不純物及びハロゲン化物イオン）
　金属不純物としては、例えば、ナトリウム、カリウム、マグネシウム、カルシウム、鉄、マンガン、銅、アルミニウム、チタン、クロム、コバルト、ニッケル、亜鉛、スズ及びこれらのイオン、並びに、ハロゲン化物イオンが挙げられる。
　なかでも、ナトリウムイオン、カリウムイオン及びハロゲン化物イオンは、混入し易い点から、下記の含有量にすることが好ましい。
　金属不純物は、転写フィルムに含まれ得る上記粒子（例えば、金属酸化物粒子）とは異なる化合物である。 (metallic impurities and halide ions)
Metal impurities include, for example, sodium, potassium, magnesium, calcium, iron, manganese, copper, aluminum, titanium, chromium, cobalt, nickel, zinc, tin and ions thereof, and halide ions.
Among them, sodium ions, potassium ions and halide ions are preferably contained in the following amounts because they are easily mixed.
Metal impurities are compounds different from the particles (eg, metal oxide particles) that may be included in the transfer film.
　金属不純物の含有量は、感光性組成物層の全質量に対して、８０質量ｐｐｍ以下が好ましく、１０質量ｐｐｍ以下がより好ましく、２質量ｐｐｍ以下が更に好ましい。下限は、感光性組成物層の全質量に対して、１質量ｐｐｂ以上が好ましく、０．１質量ｐｐｍ以上がより好ましい。 The content of metal impurities is preferably 80 mass ppm or less, more preferably 10 mass ppm or less, and even more preferably 2 mass ppm or less, relative to the total mass of the photosensitive composition layer. The lower limit is preferably 1 mass ppb or more, more preferably 0.1 mass ppm or more, relative to the total mass of the photosensitive composition layer.
　不純物の含有量を調整する方法としては、例えば、感光性組成物層の原料として不純物の含有量が少ないものを選択する方法、並びに、感光性組成物層の形成時に不純物の混入を防ぐ方法及び洗浄して除去する方法が挙げられる。
　不純物の含有量は、例えば、ＩＣＰ発光分光分析法、原子吸光分光法及びイオンクロマトグラフィー法等の公知の方法により定量できる。 Methods for adjusting the content of impurities include, for example, a method of selecting a material with a low impurity content as a raw material for the photosensitive composition layer, a method of preventing contamination of impurities during the formation of the photosensitive composition layer, and A method of removing by washing can be mentioned.
The content of impurities can be quantified by known methods such as ICP emission spectroscopy, atomic absorption spectroscopy and ion chromatography.
（残存有機溶剤）
　残存有機溶剤としては、例えば、ベンゼン、ホルムアルデヒド、トリクロロエチレン、１，３－ブタジエン、四塩化炭素、クロロホルム、Ｎ，Ｎ－ジメチルホルムアミド、Ｎ，Ｎ－ジメチルアセトアミド及びヘキサンが挙げられる。
　残存有機溶剤の含有量は、感光性組成物層の全質量に対して、１００質量ｐｐｍ以下が好ましく、２０質量ｐｐｍ以下がより好ましく、４質量ｐｐｍ以下が更に好ましい。下限は、感光性組成物層の全質量に対して、１０質量ｐｐｂ以上が好ましく、１００質量ｐｐｂ以上がより好ましい。
　残存有機溶剤の含有量を調整する方法としては、後述する転写フィルムの製造方法における乾燥処理条件を調整する方法が挙げられる。また、残存有機溶剤の含有量は、例えば、ガスクロマトグラフィー分析等の公知の方法により定量できる。 (residual organic solvent)
Residual organic solvents include, for example, benzene, formaldehyde, trichlorethylene, 1,3-butadiene, carbon tetrachloride, chloroform, N,N-dimethylformamide, N,N-dimethylacetamide and hexane.
The content of the residual organic solvent is preferably 100 ppm by mass or less, more preferably 20 ppm by mass or less, and even more preferably 4 ppm by mass or less, relative to the total mass of the photosensitive composition layer. The lower limit is preferably 10 mass ppb or more, more preferably 100 mass ppb or more, relative to the total mass of the photosensitive composition layer.
As a method for adjusting the content of the residual organic solvent, there is a method for adjusting the drying treatment conditions in the transfer film manufacturing method described below. Also, the content of the residual organic solvent can be quantified by a known method such as gas chromatography analysis.
（残存する単量体）
　感光性組成物層は、上記樹脂の各構成単位の残存する単量体を含む場合がある。
　残存する単量体の含有量は、パターニング性及び信頼性の点から、樹脂の全質量に対して、５０００質量ｐｐｍ以下が好ましく、２０００質量ｐｐｍ以下がより好ましく、５００質量ｐｐｍ以下が更に好ましい。下限は、樹脂の全質量に対して、１質量ｐｐｍ以上が好ましく、１０質量ｐｐｍ以上がより好ましい。
　アルカリ可溶性樹脂の各構成単位の残存する単量体は、パターニング性及び信頼性の点から、感光性組成物層の全質量に対して、３０００質量ｐｐｍ以下が好ましく、６００質量ｐｐｍ以下がより好ましく、１００質量ｐｐｍ以下が更に好ましい。下限は、感光性組成物層の全質量に対して、０．１質量ｐｐｍ以上が好ましく、１質量ｐｐｍ以上がより好ましい。 (remaining monomer)
The photosensitive composition layer may contain residual monomers of the constituent units of the resin.
The content of the remaining monomer is preferably 5000 ppm by mass or less, more preferably 2000 ppm by mass or less, and even more preferably 500 ppm by mass or less relative to the total mass of the resin, from the viewpoint of patterning properties and reliability. The lower limit is preferably 1 mass ppm or more, more preferably 10 mass ppm or more, relative to the total mass of the resin.
From the viewpoint of patterning properties and reliability, the residual monomer of each structural unit of the alkali-soluble resin is preferably 3000 ppm by mass or less, more preferably 600 ppm by mass or less, relative to the total mass of the photosensitive composition layer. , 100 ppm by mass or less is more preferable. The lower limit is preferably 0.1 mass ppm or more, more preferably 1 mass ppm or more, relative to the total mass of the photosensitive composition layer.
　高分子反応でアルカリ可溶性樹脂を合成する際の単量体の残存量も、上記範囲とすることが好ましい。例えば、カルボン酸側鎖にアクリル酸グリシジルを反応させてアルカリ可溶性樹脂を合成する場合、アクリル酸グリシジルの含有量を上記範囲にすることが好ましい。
　残存する単量体の含有量を調整する方法としては、例えば、上記不純物の含有量を調整する方法が挙げられる。
　残存する単量体の量は、液体クロマトグラフィー及びガスクロマトグラフィー等の公知の方法で測定できる。 It is preferable that the residual amount of the monomer when synthesizing the alkali-soluble resin by polymer reaction is also within the above range. For example, when synthesizing an alkali-soluble resin by reacting a carboxylic acid side chain with glycidyl acrylate, the content of glycidyl acrylate is preferably within the above range.
Examples of the method for adjusting the content of the remaining monomers include a method for adjusting the content of the impurities.
The amount of residual monomers can be measured by known methods such as liquid chromatography and gas chromatography.
　感光性組成物層における水の含有量は、信頼性及びラミネート性を向上させる点から、０．０１～１．０質量％が好ましく、０．０５～０．５質量％がより好ましい。 The water content in the photosensitive composition layer is preferably 0.01 to 1.0% by mass, more preferably 0.05 to 0.5% by mass, from the viewpoint of improving reliability and laminating properties.
〔感光性組成物層の特性〕
　感光性組成物層の厚み（膜厚）としては、０．１～３００μｍの場合が多く、０．２～１００μｍが好ましく、０．５～５０μｍがより好ましく、０．５～３０μｍが更に好ましく、１～２０μｍが特に好ましい。これにより、感光性組成物層の現像性が向上し、解像性を向上できる。 [Characteristics of photosensitive composition layer]
The thickness (film thickness) of the photosensitive composition layer is often 0.1 to 300 μm, preferably 0.2 to 100 μm, more preferably 0.5 to 50 μm, even more preferably 0.5 to 30 μm, 1 to 20 μm is particularly preferred. Thereby, the developability of the photosensitive composition layer can be improved, and the resolution can be improved.
　感光性組成物層に含まれる重合性基の含有量は、１．０ｍｍｏｌ／ｇ以上が好ましく、２．０ｍｍｏｌ／ｇ以上がより好ましく、本発明の効果がより優れる点から、３．０ｍｍｏｌ／ｇ以上が更に好ましい。上限は、１０．０ｍｍｏｌ／ｇ以下が好ましい。また、上記重合性の含有量を二重結合の含有量に置き換えて解釈してもよい。 The content of the polymerizable group contained in the photosensitive composition layer is preferably 1.0 mmol/g or more, more preferably 2.0 mmol/g or more, and 3.0 mmol/g from the viewpoint that the effects of the present invention are more excellent. The above is more preferable. The upper limit is preferably 10.0 mmol/g or less. Moreover, you may interpret by replacing the said polymerizable content with content of a double bond.
　感光性組成物層の酸価は、１０～１５０ｍｇＫＯＨ／ｇが好ましく、４０～１２０ｍｇＫＯＨ／ｇがより好ましく、５０～１２０ｍｇＫＯＨ／ｇが更に好ましく、５０～１００ｍｇＫＯＨ／ｇが特に好ましく、６０～１００ｍｇＫＯＨ／ｇが最も好ましい。
　上記酸価の測定方法としては、例えば、上記樹脂における酸価の測定方法及び酸価が既知の樹脂の含有量から算出する方法が挙げられる。 The acid value of the photosensitive composition layer is preferably 10 to 150 mgKOH/g, more preferably 40 to 120 mgKOH/g, still more preferably 50 to 120 mgKOH/g, particularly preferably 50 to 100 mgKOH/g, particularly preferably 60 to 100 mgKOH/g. is most preferred.
Examples of the method for measuring the acid value include a method for measuring the acid value in the resin and a method for calculating the acid value from the content of a resin whose acid value is known.
〔中間層〕
　転写フィルムは、仮支持体と感光性組成物層との間に中間層を有していてもよい。
　例えば、中間層は、熱可塑性樹脂層を有さない場合は仮支持体と感光性組成物層との間、又は、熱可塑性樹脂層を有する場合は熱可塑性樹脂層と感光性組成物層との間に配置されることが好ましい。
　中間層としては、例えば、水溶性樹脂層及び特開平５－０７２７２４号公報に「分離層」として記載される酸素遮断機能のある酸素遮断層が挙げられる。
　中間層としては、露光時の感度が向上して露光機の時間負荷が低減して生産性が向上する点から、酸素遮断層が好ましく、低い酸素透過性を示し、水又はアルカリ水溶液（２２℃の炭酸ナトリウムの１質量％水溶液）に分散又は溶解する酸素遮断層がより好ましい。
　以下、中間層が含み得る各成分について説明する。 [Intermediate layer]
The transfer film may have an intermediate layer between the temporary support and the photosensitive composition layer.
For example, the intermediate layer is between the temporary support and the photosensitive composition layer if it does not have a thermoplastic resin layer, or if it has a thermoplastic resin layer, the thermoplastic resin layer and the photosensitive composition layer is preferably placed between
Examples of the intermediate layer include a water-soluble resin layer and an oxygen barrier layer having an oxygen barrier function described as a "separation layer" in JP-A-5-072724.
As the intermediate layer, an oxygen-blocking layer is preferable from the viewpoint that the sensitivity at the time of exposure is improved, the time load of the exposure machine is reduced, and the productivity is improved. More preferred is an oxygen barrier layer dispersed or dissolved in a 1% by weight aqueous solution of sodium carbonate.
Each component that the intermediate layer may contain will be described below.
＜水溶性樹脂＞
　中間層は、水溶性樹脂を含んでいてもよい。
　水溶性樹脂としては、例えば、ポリビニルアルコール系樹脂、ポリビニルピロリドン系樹脂、セルロース系樹脂、ポリエーテル系樹脂、ゼラチン及びポリアミド樹脂が挙げられる。 <Water-soluble resin>
The intermediate layer may contain a water-soluble resin.
Examples of water-soluble resins include polyvinyl alcohol-based resins, polyvinylpyrrolidone-based resins, cellulose-based resins, polyether-based resins, gelatin, and polyamide resins.
　セルロース系樹脂としては、例えば、水溶性セルロース誘導体が挙げられる。
　水溶性セルロース誘導体としては、例えば、ヒドロキシエチルセルロース、ヒドロキシプロピルメチルセルロース、ヒドロキシプロピルセルロース、カルボキシメチルセルロース、メチルセルロース及びエチルセルロースが挙げられる。 Cellulose-based resins include, for example, water-soluble cellulose derivatives.
Water-soluble cellulose derivatives include, for example, hydroxyethylcellulose, hydroxypropylmethylcellulose, hydroxypropylcellulose, carboxymethylcellulose, methylcellulose and ethylcellulose.
　ポリエーテル系樹脂としては、例えば、ポリエチレングリコール、ポリプロピレングリコール及びこれらのアルキレンオキシサイド付加物、並びに、ビニルエーテル系樹脂が挙げられる。
　ポリアミド樹脂としては、例えば、アクリルアミド系樹脂、ビニルアミド系樹脂及びアリルアミド系樹脂が挙げられる。 Examples of polyether-based resins include polyethylene glycol, polypropylene glycol, alkylene oxide side adducts thereof, and vinyl ether-based resins.
Polyamide resins include, for example, acrylamide-based resins, vinylamide-based resins, and allylamide-based resins.
　水溶性樹脂としては、例えば、（メタ）アクリル酸／ビニル化合物の共重合体も挙げられ、（メタ）アクリル酸と（メタ）アクリル酸アリルとの共重合体が好ましく、メタクリル酸とメタクリル酸アリルと共重合体がより好ましい。
　水溶性樹脂が（メタ）アクリル酸とビニル化合物との共重合体である場合、各組成比（（メタ）アクリル酸のｍｏｌ％／ビニル化合物のｍｏｌ％）としては、９０／１０～２０／８０が好ましく、８０／２０～３０／７０がより好ましい。 Examples of water-soluble resins include copolymers of (meth)acrylic acid/vinyl compounds, preferably copolymers of (meth)acrylic acid and allyl (meth)acrylate, and methacrylic acid and allyl methacrylate. and copolymers are more preferred.
When the water-soluble resin is a copolymer of (meth)acrylic acid and a vinyl compound, each composition ratio (mol% of (meth)acrylic acid/mol% of vinyl compound) is 90/10 to 20/80. is preferred, and 80/20 to 30/70 is more preferred.
　水溶性樹脂の重量平均分子量としては、５，０００以上が好ましく、７，０００以上がより好ましく、１０，０００以上が更に好ましい。上限は、２００，０００以下が好ましく、１００，０００以下がより好ましく、５０，０００以下が更に好ましい。
　水溶性樹脂の分散度は、１～１０が好ましく、１～５がより好ましく、１～３が更に好ましい。 The weight average molecular weight of the water-soluble resin is preferably 5,000 or more, more preferably 7,000 or more, and even more preferably 10,000 or more. The upper limit is preferably 200,000 or less, more preferably 100,000 or less, even more preferably 50,000 or less.
The dispersity of the water-soluble resin is preferably 1-10, more preferably 1-5, even more preferably 1-3.
　水溶性樹脂は、１種単独で用いてもよく、２種以上で用いてもよい。
　水溶性樹脂の含有量は、中間層の全質量に対して、５０質量％以上が好ましく、７０質量％以上がより好ましい。上限は、中間層の全質量に対して、１００質量％以下が好ましく、９９．９質量％以下がより好ましく、９９．８質量％以下が更に好ましく、９９質量％以下が特に好ましい。 One type of water-soluble resin may be used alone, or two or more types may be used.
The content of the water-soluble resin is preferably 50% by mass or more, more preferably 70% by mass or more, relative to the total mass of the intermediate layer. The upper limit is preferably 100% by mass or less, more preferably 99.9% by mass or less, still more preferably 99.8% by mass or less, and particularly preferably 99% by mass or less, relative to the total mass of the intermediate layer.
＜その他成分＞
　中間層は、上記樹脂以外に、その他成分を含んでいてもよい。 <Other ingredients>
The intermediate layer may contain other components in addition to the above resins.
　その他成分としては、多価アルコール類、多価アルコール類のアルキレンオキサイド付加物、フェノール誘導体又はアミド化合物が好ましく、多価アルコール類、フェノール誘導体又はアミド化合物がより好ましい。 As other components, polyhydric alcohols, alkylene oxide adducts of polyhydric alcohols, phenol derivatives or amide compounds are preferable, and polyhydric alcohols, phenol derivatives or amide compounds are more preferable.
　多価アルコール類としては、例えば、グリセリン、ジグリセリン及びジエチレングリコールが挙げられる。
　多価アルコール類が有するヒドロキシ基の数としては、２～１０が好ましい。
　多価アルコール類のアルキレンオキサイド付加物としては、例えば、上記多価アルコール類にエチレンオキシ基及びプロピレンオキシ基等を付加した化合物が挙げられる。
　アルキレンオキシ基の平均付加数は、１～１００が好ましく、２～５０が好ましく、２～２０がより好ましい。
　フェノール誘導体としては、例えば、ビスフェノールＡ及びビスフェノールＳが挙げられる。
　アミド化合物としては、例えば、Ｎ－メチルピロリドンが挙げられる。 Polyhydric alcohols include, for example, glycerin, diglycerin and diethylene glycol.
The number of hydroxy groups possessed by the polyhydric alcohol is preferably 2-10.
Examples of alkylene oxide adducts of polyhydric alcohols include compounds obtained by adding ethyleneoxy groups, propyleneoxy groups, and the like to the above polyhydric alcohols.
The average number of alkyleneoxy groups to be added is preferably 1-100, preferably 2-50, more preferably 2-20.
Phenol derivatives include, for example, bisphenol A and bisphenol S.
Amide compounds include, for example, N-methylpyrrolidone.
　中間層は、水溶性セルロース誘導体、多価アルコール類、多価アルコール類のオキサイド付加物、ポリエーテル系樹脂、フェノール誘導体及びアミド化合物からなる群から選択される少なくとも１つを含むことが好ましい。 The intermediate layer preferably contains at least one selected from the group consisting of water-soluble cellulose derivatives, polyhydric alcohols, oxide adducts of polyhydric alcohols, polyether resins, phenol derivatives and amide compounds.
　その他成分の分子量は、５，０００未満が好ましく、４，０００以下がより好ましく、３，０００以下が更に好ましく、２，０００以下が特に好ましく、１，５００以下が最も好ましい。下限は、６０以上が好ましい。 The molecular weight of other components is preferably less than 5,000, more preferably 4,000 or less, even more preferably 3,000 or less, particularly preferably 2,000 or less, and most preferably 1,500 or less. The lower limit is preferably 60 or more.
　その他成分は、１種単独で用いてもよく、２種以上で用いてもよい。
　その他成分の含有量は、中間層の全質量に対して、０．１質量％以上が好ましく、０．５質量％以上がより好ましく、１質量％以上が更に好ましい。上限は、３０質量％未満が好ましく、１０質量％以下がより好ましく、５質量％以下が更に好ましい。 Other components may be used singly or in combination of two or more.
The content of other components is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and even more preferably 1% by mass or more, relative to the total mass of the intermediate layer. The upper limit is preferably less than 30% by mass, more preferably 10% by mass or less, and even more preferably 5% by mass or less.
＜不純物＞
　中間層は、不純物を含んでいてもよい。
　不純物としては、例えば、上記感光性組成物層に含まれる不純物が挙げられる。 <Impurities>
The intermediate layer may contain impurities.
Impurities include, for example, impurities contained in the photosensitive composition layer.
　中間層の厚みとしては、３．０μｍ以下が好ましく、２．０μｍ以下がより好ましい。下限は、１．０μｍ以上が好ましい。 The thickness of the intermediate layer is preferably 3.0 µm or less, more preferably 2.0 µm or less. The lower limit is preferably 1.0 μm or more.
〔熱可塑性樹脂層〕
　転写フィルムは、熱可塑性樹脂層を有していてもよい。
　熱可塑性樹脂層は、中間層を有さない場合は仮支持体と感光性組成物層との間、中間層を有する場合は仮支持体と中間層との間に配置されることが好ましい。
　転写フィルムが熱可塑性樹脂層を有する場合、転写フィルムと被転写体との貼合工程における被転写体への追従性が向上し、転写フィルムと被転写体との間に気泡が混入することを抑制できる。その結果、熱可塑性樹脂層に隣接する層（例えば、仮支持体）との密着性が向上する。
　熱可塑性樹脂層としては、例えば、特開２０１４－０８５６４３号公報の段落［０１８９］～［０１９３］が挙げられ、これらの内容は本明細書に組み込まれる。
　以下、熱可塑性樹脂層が含み得る各成分について説明する。 [Thermoplastic resin layer]
The transfer film may have a thermoplastic resin layer.
The thermoplastic resin layer is preferably arranged between the temporary support and the photosensitive composition layer when the intermediate layer is not provided, and between the temporary support and the intermediate layer when the intermediate layer is provided.
When the transfer film has a thermoplastic resin layer, the followability to the transferred material in the step of laminating the transfer film and the transferred material is improved, and air bubbles are prevented from entering between the transfer film and the transferred material. can be suppressed. As a result, adhesion with a layer (for example, temporary support) adjacent to the thermoplastic resin layer is improved.
Examples of the thermoplastic resin layer include paragraphs [0189] to [0193] of JP-A-2014-085643, the contents of which are incorporated herein.
Each component that the thermoplastic resin layer may contain will be described below.
＜熱可塑性樹脂＞
　熱可塑性樹脂層は、熱可塑性樹脂を含んでいてもよい。
　熱可塑性樹脂としては、アルカリ可溶性樹脂が好ましい。
　アルカリ可溶性樹脂としては、例えば、アクリル樹脂、ポリスチレン樹脂、スチレン－アクリル系共重合体、ポリウレタン樹脂、ポリビニルアルコール、ポリビニルホルマール、ポリアミド樹脂、ポリエステル樹脂、ポリアミド樹脂、エポキシ樹脂、ポリアセタール樹脂、ポリヒドロキシスチレン樹脂、ポリイミド樹脂、ポリベンゾオキサゾール樹脂、ポリシロキサン樹脂、ポリエチレンイミン、ポリアリルアミン及びポリアルキレングリコールが挙げられる。
　アルカリ可溶性樹脂としては、上述した感光性組成物層に含まれるアルカリ可溶性樹脂を用いてもよい。 <Thermoplastic resin>
The thermoplastic resin layer may contain a thermoplastic resin.
As the thermoplastic resin, an alkali-soluble resin is preferred.
Examples of alkali-soluble resins include acrylic resins, polystyrene resins, styrene-acrylic copolymers, polyurethane resins, polyvinyl alcohol, polyvinyl formal, polyamide resins, polyester resins, polyamide resins, epoxy resins, polyacetal resins, and polyhydroxystyrene resins. , polyimide resins, polybenzoxazole resins, polysiloxane resins, polyethyleneimines, polyallylamines and polyalkylene glycols.
As the alkali-soluble resin, the alkali-soluble resin contained in the photosensitive composition layer described above may be used.
　アルカリ可溶性樹脂としては、現像性及び隣接する層との密着性の点から、アクリル樹脂が好ましい。
　「アクリル樹脂」とは、（メタ）アクリル酸に由来する構成単位、（メタ）アクリル酸エステルに由来する構成単位及び（メタ）アクリル酸アミドに由来する構成単位からなる群から選択される少なくとも１つの構成単位を含む樹脂を意味する。
　アクリル樹脂において、（メタ）アクリル酸に由来する構成単位、（メタ）アクリル酸エステルに由来する構成単位及び（メタ）アクリル酸アミドに由来する構成単位の合計含有量は、アクリル樹脂の全質量に対して、３０質量％以上が好ましく、５０質量％以上がより好ましい。上限は、アクリル樹脂の全質量に対して、１００質量％以下が好ましい。
　なかでも、（メタ）アクリル酸に由来する構成単位及び（メタ）アクリル酸エステルに由来する構成単位の合計含有量が、アクリル樹脂の全質量に対して、３０～１００質量％が好ましく、５０～１００質量％がより好ましい。 As the alkali-soluble resin, an acrylic resin is preferable from the viewpoint of developability and adhesion to adjacent layers.
"Acrylic resin" means at least one selected from the group consisting of structural units derived from (meth)acrylic acid, structural units derived from (meth)acrylic acid esters, and structural units derived from (meth)acrylic acid amides. means a resin containing one constitutional unit.
In acrylic resins, the total content of structural units derived from (meth)acrylic acid, structural units derived from (meth)acrylic acid esters, and structural units derived from (meth)acrylic acid amides is equal to the total mass of the acrylic resin. On the other hand, 30% by mass or more is preferable, and 50% by mass or more is more preferable. The upper limit is preferably 100% by mass or less with respect to the total mass of the acrylic resin.
Among them, the total content of structural units derived from (meth) acrylic acid and structural units derived from (meth) acrylic acid ester is preferably 30 to 100% by mass, based on the total mass of the acrylic resin, and 50 to 100% by mass is more preferred.
　アルカリ可溶性樹脂としては、酸基を有する樹脂が好ましい。
　酸基としては、例えば、カルボキシ基、スルホ基、リン酸基及びホスホン酸基が挙げられ、カルボキシ基が好ましい。
　また、アルカリ可溶性樹脂としては、酸基を有する構成単位を含むことが好ましく、カルボキシ基を有する構成単位を含むことがより好ましく、現像性及び隣接する層との密着性の点から、（メタ）アクリル酸に由来する構成単位を有するアクリル樹脂が更に好ましい。 A resin having an acid group is preferable as the alkali-soluble resin.
The acid group includes, for example, a carboxy group, a sulfo group, a phosphoric acid group and a phosphonic acid group, with the carboxy group being preferred.
Further, the alkali-soluble resin preferably contains a structural unit having an acid group, and more preferably contains a structural unit having a carboxy group. Acrylic resins having structural units derived from acrylic acid are more preferred.
　アルカリ可溶性樹脂の酸価としては、現像性の点から、６０ｍｇＫＯＨ／ｇ以上が好ましい。上限は、３００ｍｇＫＯＨ／ｇ以下が好ましく、２５０ｍｇＫＯＨ／ｇ以下がより好ましく、２００ｍｇＫＯＨ／ｇ以下が更に好ましく、１５０ｍｇＫＯＨ／ｇ以下が特に好ましい。
　なかでも、アルカリ可溶性樹脂としては、酸価６０ｍｇＫＯＨ／ｇ以上のアルカリ可溶性樹脂が好ましく、酸価６０ｍｇＫＯＨ／ｇ以上のカルボキシ基を有するアクリル樹脂がより好ましい。 The acid value of the alkali-soluble resin is preferably 60 mgKOH/g or more from the viewpoint of developability. The upper limit is preferably 300 mgKOH/g or less, more preferably 250 mgKOH/g or less, still more preferably 200 mgKOH/g or less, and particularly preferably 150 mgKOH/g or less.
Among them, as the alkali-soluble resin, an alkali-soluble resin having an acid value of 60 mgKOH/g or more is preferable, and an acrylic resin having a carboxyl group having an acid value of 60 mgKOH/g or more is more preferable.
　酸価６０ｍｇＫＯＨ／ｇ以上のカルボキシ基を有するアクリル樹脂としては、例えば、公知の樹脂から適宜選択して使用できる。
　具体的には、特開２０１１－０９５７１６号公報の段落［００２５］、特開２０１０－２３７５８９号公報の段落［００３３］～［００５２］及び特開２０１６－２２４１６２号公報の段落［００５３］～［００６８］が挙げられる。 As the acrylic resin having a carboxyl group with an acid value of 60 mgKOH/g or more, for example, it can be appropriately selected from known resins and used.
Specifically, paragraph [0025] of JP-A-2011-095716, paragraphs [0033] to [0052] of JP-A-2010-237589 and paragraphs [0053] to [0068 of JP-A-2016-224162 ] is mentioned.
　カルボキシ基を有する構成単位の含有量は、アクリル樹脂の全質量に対して、５～５０質量％が好ましく、１０～４０質量％がより好ましく、１２～３０質量％が更に好ましい。 The content of structural units having a carboxy group is preferably 5-50% by mass, more preferably 10-40% by mass, and even more preferably 12-30% by mass, relative to the total mass of the acrylic resin.
　アルカリ可溶性樹脂は、重合性基を有していてもよい。
　重合性基としては、重合反応に関与する基であればよく、例えば、ビニル基、アクリロイル基、メタクリロイル基、スチリル基及びマレイミド基等のエチレン性不飽和基を有する基；エポキシ基及びオキセタン基等のカチオン性重合性基を有する基が挙げられる。
　なかでも、重合性基としては、エチレン性不飽和基を有する基が好ましく、アクリロイル基又はメタアクリロイル基がより好ましい。 The alkali-soluble resin may have a polymerizable group.
The polymerizable group may be any group as long as it participates in the polymerization reaction, for example, 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; an epoxy group, an oxetane group, and the like. group having a cationic polymerizable group.
Among them, as the polymerizable group, a group having an ethylenically unsaturated group is preferable, and an acryloyl group or a methacryloyl group is more preferable.
　アルカリ可溶性樹脂の重量平均分子量としては、１，０００以上が好ましく、１０，０００～１００，０００より好ましく、２０，０００～５０，０００が更に好ましい。 The weight average molecular weight of the alkali-soluble resin is preferably 1,000 or more, more preferably 10,000 to 100,000, and still more preferably 20,000 to 50,000.
　熱可塑性樹脂は、１種単独で用いてもよく、２種以上で用いてもよい。
　熱可塑性樹脂の含有量は、現像性及び隣接する層との密着性の点から、熱可塑性樹脂層の全質量に対して、１０～９９質量％が好ましく、２０～９０質量％がより好ましく、４０～８０質量％が更に好ましく、５０～７５質量％が特に好ましい。 The thermoplastic resin may be used alone or in combination of two or more.
The content of the thermoplastic resin is preferably 10 to 99% by mass, more preferably 20 to 90% by mass, based on the total mass of the thermoplastic resin layer, from the viewpoint of developability and adhesion to adjacent layers. 40 to 80 mass % is more preferred, and 50 to 75 mass % is particularly preferred.
＜色素＞
　熱可塑性樹脂層は、発色時の波長範囲４００～７８０ｎｍにおける最大吸収波長が４５０ｎｍ以上であり、酸、塩基又はラジカルにより最大吸収波長が変化する色素（以下、単に「色素Ｂ」ともいう。）を含んでいてもよい。
　色素Ｂの好適態様は、後述する点以外は、上記色素Ｎと同義であり、好適態様も同じである。 <Pigment>
The thermoplastic resin layer contains a dye having a maximum absorption wavelength of 450 nm or more in a wavelength range of 400 to 780 nm during color development, and the maximum absorption wavelength of which is changed by an acid, a base, or a radical (hereinafter simply referred to as "dye B"). may contain.
The preferred embodiments of the dye B are the same as those of the above dye N, and the preferred embodiments are also the same, except for the points described later.
　色素Ｂとしては、露光部及び非露光部の視認性、並びに、解像性の点から、酸又はラジカルにより最大吸収波長が変化する色素が好ましく、酸により最大吸収波長が変化する色素がより好ましい。
　熱可塑性樹脂層は、露光部及び非露光部の視認性、並びに、解像性の点から、色素Ｂとしての酸により最大吸収波長が変化する色素及び後述する光により酸を発生する化合物の両者を含むことが好ましい。 The dye B is preferably a dye whose maximum absorption wavelength is changed by an acid or a radical, more preferably a dye whose maximum absorption wavelength is changed by an acid, from the viewpoints of visibility in exposed and unexposed areas and resolution. .
From the viewpoint of visibility of exposed and unexposed areas and resolution, the thermoplastic resin layer contains both a dye whose maximum absorption wavelength is changed by an acid as the dye B and a compound that generates an acid by light, which will be described later. is preferably included.
　色素Ｂは、１種単独で用いてもよく、２種以上で用いてもよい。
　色素Ｂの含有量は、露光部及び非露光部の視認性の点から、熱可塑性樹脂層の全質量に対して、０．２質量％以上が好ましく、０．２～６．０質量％がより好ましく、０．２～５．０質量％が更に好ましく、０．２５～３．０質量％が特に好ましい。
　「色素Ｂの含有量」とは、熱可塑性樹脂層に含まれる色素Ｂの全てを発色状態にした場合の色素の含有量を意味する。以下に、ラジカルにより発色する色素を例に、色素Ｂの含有量の定量方法を説明する。
　メチルエチルケトン１００ｍＬに、色素Ｂ（０．００１ｇ）を溶かした溶液及び色素Ｂ（０．０１ｇ）を溶かした溶液を調製する。得られた各溶液に、光ラジカル重合開始剤（Ｉｒｇａｃｕｒｅ　ＯＸＥ０１、ＢＡＳＦジャパン社製）を加え、３６５ｎｍの光を照射することによりラジカルを発生させ、全ての色素Ｂを発色状態にする。その後、大気雰囲気下で、分光光度計（ＵＶ３１００、島津製作所社製）を用いて、液温が２５℃である各溶液の吸光度を測定し、検量線を作成する。
　次に、色素Ｂに代えて熱可塑性樹脂層（３ｇ）をメチルエチルケトンに溶かすこと以外は上記と同様の方法で、色素を全て発色させた溶液の吸光度を測定する。得られた熱可塑性樹脂層を含む溶液の吸光度から、検量線に基づいて熱可塑性樹脂層に含まれる色素Ｂの量を算出する。「熱可塑性樹脂層（３ｇ）」とは、熱可塑性樹脂組成物中の全固形分３ｇと同義である。 The dye B may be used singly or in combination of two or more.
The content of the dye B is preferably 0.2% by mass or more, and 0.2 to 6.0% by mass, based on the total mass of the thermoplastic resin layer, from the viewpoint of visibility of the exposed and unexposed areas. More preferably, 0.2 to 5.0% by mass is more preferable, and 0.25 to 3.0% by mass is particularly preferable.
The “content of dye B” means the content of the dye when all of the dye B contained in the thermoplastic resin layer is in a colored state. A method for quantifying the content of the dye B will be described below using a dye that develops color by radicals as an example.
A solution of dye B (0.001 g) and a solution of dye B (0.01 g) in 100 mL of methyl ethyl ketone are prepared. A radical photopolymerization initiator (Irgacure OXE01, manufactured by BASF Japan) is added to each of the solutions obtained, and radicals are generated by irradiation with light of 365 nm, so that all the dyes B are colored. After that, the absorbance of each solution having a liquid temperature of 25° C. is measured using a spectrophotometer (UV3100, manufactured by Shimadzu Corporation) in an air atmosphere to create a calibration curve.
Then, in the same manner as described above, except that the thermoplastic resin layer (3 g) is dissolved in methyl ethyl ketone instead of the dye B, the absorbance of the solution in which all the dyes are developed is measured. From the absorbance of the obtained solution containing the thermoplastic resin layer, the amount of dye B contained in the thermoplastic resin layer is calculated based on the calibration curve. "Thermoplastic resin layer (3 g)" is synonymous with 3 g of the total solid content in the thermoplastic resin composition.
＜光により酸、塩基又はラジカルを発生する化合物＞
　熱可塑性樹脂層は、光により酸、塩基又はラジカルを発生する化合物（以下、単に「化合物Ｃ」ともいう。）を含んでいてもよい。
　化合物Ｃとしては、紫外線及び可視光線等の活性光線を受けて、酸、塩基又はラジカルを発生する化合物が好ましい。
　化合物Ｃとしては、例えば、公知の、光酸発生剤、光塩基発生剤及び光ラジカル重合開始剤（光ラジカル発生剤）が挙げられる。 <Compound that generates an acid, base or radical upon exposure to light>
The thermoplastic resin layer may contain a compound that generates an acid, base, or radical upon exposure to light (hereinafter also simply referred to as "compound C").
Compound C is preferably a compound that generates an acid, a base, or a radical upon receiving actinic rays such as ultraviolet rays and visible rays.
Examples of the compound C include known photoacid generators, photobase generators and photoradical polymerization initiators (photoradical generators).
（光酸発生剤）
　熱可塑性樹脂層は、解像性の点から、光酸発生剤を含んでいてもよい。
　光酸発生剤としては、例えば、上記感光性組成物層に含まれ得る光カチオン重合開始剤が挙げられ、後述する点以外は、好適態様も同じである。 (Photoacid generator)
From the viewpoint of resolution, the thermoplastic resin layer may contain a photoacid generator.
The photoacid generator includes, for example, a photocationic polymerization initiator that can be contained in the photosensitive composition layer.
　光酸発生剤としては、感度及び解像性の点から、オニウム塩化合物及びオキシムスルホネート化合物からなる群から選択される少なくとも１つの化合物を含むことが好ましく、感度、解像性及び密着性の点から、オキシムスルホネート化合物を含むことがより好ましい。
　光酸発生剤としては、以下の構造を有する光酸発生剤も好ましい。 From the viewpoint of sensitivity and resolution, the photoacid generator preferably contains at least one compound selected from the group consisting of onium salt compounds and oxime sulfonate compounds. Therefore, it is more preferred to include an oxime sulfonate compound.
As the photoacid generator, a photoacid generator having the following structure is also preferable.
Figure JPOXMLDOC01-appb-C000005
Figure JPOXMLDOC01-appb-C000005
（光ラジカル重合開始剤）
　熱可塑性樹脂層は、光ラジカル重合開始剤を含んでいてもよい。
　光ラジカル重合開始剤としては、例えば、上記感光性組成物層に含まれ得る光ラジカル重合開始剤が挙げられ、好適態様も同じである。 (Photoradical polymerization initiator)
The thermoplastic resin layer may contain a radical photopolymerization initiator.
Examples of photoradical polymerization initiators include photoradical polymerization initiators that can be contained in the photosensitive composition layer, and preferred embodiments are also the same.
（光塩基発生剤）
　熱可塑性樹脂組成物は、光塩基発生剤を含んでいてもよい。
　光塩基発生剤としては、例えば、公知の光塩基発生剤が挙げられる。
　具体的には、２－ニトロベンジルシクロヘキシルカルバメート、トリフェニルメタノール、Ｏ－カルバモイルヒドロキシルアミド、Ｏ－カルバモイルオキシム、［［（２，６－ジニトロベンジル）オキシ］カルボニル］シクロヘキシルアミン、ビス［［（２－ニトロベンジル）オキシ］カルボニル］ヘキサン１，６－ジアミン、４－（メチルチオベンゾイル）－１－メチル－１－モルホリノエタン、（４－モルホリノベンゾイル）－１－ベンジル－１－ジメチルアミノプロパン、Ｎ－（２－ニトロベンジルオキシカルボニル）ピロリジン、ヘキサアンミンコバルト（ＩＩＩ）トリス（トリフェニルメチルボレート）、２－ベンジル－２－ジメチルアミノ－１－（４－モルホリノフェニル）－ブタノン、２，６－ジメチル－３，５－ジアセチル－４－（２－ニトロフェニル）－１，４－ジヒドロピリジン及び２，６－ジメチル－３，５－ジアセチル－４－（２，４－ジニトロフェニル）－１，４－ジヒドロピリジンが挙げられる。 (Photobase generator)
The thermoplastic resin composition may contain a photobase generator.
Examples of the photobase generator include known photobase generators.
Specifically, 2-nitrobenzylcyclohexylcarbamate, triphenylmethanol, O-carbamoylhydroxylamide, O-carbamoyloxime, [[(2,6-dinitrobenzyl)oxy]carbonyl]cyclohexylamine, bis[[(2- nitrobenzyl)oxy]carbonyl]hexane 1,6-diamine, 4-(methylthiobenzoyl)-1-methyl-1-morpholinoethane, (4-morpholinobenzoyl)-1-benzyl-1-dimethylaminopropane, N-( 2-nitrobenzyloxycarbonyl)pyrrolidine, hexaamminecobalt (III) tris(triphenylmethylborate), 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone, 2,6-dimethyl-3 ,5-diacetyl-4-(2-nitrophenyl)-1,4-dihydropyridine and 2,6-dimethyl-3,5-diacetyl-4-(2,4-dinitrophenyl)-1,4-dihydropyridine. be done.
　化合物Ｃは、１種単独で用いてもよく、２種以上で用いてもよい。
　化合物Ｃの含有量は、露光部及び非露光部の視認性、並びに、解像性の点から、熱可塑性樹脂層の全質量に対して、０．１～１０質量％が好ましく、０．５～５質量％がより好ましい。 Compound C may be used alone or in combination of two or more.
The content of compound C is preferably 0.1 to 10% by mass, preferably 0.5%, based on the total mass of the thermoplastic resin layer, from the viewpoints of visibility in exposed and unexposed areas and resolution. ~5% by mass is more preferred.
＜可塑剤＞
　熱可塑性樹脂層は、解像性、隣接する層との密着性及び現像性の点から、可塑剤を含んでいてもよい。
　可塑剤は、熱可塑性樹脂（好ましくは、アルカリ可溶性樹脂）よりも分子量（オリゴマー又はポリマーであり分子量分布を有する場合は重量平均分子量）が小さいことが好ましい。具体的には、可塑剤の分子量（重量平均分子量）は、２００～２，０００が好ましい。
　可塑剤は、アルカリ可溶性樹脂と相溶して可塑性を発現する化合物であれば特に制限されない。
　可塑剤は、可塑性付与の点から、分子中にアルキレンオキシ基を有することが好ましく、ポリエチレンオキシ構造又はポリプロピレンオキシ構造を有することがより好ましい。
　可塑剤としては、ポリアルキレングリコール化合物が好ましい。 <Plasticizer>
The thermoplastic resin layer may contain a plasticizer from the viewpoint of resolution, adhesion to adjacent layers, and developability.
The plasticizer preferably has a smaller molecular weight (weight-average molecular weight if it is an oligomer or polymer and has a molecular weight distribution) than the thermoplastic resin (preferably alkali-soluble resin). Specifically, the molecular weight (weight average molecular weight) of the plasticizer is preferably 200 to 2,000.
The plasticizer is not particularly limited as long as it is a compound compatible with the alkali-soluble resin and exhibits plasticity.
From the viewpoint of imparting plasticity, the plasticizer preferably has an alkyleneoxy group in the molecule, and more preferably has a polyethyleneoxy structure or a polypropyleneoxy structure.
Polyalkylene glycol compounds are preferred as plasticizers.
　可塑剤は、解像性及び保存安定性の点から、（メタ）アクリレート化合物を含むことが好ましい。相溶性、解像性及び隣接する層との密着性の点から、アルカリ可溶性樹脂がアクリル樹脂であり、かつ、可塑剤が（メタ）アクリレート化合物を含むことがより好ましい。
　（メタ）アクリレート化合物としては、例えば、上記感光性組成物層に含まれ得る重合性化合物としての（メタ）アクリレート化合物が挙げられる。
　転写フィルムにおいて、熱可塑性樹脂層と感光性組成物層とが直接接触して積層される場合（中間層を有さない場合）、熱可塑性樹脂層及び感光性組成物層がいずれも同じ（メタ）アクリレート化合物を含むことが好ましい。同じ（メタ）アクリレート化合物を熱可塑性樹脂層及び感光性組成物層がそれぞれ含むことにより、成分の層間拡散が抑制され、保存安定性が向上する。 The plasticizer preferably contains a (meth)acrylate compound from the viewpoint of resolution and storage stability. From the viewpoint of compatibility, resolution and adhesion with adjacent layers, it is more preferable that the alkali-soluble resin is an acrylic resin and the plasticizer contains a (meth)acrylate compound.
The (meth)acrylate compound includes, for example, a (meth)acrylate compound as a polymerizable compound that can be contained in the photosensitive composition layer.
In the transfer film, when the thermoplastic resin layer and the photosensitive composition layer are laminated in direct contact (when there is no intermediate layer), both the thermoplastic resin layer and the photosensitive composition layer are the same (meta ) preferably contains an acrylate compound. By containing the same (meth)acrylate compound in each of the thermoplastic resin layer and the photosensitive composition layer, the interlayer diffusion of the components is suppressed and the storage stability is improved.
　熱可塑性樹脂層が可塑剤として（メタ）アクリレート化合物を含む場合、熱可塑性樹脂層と隣接する層との密着性の点から、露光後の露光部においても（メタ）アクリレート化合物が重合しないことが好ましい。
　また、（メタ）アクリレート化合物としては、熱可塑性樹脂層の解像性、隣接する層との密着性及び現像性の点から、１分子中に２つ以上の（メタ）アクリロイル基を有する多官能（メタ）アクリレート化合物が好ましい。
　更に、（メタ）アクリレート化合物としては、酸基を有する（メタ）アクリレート化合物又はウレタン（メタ）アクリレート化合物も好ましい。 When the thermoplastic resin layer contains a (meth)acrylate compound as a plasticizer, the (meth)acrylate compound may not be polymerized even in the exposed areas after exposure from the viewpoint of adhesion between the thermoplastic resin layer and adjacent layers. preferable.
In addition, the (meth)acrylate compound is a polyfunctional compound having two or more (meth)acryloyl groups in one molecule, from the viewpoint of the resolution of the thermoplastic resin layer, the adhesion to the adjacent layer, and the developability. (Meth)acrylate compounds are preferred.
Furthermore, as the (meth)acrylate compound, a (meth)acrylate compound or a urethane (meth)acrylate compound having an acid group is also preferable.
　可塑剤は、１種単独で用いてもよく、２種以上で用いてもよい。
　可塑剤の含有量は、熱可塑性樹脂層の解像性、隣接する層との密着性及び現像性の点から、熱可塑性樹脂層の全質量に対して、１～７０質量％が好ましく、１０～６０質量％がより好ましく、２０～５０質量％が更に好ましい。 A plasticizer may be used individually by 1 type, and may be used in 2 or more types.
The content of the plasticizer is preferably from 1 to 70% by mass with respect to the total mass of the thermoplastic resin layer, from the viewpoints of resolution of the thermoplastic resin layer, adhesion to adjacent layers, and developability. ~60% by mass is more preferable, and 20 to 50% by mass is even more preferable.
＜増感剤＞
　熱可塑性樹脂層は、増感剤を含んでいてもよい。
　増感剤としては、上記感光性組成物層に含まれ得る増感剤が挙げられる。 <Sensitizer>
The thermoplastic resin layer may contain a sensitizer.
Sensitizers include sensitizers that can be contained in the photosensitive composition layer.
　増感剤は、１種単独で用いてもよく、２種以上で用いてもよい。
　増感剤の含有量は、光源に対する感度の向上、並びに、露光部及び非露光部の視認性の点から、熱可塑性樹脂層の全質量に対して、０．０１～５質量％が好ましく、０．０５～１質量％がより好ましい。 The sensitizers may be used alone or in combination of two or more.
The content of the sensitizer is preferably 0.01 to 5% by mass based on the total mass of the thermoplastic resin layer, from the viewpoint of improving sensitivity to light sources and visibility of exposed and unexposed areas. 0.05 to 1% by mass is more preferable.
＜その他添加剤＞
　熱可塑性樹脂層は、上記成分以外に、その他添加剤を含んでいてもよい。
　その他添加剤としては、例えば、上記感光性組成物層に含まれ得るその他添加剤が挙げられる。 <Other additives>
The thermoplastic resin layer may contain other additives in addition to the above components.
Other additives include, for example, other additives that can be contained in the photosensitive composition layer.
＜不純物＞
　熱可塑性樹脂層は、不純物を含んでいてもよい。
　不純物としては、例えば、上記感光性組成物層に含まれる不純物が挙げられる。 <Impurities>
The thermoplastic resin layer may contain impurities.
Impurities include, for example, impurities contained in the photosensitive composition layer.
　熱可塑性樹脂層の厚み（層厚）は、隣接する層との密着性の点から、１μｍ以上が好ましく、２μｍ以上がより好ましい。上限は、現像性及び解像性の点から、２０μｍ以下が好ましく、１０μｍ以下がより好ましく、８μｍ以下が更に好ましい。 The thickness (layer thickness) of the thermoplastic resin layer is preferably 1 μm or more, more preferably 2 μm or more, from the viewpoint of adhesion to adjacent layers. The upper limit is preferably 20 µm or less, more preferably 10 µm or less, and even more preferably 8 µm or less, from the viewpoint of developability and resolution.
〔その他部材〕
　転写フィルムは、上記部材以外に、その他部材を有していてもよい。
　その他部材としては、例えば、保護フィルムが挙げられる。 [Other parts]
The transfer film may have other members in addition to the above members.
Other members include, for example, a protective film.
　保護フィルムとしては、例えば、耐熱性及び耐溶剤性を有する樹脂フィルムが挙げられる。具体的には、ポリプロピレンフィルム及びポリエチレンフィルム等のポリオレフィンフィルム、ポリエチレンテレフタレートフィルム等のポリエステルフィルム、ポリカーボネートフィルム、並びに、ポリスチレンフィルムが挙げられる。また、保護フィルムとしては、上記仮支持体と同じ材料で構成された樹脂フィルムを用いてもよい。
　なかでも、保護フィルムとしては、ポリオレフィンフィルムが好ましく、ポリプロピレンフィルム又はポリエチレンフィルムがより好ましい。 Protective films include, for example, resin films having heat resistance and solvent resistance. Specific examples include polyolefin films such as polypropylene films and polyethylene films, polyester films such as polyethylene terephthalate films, polycarbonate films, and polystyrene films. As the protective film, a resin film made of the same material as the temporary support may be used.
Among them, the protective film is preferably a polyolefin film, more preferably a polypropylene film or a polyethylene film.
　保護フィルムの厚みとしては、１～１００μｍが好ましく、５～５０μｍがより好ましく、５～４０μｍが更に好ましく、１５～３０μｍが特に好ましい。
　保護フィルムの厚みは、機械的強度に優れる点から、１μｍ以上が好ましく、比較的安価である点から、１００μｍ以下が好ましい。 The thickness of the protective film is preferably 1 to 100 μm, more preferably 5 to 50 μm, even more preferably 5 to 40 μm, particularly preferably 15 to 30 μm.
The thickness of the protective film is preferably 1 μm or more from the viewpoint of excellent mechanical strength, and preferably 100 μm or less from the viewpoint of being relatively inexpensive.
　保護フィルムに含まれる直径８０μｍ以上のフィッシュアイ数としては、５個／ｍ２以下が好ましい。下限は、０個／ｍ２以上が好ましい。
　「フィッシュアイ」とは、材料を熱溶融し、混練、押し出し、２軸延伸及びキャスティング法等の方法によりフィルムを製造する際に、材料の異物、未溶解物及び酸化劣化物等がフィルム中に取り込まれたものを意味する。 The number of fisheyes with a diameter of 80 μm or more contained in the protective film is preferably 5/m 2 or less. The lower limit is preferably 0/m 2 or more.
"Fish eye" means that when a film is produced by methods such as heat melting, kneading, extrusion, biaxial stretching, casting, etc., foreign substances, undissolved substances, and oxidation-degraded substances of the material are found in the film. It means what is taken.
　保護フィルムに含まれる直径３μｍ以上の粒子の数は、３０個／ｍｍ２以下が好ましく、１０個／ｍｍ２以下がより好ましく、５個／ｍｍ２以下が更に好ましい。下限は、０個／ｍｍ２以上が好ましい。上記範囲である場合、保護フィルムに含まれる粒子に起因する凹凸が感光性組成物層又は導電層に転写されることにより生じる欠陥を抑制できる。 The number of particles having a diameter of 3 μm or more contained in the protective film is preferably 30 particles/mm 2 or less, more preferably 10 particles/mm 2 or less, and even more preferably 5 particles/mm 2 or less. The lower limit is preferably 0/mm 2 or more. When it is within the above range, it is possible to suppress defects caused by the unevenness caused by the particles contained in the protective film being transferred to the photosensitive composition layer or the conductive layer.
　巻き取り性を付与する点から、保護フィルムの感光性組成物層と接する面とは反対側の表面又は接する面の算術平均粗さＲａは、０．０１μｍ以上が好ましく、０．０２μｍ以上がより好ましく、０．０３μｍ以上が更に好ましい。上限は、０．５０μｍ未満が好ましく、０．４０μｍ以下がより好ましく、０．３０μｍ以下が更に好ましい。 From the viewpoint of imparting winding properties, the surface of the protective film opposite to the surface in contact with the photosensitive composition layer or the surface in contact with the surface has an arithmetic mean roughness Ra of preferably 0.01 μm or more, more preferably 0.02 μm or more. It is preferably 0.03 μm or more, and more preferably 0.03 μm or more. The upper limit is preferably less than 0.50 μm, more preferably 0.40 μm or less, even more preferably 0.30 μm or less.
［転写フィルムの製造方法］
　転写フィルムの製造方法としては、例えば、公知の方法が挙げられる。
　転写フィルム１０の製造方法としては、例えば、仮支持体１１の表面に中間層形成用組成物を塗布して塗膜を形成し、更にこの塗膜を乾燥して中間層１３を形成する工程と、中間層１３の表面に感光性組成物を塗布して塗膜を形成し、更にこの塗膜を乾燥して感光性組成物層１５を形成する工程と、を含む方法が挙げられる。
　また、上記中間層１３を形成する工程の前に、仮支持体１１の表面に熱可塑性樹脂層形成用組成物を塗布して塗膜を形成し、更にこの塗膜を乾燥して熱可塑性樹脂層を形成する工程を含んでいてもよい。 [Manufacturing method of transfer film]
Examples of the method for producing the transfer film include known methods.
A method for producing the transfer film 10 includes, for example, a step of applying an intermediate layer forming composition to the surface of the temporary support 11 to form a coating film, and drying the coating film to form the intermediate layer 13. , applying a photosensitive composition to the surface of the intermediate layer 13 to form a coating film, and further drying the coating film to form a photosensitive composition layer 15 .
In addition, before the step of forming the intermediate layer 13, the thermoplastic resin layer-forming composition is applied to the surface of the temporary support 11 to form a coating film, and the coating film is dried to form a thermoplastic resin. A step of forming a layer may be included.
　上記製造方法により製造された積層体の感光性組成物層１５上に、保護フィルム１９を圧着させることにより、転写フィルム１０が製造される。
　転写フィルムの製造方法としては、感光性組成物層１５の仮支持体１１側とは反対側の面に接するように保護フィルム１９を設ける工程を含むことにより、仮支持体１１、中間層１３、感光性組成物層１５及び保護フィルム１９を備える転写フィルム１０を製造することが好ましい。
　また、転写フィルムの製造方法としては、感光性組成物層１５の仮支持体１１側とは反対側の面に接するように保護フィルム１９を設ける工程を含むことにより、仮支持体１１、熱可塑性樹脂層、中間層１３、感光性組成物層１５及び保護フィルム１９を備える転写フィルム１０を製造することも好ましい。
　上記製造方法により製造された転写フィルム１０を巻き取ることにより、ロール形態の転写フィルムを作製及び保管してもよい。ロール形態の転写フィルムは、後述するロールツーロール方式での基板との貼合工程にそのままの形態で提供できる。
　また、転写フィルム１０の製造方法としては、保護フィルム１９上に、感光性組成物層１５及び中間層１３を形成した後、中間層１３の感光性組成物層とは反対側の表面に接するように熱可塑性樹脂層を形成してもよい。 The transfer film 10 is manufactured by pressure-bonding the protective film 19 onto the photosensitive composition layer 15 of the laminate manufactured by the manufacturing method described above.
The method for producing the transfer film includes a step of providing a protective film 19 so as to be in contact with the surface of the photosensitive composition layer 15 opposite to the temporary support 11 side, whereby the temporary support 11, the intermediate layer 13, It is preferred to manufacture transfer film 10 comprising photosensitive composition layer 15 and protective film 19 .
In addition, the transfer film manufacturing method includes a step of providing a protective film 19 so as to be in contact with the surface of the photosensitive composition layer 15 opposite to the temporary support 11 side, so that the temporary support 11, the thermoplastic It is also preferred to manufacture a transfer film 10 comprising a resin layer, an intermediate layer 13, a photosensitive composition layer 15 and a protective film 19. FIG.
A roll-shaped transfer film may be produced and stored by winding the transfer film 10 produced by the above production method. The transfer film in roll form can be provided as it is in the step of laminating with a substrate in a roll-to-roll system, which will be described later.
In addition, as a method for manufacturing the transfer film 10, after forming the photosensitive composition layer 15 and the intermediate layer 13 on the protective film 19, the surface of the intermediate layer 13 on the side opposite to the photosensitive composition layer is contacted. A thermoplastic resin layer may be formed on the substrate.
〔感光性組成物及び感光性組成物層の形成方法〕
　感光性組成物層の形成方法としては、感光性組成物層に含まれる成分（例えば、樹脂、重合性化合物及び重合開始剤等）及び溶剤を含む感光性組成物を用いて塗布する塗布方法が好ましい。
　感光性組成物層の形成方法としては、例えば、中間層上に感光性組成物を塗布して塗膜を形成し、必要に応じて、この塗膜に所定温度にて乾燥処理を施して感光性組成物層を形成する方法が好ましい。残存溶剤量は、塗膜の乾燥処理によって調整される。 [Photosensitive composition and method for forming photosensitive composition layer]
As a method for forming the photosensitive composition layer, there is a coating method in which a photosensitive composition containing components contained in the photosensitive composition layer (for example, a resin, a polymerizable compound, a polymerization initiator, etc.) and a solvent is used. preferable.
As a method for forming the photosensitive composition layer, for example, a photosensitive composition is applied on the intermediate layer to form a coating film, and if necessary, the coating film is subjected to a drying treatment at a predetermined temperature to expose it. A method of forming a liquid composition layer is preferred. The amount of residual solvent is adjusted by the drying treatment of the coating film.
　感光性組成物としては、感光性組成物層に含まれる成分と溶剤とを含むことが好ましい。感光性組成物層に含まれる各成分の含有量は、上述したとおりである。
　溶剤としては、溶剤以外の感光性組成物層に含まれる成分を溶解又は分散可能であれば特に制限されない。
　溶剤としては、例えば、アルキレングリコールエーテル溶剤、アルキレングリコールエーテルアセテート溶剤、アルコール溶剤（例えば、メタノール及びエタノール等）、ケトン溶剤（例えば、アセトン及びメチルエチルケトン等）、芳香族炭化水素溶剤（例えば、トルエン等）、非プロトン性極性溶剤（例えば、Ｎ，Ｎ-ジメチルホルムアミド等）、環状エーテル溶剤（例えば、テトラヒドロフラン等）、エステル溶剤（例えば、酢酸ｎプロピル等）、アミド溶剤、ラクトン溶剤、並びに、これらの組み合わせた混合溶剤が挙げられる。 The photosensitive composition preferably contains components and a solvent contained in the photosensitive composition layer. The content of each component contained in the photosensitive composition layer is as described above.
The solvent is not particularly limited as long as it can dissolve or disperse components other than the solvent contained in the photosensitive composition layer.
Examples of solvents include alkylene glycol ether solvents, alkylene glycol ether acetate solvents, alcohol solvents (e.g., methanol and ethanol), ketone solvents (e.g., acetone, methyl ethyl ketone, etc.), aromatic hydrocarbon solvents (e.g., toluene, etc.). , aprotic polar solvents (e.g., N,N-dimethylformamide, etc.), cyclic ether solvents (e.g., tetrahydrofuran, etc.), ester solvents (e.g., n-propyl acetate, etc.), amide solvents, lactone solvents, and combinations thereof and mixed solvents.
　溶剤は、アルキレングリコールエーテル溶剤及びアルキレングリコールエーテルアセテート溶剤からなる群から選択される少なくとも１つを含むことが好ましい。
　なかでも、アルキレングリコールエーテル溶剤及びアルキレングリコールエーテルアセテート溶剤からなる群から選択される少なくとも１つと、ケトン溶剤及び環状エーテル溶剤からなる群から選択される少なくとも１つとを含む混合溶剤がより好ましく、アルキレングリコールエーテル溶剤及びアルキレングリコールエーテルアセテート溶剤からなる群から選択される少なくとも１つ、ケトン溶剤、並びに、環状エーテル溶剤の３種を含む混合溶剤が更に好ましい。 The solvent preferably contains at least one selected from the group consisting of alkylene glycol ether solvents and alkylene glycol ether acetate solvents.
Among them, a mixed solvent containing at least one selected from the group consisting of alkylene glycol ether solvents and alkylene glycol ether acetate solvents and at least one selected from the group consisting of ketone solvents and cyclic ether solvents is more preferable. A mixed solvent containing at least one selected from the group consisting of an ether solvent and an alkylene glycol ether acetate solvent, a ketone solvent, and a cyclic ether solvent is more preferable.
　アルキレングリコールエーテル溶剤としては、例えば、エチレングリコールモノアルキルエーテル、エチレングリコールジアルキルエーテル、プロピレングリコールモノアルキルエーテル（例えば、プロピレングリコールモノメチルエーテルアセテート等）、プロピレングリコールジアルキルエーテル、ジエチレングリコールジアルキルエーテル、ジプロピレングリコールモノアルキルエーテル及びジプロピレングリコールジアルキルエーテルが挙げられる。
　アルキレングリコールエーテルアセテート溶剤としては、例えば、エチレングリコールモノアルキルエーテルアセテート、プロピレングリコールモノアルキルエーテルアセテート、ジエチレングリコールモノアルキルエーテルアセテート及びジプロピレングリコールモノアルキルエーテルアセテートが挙げられる。
　溶剤としては、例えば、国際公開第２０１８／１７９６４０号の段落［００９２］～［００９４］に記載された溶剤及び特開２０１８－１７７８８９号公報の段落［００１４］に記載された溶剤が挙げられ、これらの内容は本明細書に組み込まれる。 Alkylene glycol ether solvents include, for example, ethylene glycol monoalkyl ether, ethylene glycol dialkyl ether, propylene glycol monoalkyl ether (eg, propylene glycol monomethyl ether acetate), propylene glycol dialkyl ether, diethylene glycol dialkyl ether, dipropylene glycol monoalkyl. Ethers and dipropylene glycol dialkyl ethers.
Alkylene glycol ether acetate solvents include, for example, ethylene glycol monoalkyl ether acetate, propylene glycol monoalkyl ether acetate, diethylene glycol monoalkyl ether acetate and dipropylene glycol monoalkyl ether acetate.
Examples of the solvent include the solvents described in paragraphs [0092] to [0094] of International Publication No. 2018/179640 and the solvents described in paragraph [0014] of JP-A-2018-177889. the contents of which are incorporated herein.
　溶剤は、１種単独で用いてもよく、２種以上で用いてもよい。
　溶剤の含有量は、感光性組成物の全固形分１００質量部に対して、５０～１９００質量部が好ましく、１００～１２００質量部がより好ましく、１００～９００質量部が更に好ましい。 A solvent may be used individually by 1 type, and may be used in 2 or more types.
The content of the solvent is preferably 50 to 1,900 parts by mass, more preferably 100 to 1,200 parts by mass, and even more preferably 100 to 900 parts by mass, based on 100 parts by mass of the total solid content of the photosensitive composition.
　感光性組成物の塗布方法としては、例えば、公知の塗布方法が挙げられる。
　具体的には、印刷法、スプレー法、ロールコート法、バーコート法、カーテンコート法、スピンコート法及びダイコート法（スリットコート法）が挙げられる。 Examples of the coating method of the photosensitive composition include known coating methods.
Specific examples include a printing method, a spray method, a roll coating method, a bar coating method, a curtain coating method, a spin coating method and a die coating method (slit coating method).
　感光性組成物の塗膜の乾燥方法としては、加熱乾燥又は減圧乾燥が好ましい。
　乾燥温度としては、９０℃以上が好ましく、１００℃以上がより好ましく、１１０℃以上が更に好ましい。上限は、１３０℃以下が好ましく、１２０℃以下がより好ましい。
　また、乾燥方法としては、乾燥温度を連続的に変化させる方法であってもよい。
　乾燥時間としては、２０秒以上が好ましく、４０秒以上がより好ましく、６０秒以上が更に好ましい。上限は、６００秒以下が好ましく、４５０秒以下がより好ましく、３００秒以下が更に好ましい。 Heat drying or reduced pressure drying is preferable as a method for drying the coating film of the photosensitive composition.
The drying temperature is preferably 90° C. or higher, more preferably 100° C. or higher, and even more preferably 110° C. or higher. The upper limit is preferably 130°C or lower, more preferably 120°C or lower.
Moreover, as a drying method, a method of continuously changing the drying temperature may be used.
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 preferably 600 seconds or less, more preferably 450 seconds or less, and even more preferably 300 seconds or less.
　更に、保護フィルムを感光性組成物層に貼り合わせて転写フィルムを製造してもよい。
　保護フィルムを感光性組成物層に貼り合わせる方法としては、例えば、公知の方法が挙げられる。保護フィルムを感光性組成物層に貼り合わせる装置としては、例えば、真空ラミネーター及びオートカットラミネーター等の公知のラミネーターが挙げられる。
　ラミネーターとしては、ゴムローラー等の任意の加熱可能なローラーを備え、加圧及び加熱ができるものが好ましい。 Furthermore, a transfer film may be produced by laminating a protective film to the photosensitive composition layer.
Examples of the method for bonding the protective film to the photosensitive composition layer include known methods. Examples of the apparatus for laminating the protective film to the photosensitive composition layer include known laminators such as a vacuum laminator and an autocut laminator.
As the laminator, it is preferable to have a heatable roller such as a rubber roller and to apply pressure and heat.
〔中間層形成用組成物及び中間層の形成方法〕
　中間層の形成方法としては、中間層に含まれる成分（例えば、水溶性樹脂等）及び溶剤を含む中間層形成用組成物を用いて塗布する塗布方法が好ましい。
　中間層の形成方法としては、例えば、仮支持体上に中間層形成用組成物を塗布して塗膜を形成し、必要に応じて、この塗膜に所定温度にて乾燥処理を施して中間層を形成する方法が好ましい。残存溶剤量は、塗膜の乾燥処理によって調整される。 [Composition for Intermediate Layer Formation and Method for Forming Intermediate Layer]
As a method for forming the intermediate layer, a coating method in which a composition for forming an intermediate layer containing components contained in the intermediate layer (for example, a water-soluble resin, etc.) and a solvent is used for coating is preferable.
As a method for forming the intermediate layer, for example, the composition for forming an intermediate layer is applied onto a temporary support to form a coating film, and if necessary, the coating film is dried at a predetermined temperature to form an intermediate layer. A method of forming layers is preferred. The amount of residual solvent is adjusted by the drying treatment of the coating film.
　中間層形成用組成物としては、中間層に含まれる成分と溶剤とを含むことが好ましい。
　中間層に含まれる成分の含有量は、上述したとおりである。
　溶剤としては、中間層に含まれる成分を溶解又は分散可能であれば特に制限されない。
　溶剤としては、水及び水混和性の有機溶剤からなる群から選択される少なくとも１つが好ましく、水又は水と水混和性の有機溶剤との混合溶剤がより好ましい。
　水混和性の有機溶剤としては、例えば、炭素数１～３のアルコール、アセトン、エチレングリコール、グリセリン及びこれらの組み合わせた混合溶剤が挙げられ、炭素数１～３のアルコールが好ましく、メタノール又はエタノールがより好ましい。 It is preferable that the composition for forming the intermediate layer contains the components contained in the intermediate layer and the solvent.
The contents of the components contained in the intermediate layer are as described above.
The solvent is not particularly limited as long as it can dissolve or disperse the components contained in the intermediate layer.
The solvent is preferably at least one selected from the group consisting of water and water-miscible organic solvents, more preferably water or a mixed solvent of water and water-miscible organic solvents.
Examples of water-miscible organic solvents include alcohols having 1 to 3 carbon atoms, acetone, ethylene glycol, glycerin, and mixed solvents of these, preferably alcohols having 1 to 3 carbon atoms, and methanol or ethanol. more preferred.
　溶剤は、１種単独で用いてもよく、２種以上で用いてもよい。
　溶剤の含有量は、中間層形成用組成物の全固形分１００質量部に対して、５０～２５００質量部が好ましく、５０～１９００質量部がより好ましく、１００～９００質量部が更に好ましい。 A solvent may be used individually by 1 type, and may be used in 2 or more types.
The content of the solvent is preferably 50 to 2,500 parts by mass, more preferably 50 to 1,900 parts by mass, and even more preferably 100 to 900 parts by mass, based on 100 parts by mass of the total solid content of the intermediate layer-forming composition.
　中間層の形成方法としては、例えば、公知の塗布方法が挙げられる。
　具体的には、スリット塗布、スピン塗布、カーテン塗布及びインクジェット塗布が挙げられる。 Examples of methods for forming the intermediate layer include known coating methods.
Specific examples include slit coating, spin coating, curtain coating and inkjet coating.
　中間層形成用組成物の塗膜の乾燥方法としては、加熱乾燥又は減圧乾燥が好ましい。
　乾燥温度としては、９０℃以上が好ましく、１００℃以上がより好ましく、１１０℃以上が更に好ましい。上限は、１３０℃以下が好ましく、１２０℃以下がより好ましい。
　また、乾燥方法としては、乾燥温度を連続的に変化させる方法であってもよい。
　乾燥時間としては、２０秒以上が好ましく、４０秒以上がより好ましく、６０秒以上が更に好ましい。上限は、６００秒以下が好ましく、４５０秒以下がより好ましく、３００秒以下が更に好ましい。 Heat drying or reduced pressure drying is preferable as a method for drying the coating film of the intermediate layer forming composition.
The drying temperature is preferably 90° C. or higher, more preferably 100° C. or higher, and even more preferably 110° C. or higher. The upper limit is preferably 130°C or lower, more preferably 120°C or lower.
Moreover, as a drying method, a method of continuously changing the drying temperature may be used.
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 preferably 600 seconds or less, more preferably 450 seconds or less, and even more preferably 300 seconds or less.
〔熱可塑性樹脂層形成用組成物及び熱可塑性樹脂層の形成方法〕
　熱可塑性樹脂層の形成方法としては、熱可塑性樹脂層に含まれる成分（例えば、熱可塑性樹脂等）及び溶剤を含む熱可塑性樹脂層形成用組成物を用いて塗布する塗布方法が好ましい。
　熱可塑性樹脂層の形成方法としては、例えば、仮支持体上に中間層形成用組成物を塗布して塗膜を形成し、必要に応じて、この塗膜に所定温度にて乾燥処理を施して熱可塑性樹脂層を形成する方法が好ましい。残存溶剤量は、塗膜の乾燥処理によって調整される。 [Composition for Forming Thermoplastic Resin Layer and Method for Forming Thermoplastic Resin Layer]
As a method for forming the thermoplastic resin layer, a coating method in which a thermoplastic resin layer-forming composition containing a component contained in the thermoplastic resin layer (for example, a thermoplastic resin, etc.) and a solvent is used for coating is preferred.
As a method for forming a thermoplastic resin layer, for example, the composition for forming an intermediate layer is applied onto a temporary support to form a coating film, and if necessary, the coating film is subjected to a drying treatment at a predetermined temperature. A method of forming a thermoplastic resin layer by means of The amount of residual solvent is adjusted by the drying treatment of the coating film.
　熱可塑性樹脂層形成用組成物としては、熱可塑性樹脂層に含まれる成分と溶剤とを含むことが好ましい。
　熱可塑性樹脂層に含まれる成分の含有量は、上述したとおりである。
　溶剤としては、熱可塑性樹脂層に含まれる成分を溶解又は分散可能であれば特に制限されない。
　溶剤としては、上述した感光性組成物が含む溶剤と同義であり、好適態様も同じである。 The composition for forming a thermoplastic resin layer preferably contains the components contained in the thermoplastic resin layer and a solvent.
The contents of the components contained in the thermoplastic resin layer are as described above.
The solvent is not particularly limited as long as it can dissolve or disperse the components contained in the thermoplastic resin layer.
The solvent is synonymous with the solvent contained in the photosensitive composition described above, and the preferred embodiments are also the same.
　溶剤を、１種単独で用いてもよく、２種以上で用いてもよい。
　溶剤の含有量は、熱可塑性樹脂層形成用組成物の全固形分１００質量部に対して、５０～１９００質量部が好ましく、１００～９００質量部がより好ましい。 A solvent may be used individually by 1 type, and may be used in 2 or more types.
The content of the solvent is preferably 50 to 1,900 parts by mass, more preferably 100 to 900 parts by mass, based on 100 parts by mass of the total solid content of the composition for forming a thermoplastic resin layer.
　熱可塑性樹脂層の形成方法としては、例えば、公知の塗布方法が挙げられる。
　具体的には、スリット塗布、スピン塗布、カーテン塗布及びインクジェット塗布が挙げられる。 Examples of the method for forming the thermoplastic resin layer include known coating methods.
Specific examples include slit coating, spin coating, curtain coating and inkjet coating.
　熱可塑性樹脂層形成用組成物の塗膜の乾燥方法としては、加熱乾燥又は減圧乾燥が好ましい。
　乾燥温度としては、９０℃以上が好ましく、１００℃以上がより好ましく、１１０℃以上が更に好ましい。上限は、１３０℃以下が好ましく、１２０℃以下がより好ましい。
　また、乾燥方法としては、乾燥温度を連続的に変化させる方法であってもよい。
　乾燥時間としては、２０秒以上が好ましく、４０秒以上がより好ましく、６０秒以上が更に好ましい。上限は、６００秒以下が好ましく、４５０秒以下がより好ましく、３００秒以下が更に好ましい。 As a method for drying the coating film of the composition for forming a thermoplastic resin layer, drying by heating or drying under reduced pressure is preferable.
The drying temperature is preferably 90° C. or higher, more preferably 100° C. or higher, and even more preferably 110° C. or higher. The upper limit is preferably 130°C or lower, more preferably 120°C or lower.
Moreover, as a drying method, a method of continuously changing the drying temperature may be used.
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 preferably 600 seconds or less, more preferably 450 seconds or less, and even more preferably 300 seconds or less.
　以下に実施例に基づいて本発明を更に詳細に説明する。
　以下の実施例に示す材料、使用量、割合、処理内容及び処理手順等は、本発明の趣旨を逸脱しない限り適宜変更することができる。したがって、本発明の範囲は以下に示す実施例により限定的に解釈されるべきものではない。なお、「部」及び「％」は、特段の断りがない限り、質量基準である。
　また、以下の実施例において、樹脂の重量平均分子量は、上記ゲルパーミエーションクロマトグラフィ（ＧＰＣ）によるポリスチレン換算で求めた重量平均分子量（Ｍｗ）である。また、ガラス転移温度は、上述した方法で測定した。 The present invention will be described in more detail based on examples below.
The materials, amounts used, ratios, processing details, processing procedures, etc. shown in the following examples can be changed as appropriate without departing from the gist of the present invention. Therefore, the scope of the present invention should not be construed to be limited by the examples shown below. "Parts" and "%" are based on mass unless otherwise specified.
In the following examples, the weight average molecular weight of the resin is the weight average molecular weight (Mw) obtained in terms of polystyrene by gel permeation chromatography (GPC). Also, the glass transition temperature was measured by the method described above.
〔樹脂〕
＜樹脂Ａ１の合成＞
　プロピレングリコールモノメチルエーテル（８５質量部）をフラスコに仕込み、フラスコを窒素気流下、９０℃に加熱した。この液にスチレン（４６質量部）、メタクリル酸（２０質量部）、メタクリル酸メチル（２質量部）をプロピレングリコールモノメチルエーテル（２０質量部）に溶解させた溶液及び重合開始剤Ｖ－６０１（富士フイルム和光純薬社製）（７質量部）をプロピレングリコールモノメチルエーテル（４５質量部）に溶解させた溶液を同時に３時間かけて滴下した。滴下終了後、１時間おきに３回Ｖ－６０１を（１．０質量部）添加した。その後、更に３時間反応させた。その後、プロピレングリコールモノメチルエーテルアセテート（６０質量部）及びプロピレングリコールモノメチルエーテル（１２質量部）で希釈した。空気気流下、反応液を１００℃に昇温し、テトラエチルアンモニウムブロミド（０．７質量部）及びｐ－メトキシフェノール（０．３質量部）を添加した。これにグリシジルメタクリレート（日油社製ブレンマーＧ）（３２質量部）を２０分かけて滴下した。これを１００℃で７時間反応させ、樹脂Ａ１を含む溶液を得た。得られた溶液の固形分濃度は３０.０質量％であった。上記樹脂Ａ１の合成方法を参考に、樹脂Ａ２～Ａ４のいずれかを含む溶液を得た。得られた各溶液の固形分濃度は３０．０質量％であった。 〔resin〕
<Synthesis of Resin A1>
Propylene glycol monomethyl ether (85 parts by mass) was charged into a flask, and the flask was heated to 90°C under a nitrogen stream. A solution obtained by dissolving styrene (46 parts by mass), methacrylic acid (20 parts by mass), and methyl methacrylate (2 parts by mass) in propylene glycol monomethyl ether (20 parts by mass) and a polymerization initiator V-601 (Fuji Film Wako Pure Chemical Industries, Ltd.) (7 parts by mass) dissolved in propylene glycol monomethyl ether (45 parts by mass) was added dropwise over 3 hours at the same time. After completion of dropping, V-601 (1.0 parts by mass) was added three times at intervals of one hour. After that, the reaction was further continued for 3 hours. Then, it was diluted with propylene glycol monomethyl ether acetate (60 parts by mass) and propylene glycol monomethyl ether (12 parts by mass). The temperature of the reaction solution was raised to 100° C. under an air stream, and tetraethylammonium bromide (0.7 parts by mass) and p-methoxyphenol (0.3 parts by mass) were added. Glycidyl methacrylate (Blenmer G manufactured by NOF Corporation) (32 parts by mass) was added dropwise over 20 minutes. This was reacted at 100° C. for 7 hours to obtain a solution containing resin A1. The solid content concentration of the obtained solution was 30.0% by mass. A solution containing any one of resins A2 to A4 was obtained with reference to the method for synthesizing resin A1. The solid content concentration of each obtained solution was 30.0% by mass.
＜樹脂Ａ５の合成＞
　３つ口フラスコにプロピレングリコールモノメチルエーテルアセテート（１１６．５質量部）を入れ、窒素雰囲気下において９０℃に昇温した。Ｓｔ（５２．０質量部）、ＭＡＡ（２９．０質量部）、ＭＭＡ（１９．０質量部）、Ｖ－６０１（１０．０質量部）及びプロピレングリコールモノメチルエーテルアセテート（１１６．５質量部）を加えた溶液を、９０℃±２℃に維持した上記フラスコ溶液中に２時間かけて滴下した。滴下終了後、上記フラスコ内の溶液を９０℃±２℃にて２時間撹拌することで、樹脂Ａ５を含む溶液を得た。得られた溶液の固形分濃度は３０．０質量％であった。 <Synthesis of Resin A5>
Propylene glycol monomethyl ether acetate (116.5 parts by mass) was placed in a three-necked flask and heated to 90°C in a nitrogen atmosphere. St (52.0 parts by mass), MAA (29.0 parts by mass), MMA (19.0 parts by mass), V-601 (10.0 parts by mass) and propylene glycol monomethyl ether acetate (116.5 parts by mass) was added dropwise over 2 hours into the flask solution maintained at 90°C ± 2°C. After the dropwise addition, the solution in the flask was stirred at 90° C.±2° C. for 2 hours to obtain a solution containing resin A5. The solid content concentration of the obtained solution was 30.0% by mass.
＜樹脂Ａ６の合成＞
　３つ口フラスコにプロピレングリコールモノメチルエーテルアセテート（１１６．５質量部）を入れ、窒素雰囲気下において９０℃に昇温した。Ｓｔ（５２．０質量部）、ＭＡＡ（２９．０質量部）、ＭＭＡ（１９．０質量部）、Ｖ－６０１（４．０質量部）及びプロピレングリコールモノメチルエーテルアセテート（１１６．５質量部）を加えた溶液を、９５℃±２℃に維持した上記フラスコ溶液中に６時間かけて滴下した。滴下終了後、上記フラスコ内の溶液を９５℃±２℃にて２時間撹拌することで、樹脂Ａ６を含む溶液を得た。得られた溶液の固形分濃度は３０．０質量％であった。 <Synthesis of Resin A6>
Propylene glycol monomethyl ether acetate (116.5 parts by mass) was placed in a three-necked flask and heated to 90°C in a nitrogen atmosphere. St (52.0 parts by mass), MAA (29.0 parts by mass), MMA (19.0 parts by mass), V-601 (4.0 parts by mass) and propylene glycol monomethyl ether acetate (116.5 parts by mass) was added dropwise over 6 hours into the flask solution maintained at 95°C ± 2°C. After the dropwise addition was completed, the solution in the flask was stirred at 95° C.±2° C. for 2 hours to obtain a solution containing resin A6. The solid content concentration of the obtained solution was 30.0% by mass.
　以下、樹脂Ａ１～Ａ６を示す。 Resins A1 to A6 are shown below.
Figure JPOXMLDOC01-appb-T000006
Figure JPOXMLDOC01-appb-T000006
　表１中、各記載は以下を示す。
　ＧＭＡ－ＭＭＡ以外の構成単位は、各構成単位を形成するための単量体を示す。「ＧＭＡ－ＭＡＡ」は、メタクリル酸に由来する構成単位に対してグリシジルメタクリレートが付加した構成単位を示す。樹脂Ａ１～Ａ６は、アルカリ可溶性樹脂に該当する。
　ＭＡＡ：メタクリル酸（富士フイルム和光純薬社製）
　Ｓｔ：スチレン（富士フイルム和光純薬社製）
　ＭＭＡ：メチルメタクリレート（富士フイルム和光純薬社製）
　ＢｚＭＡ：ベンジルメタクリレート（富士フイルム和光純薬社製）
　ＧＭＡ－ＭＭＡ：メタクリル酸に由来する構成単位に対してグリシジルメタクリレートが付加した構成単位
　ＩＢＭＡ：イソボルニルメタクリレート（富士フイルム和光純薬社製）
　表中、「重合性基」欄は、「Ａ」である場合は、樹脂が重合性基を有することを示す。「Ｂ」である場合は、樹脂が重合性基を有さないことを示す。
　「Ｔｇ［℃］」欄は、樹脂のガラス転移温度を示す。
　「Ｍｗ」欄は、樹脂の重量平均分子量を示す。
　表中の構成単位における数値は、質量比を示す。 In Table 1, each description shows the following.
Structural units other than GMA-MMA represent monomers for forming each structural unit. "GMA-MAA" indicates a structural unit in which glycidyl methacrylate is added to a structural unit derived from methacrylic acid. Resins A1 to A6 correspond to alkali-soluble resins.
MAA: methacrylic acid (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.)
St: Styrene (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.)
MMA: Methyl methacrylate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.)
BzMA: benzyl methacrylate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.)
GMA-MMA: Structural unit in which glycidyl methacrylate is added to a structural unit derived from methacrylic acid IBMA: Isobornyl methacrylate (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.)
In the table, "A" in the "polymerizable group" column indicates that the resin has a polymerizable group. "B" indicates that the resin does not have a polymerizable group.
The "Tg [°C]" column indicates the glass transition temperature of the resin.
The "Mw" column indicates the weight average molecular weight of the resin.
Numerical values in structural units in the table indicate mass ratios.
〔感光性組成物〕
　下記表２に示す成分及び配合で各感光性組成物を調製した。
　表２中、各成分欄に記載の数値は、各成分の含有量（質量部）を表す。
　なお、樹脂においては、表中に示す含有量は、樹脂自体の含有量であって、各樹脂を含む溶液の添加量ではない。 [Photosensitive composition]
Each photosensitive composition was prepared with the components and formulations shown in Table 2 below.
In Table 2, the numerical value described in each component column represents the content (parts by mass) of each component.
As for the resins, the content shown in the table is the content of the resin itself, not the amount of the solution containing each resin added.
Figure JPOXMLDOC01-appb-T000007
Figure JPOXMLDOC01-appb-T000007
＜樹脂＞
　樹脂Ａ１～Ａ６は、上述したとおりである。 <Resin>
Resins A1 to A6 are as described above.
＜重合性化合物＞
　Ｂ１：ＢＰＥ－９００（エトキシ化ビスフェノールＡジメタクリレート、新中村化学工業社製）
　Ｂ２：ＢＰＥ－５００（エトキシ化ビスフェノールＡジメタクリレート、新中村化学工業社製）
　Ｂ３：ＢＰＥ－１００（エトキシ化ビスフェノールＡジメタクリレート、新中村化学工業社製）
　Ｂ４：アロニックスＭ－２７０（ポリプロピレングリコールジアクリレート、東亞合成社製）
　Ｂ５：Ａ－ＮＯＤ－Ｎ（１，９－ノナンジオールジアクリレート、新中村化学工業社製）
　Ｂ６：Ａ－ＤＯＤ－Ｎ（１，１０－デカンジオールジアクリレート、新中村化学工業社製）
　下記表に重合性化合物の特性を示す。
　表中、「エチレンオキシ基」欄は、「Ａ」である場合は、重合性化合物がエチレンオキシ基を有することを示す。「Ｂ」である場合は、重合性化合物がエチレンオキシ基を有さないことを示す。
　「官能基数［個／分子］」欄は、重合性化合物１分子当たりに含まれる官能基数を意味する。例えば、官能基数が２個／分子である重合性化合物Ｂ１は、２官能エチレン性不飽和化合物に該当する。
　「重合性基の含有量［ｍｍｏｌ／ｇ］」欄は、重合性化合物１ｇ当たりに含まれる重合性基の含有量（ｍｍｏｌ）を意味する。 <Polymerizable compound>
B1: BPE-900 (ethoxylated bisphenol A dimethacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd.)
B2: BPE-500 (ethoxylated bisphenol A dimethacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd.)
B3: BPE-100 (ethoxylated bisphenol A dimethacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd.)
B4: Aronix M-270 (polypropylene glycol diacrylate, manufactured by Toagosei Co., Ltd.)
B5: A-NOD-N (1,9-nonanediol diacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd.)
B6: A-DOD-N (1,10-decanediol diacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd.)
The properties of the polymerizable compounds are shown in the table below.
In the table, "A" in the "ethyleneoxy group" column indicates that the polymerizable compound has an ethyleneoxy group. "B" indicates that the polymerizable compound does not have an ethyleneoxy group.
The column "number of functional groups [number/molecule]" means the number of functional groups contained per molecule of the polymerizable compound. For example, the polymerizable compound B1 having 2 functional groups/molecule corresponds to a bifunctional ethylenically unsaturated compound.
The column "Content of polymerizable group [mmol/g]" means the content (mmol) of the polymerizable group per 1 g of the polymerizable compound.
Figure JPOXMLDOC01-appb-T000008
Figure JPOXMLDOC01-appb-T000008
＜重合開始剤＞
　Ｂ－ＣＩＭ：２，２’－ビス（２－クロロフェニル）－４，４’，５，５’－テトラフェニルビスイミダゾール（２－（２－クロロフェニル）－４，５－ジフェニルイミダゾール二量体）（Ｈａｍｐｆｏｒｄ社製） <Polymerization initiator>
B-CIM: 2,2′-bis(2-chlorophenyl)-4,4′,5,5′-tetraphenylbisimidazole (2-(2-chlorophenyl)-4,5-diphenylimidazole dimer) ( manufactured by Hampford)
＜増感剤＞
　ＳＢ－ＰＩ　７０１：４，４’－ビス（ジエチルアミノ）ベンゾフェノン（三洋貿易社製） <Sensitizer>
SB-PI 701: 4,4'-bis (diethylamino) benzophenone (manufactured by Sanyo Trading Co., Ltd.)
＜色素＞
　ロイコクリスタルバイオレット（東京化成工業社製） <Pigment>
Leuco Crystal Violet (manufactured by Tokyo Chemical Industry Co., Ltd.)
＜その他添加剤＞
　Ｎ－フェニルカルバモイルメチル－Ｎ－カルボキシメチルアニリン（富士フイルム和光純薬社製）
　ＴＤＰ－Ｇ：フェノチアジン（川口化学工業社製）
　ＣＢＴ－１：カルボキシベンゾトリアゾール（城北化学工業社製）
　４－ヒドロキシメチルー４―メチル－１－フェニル－３－ピラゾリドン（富士フイルム和光純薬製）
　メガファックＦ－５５２（ＤＩＣ社製） <Other additives>
N-phenylcarbamoylmethyl-N-carboxymethylaniline (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.)
TDP-G: Phenothiazine (manufactured by Kawaguchi Chemical Industry Co., Ltd.)
CBT-1: Carboxybenzotriazole (manufactured by Johoku Chemical Industry Co., Ltd.)
4-hydroxymethyl-4-methyl-1-phenyl-3-pyrazolidone (manufactured by Fujifilm Wako Pure Chemical Industries)
Megafac F-552 (manufactured by DIC)
＜溶剤＞
　ＰＧＭＥＡ：プロピレングリコールモノメチルエーテルアセテート（昭和電工社製）
　ＭＥＫ：メチルエチルケトン（三協化学社製）
　ＭＦＧ：プロピレングリコールモノメチルエーテル（日本乳化剤社製）
　ＭｅＯＨ：メタノール（三菱ガス化学社製） <Solvent>
PGMEA: propylene glycol monomethyl ether acetate (manufactured by Showa Denko)
MEK: methyl ethyl ketone (manufactured by Sankyo Chemical Co., Ltd.)
MFG: propylene glycol monomethyl ether (manufactured by Nippon Emulsifier Co., Ltd.)
MeOH: methanol (manufactured by Mitsubishi Gas Chemical Company)
〔中間層形成用組成物〕
　下記の各成分を用いて中間層形成用組成物１を調製した。

　中間層形成用組成物１の各種成分を以下に示す。
　ＰＶＡ：ポリビニルアルコール、製品名「クラレポバールＰＶＡ－２０５」（クラレ社製）
　ＰＶＰ：ポリピロリドン、製品名「ポリビニルピロリドンＫ－３０」（日本触媒社製）
　ＨＰＭＣ：ヒドロキシプロピルメチルセルロース、製品名「メトローズ　６０ＳＨ－０３」（信越化学工業社製）
　ＰＶＡ、ＰＶＰ及びＨＰＭＣを混合比（質量比）が６７．５／３１．５／１となるように各成分を混合した後、溶媒（溶媒：イオン交換水とメタノール（三菱ガス化学社製）とを混合比（質量比）４０／６０となるように混合した混合溶媒）を加えることによって、中間層形成用組成物１を作製した。　 [Composition for Intermediate Layer Formation]
An intermediate layer-forming composition 1 was prepared using the following components.

Various components of the intermediate layer forming composition 1 are shown below.
PVA: polyvinyl alcohol, product name "Kuraray Poval PVA-205" (manufactured by Kuraray Co., Ltd.)
PVP: polypyrrolidone, product name "polyvinylpyrrolidone K-30" (manufactured by Nippon Shokubai Co., Ltd.)
HPMC: hydroxypropyl methylcellulose, product name "Metolose 60SH-03" (manufactured by Shin-Etsu Chemical Co., Ltd.)
After mixing each component so that the mixing ratio (mass ratio) of PVA, PVP and HPMC is 67.5/31.5/1, a solvent (solvent: ion-exchanged water and methanol (manufactured by Mitsubishi Gas Chemical Company) and was mixed so that the mixing ratio (mass ratio) was 40/60) to prepare an intermediate layer-forming composition 1.
〔転写フィルム〕
＜実施例１～１１、比較例１～２＞
　表４に示す構成となるように、仮支持体及び感光性組成物層から構成される実施例１～１１及び比較例１～２の転写フィルムを作製した。具体的には以下のとおりである。
　まず、仮支持体（厚み１６μｍのポリエチレンテレフタレートフィルム（登録商標ルミラー１６ＫＳ４０、東レ社製））の上に、表４に示す感光性組成物を、バーコーターを用いて乾燥後の厚みが３μｍになるように塗布し、オーブンを用いて８０℃で乾燥させ、ネガ型感光性組成物層を形成した。
　得られたネガ型感光性組成物層上に、厚み１６μｍのポリエチレンテレフタレート（登録商標ルミラー１６ＫＳ４０、東レ社製）を圧着し、実施例１～１１及び比較例１～２の転写フィルムを作製した。 [Transfer film]
<Examples 1 to 11, Comparative Examples 1 to 2>
Transfer films of Examples 1 to 11 and Comparative Examples 1 and 2, which were composed of a temporary support and a photosensitive composition layer, were produced so as to have the structure shown in Table 4. Specifically, it is as follows.
First, the photosensitive composition shown in Table 4 was applied on a temporary support (16 μm thick polyethylene terephthalate film (registered trademark Lumirror 16KS40, manufactured by Toray Industries, Inc.)) using a bar coater to a thickness of 3 μm after drying. and dried at 80° C. using an oven to form a negative photosensitive composition layer.
Polyethylene terephthalate (Registered Trademark Lumirror 16KS40, manufactured by Toray Industries, Inc.) having a thickness of 16 μm was press-bonded onto the resulting negative photosensitive composition layer to prepare transfer films of Examples 1 to 11 and Comparative Examples 1 and 2.
＜実施例１２～１４＞
　表４に示す構成となるように、仮支持体、中間層及び感光性組成物層から構成される各転写フィルムを作製した。具体的には以下のとおりである。
　まず、仮支持体（厚み１６μｍのポリエチレンテレフタレートフィルム（登録商標ルミラー１６ＫＳ４０、東レ社製））の上に、上記中間層を形成するための中間層形成用組成物１を、バーコーターを用いて、乾燥後の厚みが１．０μｍになるように塗布し、オーブンを用いて９０℃で乾燥させ、中間層を形成した。
　更に、中間層の上に、表４に示す感光性組成物層を形成するための感光性組成物を、バーコーターを用いて乾燥後の厚みが３μｍになるように塗布し、オーブンを用いて８０℃で乾燥させ、ネガ型感光性組成物層を形成した。
　得られたネガ型感光性組成物層上に、厚み１６μｍのポリエチレンテレフタレート（登録商標１６ＫＳ４０、東レ社製）を圧着し、実施例１２～１４の転写フィルムを作製した。 <Examples 12 to 14>
Each transfer film composed of a temporary support, an intermediate layer and a photosensitive composition layer was produced so as to have the structure shown in Table 4. Specifically, it is as follows.
First, on a temporary support (16 μm thick polyethylene terephthalate film (registered trademark Lumirror 16KS40, manufactured by Toray Industries, Inc.)), intermediate layer forming composition 1 for forming the intermediate layer was applied using a bar coater. It was applied so that the thickness after drying was 1.0 μm, and dried at 90° C. using an oven to form an intermediate layer.
Furthermore, on the intermediate layer, a photosensitive composition for forming a photosensitive composition layer shown in Table 4 was applied using a bar coater so that the thickness after drying was 3 μm, and was dried using an oven. It was dried at 80° C. to form a negative photosensitive composition layer.
Polyethylene terephthalate (registered trademark 16KS40, manufactured by Toray Industries, Inc.) having a thickness of 16 μm was press-bonded onto the resulting negative photosensitive composition layer to prepare transfer films of Examples 12 to 14.
〔測定及び評価〕
＜ガラス転移温度＞
　ＴｇＸ及びＴｇＹの測定は、上述した測定方法で測定した。 [Measurement and evaluation]
<Glass transition temperature>
TgX and TgY were measured by the measurement method described above.
＜パターン形状（裾広がり形状）＞
　上記で作製した転写フィルムの保護フィルムを剥離し、感光性組成物層の仮支持体側とは反対側の表面を、ガラス上にＮｉメッキ（厚み１００ｎｍ）を施した導電層を有する基板上に、ラミネート（ラミネート条件：基材温度８０℃、ゴムローラー温度１１０℃、線圧３Ｎ／ｃｍ、搬送速度２ｍ／ｍｉｎ）して、積層体を得た。
　次に、得られた積層体から仮支持体を剥離し、ライン（μｍ）／スペース（μｍ）が１／１のパターンを有するフォトマスクを、得られた積層体中の感光性組成物層の基板側とは反対側の表面と密着させた。高圧水銀灯露光機（ＭＡＰ－１２００Ｌ、大日本科研社製、主波長：３６５ｎｍ）を用いて光を照射して、感光性組成物層を１００ｍＪ／ｃｍ２で露光した。その後、液温が２５℃の炭酸ナトリウム水溶液を用いて３０秒間のシャワー現像をすることによってパターンを形成した。得られたパターンの断面形状を走査型電子顕微鏡により観察して、各パターンの側面において、パターンの上面部（基板側とは反対の面）からはみ出した部分（図１の裾広がり部分３）の長さを裾長さとし、最も長い裾長さを用いて、以下の評価基準にしたがってパターン形状を評価した。
　Ａ：裾長さが０．２０μｍ未満
　Ｂ：裾長さが０．２０μｍ以上、０．３０μｍ未満
　Ｃ：裾長さが０．３０μｍ以上、０．４０μｍ以下
　Ｄ：裾長さが０．４０μｍ超 <Pattern shape (flat bottom shape)>
The protective film of the transfer film prepared above is peeled off, and the surface of the photosensitive composition layer opposite to the temporary support side is Ni-plated on glass (thickness 100 nm) on a substrate having a conductive layer, A laminate was obtained by lamination (laminating conditions: substrate temperature 80° C., rubber roller temperature 110° C., linear pressure 3 N/cm, conveying speed 2 m/min).
Next, the temporary support is peeled off from the obtained laminate, and a photomask having a pattern with a line (μm)/space (μm) ratio of 1/1 is applied to the photosensitive composition layer in the obtained laminate. It was brought into close contact with the surface on the side opposite to the substrate side. The photosensitive composition layer was exposed at 100 mJ/cm 2 by irradiating light using a high-pressure mercury lamp exposure machine (MAP-1200L, manufactured by Dainippon Kaken Co., Ltd., main wavelength: 365 nm). Thereafter, a pattern was formed by performing shower development for 30 seconds using an aqueous sodium carbonate solution having a liquid temperature of 25°C. The cross-sectional shape of the obtained pattern was observed with a scanning electron microscope. The pattern shape was evaluated according to the following evaluation criteria using the length as the tail length and using the longest tail length.
A: The tail length is less than 0.20 μm B: The tail length is 0.20 μm or more and less than 0.30 μm C: The tail length is 0.30 μm or more and 0.40 μm or less D: The tail length is more than 0.40 μm
　表４に評価結果を示す。
　表４中、各記載は以下を示す。
　「重合性基」欄は、「Ａ」である場合は、樹脂が重合性基を有し、重合性基を有する構成単位の含有量が、樹脂の全質量に対して、２０．０質量％以上であることを示す。「Ｂ」である場合は、樹脂が重合性基を有し、重合性基を有する構成単位の含有量が、樹脂の全質量に対して、０質量％超２０．０質量％未満であることを示す。「Ｃ」である場合は、樹脂が重合性を有さないことを示す。
　「重合性基の含有量２．４ｍｍｏｌ／ｇ以上」欄は、「Ａ」である場合は、重合性化合物中の重合性基の含有量が２．４ｍｍｏｌ／ｇ以上であることを示す。「Ｂ」である場合は、重合性化合物中の重合性基の含有量が２．４ｍｍｏｌ／ｇ未満であることを示す。なお、複数の重合性化合物を含む場合、全ての重合性化合物が２．４ｍｍｏｌ／ｇ以上である場合のみ、「Ａ」とした。
　「エチレンオキシ基」欄は、「Ａ」である場合は、重合性化合物がエチレンオキシ基を有することを示す。「Ｂ」である場合は、重合性化合物がエチレンオキシ基を有さないことを示す。なお、複数の重合性化合物を含む場合、全ての重合性化合物がエチレンオキシ基を有する場合のみ、「Ａ」とした。
　「ＴｇＹ－ＴｇＸ」欄は、ＴｇＹの値（℃）からＴｇＸの値（℃）を引いた値を示す。
　「ｍ／ｂ」欄は、樹脂の含有量に対する重合性化合物の含有量の質量比（重合性化合物の含有量／樹脂の含有量）を示す。
　「中間層」欄は、「Ａ」である場合は、転写フィルムが仮支持体と感光性組成物層との間に中間層を有することを示す。「Ｂ」である場合は、転写フィルムが仮支持体と感光性組成物層との間に中間層を有さないことを示す。 Table 4 shows the evaluation results.
In Table 4, each description shows the following.
If the "polymerizable group" column is "A", the resin has a polymerizable group, and the content of the structural unit having a polymerizable group is 20.0% by mass with respect to the total mass of the resin. Indicates that In the case of "B", the resin has a polymerizable group, and the content of the structural unit having a polymerizable group is more than 0% by mass and less than 20.0% by mass with respect to the total mass of the resin. indicate. "C" indicates that the resin does not have polymerizability.
If the column "content of polymerizable group is 2.4 mmol/g or more" is "A", it indicates that the content of the polymerizable group in the polymerizable compound is 2.4 mmol/g or more. "B" indicates that the content of the polymerizable group in the polymerizable compound is less than 2.4 mmol/g. In addition, when a plurality of polymerizable compounds are included, "A" is given only when all the polymerizable compounds are 2.4 mmol/g or more.
If the "ethyleneoxy group" column is "A", it indicates that the polymerizable compound has an ethyleneoxy group. "B" indicates that the polymerizable compound does not have an ethyleneoxy group. When a plurality of polymerizable compounds are included, "A" is used only when all polymerizable compounds have an ethyleneoxy group.
The "TgY-TgX" column shows the value obtained by subtracting the TgX value (°C) from the TgY value (°C).
The "m/b" column shows the mass ratio of the polymerizable compound content to the resin content (polymerizable compound content/resin content).
If the "intermediate layer" column is "A", it indicates that the transfer film has an intermediate layer between the temporary support and the photosensitive composition layer. A "B" indicates that the transfer film does not have an intermediate layer between the temporary support and the photosensitive composition layer.
Figure JPOXMLDOC01-appb-T000009
Figure JPOXMLDOC01-appb-T000009
　表４の結果から、本発明の積層体の製造方法によれば、パターン形状に優れることが確認された。
　ガラス転移温度Ｘとガラス転移温度Ｙとの差が、３５～５０℃である場合、本発明の効果がより優れることが確認された（実施例１及び実施例２の比較）。
　樹脂のガラス転移温度が、７０～１１５℃である場合、本発明の効果がより優れることが確認された（実施例１及び実施例３～４の比較）。
　重合性化合物中の重合性基の含有量が、２．４ｍｍｏｌ／ｇ以上である場合、本発明の効果がより優れることが確認された（実施例１及び実施例５の比較）。
　重合性化合物が、エチレンオキシ基を有する場合、本発明の効果がより優れることが確認された（実施例１及び実施例６の比較）。
　感光性組成物層が、３種以上の重合性化合物を含む場合、本発明の効果がより優れることが確認された（実施例１及び実施例７の比較）。
　樹脂が、重合性基を有する場合、本発明の効果がより優れることが確認され、重合性基を有する構成単位の含有量が、樹脂の全質量に対して、２０．０～４０．０質量％である場合、本発明の効果が更に優れることが確認された（実施例１、８及び９の比較）。
　樹脂の含有量に対する重合性化合物の含有量の質量比が、０．７０～１．１０である場合、本発明の効果がより優れることが確認された（実施例１及び実施例１０～１１の比較）。 From the results in Table 4, it was confirmed that the method for producing a laminate of the present invention was excellent in pattern shape.
It was confirmed that the effect of the present invention is more excellent when the difference between the glass transition temperature X and the glass transition temperature Y is 35 to 50° C. (comparison between Examples 1 and 2).
It was confirmed that the effects of the present invention are more excellent when the resin has a glass transition temperature of 70 to 115° C. (comparison between Example 1 and Examples 3 and 4).
It was confirmed that the effects of the present invention are more excellent when the content of the polymerizable group in the polymerizable compound is 2.4 mmol/g or more (comparison between Examples 1 and 5).
It was confirmed that the effects of the present invention are more excellent when the polymerizable compound has an ethyleneoxy group (comparison between Examples 1 and 6).
It was confirmed that the effects of the present invention were more excellent when the photosensitive composition layer contained three or more kinds of polymerizable compounds (comparison between Examples 1 and 7).
When the resin has a polymerizable group, it is confirmed that the effect of the present invention is more excellent, and the content of the structural unit having a polymerizable group is 20.0 to 40.0 mass with respect to the total mass of the resin. %, it was confirmed that the effect of the present invention is more excellent (comparison of Examples 1, 8 and 9).
It was confirmed that the effect of the present invention is more excellent when the mass ratio of the content of the polymerizable compound to the content of the resin is 0.70 to 1.10 (Examples 1 and 10 to 11 comparison).
〔実施例１０１〕
　厚さ５０μｍのＰＥＴフィルム（ポリエチレンテレフタレートフィルム）上にスパッタ法にて厚さ５００ｎｍの銅層を作製した銅層付きＰＥＴ基板を得た。
　上記で作製した転写フィルム１を１０ｃｍ角にカットし、保護フィルムを剥がして、露出した感光性組成物層が銅層付きＰＥＴ基板表面の銅層に接するように、ロール温度９０℃、線圧０．８ＭＰａ、線速度３．０ｍ／ｍｉｎのラミネート条件で、保護フィルムを剥がした転写フィルム１を銅層付きＰＥＴ基板にラミネートして、積層体を得た。この時点で、積層体は、「ＰＥＴフィルム－銅層－感光性組成物層－中間層－仮支持体」の順に各構成を有する。
　次に、得られた積層体から仮支持体を剥離し、中間層を露出させた。ライン（μｍ）／スペース（μｍ）が１／１、２／２、３／３、４／４、５／５、６／６、７／７、８／８、９／９及び１０／１０のいずれかのパターンを全面に有するフォトマスクを、表面に露出した上記中間層と密着させた。この時点で、積層体は、「ＰＥＴフィルム－銅層－感光性組成物層－中間層－フォトマスク」の順に各構成を有する。得られた積層体に対して高圧水銀灯露光機（ＭＡ－１２００Ａ型、大日本科研社製、主波長：３６５ｎｍ、露光時真空度－５０ｋＰａ）を用いて、フォトマスク側から光を照射した。露光量は、現像後に得られるレジストパターンが、フォトマスクのラインアンドスペース形状を再現する露光量とした。
　その後、２８℃の１．０質量％炭酸ナトリウム水溶液を現像液として使用して現像を行った。現像は、具体的には、シャワー処理を３０秒間行い、ＡｉｒＫｎｉｆｅ（エアナイフ）処理をして現像液を切った後、純水で３０秒間シャワー処理をして、更にＡｉｒＫｎｉｆｅ処理を行った。これにより、ライン幅：スペース幅＝１：１のラインアンドスペース形状のレジストパターンを有する積層体を得た。この時点で、積層体は、「ＰＥＴフィルム－銅層－レジストパターン」の順に各構成を有する。 [Example 101]
A PET substrate with a copper layer was obtained by forming a copper layer with a thickness of 500 nm on a PET film (polyethylene terephthalate film) with a thickness of 50 μm by a sputtering method.
The transfer film 1 prepared above was cut into 10 cm squares, the protective film was peeled off, and the exposed photosensitive composition layer was in contact with the copper layer on the surface of the PET substrate with the copper layer, and the roll temperature was 90 ° C. and the linear pressure was 0. The transfer film 1 from which the protective film was removed was laminated on a PET substrate with a copper layer under lamination conditions of 8 MPa and a linear velocity of 3.0 m/min to obtain a laminate. At this point, the laminate has each configuration in the order of "PET film--copper layer--photosensitive composition layer--intermediate layer--temporary support".
Next, the temporary support was peeled off from the obtained laminate to expose the intermediate layer. Line (μm)/space (μm) of 1/1, 2/2, 3/3, 4/4, 5/5, 6/6, 7/7, 8/8, 9/9 and 10/10 A photomask having any pattern on the entire surface was brought into close contact with the intermediate layer exposed on the surface. At this point, the laminate has each configuration in the order of "PET film--copper layer--photosensitive composition layer--intermediate layer--photomask". The resulting laminate was irradiated with light from the photomask side using a high-pressure mercury lamp exposure machine (MA-1200A, manufactured by Dainippon Kaken Co., Ltd., dominant wavelength: 365 nm, degree of vacuum during exposure: -50 kPa). The amount of exposure was such that the resist pattern obtained after development reproduces the line-and-space shape of the photomask.
After that, development was carried out using a 1.0% by mass sodium carbonate aqueous solution at 28° C. as a developer. Specifically, development was performed by performing shower processing for 30 seconds, performing AirKnife processing, draining the developer, performing shower processing with pure water for 30 seconds, and further performing AirKnife processing. As a result, a laminate having a line-and-space resist pattern of line width:space width=1:1 was obtained. At this point, the laminate has each configuration in the order of "PET film-copper layer-resist pattern".
＜線幅のばらつき＞
　得られた積層体において、図３に示す、縦線の実線及び横線の実線の交差点２０の計２５か所の領域におけるパターンをラインの長さ方向に対して垂直に切断し、ライン（μｍ）／スペース（μｍ）が２μｍ／２μｍのパターンの断面を走査型光学顕微鏡により観察し、各スペース幅を計測した。計測した２５点のスペース幅の標準偏差を求めて、下記の基準で線幅のばらつきを評価した。
　Ａ：標準偏差が、０．２０μｍ未満
　Ｂ：標準偏差が、０．２０μｍ以上、０．５０μｍ未満
　Ｃ：標準偏差が、０．５０μｍ以上 <Line width variation>
In the obtained laminate, the pattern in a total of 25 regions of the intersections 20 of the solid vertical lines and the solid horizontal lines shown in FIG. A cross section of a pattern with a /space (μm) of 2 μm/2 μm was observed with a scanning optical microscope, and each space width was measured. The standard deviation of the space widths measured at 25 points was determined, and the variation in line width was evaluated according to the following criteria.
A: Standard deviation is less than 0.20 μm B: Standard deviation is 0.20 μm or more and less than 0.50 μm C: Standard deviation is 0.50 μm or more
〔実施例１０２～１０４〕
　実施例１０１において、積層体の露光方法を下記のように変更したこと以外は、実施例１０１と同様にして線幅のばらつきを評価した。
　上記パターン形状の評価サンプルの作製手順を参照して「クッション材－ＰＥＴフィルム－銅層－感光性組成物層－中間層－仮支持体」の順に各構成を有する積層体を準備した。得られた上記積層体から仮支持体を剥離し、上記中間層を露出させた。ライン（μｍ）／スペース（μｍ）が１／１、２／２、３／３、４／４、５／５、６／６、７／７、８／８、９／９及び１０／１０のいずれかのパターンを全面に有するフォトマスクを、露出した中間層と密着させた。この時点で、積層体は、「クッション材－ＰＥＴフィルム－銅層－感光性組成物層－中間層－フォトマスク」の順に各構成を有する。次いで、高圧水銀灯露光機（ＭＡ－１２００Ａ型、大日本科研社製、主波長：３６５ｎｍ、露光時真空度－５０ｋＰａ）を用いて、フォトマスク側から光を照射した。 [Examples 102 to 104]
In Example 101, the variation in line width was evaluated in the same manner as in Example 101, except that the exposure method of the laminate was changed as follows.
A laminate having each configuration in the order of "cushion material--PET film--copper layer--photosensitive composition layer--intermediate layer--temporary support" was prepared by referring to the procedure for preparing the pattern shape evaluation sample. The temporary support was peeled off from the obtained laminate to expose the intermediate layer. Line (μm)/space (μm) of 1/1, 2/2, 3/3, 4/4, 5/5, 6/6, 7/7, 8/8, 9/9 and 10/10 A photomask with either pattern over the entire surface was in intimate contact with the exposed intermediate layer. At this point, the laminate has each configuration in the order of "cushion material--PET film--copper layer--photosensitive composition layer--intermediate layer--photomask". Then, light was irradiated from the photomask side using a high-pressure mercury lamp exposure machine (MA-1200A, manufactured by Dainippon Kaken Co., Ltd., dominant wavelength: 365 nm, degree of vacuum during exposure: -50 kPa).
＜クッション材＞
・クッション材１：シリコンゴムシート（厚さ１ｍｍ）
・クッション材２：シリコンゴムシート（厚さ１ｍｍ）
・クッション材３：ウレタンゴムシート（厚さ１ｍｍ）
　なお、各クッション材の硬度は、タイプＡデュロメーター硬度を示す。 <Cushion material>
・Cushion material 1: Silicon rubber sheet (thickness 1 mm)
・Cushion material 2: Silicon rubber sheet (thickness 1 mm)
・Cushion material 3: Urethane rubber sheet (thickness 1 mm)
The hardness of each cushioning material indicates type A durometer hardness.
　表５に評価結果を示す。 Table 5 shows the evaluation results.
Figure JPOXMLDOC01-appb-T000010
Figure JPOXMLDOC01-appb-T000010
　表５の結果から、露光時に積層体がクッション材を有する場合（特に、基板の感光性組成物層とは反対側の表面にクッション材がある場合）、フォトマスクと中間層との密着が改良され、レジストパターンの線幅の均一性が改良することが確認された。
　クッション材の硬度が７０以上である場合、線幅のばらつきがより優れることが確認された。 From the results in Table 5, when the laminate has a cushioning material during exposure (especially when the surface of the substrate opposite to the photosensitive composition layer has a cushioning material), the adhesion between the photomask and the intermediate layer is improved. It was confirmed that the line width uniformity of the resist pattern was improved.
It was confirmed that when the hardness of the cushioning material is 70 or more, the variation in line width is more excellent.
　１　　基板
　２　　パターン
　３　　裾広がり部分
１０　　転写フィルム
１１　　仮支持体
１３　　中間層
１５　　感光性組成物層
１７　　組成物層
１９　　保護フィルム
２０　　交差点 REFERENCE SIGNS LIST 1 substrate 2 pattern 3 spreading portion 10 transfer film 11 temporary support 13 intermediate layer 15 photosensitive composition layer 17 composition layer 19 protective film 20 intersection

Claims (19)

  1. 　仮支持体と、感光性組成物層とを有する転写フィルムの前記感光性組成物層の前記仮支持体側とは反対側の表面を基板に接触させ、前記転写フィルムと前記基板とを貼合する貼合工程と、
    　前記感光性組成物層をパターン露光する露光工程と、
    　露光された前記感光性組成物層を、現像液を用いて現像してパターンを形成する現像工程とを有し、
    　前記感光性組成物層のガラス転移温度Ｘが１１０℃以下であり、測定Ｙで求められるガラス転移温度Ｙが１２５℃以上である、積層体の製造方法。
    　測定Ｙ：前記転写フィルムの前記感光性組成物層の前記仮支持体側とは反対側の表面を前記基板に接触させ、前記転写フィルムと前記基板とを貼り合わせて、得られた積層体から前記仮支持体を剥離して、前記仮支持体が剥離された積層体中の前記感光性組成物層を前記露光工程と同様の露光条件にて全面露光して、その後、得られた硬化膜のガラス転移温度を測定し、ガラス転移温度Ｙとする。     A surface of a transfer film having a temporary support and a photosensitive composition layer, which is opposite to the temporary support side of the photosensitive composition layer, is brought into contact with a substrate, and the transfer film and the substrate are bonded together. a lamination process;
    An exposure step of pattern-exposing the photosensitive composition layer;
    a developing step of developing the exposed photosensitive composition layer with a developer to form a pattern;
    A method for producing a laminate, wherein the photosensitive composition layer has a glass transition temperature X of 110° C. or lower, and a glass transition temperature Y obtained by measurement Y of 125° C. or higher.
    Measurement Y: The surface of the photosensitive composition layer of the transfer film opposite to the temporary support side is brought into contact with the substrate, the transfer film and the substrate are bonded together, and from the obtained laminate the The temporary support is peeled off, and the entire surface of the photosensitive composition layer in the laminate from which the temporary support is peeled is exposed under the same exposure conditions as in the exposure step, and then the resulting cured film. The glass transition temperature is measured and defined as the glass transition temperature Y.
  2. 　前記ガラス転移温度Ｘと前記ガラス転移温度Ｙとの差が、３５～５０℃である、請求項１に記載の積層体の製造方法。 The method for producing a laminate according to claim 1, wherein the difference between the glass transition temperature X and the glass transition temperature Y is 35 to 50°C.
  3. 　前記感光性組成物層が、樹脂及び重合性化合物を含む、請求項１又は２に記載の積層体の製造方法。 The method for producing a laminate according to claim 1 or 2, wherein the photosensitive composition layer contains a resin and a polymerizable compound.
  4. 　前記樹脂のガラス転移温度が、７０～１１５℃である、請求項３に記載の積層体の製造方法。 The method for producing a laminate according to claim 3, wherein the resin has a glass transition temperature of 70 to 115°C.
  5. 　前記樹脂が、重合性基を有する、請求項３又は４に記載の積層体の製造方法。 The method for producing a laminate according to claim 3 or 4, wherein the resin has a polymerizable group.
  6. 　前記重合性化合物中の重合性基の含有量が、２．４ｍｍｏｌ／ｇ以上である、請求項３～５のいずれか１項に記載の積層体の製造方法。 The method for producing a laminate according to any one of claims 3 to 5, wherein the content of the polymerizable group in the polymerizable compound is 2.4 mmol/g or more.
  7. 　前記重合性化合物が、エチレンオキシ基を有する、請求項３～６のいずれか１項に記載の積層体の製造方法。 The method for producing a laminate according to any one of claims 3 to 6, wherein the polymerizable compound has an ethyleneoxy group.
  8. 　前記感光性組成物層が、３種以上の重合性化合物を含む、請求項３～７のいずれか１項に記載の積層体の製造方法。 The method for producing a laminate according to any one of claims 3 to 7, wherein the photosensitive composition layer contains three or more polymerizable compounds.
  9. 　前記樹脂の含有量に対する前記重合性化合物の含有量の質量比が、０．７０～１．１０である、請求項３～８のいずれか１項に記載の積層体の製造方法。 The method for producing a laminate according to any one of claims 3 to 8, wherein the mass ratio of the content of the polymerizable compound to the content of the resin is 0.70 to 1.10.
  10. 　前記転写フィルムが、更に、前記仮支持体と前記感光性組成物層との間に中間層を有する、請求項１～９のいずれか１項に記載の積層体の製造方法。 The method for producing a laminate according to any one of claims 1 to 9, wherein the transfer film further has an intermediate layer between the temporary support and the photosensitive composition layer.
  11. 　前記中間層が、水溶性樹脂を含む、請求項１０に記載の積層体の製造方法。 The method for manufacturing a laminate according to claim 10, wherein the intermediate layer contains a water-soluble resin.
  12. 　前記中間層が、水溶性セルロース誘導体、多価アルコール類、多価アルコール類のオキサイド付加物、ポリエーテル系樹脂、フェノール誘導体及びアミド化合物からなる群から選択される少なくとも１つを含む、請求項１０又は１１に記載の積層体の製造方法。 10. The intermediate layer comprises at least one selected from the group consisting of water-soluble cellulose derivatives, polyhydric alcohols, oxide adducts of polyhydric alcohols, polyether resins, phenol derivatives and amide compounds. Or the manufacturing method of the laminated body of 11.
  13. 　前記貼合工程と前記露光工程との間に、前記転写フィルムと前記基板との積層体から前記仮支持体を剥離する剥離工程を更に有し、
    　前記露光工程が、フォトマスクを介して、前記剥離工程にて得られた仮支持体が剥離された前記積層体の前記感光性組成物層をパターン露光する露光工程である、請求項１～１２のいずれか１項に記載の積層体の製造方法。     Further comprising a peeling step of peeling the temporary support from the laminate of the transfer film and the substrate between the bonding step and the exposure step,
    Claims 1 to 12, wherein the exposure step is an exposure step of pattern-exposing the photosensitive composition layer of the laminate from which the temporary support obtained in the peeling step has been peeled off, through a photomask. A method for producing a laminate according to any one of the above.
  14. 　前記貼合工程と前記露光工程との間に、前記転写フィルムと前記基板との積層体から前記仮支持体を剥離する剥離工程を更に有し、
    　前記露光工程が、前記剥離工程にて得られた仮支持体が剥離された前記積層体の前記基板側とは反対側の表面とフォトマスクとを接触させて、前記感光性組成物層にパターン露光する露光工程である、請求項１～１２のいずれか１項に記載の積層体の製造方法。     Further comprising a peeling step of peeling the temporary support from the laminate of the transfer film and the substrate between the bonding step and the exposure step,
    In the exposure step, the surface of the laminate from which the temporary support obtained in the peeling step is peeled off is brought into contact with the surface of the laminate opposite to the substrate side with a photomask to form a pattern on the photosensitive composition layer. The method for producing a laminate according to any one of claims 1 to 12, which is an exposure step of exposing.
  15. 　前記露光工程と前記現像工程との間に、前記転写フィルムと前記基板との積層体から前記仮支持体を剥離する剥離工程を更に有し、
    　前記露光工程が、フォトマスクを介して、前記積層体の前記感光性組成物層をパターン露光する露光工程である、請求項１～１２のいずれか１項に記載の積層体の製造方法。     Further comprising a peeling step of peeling the temporary support from the laminate of the transfer film and the substrate between the exposure step and the developing step,
    The method for producing a laminate according to any one of claims 1 to 12, wherein the exposure step is an exposure step of pattern-exposing the photosensitive composition layer of the laminate through a photomask.
  16. 　前記フォトマスクが、メッシュ状に配置された遮光部を含む、請求項１３～１５のいずれか１項に記載の積層体の製造方法。 The method for manufacturing a laminate according to any one of claims 13 to 15, wherein the photomask includes a light shielding portion arranged in a mesh pattern.
  17. 　前記フォトマスクが、円形ドット状に配置された遮光部を含む、請求項１３～１５のいずれか１項に記載の積層体の製造方法。 The method for manufacturing a laminate according to any one of claims 13 to 15, wherein the photomask includes light shielding portions arranged in circular dots.
  18. 　前記フォトマスクが、円形ドット状に配置された開口部を含む、請求項１３～１５のいずれか１項に記載の積層体の製造方法。 The method for manufacturing a laminate according to any one of claims 13 to 15, wherein the photomask includes openings arranged in circular dots.
  19. 　基板上にシード層を形成して、シード層付き基板を形成するシード層形成工程と、
    　感光性組成物層の仮支持体側とは反対側の表面を前記シード層付き基板の前記シード層と接触させ、転写フィルムと前記シード層付き基板とを貼合して、前記基板、前記シード層、前記感光性組成物層及び前記仮支持体をこの順に有する感光性組成物層付き基板を得る貼合工程と、
    　前記感光性組成物層付き基板から前記仮支持体を剥離する剥離工程と、
    　前記仮支持体が剥離された感光性組成物層付き基板の前記基板側とは反対側の表面とフォトマスクとを接触させて、前記感光性組成物層をパターン露光する露光工程と、
    　露光された前記感光性組成物層を、現像液を用いて現像してパターンを形成する現像工程と、
    　前記パターンが配置されていない領域にある前記シード層上に、めっき処理によって金属めっき層を形成する金属めっき層形成工程と、
    　前記金属めっき層上に保護層を形成する保護層形成工程と、
    　前記パターンを除去する除去工程と、
    　露出した前記シード層を除去して、導電性細線を得るシード層除去工程と、を有し、
    　前記感光性組成物層のガラス転移温度Ｘが１１０℃以下であり、測定Ｙで求められるガラス転移温度Ｙが１２５℃以上である、回路配線の製造方法。
    　測定Ｙ：前記転写フィルムの前記感光性組成物層の前記仮支持体側とは反対側の表面を前記基板に接触させ、前記転写フィルムと前記基板とを貼り合わせて、得られた積層体から前記仮支持体を剥離して、前記仮支持体が剥離された積層体中の前記感光性組成物層を前記露光工程と同様の露光条件にて全面露光して、その後、得られた硬化膜のガラス転移温度を測定し、ガラス転移温度Ｙとする。     a seed layer forming step of forming a seed layer on a substrate to form a substrate with a seed layer;
    The surface of the photosensitive composition layer opposite to the temporary support side is brought into contact with the seed layer of the substrate with the seed layer, and the transfer film and the substrate with the seed layer are bonded to form the substrate and the seed layer. , a bonding step of obtaining a substrate with a photosensitive composition layer having the photosensitive composition layer and the temporary support in this order;
    A peeling step of peeling the temporary support from the substrate with the photosensitive composition layer;
    An exposure step of pattern-exposing the photosensitive composition layer by bringing the surface of the substrate with the photosensitive composition layer from which the temporary support has been removed on the side opposite to the substrate side into contact with a photomask,
    a developing step of developing the exposed photosensitive composition layer with a developer to form a pattern;
    a metal plating layer forming step of forming a metal plating layer by plating on the seed layer in the region where the pattern is not arranged;
    a protective layer forming step of forming a protective layer on the metal plating layer;
    a removing step of removing the pattern;
    a seed layer removing step of removing the exposed seed layer to obtain a conductive thin line;
    A method for producing circuit wiring, wherein the glass transition temperature X of the photosensitive composition layer is 110° C. or lower, and the glass transition temperature Y determined by measurement Y is 125° C. or higher.
    Measurement Y: The surface of the photosensitive composition layer of the transfer film opposite to the temporary support side is brought into contact with the substrate, the transfer film and the substrate are bonded together, and from the obtained laminate the The temporary support is peeled off, and the entire surface of the photosensitive composition layer in the laminate from which the temporary support is peeled is exposed under the same exposure conditions as in the exposure step, and then the resulting cured film. The glass transition temperature is measured and defined as the glass transition temperature Y.
PCT/JP2022/006659 2021-02-26 2022-02-18 Method for manufacturing laminate and method for manufacturing circuit wiring WO2022181485A1 (en)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009038082A1 (en) * 2007-09-18 2009-03-26 Asahi Kasei E-Materials Corporation Photosensitive resin composition and laminate thereof
JP2020126251A (en) * 2015-04-08 2020-08-20 旭化成株式会社 Photosensitive resin composition

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009038082A1 (en) * 2007-09-18 2009-03-26 Asahi Kasei E-Materials Corporation Photosensitive resin composition and laminate thereof
JP2020126251A (en) * 2015-04-08 2020-08-20 旭化成株式会社 Photosensitive resin composition

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