WO2022181539A1 - 導体パターンを有する積層体の製造方法 - Google Patents

導体パターンを有する積層体の製造方法 Download PDF

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Publication number
WO2022181539A1
WO2022181539A1 PCT/JP2022/006927 JP2022006927W WO2022181539A1 WO 2022181539 A1 WO2022181539 A1 WO 2022181539A1 JP 2022006927 W JP2022006927 W JP 2022006927W WO 2022181539 A1 WO2022181539 A1 WO 2022181539A1
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Prior art keywords
photosensitive layer
laminate
conductor pattern
exposure
mass
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PCT/JP2022/006927
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English (en)
French (fr)
Japanese (ja)
Inventor
壮二 石坂
悠 鬼塚
浩二 新田
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Fujifilm Corp
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Fujifilm Corp
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Priority to CN202280016396.1A priority Critical patent/CN116917806A/zh
Priority to JP2023502388A priority patent/JPWO2022181539A1/ja
Publication of WO2022181539A1 publication Critical patent/WO2022181539A1/ja
Anticipated expiration legal-status Critical
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • 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
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/09—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
    • 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 method for manufacturing a laminate having conductor patterns.
  • Patent Document 1 discloses a photosensitive resin laminate obtained by sequentially laminating a predetermined intermediate layer and a predetermined photosensitive resin layer on a support film.
  • an object of the present invention is to provide a method for manufacturing a laminate having a conductor pattern that can produce a laminate having a conductor pattern with excellent linearity.
  • a transfer film having a temporary support and a photosensitive layer is laminated to the transfer film and the substrate such that the photosensitive layer side is in contact with the metal layer of a substrate having a metal layer on the surface.
  • process and An exposure step of pattern-exposing the photosensitive layer a development step of performing a development treatment on the exposed photosensitive layer using an aqueous solution containing an alkali metal salt to form a resist pattern; an etching process of performing an etching process or a plating process of performing a plating process on the metal layer in a region where the resist pattern is not arranged; a resist stripping step of stripping the resist pattern;
  • the method for manufacturing a laminate having a conductor pattern includes a removal step of removing the metal layer exposed by the resist stripping step and forming a conductor pattern on the substrate.
  • Measurement X After exposing the photosensitive layer with a line pattern having a line width and a space width of 1:1, the cross section of the resist pattern obtained by developing with the aqueous solution used in the developing step was observed. Let length X be the penetration length of the alkali metal on the side surface of the resist pattern.
  • [3] The method for producing a laminate having a conductor pattern according to [1] or [2], wherein the photosensitive layer contains a polymerization initiator and a polymerizable compound.
  • [4] The method for producing a laminate having a conductor pattern according to [3], wherein the polymerizable compound contains a polymerizable compound having a functionality of two or more.
  • [5] The method for producing a laminate having a conductor pattern according to [3] or [4], wherein the polymerizable compound contains a trifunctional or higher polymerizable compound.
  • [6] The method for producing a laminate having a conductor pattern according to any one of [3] to [5], wherein the polymerizable compound contains a polymerizable compound having an ethyleneoxy group.
  • the intermediate layer contains one or more selected from the group consisting of water-soluble cellulose derivatives, polyhydric alcohols, alkylene oxide adducts of polyhydric alcohols, polyethers, phenol derivatives, and amide compounds [12]. Or a method for producing a laminate having a conductor pattern according to [13]. [15] Between the bonding step and the exposure step, the temporary support peeling step is provided, The method for producing a laminate having a conductor pattern according to any one of [1] to [11], wherein the exposure step is a step of performing pattern exposure through a photomask.
  • the temporary support peeling step Manufacture of a laminate having a conductor pattern according to any one of [1] to [11], wherein the exposure step is a step of performing pattern exposure by bringing the exposed surface of the photosensitive layer into contact with a photomask. Method.
  • the temporary support peeling step is provided, The method for producing a laminate having a conductor pattern according to any one of [12] to [14], wherein the exposure step is a step of performing pattern exposure by bringing the exposed surface of the intermediate layer into contact with a photomask. .
  • the temporary support peeling step is provided, The method for producing a laminate having a conductor pattern according to any one of [1] to [11], wherein the exposure step is a step of performing pattern exposure through a photomask.
  • FIG. 4 is a partial schematic diagram of a cross section of a laminate having a line-shaped resist pattern; It is a schematic diagram which shows an example of a transfer film.
  • a numerical range represented by "to” means a range including the numerical values 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 the numerical range described in other steps.
  • the upper limit or lower limit described in a certain numerical range may be replaced with the values shown in the examples.
  • process is not only an independent process, but even if it cannot be clearly distinguished from other processes, it is included in this term as long as the intended purpose of the process is achieved. .
  • the term “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 a spectrophotometer U-3310 manufactured by Hitachi, Ltd., for example.
  • the weight average molecular weight (Mw) and number average molecular weight (Mn) are measured using TSKgel GMHxL, TSKgel G4000HxL, or TSKgel G2000HxL (all manufactured by Tosoh Corporation). (trade name), THF (tetrahydrofuran) as an eluent, a differential refractometer as a detector, polystyrene as a standard substance, and a value converted using polystyrene as a standard substance measured by a gel permeation chromatography (GPC) analyzer. is.
  • GPC gel permeation chromatography
  • the molecular weight of a compound having a molecular weight distribution is the weight average molecular weight (Mw).
  • Mw weight average molecular weight
  • the content of metal elements is a value measured using an inductively coupled plasma (ICP) spectroscopic analyzer.
  • (meth)acryl is a concept that includes both acryl and methacryl
  • (meth)acryloyloxy group is a concept that includes both acryloyloxy and methacryloyloxy groups
  • (meth)acrylamide group is a concept that includes both acrylamide group and methacrylamide group
  • (meth)acrylate is a concept that includes both acrylate and methacrylate.
  • alkali-soluble means that the solubility in 100 g of a 1% by mass sodium carbonate aqueous solution with a liquid temperature of 22°C is 0.1 g or more.
  • an alkali-soluble resin is intended to be a resin that satisfies the solubility conditions described above.
  • 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.
  • water-soluble resin is intended a resin that satisfies the solubility conditions set forth above.
  • the "solid content" of the composition means a component that forms a composition layer (e.g., photosensitive layer or intermediate layer) formed using the composition, and the composition contains solvents (e.g., organic solvents and water). etc.) means all ingredients except the solvent.
  • a liquid component is also regarded as a solid content.
  • the method for producing a laminate having a conductor pattern of the present invention comprises: A transfer film having a temporary support and a photosensitive layer is laminated to the transfer film and the substrate such that the photosensitive layer side is in contact with the metal layer of a substrate having a metal layer on the surface.
  • the method for manufacturing a laminate having a conductor pattern includes a removal step of removing the metal layer exposed by the resist stripping step and forming a conductor pattern on the substrate.
  • Measurement X After exposing the photosensitive layer with a line pattern having a line width and a space width of 1:1, the cross section of the resist pattern obtained by developing with the aqueous solution used in the developing step was observed. Let length X be the penetration length of the alkali metal on the side surface of the resist pattern.
  • the length X obtained by the measurement X of the photosensitive layer used in the method of the present invention is 1.0 ⁇ m or less. That is, penetration of the developer used in the development step is suppressed in the exposed portion of the photosensitive layer used in the method of the present invention.
  • the resist pattern formed from the photosensitive layer tends to spread toward the bottom, and the fluctuation of the shape of the bottom tends to increase. It is believed that forming a conductor pattern using such a resist pattern will adversely affect the linearity of the obtained conductor pattern.
  • the length X is 1.0 ⁇ m or less and the permeation of the developer is suppressed, the spread of the bottom of the resist pattern formed from the photosensitive layer is suppressed, and a bottom shape is formed. Also, the fluctuation of the shape is suppressed. And, as a result of forming a conductor pattern using such a resist pattern, it is believed that the linearity of the obtained conductor pattern is also improved. Also, the method of the present invention can form a conductor pattern with a small line width.
  • the more excellent linearity of the conductor pattern of the laminate and/or the smaller line width of the conductor pattern of the laminate is also referred to as the more excellent effect of the present invention.
  • the length X determined by the measurement X is 1.0 ⁇ m or less, preferably 0.6 ⁇ m or less, more preferably 0.4 ⁇ m or less. There is no lower limit to the length X, which is, for example, 0.0 ⁇ m or more.
  • Measurement X is performed as follows. Measurement X: After exposing the photosensitive layer with a line pattern having a line width and a space width of 1:1, the cross section of the resist pattern obtained by developing with the aqueous solution used in the developing step is observed, and the resist pattern is measured. Let length X be the penetration length of the alkali metal on the side surface.
  • measurement X using the transfer film used in the method of the present invention, on a substrate having a metal layer on the surface used in the method of the present invention, lamination under the same conditions as in the method of the present invention
  • the photosensitive layer disposed after the process and the temporary support peeling process is used as the measurement X target.
  • the transfer film, the photosensitive layer, the substrate having a metal layer on its surface, the bonding step, and the temporary support peeling step will be described later.
  • the same exposure light source as that used for exposure in the method of the present invention is used.
  • the amount of exposure is adjusted so that a resist pattern having a line width and a space width of 1:1 can be obtained after development.
  • the transfer film has an intermediate layer, which will be described later, and the photosensitive layer disposed on the substrate having a metal layer on its surface has an intermediate layer on its surface, the exposure is carried out from the intermediate layer side.
  • the line width of the resist pattern formed for the measurement X is set so that the areas where the alkali metal permeates starting from both sides of the line-shaped resist pattern (hereinafter also simply referred to as “line”) do not overlap.
  • the line width may be 10 ⁇ m.
  • the pattern of the photomask used for exposure is appropriately adjusted so that a line with an appropriate width can be obtained.
  • measurement X after exposure, development is performed under the same conditions as in the development step carried out in the method of the present invention.
  • the developer (aqueous solution) used for development is also the same developer (aqueous solution) used in the development step carried out in the method of the present invention. The developing process and developer will be described later.
  • the laminate having the obtained resist pattern is cut in the direction perpendicular to the length direction of the lines, and the cross section of the resist pattern is observed.
  • JSM-7200F type FE-SEM field emission scanning electron microscope
  • SEM-EDX scanning electron microscope-energy dispersive X-ray analysis
  • a region from the outermost surface of the side wall of the resist pattern to a portion where the detection intensity of the alkali metal on the inner side of the resist pattern is half of the above peak is defined as a region where the alkali metal permeates.
  • FIG. 1 is a partial schematic view of a cross section (a cross section perpendicular to the length direction of the line) of a laminate having a linear resist pattern (line), and the laminate is a substrate having a metal layer on its surface. 101 and a line-shaped resist pattern (line) 107 are sequentially provided. A substrate 101 having a metal layer on its surface has a substrate 103 and a metal layer 105 in this order.
  • the line 107 has a region 109 in which the alkali metal has permeated and a region 111 in which the alkali metal has not permeated.
  • the length x is the length of the region where alkali metal penetration occurs.
  • the length x means the length in the width direction of the line, in the cross-sectional view of the line, in the area where the alkali metal permeates from the side surface of the line.
  • FIG. 1 shows a line with no skirting, but when the line is skirted (for example, in the vicinity of the metal layer 105 in the line 107, the width of the line 107 is widened). case), the length x is obtained at a position where the line width does not increase due to skirting.
  • the length x is determined from 10 random lines on the cross section of the laminate, and the average value is defined as the length X (the penetration length of the alkali metal) determined by the measurement X.
  • the photosensitive layer used in the method of the present invention preferably has a crosslinking reaction amount of 0.10 mmol/g or more, more preferably 0.20 mmol/g or more, as determined by the formula Y described below. , 0.30 mmol/g or more.
  • the upper limit of the amount of crosslinking reaction is preferably 1.20 mmol/g or less, more preferably 1.00 mmol/g or less, and even more preferably 0.80 mmol/g or less.
  • A is the value of the double bond equivalent (unit: mmol/g) of the photosensitive layer before exposure.
  • the double bond equivalent means the content of polymerizable carbon-carbon double bonds with respect to the total weight of the photosensitive layer.
  • the above double bond equivalent is determined by measuring the photosensitive layer with FT-IR (Fourier Transform Infrared Spectroscopy).
  • the value of Ammol/g is, for example, 0.50 to 3.20 mmol/g, preferably 0.60 to 2.60 mmol/g, more preferably 1.20 to 2.50 mmol/g.
  • B exposes the photosensitive layer using a high-pressure mercury lamp exposure machine so that the exposure amount of light with a wavelength of 365 nm is 20 mJ/cm 2 (overall exposure), and the photosensitive layer after exposure is FT.
  • - means the double bond reaction rate (unit: %) obtained by observing with IR.
  • the dominant wavelength of the high pressure mercury lamp exposure machine is 365 nm.
  • MAP-1200L manufactured by Dainippon Kaken Co., Ltd. is usually used. That is, the amount of carbon-carbon double bonds in the photosensitive layer before exposure is 100%, the amount of carbon-carbon double bonds in the photosensitive layer after exposure (Z%) is obtained, and Z is calculated from 100.
  • the value obtained by subtraction is the value of B.
  • the amount of carbon-carbon double bonds in the photosensitive layer before and after exposure is measured by FT-IR.
  • the B% value is preferably 5 to 70%, more preferably 10 to 50%.
  • the photosensitive layer used for determining the value of B is formed by the method of the present invention on a substrate having a metal layer on the surface used in the method of the present invention using the transfer film used in the method of the present invention. It is preferable that the photosensitive layer is arranged by carrying out the lamination step and the temporary support peeling step under the same conditions as those carried out.
  • the transfer film has an intermediate layer described below and the photosensitive layer disposed on the substrate having a metal layer on its surface has an intermediate layer on its surface, the exposure for obtaining the value of B is performed on the intermediate layer. do it from the side.
  • the exposure for obtaining the value of B is performed in the same manner as the exposure step performed in the method of the present invention except for the items specified as the exposure conditions for obtaining the value of B as described above. is preferred.
  • the film thickness of the photosensitive layer exposed using a high-pressure mercury lamp exposing machine is assumed to be 3 ⁇ m.
  • the test is performed after adjusting the thickness of the photosensitive layer to 3 ⁇ m.
  • the photosensitive layer of the transfer film is adjusted in advance by scraping to a thickness of 3 ⁇ m, and then the transfer film is used.
  • a procedure for determining the value of B may be performed.
  • the transfer film may be cooled appropriately.
  • the thickness of the photosensitive layer of the transfer film can be adjusted to 3 ⁇ m by the following procedure. That is, first, the photosensitive layer of the transfer film is scraped out, and a solution is prepared by dissolving the scraped photosensitive layer in an organic solvent (PGMEA: propylene glycol monomethyl ether acetate, etc.). The solution is applied on a release film and then dried to obtain a coating film (a photosensitive layer formed using the solution).
  • PMEA propylene glycol monomethyl ether acetate
  • the film thickness of the coating film is adjusted so as to be 3 ⁇ m in total with the film thickness of the photosensitive layer of the transfer film.
  • the transfer film is laminated on the coating film arranged on the surface of the release film so that the photosensitive layer overlaps.
  • a photosensitive layer having a total thickness of 3 ⁇ m which is composed of the coating film (the photosensitive layer formed using the solution) and the original photosensitive layer of the transfer film, is transferred.
  • the film will have.
  • the release film is removed from the transfer film, and a procedure for obtaining the value of B is performed using the transfer film having the photosensitive layer (a photosensitive layer having a total thickness of 3 ⁇ m). good.
  • the transfer film, the photosensitive layer, the substrate having a metal layer on its surface, the bonding step, and the temporary support peeling step will be described later.
  • the method of the present invention is roughly divided into a method of manufacturing a laminate having a conductor pattern through an etching process and a method of manufacturing a laminate having a conductor pattern through a plating process.
  • the method of manufacturing a laminate having a conductor pattern through an etching process is also referred to as the first embodiment of the method of the present invention.
  • a method of manufacturing a laminate having a conductor pattern through a plating process is also called a second embodiment of the method of the present invention. First, the first embodiment will be described, and then the second embodiment will be described.
  • the first embodiment of the present invention has at least the following steps (1-1) to (1-5) in order.
  • Step (1-1) laminate step: a transfer film having a temporary support and a photosensitive layer so that the photosensitive layer side is in contact with the metal layer of a substrate having a metal layer on the surface, A step of bonding the transfer film and the substrate.
  • Step (1-2) exposure step: a step of pattern-exposing the photosensitive layer
  • Step (1-3) development step): using an aqueous solution containing an alkali metal salt on the exposed photosensitive layer Steps and steps (1-4)
  • etching step of developing and forming a resist pattern: a step of etching the metal layer in the region where the resist pattern is not arranged.
  • Step (1-5) resist stripping step: a step of stripping the resist pattern
  • the first embodiment of the present invention includes steps (1-1) and (1-2), or step (1-2). ) and (1-3) have the following step (1-A).
  • Step (1-A) temporary support stripping step: a step of stripping the temporary support.
  • the length X obtained by the above measurement X is within a predetermined range.
  • the photosensitive layer used in the first embodiment of the present invention preferably has a cross-linking reaction amount determined by the formula Y within a predetermined range.
  • a transfer film having a temporary support and a photosensitive layer is bonded to the substrate such that the photosensitive layer is in contact with the metal layer of a substrate having a metal layer on its surface. It is a process of matching.
  • 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 transfer film preferably further has an intermediate layer between the temporary support and the photosensitive layer. The transfer film will be described later.
  • the photosensitive layer side of the transfer film (the surface opposite to the temporary support side) is brought into contact with the metal layer on the substrate and pressed.
  • the pressure-bonding method include known transfer methods and lamination methods, and a method in which the surface of the photosensitive layer of the transfer film opposite to the temporary support side is superimposed on the substrate, and pressure and heat are applied using rolls or the like is preferable.
  • 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.
  • a substrate having a metal layer on its surface has a substrate and a metal layer disposed on the surface of the substrate.
  • the substrate with a metal layer any layer other than the above metal layer may be formed on the substrate, if necessary. That is, the substrate with a metal layer preferably has at least a substrate and a metal layer arranged on the surface of the substrate.
  • substrates include resin substrates, glass substrates, ceramic substrates, and semiconductor substrates, and substrates described in paragraph [0140] of WO2018/155193 are preferable.
  • As a material for the resin substrate polyethylene terephthalate, cycloolefin polymer, or polyimide is preferable.
  • the thickness of the resin substrate is preferably 5-200 ⁇ m, more preferably 10-100 ⁇ m.
  • a transparent substrate when using a photomask including light shielding portions arranged in a mesh pattern, it is preferable to use a transparent substrate.
  • transparent means that the transmittance of the exposure wavelength is 50% or more.
  • the total light transmittance is preferably 80% or more, more preferably 90%, and even more preferably 95%.
  • 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 transparent substrate is preferably a polyamide film, a polyethylene terephthalate film, a cycloolefin polymer, a polyethylene naphthalate film, a polyimide film, or a polycarbonate film, and more preferably a polyethylene terephthalate film.
  • 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 perpendicular to the main surface of the transparent substrate (that is, thickness direction). Based on the observed image obtained, the thickness of the transparent base material is measured at 10 points.
  • the average thickness of the transparent substrate is determined by arithmetically averaging the measured values.
  • the base material may be a silicon substrate, a glass substrate, or FR4 (Flame Retardant Type 4) or the like is preferably used.
  • the thickness of the base material is not particularly limited, and the wiring pattern may be formed on a part of the base material, and the wiring layer may be laminated.
  • a photomask including light shielding portions arranged in circular dots or openings arranged in circular dots will be described later.
  • the metal layer is a layer containing metal, and the metal is not particularly limited, and known metals can be used.
  • the metal layer is a conductive layer.
  • Main components (so-called main metals) of the metal layer include, for example, copper, chromium, lead, nickel, gold, silver, tin, and zinc.
  • the said main component intends the metal with the largest content among the metals contained in a metal layer.
  • the thickness of the metal layer is not particularly limited, preferably 50 nm or more, more preferably 100 nm or more. Although the upper limit is not particularly limited, it is preferably 2 ⁇ m or less.
  • the method for forming the metal layer is not particularly limited, and examples 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.
  • One or more metal layers may be arranged on the substrate.
  • the two or more metal layers may be the same or different, and are preferably made of different materials.
  • a substrate having at least one of a transparent electrode and lead wiring is also preferable, and the 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 metal fine 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, Copper is more preferred.
  • the exposure step is a step of patternwise exposing the photosensitive 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 direction the exposure may be performed from the side of the photosensitive layer or the side opposite to the side of the photosensitive layer (substrate side).
  • the exposure step is typically a step of performing pattern exposure through a photomask. In the exposure step, the photomask and the layered product to be exposed may or may not be in contact with each other.
  • the exposure step includes the substrate side of the laminate from which the temporary support obtained in the temporary support peeling step has been peeled off.
  • the exposure step is carried out by bringing the surface on the opposite side into contact with a photomask and performing pattern exposure.
  • the surface (the surface of the photosensitive layer, the surface of the intermediate layer, etc.) exposed by peeling the temporary support of the laminate from which the temporary support is peeled off is brought into contact with the photomask, and the photosensitive layer is exposed.
  • An exposure step in which the layer is pattern-exposed is preferred.
  • the transfer film has a two-layer structure of a temporary support and a photosensitive layer
  • the exposed surface corresponds to the surface of the photosensitive layer
  • the transfer film includes the temporary support, the intermediate layer, and the photosensitive layer.
  • the surface of the intermediate layer corresponds.
  • a curing reaction of the components contained in the photosensitive layer may occur in the exposed regions of the photosensitive layer (regions corresponding to the openings of the photomask).
  • a development step is performed after the exposure to remove the non-exposed areas of the photosensitive layer to form a pattern.
  • the method of the present invention has a photomask stripping step of stripping 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 that can irradiate at least light in a wavelength range (for example, 365 nm and 405 nm) capable of curing the photosensitive layer, and 365 nm is preferable.
  • a wavelength range for example, 365 nm and 405 nm
  • 365 nm is preferable.
  • 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.
  • a temporary support peeling step is performed between the bonding step and the exposure step, or between the exposure step and the developing step. Above all, it is more preferable to have a peeling step between the bonding step and the exposure 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 development step is a step of developing the exposed photosensitive layer using an aqueous solution containing an alkali metal salt as a developer to form a pattern. By developing with the developer, the non-exposed regions of the photosensitive layer are removed, and a resist pattern having projections corresponding to the openings of the photomask is formed.
  • an alkaline aqueous solution containing an alkali metal salt is preferred.
  • the alkali metal salt contained in the developer is preferably a compound that dissolves in water and exhibits alkalinity.
  • Alkali metal salts include, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, and potassium hydrogen carbonate.
  • the developer may contain compounds other than alkali metal salts that dissolve in water and exhibit alkalinity.
  • Examples of such compounds include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutyl ammonium hydroxide and choline (2-hydroxyethyltrimethylammonium hydroxide).
  • the content of water in the developer is preferably 50% by mass or more and less than 100% by mass, more preferably 90% by mass or more and less than 100% by mass, relative to the total mass of the developer.
  • the content of the alkali metal salt in the developer is preferably 0.01 to 20% by mass, more preferably 0.1 to 10% by mass, based on the total mass of the developer.
  • 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.
  • a rinse treatment for removing the developer remaining on the substrate with the metal layer before proceeding to the next step.
  • Water or the like can be used for the rinsing treatment.
  • a drying treatment for removing excess liquid from the substrate with the metal layer may be performed.
  • the position and size of the resist pattern formed on the metal layer-coated substrate are not particularly limited, but fine lines are preferred.
  • the line width of the resist 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.
  • a lower limit is 1.0 micrometers or more, for example.
  • Step (1-B) post-exposure step
  • Step (1-C) post-baking step
  • the resist pattern obtained on the substrate with the metal layer is further exposed (hereinafter, “step (1-B)” or “post Also referred to as an exposure step”) and/or a heating step (hereinafter also referred to as a “step (1-C)” or a “post-baking step”).
  • step (1-B) post-exposure step
  • step (1-C) post-exposure step
  • post-C post-baking 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.
  • the etching step is a step of etching the metal layer in the region where the resist pattern is not arranged. Specifically, in the etching step, the resist pattern obtained by the above steps is used as an etching resist to etch the metal layer. When the etching process is performed, the metal layer is removed at the openings of the resist pattern, and the metal layer has the same pattern shape as the resist pattern.
  • 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 Wet etching by immersion and dry etching such as 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 at least one selected from the group consisting of an acidic compound, ferric chloride, ammonium fluoride, and potassium permanganate. and an acidic mixed aqueous solution of
  • the acidic compound contained in the acidic aqueous solution is preferably at least one selected from the group consisting of hydrochloric acid, sulfuric acid, nitric acid, acetic acid, hydrofluoric acid, oxalic acid, and phosphoric acid.
  • 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, etc.).
  • Examples of alkaline compounds contained in the alkaline aqueous solution include sodium hydroxide, potassium hydroxide, ammonia, organic amines, and salts of organic amines (e.g., tetramethylammonium hydroxide etc.) is preferred.
  • the etchant preferably does not dissolve the resist pattern.
  • the developer used in the development step may also serve as the etchant used in the etching process. In this case, the development process and the etching process may be performed simultaneously.
  • etching treatment it is also preferable to perform a rinsing treatment to remove the etchant remaining on the substrate with the metal layer before proceeding to the next step.
  • a rinsing treatment Water or the like can be used for the rinse treatment.
  • a drying process for removing excess liquid from the substrate with the metal layer may be performed.
  • the resist stripping process is a process of removing the remaining resist pattern after the etching process.
  • a method of removing the remaining resist pattern includes, for example, a method of removing by chemical treatment, and a method of removing using a remover is preferable.
  • Examples of the method for removing the remaining resist pattern include a method of removing by a known method such as a spray method, a shower method, or a puddle method using a remover.
  • stripping solutions include removal solutions in which an alkaline compound is dissolved in at least one selected from the group consisting of water, dimethylsulfoxide, and N-methylpyrrolidone.
  • alkaline compounds compounds that exhibit alkalinity when dissolved in water
  • alkaline inorganic compounds such as sodium hydroxide and potassium hydroxide, primary amine compounds, secondary amine compounds, and tertiary amine compounds.
  • alkaline organic compounds such as quaternary ammonium salt compounds.
  • the liquid temperature of the stripping 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 stripping solution being stirred at a liquid temperature of 50 to 80° C. for 1 to 30 minutes. It is also preferable that the stripping solution does not dissolve the metal layer.
  • a rinse treatment for removing the stripping solution remaining on the substrate.
  • Water or the like can be used for the rinse treatment.
  • a drying process for removing excess liquid from the substrate may be performed.
  • the resist pattern remaining on the substrate is removed, thereby removing the metal layer existing between the substrate and the resist pattern (the metal layer having the same pattern shape as the removed resist pattern).
  • a laminate having a conductive pattern exposed on the surface is obtained.
  • the second embodiment of the present invention has at least the following steps (2-1) to (2-6) in order.
  • Step (2-1) laminate step: a transfer film having a temporary support and a photosensitive layer so that the photosensitive layer side is in contact with the metal layer of a substrate having a metal layer on the surface, A step of bonding the transfer film and the substrate.
  • Step (2-5) resist stripping step: a step of stripping the resist pattern
  • Step (2-6) removing the metal layer exposed by the resist stripping step, and placing the conductor pattern on the substrate
  • Step (2-A) temporary support stripping step: a step of stripping the temporary support.
  • the length X obtained by the above measurement X is within a predetermined range.
  • the photosensitive layer used in the second embodiment of the present invention preferably has a cross-linking reaction amount determined by the formula Y within a predetermined range.
  • step (2-B) or “post-exposure step”
  • step (2-C) or “post-baking step”
  • You may have The steps (2-B) and (2-C) in the second embodiment are the same as the steps (1-B) and (1-C) in the first embodiment, respectively.
  • the plating step is a step of forming a plated layer by plating on the metal layer (the metal layer exposed to the surface by the development step) in the area where the resist pattern is not arranged.
  • Examples of plating methods include electroplating and electroless plating, with electroplating being preferred from the standpoint of productivity.
  • a plating layer having a pattern shape similar to that of the area where the resist pattern is not arranged (opening of the resist pattern) is obtained on the substrate with the metal layer.
  • the metal contained in the 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. Above all, the plated layer preferably contains copper or its alloy from the viewpoint of better conductivity of the conductive pattern. In addition, the plating layer preferably contains copper as a main component in order to improve the conductivity of the conductive pattern.
  • the thickness of the plating layer is preferably 0.1 ⁇ m or more, more preferably 1 ⁇ m.
  • the upper limit is preferably 20 ⁇ m or less.
  • the protective layer laminating step is a step of forming a protective layer on the plating layer.
  • a material for the protective layer a material having resistance to stripping solution and/or etching solution in the resist stripping process and/or removal process is preferable. Examples include metals such as nickel, chromium, tin, zinc, magnesium, gold, and silver, alloys thereof, and resins. Among them, nickel or chromium is preferable as the material for the protective layer.
  • Examples of methods for forming the protective layer include electroless plating and electroplating, with electroplating being preferred.
  • the lower limit of the thickness of the protective layer is not particularly limited, it is preferably 0.3 ⁇ m or more, more preferably 0.5 ⁇ m or more.
  • the upper limit is not particularly limited, it is preferably 3.0 ⁇ m or less, more preferably 2.0 ⁇ m or less.
  • resist stripping step is a step of removing the remaining resist pattern after the plating step or protective layer forming step.
  • Step (2-5) can be performed in the same manner as step (1-5) described in the first embodiment.
  • the removal step is a step of removing the metal layer exposed by the resist stripping step to obtain a conductor pattern on the substrate.
  • the plating layer formed by the plating step is used as an etching resist, and the metal layer located in the non-pattern forming region (in other words, the region not protected by the plating layer) is etched.
  • the method for removing part of the metal layer is not particularly limited, it is preferable to use a known etchant.
  • known etching solutions include ferric chloride solution, cupric chloride solution, ammonia alkali solution, sulfuric acid-hydrogen peroxide mixed solution, and phosphoric acid-hydrogen peroxide mixed solution. .
  • the metal layer exposed to the surface from the substrate is removed, and the plated layer (conductor pattern) having a pattern shape remains to obtain a laminate having the conductor pattern.
  • the upper limit of the line width of the formed conductor pattern is preferably 8 ⁇ m or less, more preferably 6 ⁇ m or less. Although the lower limit is not particularly limited, it is often 2 ⁇ m or more.
  • the method of the present invention may have other steps in addition to the above steps.
  • Other steps include, for example, the step of reducing the visible light reflectance described in paragraph [0172] of WO 2019/022089 and the surface of the insulating film described in paragraph [0172] of WO 2019/022089 , a step of forming a new conductive layer.
  • the method of the present invention may include a step of performing a process for reducing the visible light reflectance of part or all of the conductor pattern of the laminate.
  • the treatment for reducing the visible light reflectance includes, for example, oxidation treatment.
  • the method of the present invention may include a step of forming an insulating film on the surface of the laminate having the conductor pattern, and a step of forming a new conductive layer (such as a conductor pattern) on the surface of the insulating film.
  • a first electrode pattern and an insulated second electrode pattern can be formed.
  • Examples of the process of forming the insulating film include 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 the present invention uses a substrate having a plurality of conductive layers (such as metal layers) on both surfaces of the laminate, and sequentially or simultaneously using the conductive layers formed on both surfaces of the substrate. It is also preferred to form 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.
  • conductive layers such as metal layers
  • the method for producing a laminate according to the present invention includes the production of conductive films such as touch panels, transparent heaters, transparent antennas, electromagnetic shielding materials, and light control films; the production of printed wiring boards and semiconductor packages; Manufacture of interconnect pillars and pins; Manufacture of metal masks; Manufacture of tape substrates such as COF (Chip on Film) and TAB (Tape Automated Bonding); Moreover, as said touch panel, a capacitive touch panel is mentioned.
  • the method for manufacturing a laminate according to the present invention can be used for forming a conductive film and peripheral circuit wiring in a touch panel.
  • the touch panel can be applied to, for example, display devices such as organic EL (electro-luminescence) display devices and liquid crystal display devices.
  • a photomask including a light shielding portion arranged in a mesh pattern is used during the exposure step.
  • the mode of using is mentioned.
  • the manufacturing method described above is suitable as a method for manufacturing a mesh-like metal wiring pattern.
  • a laminate having a conductive pattern 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.
  • the sheet resistance value of the mesh pattern region is preferably as low as possible, preferably 100 ⁇ / ⁇ or less, more preferably 20 ⁇ / ⁇ or less, and particularly preferably 5 ⁇ / ⁇ or less.
  • the second embodiment light shielding portions arranged in circular dots are formed during the exposure step.
  • An embodiment using a photomask containing The manufacturing method described above can be suitably used as a method for manufacturing vias and a method for manufacturing pillars and pins for interconnects between semiconductor chips and 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.
  • a photomask including openings arranged in the form of circular dots is used in the exposure step.
  • the manufacturing method described above is suitable 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 method for manufacturing a laminate having a conductor pattern manufactured by the method of the present invention for example, in the first embodiment, light shielding portions arranged in circular dots are formed during the exposure step.
  • An embodiment using a photomask containing The manufacturing method described above is suitable 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 or less.
  • 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 transfer film used in the method of the invention has a temporary support and a photosensitive layer.
  • the length X determined by the measurement X described above is within a predetermined range.
  • the photosensitive layer used in the first embodiment of the present invention preferably has a cross-linking reaction amount determined by the formula Y within a predetermined range.
  • the transfer film may have other layers in addition to the photosensitive layer described below. Other layers include, for example, an intermediate layer to be described later. Moreover, 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 (2).
  • the transfer film preferably has an intermediate layer, and the following configuration (2) is more preferable.
  • a negative photosensitive 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 obtain a three-dimensional surface image.
  • 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.
  • the photosensitive layer of the transfer film when it has another composition layer (for example, a photosensitive layer and / or an intermediate layer, etc.) on the side opposite to the temporary support side of the photosensitive layer, another composition
  • another composition layer for example, a photosensitive layer and / or an intermediate layer, etc.
  • the total thickness of the layers is preferably 0.1 to 30%, more preferably 0.1 to 20%, of the thickness of the photosensitive layer.
  • the transmittance of the photosensitive layer for light with a wavelength of 365 nm is preferably 10% or more, more preferably 30% or more, and even more preferably 50% or more.
  • the upper limit is preferably 99.9% or less, more preferably 99.0% or less.
  • the transfer film 10 shown in FIG. 2 has a temporary support 11, a composition layer 17 including an intermediate layer 13 and a photosensitive layer 15, and a protective film 19 in this order.
  • the transfer film 10 shown in FIG. 2 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 layer and an intermediate 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 has a temporary support.
  • the temporary support is a member that supports the photosensitive layer, and is finally removed by the temporary support peeling process.
  • 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.
  • films include polyethylene terephthalate film (e.g., biaxially stretched polyethylene terephthalate film), polymethyl methacrylate film, cellulose triacetate film, polystyrene film, polyimide film, and polycarbonate film, and polyethylene terephthalate film is 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, even 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 layer may be subjected to a surface modification treatment.
  • Surface modification treatment includes, for example, treatment 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 (LEDs) may be mentioned.
  • low-pressure mercury lamps high-pressure mercury lamps
  • ultra-high-pressure mercury lamps carbon arc lamps
  • metal halide lamps metal halide lamps
  • xenon lamps xenon lamps
  • chemical lamps electrodeless discharge lamps
  • LEDs 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 and Lumirror 16FB40 (manufactured by Toray Industries, Inc.); Cosmoshine A4100, Cosmoshine A4300, and Cosmoshine A8300 (manufactured by Toyobo).
  • the transfer film has a photosensitive layer.
  • a photosensitive layer As the photosensitive layer, a negative photosensitive layer is preferred.
  • the photosensitive layer is a negative photosensitive layer, the pattern formed corresponds to a cured film.
  • the photosensitive layer preferably contains a resin to be described later and a polymerizable compound to be described later, or preferably contains a polymerizable compound to be described later and a polymerization initiator to be described later. It is more preferable to contain a polymerizable initiator, which will be described later.
  • the resin described later contains an alkali-soluble resin. That is, the photosensitive layer preferably contains a resin containing an alkali-soluble resin and a polymerizable compound.
  • the photosensitive layer contains 10.0 to 90.0% by weight of a resin, 5.0 to 70.0% by weight of a polymerizable compound, and 0.01 of a polymerization initiator, based on the total weight of the photosensitive layer. It is preferable to contain up to 20.0% by mass. Each component that the photosensitive layer may contain will be described below.
  • the photosensitive layer may contain a resin.
  • a resin an alkali-soluble resin is preferable.
  • 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. % or more 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 content of structural units derived from monomers having aromatic hydrocarbon groups 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 a monomer having an aralkyl group or styrene, more preferably styrene.
  • monomers having an aralkyl group 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 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.
  • the aralkyl group includes, for example, a phenylalkyl group optionally having a substituent (excluding a benzyl group) and a benzyl group optionally having a substituent.
  • An optional benzyl group 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. and preferably a (meth)acrylate having a benzyl group, more preferably a benzyl (meth)acrylate.
  • 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 It is preferably obtained by polymerizing at least one of the second monomers.
  • 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.
  • the structural unit derived from the first monomer in the resin may react with the third structural unit.
  • the content of structural units derived from the first monomer and not reacted with the third monomer in the resin is 0 with respect to the total mass of the resin. ⁇ 50.0% by mass is preferable, 0.0 to 20.0% by mass is more preferable, and 0.0 to 10.0% by mass is even more preferable.
  • the second monomer is a monomer that is non-acidic 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 below, 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 (meth)acrylates such as 2-ethylhexyl (meth)acrylate; esters of vinyl alcohol such as vinyl acetate; and (meth)acrylonitrile.
  • methyl (meth)acrylate, ethyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, or n-butyl (meth)acrylate is preferable, and methyl (meth)acrylate or ethyl (meth)acrylate is more preferable.
  • 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 (meth)acrylic acid and tert-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, and cyclohexyl (meth)acrylate, (nor)bornyl (meth)acrylate, isobornyl (meth)acrylate, More preferred is 2-adamantyl (meth)acrylate or tricyclodecane (meth)acrylate.
  • 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. It is also preferred that the resin having polymerizable groups also meet the preferred requirements as described above or below.
  • 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 its molecule, preferably a monomer having two polymerizable groups in its molecule.
  • the polymerizable group include a polymerizable group possessed by a polymerizable compound to be described later.
  • the third monomer preferably has two kinds 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, allyl (meth)acrylate, and the like.
  • 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 groups in which these are combined. be done.
  • RN represents a hydrogen atom or 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 preferred, and 15.0 to 40.0% by mass is even more preferred.
  • a method for introducing a polymerizable group into a resin for example, epoxy compounds, blocked isocyanate compounds, isocyanate compounds, vinyl sulfone compounds, aldehyde compounds, methylol compounds, and carboxylic acid anhydrides.
  • 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 a polymerization initiator, V-601 (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) as a polymerization initiator, or V- 65 (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.) is more preferable.
  • the resin includes 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, or a structural unit derived from methacrylic acid and styrene.
  • a resin containing a structural unit derived from is preferable, and a resin containing a structural unit having a polymerizable group is more preferable.
  • the Tg of the resin is preferably 30 to 180°C, more preferably 40 to 150°C, even more preferably 50 to 120°C.
  • the acid value of the resin is preferably 220 mgKOH/g or less, more preferably 200 mgKOH/g or less, still more preferably 190 mgKOH/g or less, and particularly preferably 170 mgKOH/g or less, 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 80 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 according to JIS K0070:1992, for example.
  • 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. Resins satisfying the above acid value range preferably also satisfy the preferred requirements as described above or below.
  • the content of the resin satisfying the acid value range is preferably 10 to 100% by mass, more preferably 60 to 100% by mass, more preferably 90% by mass, based on the total resin. ⁇ 100% by mass is more preferred.
  • the I/O value of the resin is preferably 0.90 or less, more preferably less than 0.70.
  • the I/O value of the resin is preferably 0.10 or more, more preferably 0.30 or more, and even more preferably 0.50 or more.
  • the I/O value is a parameter that represents a measure of the hydrophilicity/lipophilicity of a resin.
  • For the I/O value refer to "Organic Conceptual Diagram" (Yoshio Koda, Sankyo Publishing, 1984). The closer the I/O value of the resin is to 0 (zero), the lower the polarity of the resin (lipophilicity of the resin). high hydrophilicity).
  • the I/O value is an I/O value obtained by calculating I (hydrophilicity) and O (lipophilicity) based on the chemical structure of the resin.
  • Resins satisfying the above I/O value ranges also preferably satisfy the preferred requirements as described above or below.
  • the content of the resin satisfying the I/O value range is preferably 10 to 100% by mass, more preferably 60 to 100% by mass, based on the total resin. , more preferably 90 to 100% by mass.
  • the weight average molecular weight of the resin is preferably 500,000 or less, more preferably 100,000 or less, even more preferably 30,000 or less, and particularly preferably 25,000 or less.
  • the weight average molecular weight of the resin is preferably 3,000 or more, more preferably 4,000 or more, still more preferably 5,000 or more, and particularly preferably 10,000 or more.
  • the weight average molecular weight is 500,000 or less, resolution and developability can be improved.
  • the weight-average molecular weight is 3,000 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 “edge fuse property” means the degree of easiness of protrusion of the photosensitive layer from the end face of the roll when the transfer film is wound into a roll.
  • the term “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 or the like, it will be transferred to the mask in the subsequent exposure process or the like, resulting in defective products.
  • the dispersity of the resin is preferably 1.0 to 6.0, more preferably 1.0 to 5.0, still more preferably 1.0 to 4.0, and particularly preferably 1.0 to 3.0. Resins satisfying the above weight average molecular weight and/or dispersity ranges preferably also satisfy the preferred requirements as described above or below.
  • the content of the resin that satisfies the above weight average molecular weight and/or dispersity range is preferably 10 to 100% by mass, preferably 60 to 100% by mass, based on the total resin. % is more preferred, and 90 to 100% by mass is even more preferred.
  • 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.
  • the upper limit is preferably 100.0% by mass or less with respect to the total mass of the 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 with respect to the total mass of the photosensitive layer. is more preferred, and 40.0 to 60.0% by mass is particularly preferred.
  • the resin content is 90.0% by mass or less with respect to the total mass of the photosensitive layer, the development 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 layer, the edge fuse resistance can be improved.
  • a method for synthesizing the resin for example, a method of adding an appropriate amount of a radical polymerization initiator to a solution obtained by diluting the above-described monomer with a solvent and heating and stirring the solution can be mentioned. You may synthesize
  • a solvent may be further added to adjust the desired concentration.
  • bulk polymerization, suspension polymerization, and emulsion polymerization can be used as methods for synthesizing the resin.
  • the photosensitive 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.
  • the photosensitive 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.
  • a group having a cationic polymerizable group such as an epoxy group and an oxetane group;
  • 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 from the viewpoint of better photosensitivity of the photosensitive layer.
  • Compounds having two or more ethylenically unsaturated groups (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.
  • the alkylene group is preferably an ethyleneoxy group or a propyleneoxy group, more preferably an ethyleneoxy group.
  • the number of alkyleneoxy groups added to the polymerizable compound is preferably 2 to 60, more preferably 2 to 30, and even more preferably 2 to 20 per molecule.
  • the content of the polymerizable compound having an alkyleneoxy group (preferably an ethyleneoxy group) is preferably 10 to 100% by mass, more preferably 60 to 100% by mass, based on the total polymerizable compound in the photosensitive layer, and 90 ⁇ 100% by mass is more preferred.
  • the polymerizable compound preferably contains a bifunctional or higher polymerizable compound, more preferably a trifunctional or higher polymerizable compound.
  • N is an integer of 1 or more
  • the value of N means the number of polymerizable groups (preferably ethylenically unsaturated groups) possessed by the polymerizable compound.
  • the polymerizable compound is a bifunctional or trifunctional ethylenically unsaturated group having 2 or 3 ethylenically unsaturated groups in the molecule from the viewpoint of better balance between photosensitivity, resolution and peelability of the photosensitive layer.
  • the polymerizable compound is a bifunctional polymerizable compound (preferably a bifunctional ethylenically unsaturated compound) and a trifunctional or higher polymerizable compound (preferably a trifunctional or higher ethylenically unsaturated compound). It is also preferred to include both.
  • the content of the bifunctional polymerizable compound is preferably 20.0% by mass or more, based on the total mass of the polymerizable compound, from the viewpoint of excellent peelability, and 40% by mass. More than 0.0% by mass is more preferable, 55.0% by mass or more is still 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 layer may be bifunctional polymerizable compounds.
  • the content of the trifunctional or higher polymerizable compound is 10.0 with respect to the total mass of the polymerizable compound. % by mass or more is preferable, and 20.0% by mass or more is more preferable.
  • 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 layer may be trifunctional or higher polymerizable compounds.
  • a (meth)acrylate compound having a (meth)acryloyl group as a polymerizable group is preferable.
  • the photosensitive 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; thiophene ring, furan ring, pyrrole ring, imidazole ring, triazole ring, and pyridine ring. Aromatic heterocycles such as; 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 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).
  • the F structure and the bisphenol B structure derived from bisphenol B (2,2-bis(4-hydroxyphenyl)butane) can be mentioned, with the bisphenol A structure 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.) ), 2,2-bis(4-(methacryloxyethoxypropoxy)phenyl)propane, and ethoxylated bisphenol A dimethacrylate (BPE) such as 2,2-bis(4-(methacryloxypentaethoxy)phenyl)propane series, manufactured by Shin-Nakamura Chemical Co., Ltd.), 2,2-bis(4-(methacryloxidedodecaethoxytetrapropoxy)phenyl)propane (FA-3200MY, manufactured by Hitachi Chemical Co., Ltd.), and ethoxylated (10) bisphenol A di Acrylate (NK Ester A-BPE-10, manufactured by Shin-Nakamura Chemical Co., Ltd.) can be mentioned.
  • 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, more preferably 25.0% by mass, based on the total mass of the photosensitive layer, from the viewpoint of better resolution. % or more by mass 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, and even more preferably 95.0% by mass or less, based on the total mass of the polymerizable compound, from the viewpoint of releasability.
  • the photosensitive 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 examples include alkylene glycol di(meth)acrylate, polyalkylene glycol di(meth)acrylate, urethane di(meth)acrylate, and trimethylolpropane diacrylate. be done.
  • Alkylene glycol di(meth)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
  • polyalkylene glycol di(meth)acrylate examples include polyethylene glycol di(meth)acrylate (NK Ester 4G, etc., manufactured by Shin-Nakamura Chemical Co., Ltd.), dipropylene glycol diacrylate, tripropylene glycol diacrylate, and polypropylene glycol. di(meth)acrylates (Aronix M-270, manufactured by Toagosei Co., Ltd.).
  • 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 examples 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.). is mentioned.
  • 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, isocyanurate 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 trifunctional 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 Shin-Nakamura Chemical Co., Ltd.
  • KAYARAD registered trademark
  • DPCA-20 manufactured by Nippon Kayaku Co., Ltd.
  • a -9300-1CL, etc. alkylene oxide-modified (meth)acrylate compounds
  • KAYARAD RP-1040 manufactured by Nippon Kayaku, ATM-35E and A-9300 manufactured by Shin-Nakamura Chemical Co., Ltd.
  • EBECRYL manufactured by Daicel Allnex (registered Trademark) 135, etc.
  • ethoxylated glycerin triacrylate A-GLY-9E, etc.
  • the polymerizable compound may be a polymerizable compound having an acid group (for example, a carboxyl group, etc.).
  • the acid group may form an acid anhydride group.
  • the polymerizable compound having an acid group for example, 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 polymerizable compound preferably contains a polymerizable compound having a viscosity of 10 to 30000 mPa s, more preferably a polymerizable compound having a viscosity of 300 to 5000 mPa s or more, and a polymerizable compound having a viscosity of 500 to 3000 mPa s or more. It is further preferred to contain The polymerizable compound satisfying the above viscosity range also preferably satisfies the preferred requirements as described above or below.
  • the content of the polymerizable compounds satisfying the above range of viscosity is 10 to 100 with respect to all polymerizable compounds. % by mass is preferable, 40 to 100% by mass is more preferable, and 90 to 99% by mass is even more preferable. Further, for example, the content of the polymerizable compound having a clogP of 500 or more is preferably 10 to 100% by mass, more preferably 20 to 99% by mass, more preferably 35 to 65% by mass, based on the total polymerizable compound. .
  • the viscosity of a polymerizable compound is the viscosity measured at a temperature of 25° C. using a Brookfield viscometer (TVB-15 manufactured by Toki Sangyo Co., Ltd.).
  • 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 3.0 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.
  • Polymerizable group content means the equivalent amount (mol) of polymerizable groups contained per 1 g of the polymerizable compound.
  • the polymerizable compound preferably has a clogP of 1.0 or more, more preferably 3.0 or more, still more preferably 5.0 or more, and particularly preferably more than 5.5. .
  • the clogP of the polymerizable compound is preferably 10.0 or less, more preferably 7.0 or less.
  • clogP is a value obtained by calculating the common logarithm logP of the partition coefficient P to 1-octanol and water.
  • the polymerizable compound satisfying the above clogP range preferably also satisfies the preferred requirements as described above or below.
  • the content of the polymerizable compound clogP satisfies the above range (for example, the range of 5.0 or more), relative to the total polymerizable compound, 10 to 100 mass %, more preferably 40 to 100% by mass, even more preferably 90 to 99% by mass.
  • the content of the polymerizable compound having a clogP of more than 5.5 is preferably 10 to 100% by mass, more preferably 20 to 99% by mass, and 35 to 65% by mass with respect to the total polymerizable compound. More preferred.
  • the polymerizable compound may be used alone or in combination of two or more. Among them, it is also preferable to use three or more kinds of polymerizable compounds from the viewpoint that the effects of the present invention are more excellent.
  • 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 70.0% by mass, based on the total mass of the photosensitive layer. % by 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 layer preferably contains the polymerizable compound B1 and a trifunctional or higher 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 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 layer preferably contains a photopolymerization initiator.
  • a photopolymerization initiator is a compound that initiates polymerization of a polymerizable compound upon receiving 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. structure and a photopolymerization initiator having an N-phenylglycine structure.
  • the photoradical polymerization initiator is selected from the group consisting of 2,4,5-triarylimidazole dimers and derivatives thereof from the viewpoints of photosensitivity, visibility of exposed and unexposed areas, and resolution. preferably includes at least 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 initiators include, for example, paragraphs [0031] to [0042] of JP-A-2011-095716, and paragraphs [0064] to [0081] of JP-A-2015-014783.
  • a radical polymerization initiator is mentioned.
  • 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) and generates an acid.
  • the sensitizer can be used.
  • 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 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 layer.
  • the photosensitive 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 , acids, bases, or radicals to change the maximum absorption wavelength dye (color coupler).
  • the dye (color former) is 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 due to acid, base, or radical” means that the dye in the colored state is decolored by acid, base, or radical, and the dye in the decolored state is acid or base. Alternatively, it may mean any one of a mode in which a color is developed by a radical and a mode in which a dye in a coloring state changes to a 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.
  • it may be a dye that changes the state of color development or decoloration due to the action of an acid, a base, or a radical generated in the photosensitive layer by exposure, and an acid, a base, or a radical
  • It may be a dye that changes the state of coloring or decoloring by changing the state (for example, pH) in the photosensitive layer due to the presence of the dye.
  • 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, and a dye whose maximum absorption wavelength is changed by radicals is preferable from the viewpoint of visibility of exposed and unexposed areas and resolution. More preferred.
  • the photosensitive layer preferably contains both a dye whose maximum absorption wavelength is changed by radicals and a photoradical polymerization initiator as the dye N.
  • 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 layer, and the photoradical polymerization initiator is added after exposure.
  • a radical-reactive dye, an acid-reactive dye, or a base-reactive dye e.g., a leuco dye develops color by radicals, acids, or bases generated from a photocationic polymerization initiator or a photobase generator. mentioned.
  • 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-based dyes, oxazine-based dyes, xanthene-based dyes, iminonaphthoquinone-based dyes, azomethine-based dyes, and anthraquinone-based 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 examples 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.
  • triarylmethane dyes triarylmethane dyes
  • spiropyran dyes spiropyran dyes
  • fluorane skeleton fluorane skeleton
  • diarylmethane skeletons examples 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 (diarylmethane dye), a leuco compound having a rhodamine lactam skeleton (rhodamine lactam dye), a leuco compound having an indolylphthalide skeleton (indolylphthalide dye), and a leuco auramine skeleton leuco compounds (leuco auramine dyes) having 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.
  • 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 photoradical polymerization initiator or an acid generated from a photocationic polymerization initiator to change the leuco compound into a ring-closed state.
  • the color can be developed by changing the leuco compound into 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 a color when the lactone ring, sultine ring, or sultone ring is opened by a radical or an acid, and has a lactone ring. , a radical or an acid to open the lactone ring to develop a color.
  • 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 dye N is 0.1% by mass or more with respect to the total mass of the photosensitive layer from the viewpoint of excellent visibility of exposed and unexposed areas, and pattern visibility and resolution after development. is preferred, 0.1 to 10% by mass is more preferred, 0.1 to 5% by mass is even more preferred, and 0.1 to 1% by mass is particularly preferred.
  • 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 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 layer (3 g) is dissolved in methyl ethyl ketone. From the absorbance of the obtained solution containing the photosensitive layer, the content of dye N contained in the photosensitive layer is calculated based on the calibration curve.
  • Photosensitive layer (3 g) is synonymous with 3 g of total solid content in the photosensitive composition.
  • the photosensitive layer may contain a thermally crosslinkable compound from the viewpoint of the strength of the resulting cured film and the tackiness 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 layer When the cured film is used as a protective film, the function tends to be enhanced.
  • 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.
  • Block isocyanate compounds include, for example, AOI-BM, MOI-BM, and MOI-BP, etc.
  • Karenz series registered trademark
  • series registered trademark
  • As the blocked isocyanate compound 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 layer.
  • the photosensitive 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 amide, 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 an inorganic suspending agent, 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, or 4-methoxyphenol is preferred.
  • examples of the radical polymerization inhibitor include naphthylamine, cuprous chloride, nitrosophenylhydroxyamine aluminum salt, and diphenylnitrosamine. Nitrosophenylhydroxyamine aluminum salt is preferred from the viewpoint of not impairing the sensitivity of the photosensitive 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, and 0.02 to 2.0% by mass, based on the total mass of the photosensitive layer. 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 for example, function as rust inhibitors.
  • Carboxybenzotriazoles include, for example, carboxybenzotriazole (4-carboxy-1,2,3-benzotriazole and 5-carboxy-1,2,3-benzotriazole), N-(N,N- di-2-ethylhexyl)aminomethylenecarboxybenzotriazole, N-(N,N-di-2-hydroxyethyl)aminomethylenecarboxybenzotriazole, and N-(N,N-di-2-ethylhexyl)aminoethylenecarboxy Benzotriazoles are included.
  • 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 layer. preferable.
  • the content is 0.01% by mass or more, the storage stability of the photosensitive 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-triazole), 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 preferably 0.01 to 5% by mass based on the total mass of the photosensitive 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. 0.05 to 1% by mass is more preferable.
  • surfactant examples include those 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, 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.
  • fluorine-based surfactants include DIC's Megafac DS series (The Chemical Daily (February 22, 2016) and Nikkei Sangyo Shimbun (February 23, 2016)). be done.
  • 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 the fluorosurfactant include fluoropolymers having an ethylenically unsaturated group in the side chain, 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), polyoxyethylene lauryl ether, polyoxy Ethylene 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 Nippon Lu
  • 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 (manufactured by Dow Corning Toray); 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-
  • 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 0.8% by mass, based on the total mass of the photosensitive layer. % by mass 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 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 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 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 layer, a method of preventing contamination of impurities during the formation of the photosensitive layer, and a method of washing. a method of removing by The content of impurities can be quantified by known methods such as ICP emission spectroscopy, atomic absorption spectroscopy, and ion chromatography.
  • residual organic solvent examples include 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 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 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 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, more preferably 100 ppm by mass or less, relative to the total mass of the photosensitive layer.
  • Mass ppm 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 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 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 lamination properties.
  • the photosensitive layer satisfies at least one or more (eg, 1 to 4) requirements selected from the following requirements 1 to 4. preferable.
  • the photosensitive layer has a weight average molecular weight of 30,000 or less and contains a resin having a polymerizable group.
  • Requirement 2 The photosensitive layer contains a resin having a weight average molecular weight of 30,000 or less and a polymerizable compound having a clogP of 5.0 or more (preferably more than 5.5).
  • the photosensitive layer contains a resin having a weight average molecular weight of 30,000 or less and a polymerizable compound having a viscosity of 300 to 5000 mPa ⁇ s.
  • the photosensitive layer contains a resin having a weight average molecular weight of 30,000 or less, and contains a trifunctional or higher polymerizable compound.
  • the reaction rate in the photosensitive layer is improved by containing a resin having a weight average molecular weight of 30,000 or less, and the resin has a crosslinkable group, thereby forming a dense crosslinked structure. can be constructed, and penetration of the developer into the photosensitive layer after exposure is suppressed.
  • the reaction rate in the photosensitive layer is improved by containing a resin having a weight average molecular weight of 30,000 or less, and clogP is a predetermined value or more and contains a hydrophobic polymerizable compound to improve the photosensitive It is believed that the layer becomes hydrophobic and the penetration of the developer into the photosensitive layer after exposure is suppressed.
  • the reaction rate in the photosensitive layer is improved by containing a resin having a weight average molecular weight of 30,000 or less, and the photosensitive layer absorbs moisture by containing a polymerizable compound having a viscosity of a predetermined value or more. It is thought that the penetration of the developing solution into the photosensitive layer after exposure is suppressed.
  • the reaction rate in the photosensitive layer is improved by containing a resin having a weight average molecular weight of 30,000 or less, and a dense crosslinked structure can be formed by containing a trifunctional or higher polymerizable compound. It is thought that the penetration of the developing solution into the photosensitive layer after exposure is suppressed.
  • the thickness (film thickness) of the photosensitive layer is often 0.1 ⁇ m or more, preferably 0.2 ⁇ m or more, more preferably 0.5 ⁇ m or more, and particularly preferably 1.0 ⁇ m or more.
  • the upper limit of the film thickness is often 300 ⁇ m or less, preferably 100 ⁇ m or less, more preferably 50 ⁇ m or less, even more preferably 20 ⁇ m or less, and particularly preferably 5 ⁇ m or less.
  • the content of the polymerizable group in the photosensitive layer is preferably 1.0 mmol/g or more, more preferably 2.0 mmol/g or more, and further preferably 3.0 mmol/g or more from the viewpoint that the effect of the present invention is more excellent.
  • 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 layer is preferably 10 to 150 mgKOH/g, more preferably 40 to 100 mgKOH/g, still more preferably 50 to 100 mgKOH/g, particularly preferably 50 to 90 mgKOH/g, most preferably 60 to 80 mgKOH/g. preferable.
  • 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 layer.
  • the intermediate layer is preferably arranged between the temporary support and the photosensitive layer.
  • the intermediate layer include a water-soluble resin layer and an oxygen blocking layer having an oxygen blocking function described as a "separation layer" in JP-A-5-072724.
  • an oxygen-blocking layer is also 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.
  • the oxygen barrier layer exhibits low oxygen permeability and is dispersed or dissolved in water or an alkaline aqueous solution (1% by weight aqueous solution of sodium carbonate at 22°C). 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 include, for example, polyethylene glycol, polypropylene glycol, their alkylene oxide side adducts, 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 99.99% by mass or less, and even more preferably 99.9% 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 bisphenol A and bisphenol S.
  • Amide compounds include, for example, N-methylpyrrolidone.
  • the intermediate layer may contain at least one selected from the group consisting of water-soluble cellulose derivatives, polyhydric alcohols, alkylene oxide adducts of polyhydric alcohols, polyether resins, phenol derivatives, and amide compounds. preferable.
  • 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 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 0.3 ⁇ m or more, more preferably 1.0 ⁇ m or more.
  • 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. Especially, as a protective film, a polyolefin film is preferable, and a polypropylene film or a polyethylene film is more preferable.
  • 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 transferring irregularities caused by particles contained in the protective film to the photosensitive layer or the conductive layer.
  • the surface of the protective film opposite to the surface in contact with the photosensitive layer or the surface in contact thereof preferably has an arithmetic mean roughness Ra of 0.01 ⁇ m or more, more preferably 0.02 ⁇ m or more. 0.03 ⁇ m or more is more preferable.
  • 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. a) coating a photosensitive composition on the surface of the intermediate layer 13 to form a coating film, and drying the coating film to form the photosensitive layer 15;
  • a method for producing a transfer film a method including a step of applying a photosensitive composition to the surface of a temporary support to form a coating film, and further drying this coating film to form a photosensitive layer. be done. In this case the transfer film does not have an intermediate layer 13 .
  • the transfer film 10 is manufactured by pressure-bonding the protective film 19 onto the photosensitive layer 15 of the laminate manufactured by the manufacturing method described above.
  • 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 layer 15 opposite to the temporary support 11 side, so that the temporary support 11, the intermediate layer 13, the photosensitive It is preferred to manufacture transfer film 10 with layer 15 and protective film 19 .
  • a method for producing the transfer film by including a step of providing a protective film 19 so as to be in contact with the surface of the photosensitive layer 15 opposite to the temporary support 11 side, the temporary support 11, the intermediate layer 13, It is also preferred to manufacture the transfer film 10 with a photosensitive layer 15 and a protective film 19 .
  • 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 bonding with a substrate (substrate with a metal layer) in a roll-to-roll method, which will be described later.
  • Photosensitive composition and method for forming photosensitive layer As a method for forming the photosensitive layer, a coating method in which a photosensitive composition containing components contained in the photosensitive layer (for example, a resin, a polymerizable compound, a polymerization initiator, etc.) and a solvent is used is preferred. As a method for forming the photosensitive layer, for example, a photosensitive composition is applied on the intermediate layer to form a coating film, and if necessary, the coating film is dried at a predetermined temperature to form a photosensitive layer. is preferred. The amount of residual solvent is adjusted by the drying treatment of the coating film.
  • a photosensitive composition containing components contained in the photosensitive layer for example, a resin, a polymerizable compound, a polymerization initiator, etc.
  • a solvent for example, a photosensitive composition is applied on the intermediate layer to form a coating film, and if necessary, the coating film is dried at a predetermined temperature to form a photosensitive layer. is preferred. The amount of residual solvent
  • the photosensitive composition preferably contains components contained in the photosensitive layer and a solvent.
  • the content of each component contained in the photosensitive 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 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 layer.
  • methods for bonding the protective film to the photosensitive layer include known methods.
  • Apparatuses for bonding the protective film to the photosensitive layer include, for example, known laminators such as a vacuum laminator and an autocut laminator.
  • 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 thereof, preferably alcohols having 1 to 3 carbon atoms, methanol or Ethanol is 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.
  • the photosensitive layer of the transfer film was formed using a photosensitive composition.
  • the components used for the preparation of the photosensitive composition are as follows, and each component shown below was mixed according to the formulation shown in the table shown later, and each photosensitive composition used in Examples or Comparative Examples was prepared. Obtained.
  • the "composition” column shows the types of structural units possessed by each resin (compound), and the mass ratio of the content of each structural unit is shown in parentheses.
  • the name of the monomer from which each structural unit is derived is shown.
  • compound 1 is a resin having structural units based on styrene, structural units based on methyl methacrylate, and structural units based on methacrylic acid in a mass ratio of 52:19:29, respectively.
  • the structural unit represented as "methacrylic acid-glycidyl methacrylate” means a structural unit obtained by reacting a carboxy group of a structural unit based on methacrylic acid with glycidyl methacrylate.
  • the structural unit described as "methacrylic acid” is a structural unit that does not correspond to the structural unit described as "methacrylic acid-glycidyl methacrylate”.
  • ⁇ Antirust agent> ⁇ CBT-1 Carboxybenzotriazole, manufactured by Johoku Chemical Co., Ltd.
  • the intermediate layer of the transfer film was formed using the intermediate layer-forming composition.
  • the components used in the preparation of the composition for forming the intermediate layer are as follows. A composition for
  • ⁇ Resin> ⁇ 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.
  • Each transfer film composed of a temporary support, an intermediate layer, and a photosensitive layer was produced. Specifically, it is as follows. First, on a temporary support (16 ⁇ m thick polyethylene terephthalate film (Lumirror 16KS40, manufactured by Toray Industries, Inc.)), an intermediate layer forming composition was applied using a bar coater so that the thickness after drying was 1.0 ⁇ m. and dried in an oven at 90° C. to form an intermediate layer. Furthermore, on the intermediate layer, a photosensitive composition is applied using a bar coater so that the thickness after drying becomes 3.0 ⁇ m, dried at 80° C. using an oven, and the photosensitive layer (negative type A photosensitive layer) was formed. A 16 ⁇ m-thick polyethylene terephthalate (16KS40, manufactured by Toray Industries, Inc.) was pressure-bonded onto the obtained photosensitive layer as a protective film to prepare a transfer film used in each example or comparative example.
  • a temporary support (16 ⁇ m thick polyethylene terephthalate film (Lumir
  • a copper layer with a thickness of 500 nm was prepared by sputtering on a PET film (polyethylene terephthalate film) with a thickness of 188 ⁇ m. , a roll temperature of 90° C., a linear pressure of 0.8 MPa, and a linear velocity of 3.0 m/min. was laminated on a PET substrate with a copper layer under the lamination conditions of , to obtain a laminate.
  • the laminate has a configuration of "PET film-copper layer-photosensitive layer-intermediate layer-temporary support". The steps up to this point are referred to as a layered product manufacturing stage.
  • the temporary support was peeled off from the obtained laminate to expose the intermediate layer on the surface of the laminate.
  • a photomask having a pattern with a line ( ⁇ m)/space ( ⁇ m) ratio of 10/10 was brought into close contact with the intermediate layer exposed on the surface of the laminate.
  • Light was irradiated using a high-pressure mercury lamp exposure machine (MAP-1200L, manufactured by Dai Nippon Kaken Co., Ltd., dominant wavelength: 365 nm). 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% sodium carbonate aqueous solution at 28° C. as a developer.
  • a laminate having a line-and-space resist pattern with an average line width of 10 ⁇ m was obtained.
  • the steps up to this point are referred to as a first pattern formation step.
  • the laminate has a configuration of "PET film-copper layer-resist pattern".
  • the obtained laminate was cut perpendicularly to the length direction of the line, and the cross section was observed to determine the permeation length X (unit: ⁇ m) of the developing solution. Specifically, X was obtained by observing by the method described in the specification.
  • a photomask is brought into close contact with the intermediate layer exposed on the surface of the laminate, and a high-pressure mercury lamp exposure machine (MAP-1200L, manufactured by Dainippon Kaken Co., Ltd., dominant wavelength: 365 nm). was used to irradiate (exposure) light.
  • exposure whole surface exposure
  • the photosensitive layer after exposure is observed by FT-IR, and the amount of carbon-carbon double bonds in the photosensitive layer before exposure is assumed to be 100%, and the carbon-carbon double reacted by exposure
  • LWR Line Width Roughness
  • the following table shows the evaluation results of each example or comparative example.
  • formulations of the photosensitive composition and the composition for forming the intermediate layer used to prepare the transfer film used in each example or comparative example are shown.
  • Compounds 1 to 4 (resin) are used in the formulation of the photosensitive composition in the form of a solution (resin solution) containing a compound that is a resin. ).
  • the photosensitive composition used in Example 1 contains 25.2 parts by mass of a resin solution having a solid content (compound 1) of 30% by mass with respect to the total mass.
  • the solvent in the resin solution is PGMEA (propylene glycol monomethyl ether acetate).
  • the viscosity of the polymerizable compound is measured at a temperature of 25° C. using a Brookfield viscometer (TVB-15 manufactured by Toki Sangyo Co., Ltd.).
  • the effect of the present invention is more excellent when the penetration length X of the developer, which is obtained by the measurement X, is 0.6 ⁇ m or less, and the present invention is obtained when it is 0.4 ⁇ m or less. It was confirmed that the effect of
  • Comparison between Examples 1 and 7 and between Examples 2 and 4 shows that the photosensitive layer of the transfer film used in the method of the present invention contains a polymerizable compound having 3 or more polymerizable groups. It was confirmed that the effect of the present invention is more excellent when it is included.
  • the effect of the present invention is more excellent when the photosensitive layer of the transfer film used in the method of the present invention contains a polymerizable compound having a clogP of 5.0 or more. It was confirmed that the effects of the present invention are more excellent when the polymerizable compound having a clogP of more than 5.5 is included.
  • a laminate having a conductor pattern was produced as follows. First, the steps up to the first pattern formation step in [Measurement X] described above were performed in the same manner to obtain a substrate on which a resist pattern was formed (a laminate having a resist pattern). (However, when evaluating the conductor pattern resolution (minimum resolution line width), the line width of the finally formed conductor pattern was adjusted by varying the exposure dose during exposure.)
  • the laminate had a configuration of "PET film-copper layer-resist pattern", and the copper layer was used as a seed layer.
  • the laminate was placed in a copper sulfate plating solution (copper sulfate 75 g/L, sulfuric acid 190 g/L, chloride ion 50 ppm by mass, manufactured by Meltex Inc., "Coppergleam PCM", 5 mL/L), and 1 A/dm 2 Copper plating treatment was performed under the conditions of After the laminate after the copper plating treatment is washed with water and dried, the resist pattern is peeled off by immersing it in a stripping solution (Mitsubishi Gas Chemical Co., Ltd., "R-100", 0.2% by volume) at 50 ° C.
  • a stripping solution Mitsubishi Gas Chemical Co., Ltd., "R-100", 0.2% by volume
  • the copper layer (seed layer) of the laminate was removed with an aqueous solution containing 0.1% by mass sulfuric acid and 0.1% by mass hydrogen peroxide.
  • a substrate laminate having a conductor pattern
  • conductor pattern linearity (LWR) and conductor pattern resolution (minimum resolution line width) are measured in the same manner as described above. evaluated to

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JP2013024913A (ja) * 2011-07-15 2013-02-04 Asahi Kasei E-Materials Corp 感光性エレメント
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JP2013024913A (ja) * 2011-07-15 2013-02-04 Asahi Kasei E-Materials Corp 感光性エレメント
JP2016033637A (ja) * 2014-07-28 2016-03-10 日立化成株式会社 感光性樹脂組成物、感光性エレメント、レジストパターンの形成方法及びプリント配線板の製造方法

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