WO2022092160A1 - 積層体の製造方法、回路配線基板の製造方法、転写フィルム - Google Patents

積層体の製造方法、回路配線基板の製造方法、転写フィルム Download PDF

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WO2022092160A1
WO2022092160A1 PCT/JP2021/039686 JP2021039686W WO2022092160A1 WO 2022092160 A1 WO2022092160 A1 WO 2022092160A1 JP 2021039686 W JP2021039686 W JP 2021039686W WO 2022092160 A1 WO2022092160 A1 WO 2022092160A1
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Prior art keywords
intermediate layer
preferable
mass
compound
meth
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PCT/JP2021/039686
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English (en)
French (fr)
Japanese (ja)
Inventor
悠 鬼塚
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Fujifilm Corp
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Fujifilm Corp
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Priority to JP2022559206A priority Critical patent/JP7761581B2/ja
Priority to CN202180066830.2A priority patent/CN116472494A/zh
Publication of WO2022092160A1 publication Critical patent/WO2022092160A1/ja
Anticipated expiration legal-status Critical
Priority to JP2025173498A priority patent/JP2025188224A/ja
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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
    • G03F7/09—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
    • G03F7/38—Treatment before imagewise removal, e.g. prebaking
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/26—Processing photosensitive materials; Apparatus therefor
    • G03F7/40—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
    • H05K3/10—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 laminated body, a method for manufacturing a circuit wiring board, and a transfer film.
  • a pattern forming method using a transfer film is widely used. Specifically, it is a method of forming a pattern by arranging a photosensitive layer on an arbitrary substrate using a transfer film, exposing the photosensitive layer through a mask, and then developing the photosensitive layer.
  • a support (A) is provided on a metal-coated surface of a metal-coated insulating plate having a metal conductor layer on one or both sides, and a negative photosensitive composition layer having a thickness of 1 to 35 ⁇ m.
  • B) and the photosensitive resin laminate having the protective layer (C) are laminated so that the negative photosensitive composition layer (B) is in close contact with the metal-coated surface of the metal-coated insulating plate, and the photomask is passed through.
  • a method for exposing a photosensitive composition layer which comprises peeling off a support before exposure and then projecting an image of a photomask through a lens during ultraviolet exposure.
  • the present inventor refers to the exposure method described in Patent Document 1, peels off the support (temporary support) before exposure, and photo-photographs the photosensitive composition layer (photosensitive layer) exposed by the peeling.
  • the photosensitive layer and the photomask may be excessively adhered to each other, making peeling difficult. If the peelability between the photosensitive layer and the photomask after exposure is poor, various problems such as deterioration of workability due to difficulty in peeling and mask contamination due to adhesion of the photosensitive layer forming material may occur.
  • the present invention provides a method for producing a laminated body, which can suppress excessive adhesion between the photosensitive layer after exposure and a photomask and also has excellent resolution of a pattern formed from the photosensitive layer. That is the issue.
  • Another object of the present invention is to provide a method for manufacturing a circuit wiring board.
  • the present invention is a transfer film suitable for an exposure method in which a temporary support is peeled off and then exposed, and can suppress excessive adhesion between the photosensitive layer and a photomask after exposure, and has resolvability. It is also an issue to provide an excellent transfer film.
  • [2] The method for producing a laminate according to [1], wherein the arithmetic average roughness Ra of the surface of the intermediate layer on the temporary support side is 50 nm or less.
  • [3] The method for producing a laminate according to [1] or [2], wherein the surface free energy of the temporary support on the intermediate layer side is 25.0 to 50.0 mJ / m 2 .
  • [4] The method for producing a laminate according to any one of [1] to [3], wherein the intermediate layer contains polyvinyl alcohol.
  • [5] The method for producing a laminate according to [4], wherein the content of the polyvinyl alcohol is 5 to 95% by mass with respect to the total mass of the intermediate layer.
  • [10] The method for producing a laminate according to any one of [1] to [9], wherein the thickness of the intermediate layer is 3.0 ⁇ m or less.
  • a method for manufacturing a circuit wiring including the method for manufacturing a laminate according to any one of [1] to [11]. The process of forming a seed layer on a substrate to form a substrate with a seed layer, The transfer film and the seed so that the surface of the transfer film having the temporary support, the intermediate layer, and the photosensitive layer on the opposite side of the photosensitive layer from the intermediate layer side is in contact with the substrate with the seed layer.
  • a method for manufacturing a circuit wiring board wherein the surface free energy of the surface of the intermediate layer on the temporary support side is 68.0 mJ / m 2 or less.
  • the transfer film according to [13], wherein the surface free energy on the intermediate layer side of the temporary support is 25.0 to 50.0 mJ / m 2 .
  • the laminated body can suppress excessive adhesion between the photosensitive layer and the photomask after exposure, and can form a pattern having excellent resolution of the pattern formed from the photosensitive layer.
  • a manufacturing method can be provided. Further, according to the present invention, it is also possible to provide a method for manufacturing a circuit wiring board. Further, the present invention is a transfer film suitable for an exposure method in which a temporary support is peeled off and then exposed, and can suppress excessive adhesion between the photosensitive layer and a photomask after exposure, and has resolvability. It is also possible to provide a transfer film capable of forming an excellent pattern.
  • the numerical range represented by using “-" means a range including the numerical values before and after "-" as the lower limit value and the upper limit value.
  • the upper limit value or the lower limit value described in one numerical range may be replaced with the upper limit value or the lower limit value of another numerical range described in stages. ..
  • the upper limit value or the lower limit value described in a certain numerical range may be replaced with the value shown in the examples.
  • process is included in this term not only as an independent process but also as long as the intended purpose of the process is achieved even if it cannot be clearly distinguished from other processes. ..
  • transparent means that the average transmittance of visible light having a wavelength of 400 to 700 nm is 80% or more, and is preferably 90% or more.
  • the average transmittance of visible light is a value measured by using a spectrophotometer, and can be measured by, for example, a spectrophotometer U-3310 manufactured by Hitachi, Ltd.
  • the weight average molecular weight (Mw) and the number average molecular weight (Mn) are TSKgel GMHxL, TSKgel G4000HxL, or TSKgel G2000HxL (all manufactured by Toso Co., Ltd.) as columns. Name), THF (tetrahexyl) as the eluent, polystyrene as the standard material, and polystyrene as the standard material measured by a gel permeation chromatography (GPC) analyzer. Is. Further, in the present specification, unless otherwise specified, the molecular weight of a compound having a molecular weight distribution is the weight average molecular weight (Mw).
  • the content of the metal element is a value measured by using an inductively coupled plasma (ICP) spectroscopic analyzer.
  • the refractive index is a value measured using an ellipsometer at a wavelength of 550 nm.
  • the hue is a value measured using a color difference meter (CR-221, manufactured by Minolta Co., Ltd.).
  • (meth) acrylic is a concept that includes both acrylic and methacrylic
  • (meth) acryloyloxy group is a concept that includes both acryloyloxy group and methacryloyloxy group
  • (Meta) acrylamide group is a concept that includes both an acrylamide group and a methacrylicamide 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 having a liquid temperature of 22 ° C. is 0.1 g or more. Therefore, for example, the alkali-soluble resin is intended to be a resin that satisfies the above-mentioned solubility conditions.
  • water-soluble means that the solubility in 100 g of water having a liquid temperature of 22 ° C. and a pH of 7.0 is 0.1 g or more. Therefore, for example, the water-soluble resin is intended to be a resin satisfying the above-mentioned solubility conditions.
  • the "solid content" of a composition means a component forming a composition layer formed by using the composition, and when the composition contains a solvent (organic solvent, water, etc.), the solvent is used. Means all ingredients except. Further, if the component forms a composition layer, the liquid component is also regarded as a solid content.
  • the method for producing a laminate of the present invention is: The transfer film and the substrate are bonded so that the surface of the transfer film having the temporary support, the intermediate layer, and the photosensitive layer on the side opposite to the intermediate layer side of the photosensitive layer is in contact with the substrate. (Hereinafter, also referred to as "transfer film bonding process”) and A step of peeling the temporary support between the temporary support and the intermediate layer (hereinafter, also referred to as a “temporary support peeling step”). It has a step of contacting the exposed intermediate layer with a mask to perform an exposure process, and further performing a development process after the exposure to form a pattern (hereinafter, also referred to as a "pattern forming step”). , The surface free energy of the surface of the intermediate layer on the temporary support side is 68.0 mJ / m 2 or less.
  • the features of the method for manufacturing a laminated body of the present invention are that an intermediate layer is provided between the temporary support and the photosensitive layer, and that the surface free energy of the intermediate layer on the temporary support side is set to a predetermined numerical range or less. There are some points. According to the method for producing a laminated body of the present invention, excessive adhesion between the photosensitive layer and the photomask after exposure can be suppressed, and the resolution is also excellent.
  • the present inventor speculates as follows.
  • an intermediate layer is provided between the temporary support and the photosensitive layer, whereby the intermediate layer is interposed in the pattern forming step after the temporary support peeling step.
  • the mask and the photosensitive layer do not come into direct contact with each other.
  • excessive adhesion between the photosensitive layer and the mask after exposure is suppressed.
  • the present inventor found that when the surface free energy of the surface of the intermediate layer on the temporary support side exceeds 68.0 mJ / m 2 , it is intermediate in the temporary support peeling step.
  • the method for producing the laminated body of the present invention will be described in detail for each step.
  • the description of the constituent elements described below may be based on a typical embodiment of the present invention, but the present invention is not limited to such an embodiment.
  • excessive adhesion between the photosensitive layer after exposure and the photomask can be further suppressed (hereinafter, also referred to as “the mask non-adhesiveness is more excellent”), and / or in the region of the concave portion of the pattern. It is also referred to as “the effect of the present invention is more excellent” that it is possible to form a fine pattern in which the residue of the above is suppressed (hereinafter, also referred to as "more excellent in resolution").
  • the first embodiment of the method for producing a laminated body includes a transfer film bonding step, a temporary support peeling step, and a pattern forming step, which are shown below, in this order.
  • Transfer film bonding step A surface of a transfer film having a temporary support, an intermediate layer, and a photosensitive layer (hereinafter, also referred to as “transfer film X”) on the side opposite to the intermediate layer side of the photosensitive layer.
  • Temporary support peeling step The temporary support and the intermediate layer A step of peeling off the temporary support between them.
  • Pattern forming step A step of bringing the exposed intermediate layer into contact with a mask to perform an exposure process, and further performing a development process after the exposure to form a pattern. (Hereinafter also referred to as "pattern forming process") Further, in the transfer film X, the surface free energy of the surface of the intermediate layer on the temporary support side is 68.0 mJ / m 2 or less.
  • the transfer film bonding step the transfer film is transferred so that the surface of the transfer film (transfer film X) having the temporary support, the intermediate layer, and the photosensitive layer on the opposite side of the photosensitive layer is in contact with the substrate. This is a process of bonding the film X and the substrate.
  • the transfer film X has a protective film, the protective film is peeled off and then the bonding step is performed.
  • the substrate and the surface of the transfer film X opposite to the intermediate layer side of the photosensitive layer are pressure-bonded so as to be in contact with each other.
  • the crimping method is not particularly limited, and a known transfer method and laminating method can be used. Above all, it is preferable to superimpose the surface of the transfer film X on the side opposite to the intermediate layer side of the photosensitive layer on the substrate, and perform pressurization and heating by a roll or the like.
  • a known laminator such as a vacuum laminator and an auto-cut laminator can be used for bonding.
  • the laminating temperature is not particularly limited, but is preferably 70 to 130 ° C., for example.
  • the substrate is preferably a conductive substrate having a support substrate and a conductive layer arranged on the support substrate.
  • the conductive substrate any layer other than the above-mentioned conductive layer may be formed on the support substrate, if necessary. That is, the substrate is preferably a conductive substrate having at least a support substrate and a conductive layer arranged on the support substrate.
  • the support substrate examples include a resin substrate, a glass substrate, and a semiconductor substrate. Preferred embodiments of the support substrate are described, for example, in paragraph [0140] of WO 2018/155193, the contents of which are incorporated herein.
  • the material of the resin substrate is preferably cycloolefin polymer and polyimide, and the thickness of the resin substrate is preferably 5 to 200 ⁇ m, more preferably 10 to 100 ⁇ m.
  • the conductive layer is at least one layer selected from the group consisting of a metal layer, a conductive metal oxide layer, a graphene layer, a carbon nanotube layer, and a conductive polymer layer from the viewpoint of conductivity and fine wire forming property. It is preferable to have it. Further, only one conductive layer may be arranged on the support substrate, or two or more conductive layers may be arranged. When two or more conductive layers are arranged, it is preferable to have conductive layers made of different materials. Preferred embodiments of the conductive layer are described, for example, in paragraph [0141] of WO 2018/155193, the contents of which are incorporated herein.
  • a substrate having at least one of a transparent electrode and a routing wire is preferable.
  • a conductive substrate having such a configuration can be suitably used as a substrate for a touch panel.
  • the transparent electrode may function suitably as a touch panel electrode.
  • the transparent electrode is preferably composed of a metal oxide film such as ITO (indium tin oxide) and IZO (indium zinc oxide), and a thin metal wire such as a metal mesh and a metal nanowire.
  • the thin metal wire include thin wires such as silver and copper. Of these, silver conductive materials such as silver mesh and silver nanowires are preferable.
  • Metal is preferable as the material of the routing wiring.
  • the metal that is the material of the routing wiring include gold, silver, copper, molybdenum, aluminum, titanium, chromium, zinc, and manganese, and alloys composed of two or more of these metal elements.
  • copper, molybdenum, aluminum, or titanium is preferable, and copper is particularly preferable.
  • the electrodes and the like that is, at least one of the touch panel electrode and the touch panel wiring
  • the electrodes and the like are provided so as to cover them directly or via another layer.
  • the temporary support peeling step is a step of peeling the temporary support between the temporary support and the intermediate layer.
  • the method for peeling the temporary support is not particularly limited, and the method can be carried out based on a known method.
  • a mechanism similar to the cover film peeling mechanism described in paragraphs [0161] to [0162] of JP2010-072589 can be used.
  • the surface free energy of the surface of the intermediate layer on the temporary support side is 68.0 mJ / m 2 or less.
  • the surface free energy of the surface of the intermediate layer on the temporary support side (hereinafter, also referred to as “surface free energy EI ”) is the surface free energy of the intermediate layer on the temporary support side exposed by peeling the temporary support in the temporary support peeling step.
  • the surface free energy on the surface (the surface exposed after the temporary support is peeled off in the intermediate layer) is intended.
  • the upper limit of the surface free energy EI is 68.0 mJ / m 2 or less, and 65.0 mJ / m 2 or less is preferable, and 63.0 mJ / m 2 or less is more preferable in that the effect of the present invention is more excellent. It is preferable, and 60.0 mJ / m 2 or less is more preferable. Further, as the lower limit value, for example, 45.0 mJ / m 2 or more is preferable, 50.0 mJ / m 2 or more is more preferable, and 55.0 mJ / m 2 or more is further preferable.
  • the surface free energy EI of the surface of the intermediate layer on the temporary support side is calculated by the following method.
  • the contact angles ⁇ H2O and ⁇ CH2I2 of the measured pure water H2O and methylene iodide CH2I2 are used, respectively , and the Owens equations (simultaneous equations (A) and (B)) shown below are used. ).
  • the support peeling method and the type of the base material are not particularly limited.
  • the contact angle of water ( ⁇ H2O ) is measured by the following method. After laminating the transfer film on the substrate, the temporary support is peeled off. Next, in an atmosphere where the room temperature is 25 ° C. and the relative humidity is 50%, 12 ⁇ L of pure water is dropped on the surface of the intermediate layer on the temporary support side (the surface exposed after the temporary support is peeled off), and 20 seconds later, the contact angle meter. The contact angle is measured using a CA-D type (Kyowa Interface Science Co., Ltd.). Perform the above measurement 5 times in total. Then, the arithmetic mean of the three measured values excluding the maximum and minimum values among the five measured values is defined as the water contact angle ( ⁇ H2O ).
  • the contact angle of diiodomethane ( ⁇ CH2I2 ) is measured by the following method. After laminating the transfer film on the substrate, the temporary support is peeled off. Next, in an atmosphere where the room temperature is 25 ° C. and the relative humidity is 50%, 12 ⁇ L of diiodomethane (manufactured by Wako Pure Chemical Industries, Ltd.) is dropped on the surface of the intermediate layer on the temporary support side (the surface exposed after the temporary support is peeled off). After 20 seconds, the contact angle is measured using a contact angle meter CA-D type (Kyowa Interface Science Co., Ltd.). Perform the above measurement 5 times in total. Then, the arithmetic mean of the three measured values excluding the maximum and minimum values among the five measured values is taken as the contact angle of diiodomethane ( ⁇ CH2I2 ).
  • the arithmetic mean roughness Ra of the surface of the intermediate layer on the temporary support side is the surface of the intermediate layer on the temporary support side exposed by peeling the temporary support in the temporary support peeling step (exposed after the temporary support is peeled in the intermediate layer).
  • the arithmetic mean roughness Ra of the surface) is intended.
  • the upper limit of the arithmetic average roughness Ra of the surface of the intermediate layer on the temporary support side is preferably 50 nm or less, more preferably 30 nm or less, still more preferably 20 nm or less, because the effect of the present invention is more excellent.
  • the arithmetic mean roughness Ra of the surface of the intermediate layer on the temporary support side is a value measured by the following method.
  • the arithmetic average roughness Ra of the surface of the intermediate layer on the temporary support side is measured by the following method. Using a three-dimensional optical profiler (New View7300, Zygo), the surface profile of the object to be measured is obtained under the following conditions. As the measurement and analysis software, Microscope Application of MetroPro ver8.3.2 is used. Next, the Surface Map screen is displayed using the above software, and histogram data is obtained in the Surface Map screen. From the obtained histogram data, the arithmetic mean roughness Ra of the surface of the object to be measured is obtained.
  • the thickness of the intermediate layer is not particularly limited, and the upper limit thereof is preferably, for example, 10 ⁇ m or less, more preferably 5.0 ⁇ m or less, still more preferably 4.0 ⁇ m or less, because the effect of the present invention is more excellent. 3.0 ⁇ m or less is particularly preferable. Further, as the lower limit value, for example, 50 nm or more is preferable, and 100 nm or more is more preferable because the oxygen permeability is more excellent.
  • the thickness of the intermediate layer is calculated as an average value of any five points measured by cross-sectional observation with an SEM (Scanning Electron Microscope).
  • the surface free energy of the surface of the temporary support on the intermediate layer side (hereinafter, also referred to as “surface free energy ES ”) is the intermediate layer of the temporary support that is exposed by peeling the temporary support in the temporary support peeling step.
  • the surface free energy of the side surface (the surface exposed after separation from the intermediate layer in the temporary support) is intended.
  • As the upper limit of the surface free energy ES for example, 60.0 mJ / m 2 or less is preferable, 54.0 mJ / m 2 or less is more preferable, and 50.0 mJ / m 2 or less is further preferable.
  • the surface free energy ES of the surface of the temporary support on the intermediate layer side is a value obtained by the same method as the surface free energy EI of the surface of the temporary support of the intermediate layer described above.
  • the surface free energy EI and the surface free energy ES satisfy the following relationships (1) and / or (2).
  • the difference between the surface free energy EI ( mJ / m 2 ) and the surface free energy ES (mJ / m 2 ) is 3.0 to 40 mJ / m 2 (preferably 3.0 to 30 mJ / m 2 ). ).
  • the pattern forming step is a step of bringing the exposed intermediate layer into contact with the mask to perform an exposure process, and further performing a development process to form a pattern.
  • the exposure process is a process of exposing the pattern to the photosensitive layer of the laminated body in which the temporary support is peeled off to expose the intermediate layer.
  • the "pattern exposure” means an exposure in a form of exposure in a pattern, that is, a form in which an exposed portion and a non-exposed portion are present.
  • the positional relationship between the exposed portion and the non-exposed portion in the pattern exposure is not particularly limited and is appropriately adjusted.
  • a mask having an opening at a predetermined position is placed on the intermediate layer exposed by peeling of the temporary support so as to be in close contact with the mask, and the exposure process is performed.
  • the photosensitive layer is a negative photosensitive layer
  • a component contained in the photosensitive layer in the exposed portion (position corresponding to the opening of the mask) of the photosensitive layer can occur.
  • a developing process particularly, an alkaline developing process
  • the non-exposed portion of the photosensitive layer is removed and a pattern is formed.
  • the light source for pattern exposure is appropriately selected as long as it can irradiate light in a wavelength range that can cure the photosensitive layer (for example, 365 nm or 405 nm). Can be used.
  • the main wavelength of the exposure light for pattern exposure is preferably 365 nm.
  • the main wavelength is the wavelength having the highest intensity.
  • the light source include various lasers, light emitting diodes (LEDs), ultra-high 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 .
  • the mask used in the exposure treatment after the exposure treatment and before the development treatment.
  • the development process is a process of developing a photosensitive layer exposed in a pattern obtained by an exposure process to form a pattern.
  • the development of the photosensitive layer can be carried out using a developing solution.
  • the photosensitive layer is a negative photosensitive layer
  • the non-exposed portion of the photosensitive layer is removed by a development process using an alkaline developer, and as a result, a pattern is formed in which the opening of the mask is a convex portion. can.
  • an alkaline aqueous solution is preferable as the developing solution.
  • the alkaline compound that can be contained in the alkaline aqueous solution include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogencarbonate, potassium hydrogencarbonate, tetramethylammonium hydroxide, tetraethylammonium hydroxide, and tetrapropylammonium hydroxy.
  • Do tetrabutylammonium hydroxide, and choline (2-hydroxyethyltrimethylammonium hydroxide).
  • Examples of the development method include paddle development, shower development, spin development, and dip development.
  • Examples of the developer preferably used in the present specification include the developer described in paragraph [0194] of International Publication No. 2015/093271, and examples of the developing method preferably used include International Publication No. 1.
  • the development method described in paragraph [0195] of 2015/093271 can be mentioned.
  • the first embodiment of the method for producing a laminate may include a step of exposing a pattern obtained by a developing process (post-exposure step) and / or a step of heating (post-baking step).
  • post-exposure step a step of exposing a pattern obtained by a developing process
  • post-baking step a step of heating
  • the exposure amount for post exposure is preferably 100 to 5000 mJ / cm 2 , more preferably 200 to 3000 mJ / cm 2 .
  • the post-bake temperature is preferably 80 to 250 ° C, more preferably 90 to 160 ° C.
  • the post-baking time is preferably 1 to 180 minutes, more preferably 10 to 60 minutes.
  • the position and size of the pattern formed on the substrate through the above procedure are not particularly limited.
  • the pattern is preferably fine lines, preferably 20 ⁇ m or less in width, and more preferably 15 ⁇ m or less.
  • the lower limit is not particularly limited, but is preferably 1 ⁇ m or more, preferably 5 ⁇ m or more, for example.
  • the transfer film X is a transfer film having a temporary support, an intermediate layer, and a photosensitive layer, and the surface free energy of the surface of the intermediate layer on the temporary support side is 68.0 mJ / m 2 or less. If there is, there is no particular limitation, and a known transfer film can be used. Hereinafter, embodiments of the transfer film X will be described.
  • the configuration of the transfer film X is not particularly limited, and examples thereof include the following configurations. (1) “Temporary support / intermediate layer / photosensitive layer / protective film” (2) “Temporary support / intermediate layer / photosensitive layer / refractive index adjusting layer / protective film”
  • the photosensitive layer is preferably a negative photosensitive layer. It is also preferable that the photosensitive layer is a colored resin layer.
  • the intermediate layer may be formed of two layers. Specifically, the configuration may be "temporary support / second intermediate layer / first intermediate layer / photosensitive layer / protective film".
  • the transfer film X may be a transfer film for an etching resist or a transfer film for a wiring protection film.
  • the structure of the transfer film X is preferably, for example, the above-mentioned structure (1).
  • the configuration of the transfer film X is preferably, for example, the configuration of (1) or (2) described above.
  • the maximum width of the undulation of the transfer film X is preferably 300 ⁇ m or less, more preferably 200 ⁇ m or less, still more preferably 60 ⁇ m or less.
  • the lower limit of the maximum width of the swell is 0 ⁇ m or more, preferably 0.1 ⁇ m or more, and more preferably 1 ⁇ m or more.
  • the maximum width of the waviness of the transfer film X is a value measured by the following procedure. First, the transfer film X is cut in a direction perpendicular to the main surface so as to have a size of 20 cm in length ⁇ 20 cm in width to prepare a test sample.
  • the transfer film X has a protective film
  • the protective film is peeled off.
  • the test sample is placed on a stage having a smooth and horizontal surface so that the surface of the temporary support faces the stage.
  • the surface of the sample sample was scanned with a laser microscope (for example, VK-9700SP manufactured by KEYENCE CORPORATION) for a range of 10 cm square in the center of the test sample to obtain a three-dimensional surface image, and the obtained 3 Subtract the minimum concave height from the maximum convex height observed in the 3D surface image.
  • the above operation is performed on 10 test samples, and the arithmetic mean value thereof is defined as the "maximum undulation width of the transfer film X".
  • the transfer film X1 of the first embodiment which will be described later as a specific embodiment of the transfer film X, has a configuration that can be suitably used as a transfer film for an etching resist, and the transfer film X2 of the second embodiment. Is a configuration that can be suitably used for a transfer film for a wiring protective film.
  • the intermediate layer of the transfer film X has a surface free energy (surface free energy EI ) of 68.0 mJ / m 2 or less on the surface on the temporary support side.
  • the surface free energy EI is intended to be the surface free energy on the surface of the intermediate layer on the temporary support side, which is exposed by peeling the temporary support from the transfer film X.
  • the preferred mode and measuring method of the surface free energy EI are as described above.
  • the upper limit of the arithmetic average roughness Ra of the surface of the intermediate layer of the transfer film X on the temporary support side is preferably 50 nm or less because the effect of the present invention is more excellent.
  • the arithmetic average roughness Ra of the surface of the intermediate layer on the temporary support side is intended to be the arithmetic average roughness Ra of the surface of the intermediate layer exposed by peeling the temporary support from the transfer film X.
  • the preferred mode and measuring method of the arithmetic mean roughness Ra on the surface of the intermediate layer are as described above.
  • the upper limit of the thickness of the intermediate layer of the transfer film X is preferably 10 ⁇ m or less because the effect of the present invention is more excellent.
  • the preferred mode and measuring method of the thickness of the intermediate layer are as described above.
  • the intermediate layer is preferably a water-soluble resin layer containing a water-soluble resin. Further, the intermediate layer preferably has an oxygen blocking ability. It is preferable that the intermediate layer has an oxygen blocking ability because the sensitivity at the time of exposure is improved, the time load of the exposure machine is reduced, and the productivity is improved. Further, when the photosensitive layer in the transfer film X is a negative photosensitive layer containing a radically polymerizable compound, there is an advantage that oxygen inhibition is less likely to occur in the polymerization reaction during exposure.
  • the intermediate layer is preferably a layer that exhibits low oxygen permeability and is dispersed or dissolved in water or an alkaline aqueous solution (1% by mass aqueous solution of sodium carbonate at 22 ° C.).
  • the intermediate layer preferably contains a resin.
  • the resin preferably contains a water-soluble resin in part or in whole.
  • the resin that can be used as the water-soluble resin include polyvinyl alcohol-based resin, polyvinylpyrrolidone-based resin, cellulose-based resin (for example, water-soluble cellulose derivatives such as hydroxypropyl cellulose and hydroxypropylmethyl cellulose), acrylamide-based resin, and polyether.
  • examples thereof include based resins (for example, polyalkylene oxide-based resins such as polyethylene glycol and polypropylene glycol), gelatin, vinyl ether-based resins, polyamide resins, and resins such as copolymers thereof.
  • the water-soluble resin a (meth) acrylic acid / vinyl compound copolymer or the like can also be used.
  • a copolymer of (meth) acrylic acid / vinyl compound a copolymer of (meth) acrylic acid / allyl (meth) acrylic acid is preferable, and a copolymer of methacrylic acid / allyl methacrylate is more preferable.
  • the composition ratio (mol%) is preferably 90/10 to 20/80, preferably 80/20 to 30/70. More preferred.
  • the lower limit of the weight average molecular weight of the water-soluble resin is preferably 5,000 or more, more preferably 7,000 or more, still more preferably 10,000 or more.
  • the upper limit thereof is preferably 200,000 or less, more preferably 100,000 or less, and even more preferably 50,000 or less.
  • the dispersity (Mw / Mn) of the water-soluble resin is preferably 1 to 10, more preferably 1 to 5.
  • the water-soluble resin preferably contains one or more of polyvinyl alcohol and polyvinylpyrrolidone, and more preferably contains polyvinyl alcohol, because the effect of the present invention is more excellent and / or the oxygen blocking ability is more excellent. It is preferable to contain both polyvinyl alcohol and polyvinylpyrrolidone. Further, it is also preferable to use one or more of polyvinyl alcohol and polyvinylpyrrolidone in combination with one or more of water-soluble cellulose derivatives and polyethers, and one or more of polyvinyl alcohol and polyvinylpyrrolidone and a water-soluble cellulose derivative. It is more preferable to use them together.
  • the water-soluble cellulose derivative is not particularly limited, and examples thereof include hydroxyethyl cellulose, hydroxypropylmethyl cellulose, hydroxypropyl cellulose, methyl cellulose, and ethyl cellulose.
  • the polyethers include polyethylene glycol and polypropylene glycol.
  • the water-soluble resin may be used alone or in combination of two or more.
  • the content of the water-soluble resin is not particularly limited, but is preferably 50% by mass or more with respect to the total mass of the intermediate layer in that the effect of the present invention is more excellent and / or the oxygen blocking ability is more excellent. 70% by mass or more is more preferable.
  • the upper limit is not particularly limited, but is, for example, 100% by mass or less, preferably 99.9% by mass or less, more preferably 99.8% by mass or less, and further preferably 99% by mass or less.
  • the intermediate layer may have components other than the above resin.
  • the upper limit of the molecular weight of the other components is not particularly limited, and is preferably less than 5,000, more preferably 4,000 or less, further preferably 3,000 or less, still more preferably 2,000 or less. 1,500 or less is particularly preferable.
  • the lower limit is, for example, 60 or more.
  • polyhydric alcohols, alkylene oxide adducts of polyhydric alcohols, phenol derivatives, or amide compounds are particularly easy to adjust the surface free energy EI on the temporary support side of the intermediate layer. Is preferable, and polyhydric alcohols or phenol derivatives are more preferable.
  • the number of hydroxyl groups contained in the polyhydric alcohol is not particularly limited, and is preferably 2 to 10, for example.
  • polyhydric alcohols include glycerin, diglycerin, diethylene glycol and the like.
  • alkylene oxide adduct of polyhydric alcohols include compounds obtained by adding ethylene oxide, propylene oxide and the like to the above-mentioned polyhydric alcohols.
  • the average number of additions is not particularly limited, and is, for example, 1 to 100, preferably 2 to 50, and more preferably 2 to 20.
  • examples of the phenol derivative include bisphenol A and bisphenol S.
  • examples of the amide compound include N-methylpyrrolidone and the like.
  • the above-mentioned other components may be used alone or in combination of two or more.
  • the content of the above other components is not particularly limited, but is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, based on the total mass of the intermediate layer, in that the effect of the present invention is more excellent. 1% by mass or more is more preferable.
  • the upper limit is not particularly limited, but for example, it is preferably less than 30% by mass, more preferably 10% by mass or less, and further preferably 5% by mass or less.
  • the intermediate layer one or more of polyvinyl alcohol and polyvinylpyrrolidone, and water-soluble cellulose derivatives and polyethers, among others, in that the effect of the present invention is more excellent and / or the oxygen blocking ability is more excellent. It preferably contains a phenol derivative and a compound X selected from the group consisting of glycerin.
  • the compound X tends to be unevenly distributed on the surface of the intermediate layer on the temporary support side, and / or is a WBL (weak boundary layer) layer formed by mixing the intermediate layer and the photosensitive layer.
  • the surface free energy EI on the temporary support side of the intermediate layer and the arithmetic average roughness Ra on the same surface can be easily adjusted to more appropriate values.
  • the intermediate layer does not coagulate and break when the temporary support is peeled off. , Peeling easily occurs at the interface between the temporary support and the intermediate layer, and a pattern having excellent resolvability is easily formed.
  • the composition of the intermediate layer is more preferably one or more of polyvinyl alcohol and polyvinylpyrrolidone, and more preferably one or more of a water-soluble cellulose derivative and polyethers as compound X, further suppressing the plasticization of the intermediate layer. It is more preferable to contain one or more of polyvinyl alcohol and polyvinylpyrrolidone and a water-soluble cellulose derivative as compound X in terms of ease of use, and one or more of polyvinyl alcohol and polyvinylpyrrolidone in that the temporary support peeling property is more excellent. And, it is particularly preferable to contain hydroxypropylmethyl cellulose as the compound X. Further, polyvinyl alcohol and polyvinylpyrrolidone are preferably used in combination.
  • the total content of polyvinyl alcohol and polyvinylpyrrolidone is preferably 50% by mass or more, preferably 70% by mass, based on the total mass of the intermediate layer, in that the effect of the present invention is more excellent.
  • the above is more preferable.
  • the upper limit is not particularly limited, but is, for example, 100% by mass or less, preferably 99.9% by mass or less, more preferably 99.8% by mass or less, and further preferably 99% by mass or less.
  • the content of polyvinyl alcohol is preferably 5 to 95% by mass with respect to the total mass of the intermediate layer.
  • the compounding ratio (mass ratio) of polyvinyl alcohol and polyvinylpyrrolidone is preferably 5/95 to 95/5, more preferably 20/80 to 80/20. , 25/75 to 70/25 are more preferable, and 60/40 to 75/25 are particularly preferable.
  • the content of the compound X is not particularly limited, but 0.1% by mass or more is preferable with respect to the total mass of the intermediate layer in that the effect of the present invention is more excellent. 0.5% by mass or more is more preferable, and 1% by mass or more is further preferable.
  • the upper limit is preferably less than 30% by mass, more preferably 15% by mass or less.
  • the content of the compound X is less than 30% by mass with respect to the total mass of the intermediate layer, the phase separation of the intermediate layer forming component is likely to be suppressed, and the surface roughening of the intermediate layer due to this is unlikely to occur. Therefore, it is superior in resolution.
  • the transfer film X has a temporary support.
  • the temporary support is a member that supports the photosensitive layer, and is finally removed by a peeling treatment.
  • the temporary support may have a single-layer structure or a multi-layer structure.
  • the temporary support is preferably a film, more preferably a resin film.
  • the temporary support is preferably a film that is flexible and does not undergo significant deformation, shrinkage, or elongation under pressure, or under pressure and heating.
  • the film include a polyethylene terephthalate film (for example, a biaxially stretched polyethylene terephthalate film), a polymethylmethacrylate film, a cellulose triacetate film, a polystyrene film, a polyimide film, and a polycarbonate film.
  • a polyethylene terephthalate film is preferable as the temporary support.
  • the film used as the temporary support is free from deformation such as wrinkles and scratches.
  • the temporary support is preferably highly transparent from the viewpoint that the pattern can be exposed through the temporary support, and the transmittance at 365 nm is preferably 60% or more, more preferably 70% or more. From the viewpoint of pattern formation during pattern exposure via the temporary support and transparency of the temporary support, it is preferable that the haze of the temporary support is small. Specifically, the haze value of the temporary support is preferably 2% or less, more preferably 0.5% or less, still more preferably 0.1% or less. From the viewpoint of pattern formation during pattern exposure via the temporary support and transparency of the temporary support, it is preferable that the number of fine particles, foreign substances, and defects contained in the temporary support is small.
  • the number of fine particles, foreign matter, and defects having a diameter of 1 ⁇ m or more in the temporary support is preferably 50 pieces / 10 mm 2 or less, more preferably 10 pieces / 10 mm 2 or less, further preferably 3 pieces / 10 mm 2 or less, and 0. Pieces / 10 mm 2 are particularly preferred.
  • the thickness of the temporary support is not particularly limited, but is preferably 5 to 200 ⁇ m, more preferably 5 to 150 ⁇ m, still more preferably 5 to 50 ⁇ m, and most 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 any five points measured by cross-sectional observation with an SEM (Scanning Electron Microscope).
  • Examples of the temporary support include a biaxially stretched polyethylene terephthalate film having a film thickness of 16 ⁇ m, a biaxially stretched polyethylene terephthalate film having a film thickness of 12 ⁇ m, and a biaxially stretched polyethylene terephthalate film having a film thickness of 9 ⁇ m.
  • Preferred forms of the temporary support include, for example, paragraphs [0017] to [0018] of JP-A-2014-085643, paragraphs [0019]-[0026] of JP-A-2016-0273363, and International Publication No. 2012 /.
  • the description is given in paragraphs [0041] to [0057] of No. 081680 and paragraphs [0029] to [0040] of International Publication No. 2018/179370, and the contents of these publications are incorporated in the present specification.
  • a layer containing fine particles may be provided on the surface of the temporary support from the viewpoint of imparting handleability.
  • the lubricant layer may be provided on one side of the temporary support or on both sides.
  • the diameter of the particles contained in the lubricant layer is preferably 0.05 to 0.8 ⁇ m.
  • the film thickness of the lubricant layer is preferably 0.05 to 1.0 ⁇ m.
  • the surface free energy (surface free energy ES ) of the surface on the intermediate layer side of the temporary support is preferably 60.0 mJ / m 2 or less.
  • the surface free energy ES is intended to be the surface free energy on the surface of the temporary support on the intermediate layer side, which is exposed by peeling the temporary support from the transfer film X.
  • the preferred mode and measuring method of the surface free energy ES are as described above.
  • Examples of commercially available temporary supports include Lumirror 16KS40, Lumirror 16FB40 (above, manufactured by Toray Industries, Inc.), Cosmo Shine A4100, Cosmo Shine A4300, and Cosmo Shine A8300 (above, manufactured by Toyobo Co., Ltd.).
  • the transfer film X1 of the first embodiment has a configuration that can be suitably used for a transfer film for an etching resist
  • the transfer film X2 of the second embodiment is suitable for a transfer film for a wiring protective film. It is a configuration that can be used for.
  • the thickness of the photosensitive layer is not particularly limited, but is often 30 ⁇ m or less, and is preferably 20 ⁇ m or less, more preferably 15 ⁇ m or less, still more preferably 10 ⁇ m or less, and further preferably 5.0 ⁇ m in that the effect of the present invention is more excellent. The following are particularly preferred.
  • the thickness of the photosensitive layer is calculated as an average value of any five points measured by cross-sectional observation with an SEM (Scanning Electron Microscope).
  • the transfer film 10 shown in FIG. 1 has a temporary support 1, a composition layer 7 including an intermediate layer 3 and a photosensitive layer 5, and a protective film 9 in this order.
  • the transfer film 10 shown in FIG. 1 has a form in which the protective film 9 is arranged, but the protective film 9 may not be arranged.
  • each layer excluding the protective film 9 that can be arranged on the temporary support 1 is referred to as a composition layer 7.
  • each element constituting the transfer film X1 will be described.
  • the configurations of the intermediate layer and the temporary support constituting the transfer film X1 are as described above.
  • the photosensitive layer is preferably a negative photosensitive layer.
  • the negative photosensitive layer is a photosensitive layer whose solubility in a developing solution is reduced by exposure.
  • the formed pattern corresponds to a cured layer.
  • the negative photosensitive layer preferably contains a resin, a polymerizable compound, and a polymerization initiator.
  • an alkali-soluble resin polymer A, which is an alkali-soluble resin
  • the photosensitive layer preferably contains a resin containing an alkali-soluble resin, a polymerizable compound, and a polymerization initiator.
  • Such a photosensitive layer (negative photosensitive layer) has a resin: 10 to 90% by mass; a polymerizable compound: 5 to 70% by mass; a polymerization initiator: 0.01, based on the total mass of the photosensitive layer. It is preferably contained in an amount of about 20% by mass.
  • a resin 10 to 90% by mass
  • a polymerizable compound 5 to 70% by mass
  • a polymerization initiator 0.01, based on the total mass of the photosensitive layer. It is preferably contained in an amount of about 20% by mass.
  • the resin contained in the photosensitive layer is also referred to as a polymer A in particular.
  • the polymer A is preferably an alkali-soluble resin.
  • the acid value of the polymer A is preferably 220 mgKOH / g or less, more preferably less than 200 mgKOH / g, and 190 mgKOH / g from the viewpoint of better resolution by suppressing the swelling of the negative photosensitive layer due to the developing solution. Less than g is more preferable.
  • the lower limit of the acid value of the polymer A is not particularly limited, but from the viewpoint of better developability, 60 mgKOH / g or more is preferable, 120 mgKOH / g or more is more preferable, 150 mgKOH / g or more is further preferable, and 170 mgKOH / g or more is more preferable. Especially preferable.
  • the acid value (mgKOH / g) is the mass [mg] of potassium hydroxide required to neutralize 1 g of the sample.
  • the acid value can be determined, for example, according to the method described in JIS K0070: 1992.
  • the acid value of the polymer A may be adjusted according to the type of the structural unit constituting the polymer A and the content of the structural unit containing the acid group.
  • the weight average molecular weight of the polymer A is preferably 5,000 to 500,000. When the weight average molecular weight is 500,000 or less, it is preferable from the viewpoint of improving resolution and developability.
  • the weight average molecular weight is more preferably 100,000 or less, further preferably 60,000 or less.
  • the weight average molecular weight is more preferably 10,000 or more, further preferably 20,000 or more, and particularly preferably 30,000 or more.
  • the edge fuse property refers to the degree of ease with which the negative photosensitive layer protrudes from the end face of the roll when the negative photosensitive resin laminate is wound into a roll.
  • the cut chip property refers to the degree of ease of chip flying when the unexposed film is cut with a cutter. When this chip adheres to the upper surface of the negative photosensitive resin laminate or the like, it is transferred to the mask in a later exposure step or the like, which causes a defective product.
  • the dispersity of the polymer A is preferably 1.0 to 6.0, more preferably 1.0 to 5.0, still more preferably 1.0 to 4.0, and particularly preferably 1.0 to 3.0. ..
  • the degree of dispersion is the ratio of the weight average molecular weight to the number average molecular weight (weight average molecular weight / number average molecular weight).
  • the weight average molecular weight and the number average molecular weight are values measured by gel permeation chromatography.
  • the polymer A is a structural unit based on a monomer having an aromatic hydrocarbon group from the viewpoint of suppressing line width thickening and deterioration of resolution when the focal position is deviated during exposure. It is preferable to include it.
  • aromatic hydrocarbon groups include substituted or unsubstituted phenyl groups and substituted or unsubstituted aralkyl groups.
  • the content of the structural unit based on the monomer having an aromatic hydrocarbon group in the polymer A is preferably 20% by mass or more, more preferably 30% by mass or more, based on the total mass of the polymer A.
  • the upper limit is not particularly limited, but is preferably 95% by mass or less, and more preferably 85% by mass or less.
  • the average value of the content of the structural unit based on the monomer having an aromatic hydrocarbon group is within the above range.
  • the monomer having an aromatic hydrocarbon group examples include a monomer having an aralkyl group, styrene, and a polymerizable styrene derivative (for example, methyl styrene, vinyl toluene, tert-butoxy styrene, acetoxy styrene, 4-vinyl scent). Acids, styrene dimers, styrene trimers, etc.). Of these, a monomer having an aralkyl group or styrene is preferable.
  • the content of the structural unit based on styrene is 20 to 70% by mass with respect to the total mass of the polymer A. Is preferable, 25 to 65% by mass is more preferable, 30 to 60% by mass is further preferable, and 30 to 55% by mass is particularly preferable.
  • the photosensitive layer contains a plurality of types of polymers A, the content of the structural unit having an aromatic hydrocarbon group is determined as a weight average value.
  • aralkyl group examples include a substituted or unsubstituted phenylalkyl group (excluding a benzyl group), a substituted or unsubstituted benzyl group and the like, and a substituted or unsubstituted benzyl group is preferable.
  • Examples of the monomer having a phenylalkyl group include phenylethyl (meth) acrylate and the like.
  • Examples of the monomer having a benzyl group include (meth) acrylate having a benzyl group, for example, benzyl (meth) acrylate, and chlorobenzyl (meth) acrylate; a vinyl monomer having a benzyl group, for example, vinylbenzyl chloride, and the like. Examples include vinylbenzyl alcohol. Of these, benzyl (meth) acrylate is preferable.
  • the monomer component having an aromatic hydrocarbon group in the polymer A is benzyl (meth) acrylate
  • the content of the structural unit based on the benzyl (meth) acrylate is the total mass of the polymer A.
  • 50 to 95% by mass is preferable, 60 to 90% by mass is more preferable, 70 to 90% by mass is further preferable, and 75 to 90% by mass is particularly preferable.
  • the polymer A containing a structural unit based on a monomer having an aromatic hydrocarbon group includes a monomer having an aromatic hydrocarbon group, at least one of the first monomers described later, and / or described below. It is preferably obtained by polymerizing with at least one of the second monomers.
  • the polymer A containing no structural unit based on a monomer having an aromatic hydrocarbon group is preferably obtained by polymerizing at least one of the first monomers described later, and is preferably the first single amount. It is more preferable to obtain it by copolymerizing at least one kind of the body and at least one kind of the second monomer described later.
  • the first monomer is a monomer having a carboxyl group in the molecule.
  • the first monomer include (meth) acrylic acid, fumaric acid, cinnamic acid, crotonic acid, itaconic acid, 4-vinylbenzoic acid, maleic acid anhydride, maleic acid semi-ester and the like. .. Among these, (meth) acrylic acid is preferable.
  • the content of the structural unit based on the first monomer in the polymer A is preferably 5 to 50% by mass, more preferably 10 to 40% by mass, and 15 to 30% by mass with respect to the total mass of the polymer A. % Is more preferable.
  • the content is 5% by mass or more from the viewpoint of exhibiting good developability, controlling edge fuseability, and the like. It is preferable that the content is 50% by mass or less from the viewpoint of high resolution of the resist pattern and the shape of the resist pattern, and further from the viewpoint of chemical resistance of the resist pattern.
  • the second monomer is a monomer that is non-acidic and has at least one polymerizable unsaturated group in the molecule.
  • Examples of the second monomer include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, and isobutyl (meth) acrylate.
  • examples thereof include esters of vinyl alcohols such as vinyl; and (meth) acrylonitrile.
  • methyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, or n-butyl (meth) acrylate is preferable, and methyl (meth) acrylate is more preferable.
  • the content of the structural unit based on the second monomer in the polymer A is preferably 5 to 60% by mass, more preferably 15 to 50% by mass, and 17 to 45% by mass with respect to the total mass of the polymer A. % Is more preferable.
  • the polymer A contains a monomer-based structural unit having an aralkyl group and / or a styrene-based monomer-based structural unit, it suppresses line width thickening and deterioration of resolution when the focal position shifts during exposure. It is preferable from the viewpoint of For example, a copolymer containing a methacrylic acid-based constituent unit, a benzyl methacrylate-based constituent unit, and a styrene-based constituent unit, a methacrylic acid-based constituent unit, a methyl methacrylate-based constituent unit, a benzyl methacrylate-based constituent unit, and a styrene.
  • the polymer A has a structural unit based on a monomer having an aromatic hydrocarbon group of 25 to 55% by mass, a structural unit based on the first monomer of 20 to 35% by mass, and a second component. It is preferably a polymer containing 15 to 45% by mass of a constituent unit based on a monomer. In another embodiment, the polymer contains 70 to 90% by mass of a structural unit based on a monomer having an aromatic hydrocarbon group and 10 to 25% by mass of a structural unit based on the first monomer. Is preferable.
  • the polymer A may have any of a linear structure, a branched structure, and an alicyclic structure in the side chain.
  • a monomer having a group having a branched structure in the side chain or a monomer having a group having an alicyclic structure in the side chain a branched structure or an alicyclic structure can be introduced into the side chain of the polymer A. ..
  • the group having an alicyclic structure may be a monocyclic ring or a polycyclic ring.
  • 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, and (. Isoamyl (meth) acrylate, tert-amyl (meth) acrylate, sec-amyl (meth) acrylate, 2-octyl (meth) acrylate, 3-octyl (meth) acrylate and tert-octyl (meth) acrylate. And so on.
  • isopropyl (meth) acrylate, isobutyl (meth) acrylate, and tert-butyl methacrylate are preferable, and isopropyl methacrylate or tert-butyl methacrylate are more preferable.
  • the monomer having a group having an alicyclic structure in the side chain include a monomer having a monocyclic aliphatic hydrocarbon group and a monomer having a polycyclic aliphatic hydrocarbon group.
  • (meth) acrylate having an alicyclic hydrocarbon group having 5 to 20 carbon atoms can be mentioned.
  • More specific examples include (meth) acrylic acid (bicyclo [2.2.1] heptyl-2), (meth) acrylic acid-1-adamantyl, (meth) acrylic acid-2-adamantyl, (meth). -3-Methyl-1-adamantyl acrylate, -3,5-dimethyl-1-adamantyl (meth) acrylate, -3-ethyladamantyl (meth) acrylate, -3-methyl-5-methyl (meth) acrylate Ethyl-1-adamantyl, (meth) acrylic acid-3,5,8-triethyl-1-adamantyl, (meth) acrylic acid-3,5-dimethyl-8-ethyl-1-adamantyl, (meth) acrylic acid 2 -Methyl-2-adamantyl, 2-ethyl-2-adamantyl (meth) acrylate, 3-hydroxy-1-adamantyl (meth) acrylate, o
  • (meth) acrylic acid esters (meth) acrylic acid cyclohexyl, (meth) acrylic acid (nor) boronyl, (meth) acrylic acid isobornyl, (meth) acrylic acid-1-adamantyl, (meth) acrylic acid -2-adamantyl, fentyl (meth) acrylate, 1-mentyl (meth) acrylate, or tricyclodecane (meth) acrylate is preferred, cyclohexyl (meth) acrylate, (nor) bornyl, (meth) acrylate, Isobornyl (meth) acrylate, -2-adamantyl (meth) acrylate, or tricyclodecane (meth) acrylate are more preferred.
  • the polymer A may be used alone or in combination of two or more.
  • two kinds of polymer A containing a structural unit based on a monomer having an aromatic hydrocarbon group may be mixed and used, or based on a monomer having an aromatic hydrocarbon group. It is preferable to mix and use the polymer A containing a structural unit and the polymer A not containing a structural unit based on a monomer having an aromatic hydrocarbon group.
  • the ratio of the polymer A containing the structural unit based on the monomer having an aromatic hydrocarbon group is preferably 50% by mass or more, preferably 70% by mass or more, based on the total mass of the polymer A. More preferably, 80% by mass or more is preferable, and 90% by mass or more is more preferable.
  • a radical polymerization initiator such as benzoyl peroxide and azoisobutyronitrile is prepared by diluting the above-mentioned one or more monomers with a solvent such as acetone, methyl ethyl ketone, and isopropanol. Is preferably added in an appropriate amount and heated and stirred. In some cases, a part of the mixture is added dropwise to the reaction solution for synthesis. After completion of the reaction, a solvent may be further added to adjust the concentration to a desired level.
  • a solvent may be further added to adjust the concentration to a desired level.
  • the synthesis means bulk polymerization, suspension polymerization, or emulsion polymerization may be used in addition to solution polymerization.
  • the glass transition temperature Tg of the polymer A is preferably 30 to 135 ° C.
  • the Tg of the polymer A is preferably 130 ° C. or lower, more preferably 120 ° C. or lower, and particularly preferably 110 ° C. or lower.
  • the polymer A having a Tg of 30 ° C. or higher from the viewpoint of improving the edge fuse resistance.
  • the Tg of the polymer A is more preferably 40 ° C. or higher, further preferably 50 ° C. or higher, particularly preferably 60 ° C. or higher, and most preferably 70 ° C. or higher.
  • the negative photosensitive layer may contain a resin other than the above as the polymer A.
  • resins include acrylic resin, styrene-acrylic copolymer, polyurethane resin, polyvinyl alcohol, polyvinyl formal, polyamide resin, polyester resin, polyamide resin, epoxy resin, polyacetal resin, polyhydroxystyrene resin, polyimide resin, and poly. Examples thereof include benzoxazole resin, polysiloxane resin, polyethyleneimine, polyallylamine, and polyalkylene glycol.
  • the alkali-soluble resin described in the description of the thermoplastic resin layer described later may be used.
  • the content of the polymer A is preferably 10 to 90% by mass, more preferably 20 to 80% by mass, further preferably 30 to 70% by mass, and 40 to 60% by mass with respect to the total mass of the negative photosensitive layer. % Is particularly preferable. It is preferable that the content of the polymer A is 90% by mass or less from the viewpoint of controlling the developing time. On the other hand, it is preferable that the content of the polymer A is 10% by mass or more from the viewpoint of improving the edge fuse resistance.
  • the photosensitive layer is a negative photosensitive layer
  • the negative photosensitive layer preferably contains a polymerizable compound having a polymerizable group.
  • the "polymerizable compound” means a compound that polymerizes under the action of a polymerization initiator described later, and is different from the above-mentioned polymer A.
  • the polymerizable group of the polymerizable compound is not particularly limited as long as it is a group involved in the polymerization reaction, and has, for example, an ethylenically unsaturated group such as a vinyl group, an acryloyl group, a methacryloyl group, a styryl group and a maleimide group. Groups; and groups having a cationically polymerizable group such as an epoxy group and an oxetane group can be mentioned.
  • a group having an ethylenically unsaturated group is preferable, and an acryloyl group or a metaacryloyl group is more preferable.
  • a compound having one or more ethylenically unsaturated groups is preferable, and two or more compounds in one molecule are preferable because the negative photosensitive layer has more excellent photosensitivity.
  • a compound having an ethylenically unsaturated group is more preferable.
  • the number of ethylenically unsaturated groups contained in one molecule of the ethylenically unsaturated compound is preferably 6 or less, more preferably 3 or less, and 2 or less in terms of excellent resolution and peelability. More preferred.
  • the content of the bifunctional ethylenically unsaturated compound with respect to the total mass of the polymerizable compound is preferably 20% by mass or more, preferably more than 40% by mass, with respect to the total mass of the negative photosensitive layer from the viewpoint of excellent peelability. More preferably, 55% by mass or more is further preferable.
  • the upper limit is not particularly limited and may be 100% by mass. That is, all the polymerizable compounds may be bifunctional ethylenically unsaturated compounds. Further, as the ethylenically unsaturated compound, a (meth) acrylate compound having a (meth) acryloyl group as a polymerizable group is preferable.
  • the negative photosensitive layer 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 one molecule among the above-mentioned polymerizable compounds B.
  • the mass ratio of the content of the polymerizable compound B1 to the total mass of the polymerizable compound in the negative photosensitive layer is preferably 40% or more, more preferably 50% by mass or more, 55 from the viewpoint of better resolution. By mass or more is more preferable, and 60% by mass or more is particularly preferable.
  • the upper limit is not particularly limited, but from the viewpoint of peelability, for example, it is 100% by mass or less, preferably 99% by mass or less, more preferably 95% by mass or less, further preferably 90% by mass or less, and particularly preferably 85% by mass or less. preferable.
  • aromatic ring contained in 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. Heterocycles and fused rings thereof are mentioned, and aromatic hydrocarbon rings are preferable, and benzene rings are more preferable.
  • the aromatic ring may have a substituent.
  • the polymerizable compound B1 may have only one aromatic ring or may have two or more aromatic rings.
  • the polymerizable compound B1 preferably has a bisphenol structure from the viewpoint of improving the resolution by suppressing the swelling of the photosensitive layer due to the developing solution.
  • the bisphenol structure include a bisphenol A structure derived from bisphenol A (2,2-bis (4-hydroxyphenyl) propane) and a bisphenol derived from bisphenol F (2,2-bis (4-hydroxyphenyl) methane).
  • examples thereof include an F structure and a bisphenol B structure derived from bisphenol B (2,2-bis (4-hydroxyphenyl) butane), and a bisphenol A structure is preferable.
  • Examples of the polymerizable compound B1 having a bisphenol structure include a compound having a bisphenol structure and two polymerizable groups (preferably (meth) acryloyl groups) bonded to both ends of the bisphenol structure. Both ends of the bisphenol structure and the two polymerizable groups may be directly bonded or may be bonded via one or more alkyleneoxy groups. As the alkyleneoxy group added to both ends of the bisphenol structure, an ethyleneoxy group or a propyleneoxy group is preferable, and an ethyleneoxy group is more preferable.
  • the number of alkyleneoxy groups added to the bisphenol structure is not particularly limited, but is preferably 4 to 16 per molecule, more preferably 6 to 14.
  • the polymerizable compound B1 having a bisphenol structure is described in paragraphs 0072 to 0080 of JP-A-2016-224162, and the contents described in this publication are incorporated in the present specification.
  • the polymerizable compound B1 a bifunctional ethylenically unsaturated compound having a bisphenol A structure is preferable, and 2,2-bis (4-((meth) acryloxypolyalkoxy) phenyl) propane is more preferable.
  • 2,2-bis (4-((meth) acryloxypolyalkoxy) phenyl) propane examples include 2,2-bis (4- (methacryloxydiethoxy) phenyl) propane (FA-324M, Hitachi Chemical Co., Ltd.).
  • polymerizable compound B1 a compound represented by the following general formula (B1) is also preferable.
  • R 1 and R 2 independently represent a hydrogen atom or a methyl group, respectively.
  • A represents C 2 H 4 .
  • B represents C 3 H 6 .
  • n1 and n3 are independently integers of 1 to 39, and n1 + n3 are integers of 2 to 40.
  • n2 and n4 are independently integers of 0 to 29, and n2 + n4 are integers of 0 to 30.
  • the sequence of constituent units of-(AO)-and-(BO)- may be random or block. In the case of a block, either ⁇ (A—O) ⁇ or ⁇ (BO) ⁇ may be on the bisphenyl group side.
  • 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, further preferably 0 to 2, and particularly preferably 0.
  • the polymerizable compound B1 may be used alone or in combination of two or more.
  • the content of the polymerizable compound B1 is preferably 10% by mass or more, more preferably 20% by mass or more, based on the total mass of the negative photosensitive layer, from the viewpoint of better resolution.
  • the upper limit is not particularly limited, but from the viewpoint of transferability and edge fusion (a phenomenon in which the photosensitive resin exudes from the end of the transfer member), 70% by mass or less is preferable, and 60% by mass or less is more preferable.
  • the negative photosensitive layer may contain a polymerizable compound other than the above-mentioned polymerizable compound B1.
  • the polymerizable compound other than the polymerizable compound B1 is not particularly limited and may be appropriately selected from known compounds. For example, a compound having one ethylenically unsaturated group in one molecule (monofunctional ethylenically unsaturated compound), a bifunctional ethylenically unsaturated compound having no aromatic ring, and a trifunctional or higher functional ethylenically unsaturated compound. Can be mentioned.
  • Examples of the monofunctional ethylenically unsaturated compound include ethyl (meth) acrylate, ethylhexyl (meth) acrylate, 2- (meth) acryloyloxyethyl succinate, polyethylene glycol mono (meth) acrylate, and polypropylene glycol mono (meth) acrylate. , And phenoxyethyl (meth) acrylate.
  • Examples of the bifunctional ethylenically unsaturated compound having no aromatic ring include alkylene glycol di (meth) acrylate, polyalkylene glycol di (meth) acrylate, urethane di (meth) acrylate, and trimethylolpropane diacrylate. ..
  • Examples of the alkylene glycol di (meth) acrylate include tricyclodecanedimethanol diacrylate (A-DCP, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), tricyclodecanedimethanol dimethacrylate (DCP, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), and the like.
  • 1,9-Nonandiol diacrylate (A-NOD-N, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), 1,6-hexanediol diacrylate (A-HD-N, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), ethylene glycol dimethacrylate , 1,10-decanediol diacrylate, and neopentyl glycol di (meth) acrylate.
  • the polyalkylene glycol di (meth) acrylate include polyethylene glycol di (meth) acrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, and polypropylene glycol di (meth) acrylate.
  • Examples of the urethane di (meth) acrylate include propylene oxide-modified urethane di (meth) acrylate, and ethylene oxide and propylene oxide-modified urethane di (meth) acrylate.
  • Examples of commercially available products include 8UX-015A (manufactured by Taisei Fine Chemical Industry Co., Ltd.), UA-32P (manufactured by Shin Nakamura Chemical Industry Co., Ltd.), and UA-1100H (manufactured by Shin Nakamura Chemical Industry Co., Ltd.).
  • Examples of the trifunctional or higher functional ethylenically unsaturated compound include dipentaerythritol (tri / tetra / penta / hexa) (meth) acrylate, pentaerythritol (tri / tetra) (meth) acrylate, and trimethylolpropane tri (meth).
  • Examples thereof include acrylates, trimethylolpropane tetra (meth) acrylates, trimethylolethanetri (meth) acrylates, isocyanuric acid tri (meth) acrylates, glycerintri (meth) acrylates, and alkylene oxide modifications thereof.
  • (tri / tetra / penta / hexa) (meth) acrylate) is a concept including tri (meth) acrylate, tetra (meth) acrylate, penta (meth) acrylate, and hexa (meth) acrylate.
  • (Tri / tetra) (meth) acrylate” is a concept that includes tri (meth) acrylate and tetra (meth) acrylate.
  • the negative photosensitive layer preferably contains the above-mentioned polymerizable compound B1 and a trifunctional or higher ethylenically unsaturated compound, and the above-mentioned polymerizable compound B1 and two or more trifunctional or higher ethylenic compounds. It is more preferable to contain unsaturated compounds.
  • the negative photosensitive layer preferably contains the above-mentioned polymerizable compound B1 and two or more trifunctional ethylenically unsaturated compounds.
  • alkylene oxide-modified product of the trifunctional or higher ethylenically unsaturated compound examples include caprolactone-modified (meth) acrylate compound (KAYARAD (registered trademark) DPCA-20 manufactured by Nippon Kayaku Co., Ltd. and A-9300-1CL manufactured by Shin-Nakamura Chemical Industry Co., Ltd.).
  • KAYARAD registered trademark
  • DPCA-20 Nippon Kayaku Co., Ltd.
  • A-9300-1CL manufactured by Shin-Nakamura Chemical Industry Co., Ltd.
  • alkylene oxide-modified (meth) acrylate compound (KAYARAD RP-1040 manufactured by Nippon Kayaku Co., Ltd., ATM-35E and A-9300 manufactured by Shin-Nakamura Chemical Industry Co., Ltd., EBECRYL (registered trademark) 135 manufactured by Daicel Ornex Co., Ltd., etc.), Ethoxylated glycerin triacrylate (A-GLY-9E manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), Aronix (registered trademark) TO-2349 (manufactured by Toagosei Co., Ltd.), Aronix M-520 (manufactured by Toagosei Co., Ltd.), and Aronix M- 510 (manufactured by Toagosei Co., Ltd.) can be mentioned.
  • Aronix registered trademark
  • a polymerizable compound having an acid group (carboxy group or the like) may be used.
  • the acid group may form an acid anhydride group.
  • Polymerizable compounds having an acid group include Aronix (registered trademark) TO-2349 (manufactured by Toagosei), Aronix (registered trademark) M-520 (manufactured by Toagosei), and Aronix (registered trademark) M-510 (registered trademark). Toagosei Co., Ltd.).
  • the polymerizable compound having an acid group for example, the polymerizable compound having an acid group described in paragraphs 0025 to 0030 of JP-A-2004-239942 may be used.
  • the polymerizable compound may be used alone or in combination of two or more.
  • the content of the polymerizable compound is preferably 10 to 70% by mass, more preferably 15 to 70% by mass, still more preferably 20 to 70% by mass, based on the total mass of the negative photosensitive layer.
  • the molecular weight (weight average molecular weight when having a molecular weight distribution) of the polymerizable compound (including the polymerizable compound B1) is preferably 200 to 3,000, more preferably 280 to 2,200, and preferably 300 to 2,200. More preferred.
  • the photosensitive layer is a negative type photosensitive layer
  • the negative type photosensitive layer contains a polymerization initiator.
  • the polymerization initiator is selected according to the type of the polymerization reaction, and examples thereof include a thermal polymerization initiator and a photopolymerization initiator.
  • the polymerization initiator may be a radical polymerization initiator or a cationic polymerization initiator.
  • the negative photosensitive layer preferably contains a photopolymerization initiator.
  • the photopolymerization initiator is a compound that initiates the polymerization of a polymerizable compound by receiving active rays such as ultraviolet rays, visible rays and X-rays.
  • the photopolymerization initiator is not particularly limited, and a known photopolymerization initiator can be used. Examples of the photopolymerization initiator include a photoradical polymerization initiator and a photocationic polymerization initiator, and a photoradical polymerization initiator is preferable.
  • Examples of the photoradical polymerization initiator include a photopolymerization initiator having an oxime ester structure, a photopolymerization initiator having an ⁇ -aminoalkylphenone structure, a photopolymerization initiator having an ⁇ -hydroxyalkylphenone structure, and an acylphosphine oxide. Examples thereof include a photopolymerization initiator having a structure and a photopolymerization initiator having an N-phenylglycine structure.
  • the negative photosensitive layer is a photoradical polymerization initiator such as a 2,4,5-triarylimidazole dimer from the viewpoints of photosensitivity, visibility of exposed and unexposed areas, and resolution. It is preferable to contain at least one selected from the group consisting of the derivatives.
  • the two 2,4,5-triarylimidazole structures in the 2,4,5-triarylimidazole dimer and its derivatives may be the same or different.
  • Derivatives of the 2,4,5-triarylimidazole dimer include, for example, 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer, 2- (o-chlorophenyl) -4,5-di.
  • the photoradical polymerization initiator for example, the polymerization initiator described in paragraphs 0031 to 0042 of JP-A-2011-95716 and paragraphs 0064-0081 of JP-A-2015-14783 may be used.
  • photoradical polymerization initiator examples include ethyl dimethylaminobenzoate (DBE, CAS No. 10287-53-3), benzoin methyl ether, anisyl (p, p'-dimethoxybenzyl), and TAZ-110 (trade name:).
  • the photocationic polymerization initiator is a compound that generates an acid by receiving active light rays.
  • a compound that is sensitive to active light having a wavelength of 300 nm or more, preferably a wavelength of 300 to 450 nm and generates an acid is preferable, but its chemical structure is not limited.
  • a photocationic polymerization initiator that is not directly sensitive to active light with a wavelength of 300 nm or more is also a sensitizer if it is a compound that is sensitive to active light with a wavelength of 300 nm or more and generates an acid when used in combination with a sensitizer. Can be preferably used in combination with.
  • a photocationic polymerization initiator that generates an acid having a pKa of 4 or less is preferable, a photocationic polymerization initiator that generates an acid having a pKa of 3 or less is more preferable, and an acid having a pKa of 2 or less is used.
  • the generated photocationic polymerization initiator is particularly preferred.
  • the lower limit of pKa is not particularly defined, but is preferably -10.0 or higher, for example.
  • Examples of the photocationic polymerization initiator include an ionic photocationic polymerization initiator and a nonionic photocationic polymerization initiator.
  • Examples of the ionic photocationic polymerization initiator include onium salt compounds such as diaryliodonium salts and triarylsulfonium salts, and quaternary ammonium salts.
  • the ionic photocationic polymerization initiator described in paragraphs 0114 to 0133 of JP-A-2014-085643 may be used.
  • nonionic photocationic polymerization initiator examples include trichloromethyl-s-triazines, diazomethane compounds, imide sulfonate compounds, and oxime sulfonate compounds.
  • trichloromethyl-s-triazines the diazomethane compound and the imide sulfonate compound
  • the compounds described in paragraphs 0083 to 886 of JP-A-2011-22149 may be used.
  • the oxime sulfonate compound the compound described in paragraphs 0083 to 0088 of International Publication No. 2018/179640 may be used.
  • the negative photosensitive layer preferably contains a photoradical polymerization initiator, and more preferably contains at least one selected from the group consisting of 2,4,5-triarylimidazole dimers and derivatives thereof.
  • the polymerization initiator may be used alone or in combination of two or more.
  • the content of the polymerization initiator (preferably photopolymerization initiator) is not particularly limited, but is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, based on the total mass of the negative photosensitive layer. , 1.0% by mass or more is more preferable.
  • the upper limit is not particularly limited, but is preferably 20% by mass or less, more preferably 15% by mass or less, still more preferably 10% by mass or less, based on the total mass of the negative photosensitive layer.
  • the dye photosensitive layer has a maximum absorption wavelength of 450 nm or more in the wavelength range of 400 to 780 nm at the time of color development from the viewpoint of visibility of exposed and unexposed areas, pattern visibility after development, and resolution. It is also preferable to include a dye (also referred to as "dye N") whose maximum absorption wavelength is changed by an acid, a base, or a radical.
  • a dye also referred to as "dye N”
  • the detailed mechanism is unknown, but the adhesion to the adjacent layer (for example, a water-soluble resin layer) is improved, and the resolution is more excellent.
  • the term "the maximum absorption wavelength is changed by an acid, a base, or a radical” means that the dye in a color-developing state is decolorized by an acid, a base, or a radical, and the dye in a decolorized state is decolorized. It may mean any aspect of a mode in which a color is developed by an acid, a base, or a radical, and a mode in which a dye in a color-developing state changes to a color-developing state of another hue.
  • the dye N may be a compound that changes its color from the decolorized state by exposure and may be a compound that changes its color from the decolorized state by exposure.
  • it may be a dye whose color development or decolorization state is changed by the acid, base, or radical generated and acted on in the photosensitive layer by exposure, and the state in the photosensitive layer by the acid, base, or radical. It may be a dye whose color development or decolorization state changes by changing (for example, pH). Further, it may be a dye that changes the state of color development or decolorization by directly receiving an acid, a base, or a radical as a stimulus without going through exposure.
  • the dye N is preferably a dye whose maximum absorption wavelength is changed by an acid or a radical, and more preferably a dye whose maximum absorption wavelength is changed by a radical. ..
  • the photosensitive layer is a negative photosensitive layer
  • the negative photosensitive layer is a dye whose maximum absorption wavelength is changed by radicals as dye N from the viewpoint of visibility and resolution of exposed and unexposed areas.
  • the dye N is preferably a dye that develops color by an acid, a base, or a radical.
  • a photoradical polymerization initiator, a photocationic polymerization initiator (photoacid generator), or a photobase generator is added to the photosensitive layer, and the photoradical polymerization initiator is added after exposure.
  • a radical-reactive dye, an acid-reactive dye, or a base-reactive dye for example, a leuco dye
  • a radical-reactive dye, an acid-reactive dye, or a base-reactive dye for example, a leuco dye
  • the dye N preferably has a maximum absorption wavelength of 550 nm or more in the wavelength range of 400 to 780 nm at the time of color development, more preferably 550 to 700 nm. It is more preferably ⁇ 650 nm. Further, the dye N may have only one maximum absorption wavelength in the wavelength range of 400 to 780 nm at the time of color development, or may have two or more. When the dye N has two or more maximum absorption wavelengths in the wavelength range of 400 to 780 nm at the time of color development, the maximum absorption wavelength having the highest absorbance among the two or more maximum absorption wavelengths may be 450 nm or more.
  • the maximum absorption wavelength of the dye N is the transmission spectrum of the solution containing the dye N (liquid temperature 25 ° C.) in the range of 400 to 780 nm using a spectrophotometer: UV3100 (manufactured by Shimadzu Corporation) in an atmospheric atmosphere. Is measured, and the wavelength at which the light intensity becomes the minimum (maximum absorption wavelength) is detected.
  • Examples of the dye that develops or decolorizes by exposure include leuco compounds.
  • Examples of the dye that is decolorized by exposure include a leuco compound, a diarylmethane dye, an oxadin dye, a xanthene dye, an iminonaphthoquinone dye, an azomethin dye, and an anthraquinone dye.
  • As the dye N a leuco compound is preferable from the viewpoint of visibility of the exposed portion and the non-exposed portion.
  • the leuco compound examples include a leuco compound having a triarylmethane skeleton (triarylmethane dye), a leuco compound having a spiropyran skeleton (spiropylan dye), a leuco compound having a fluorane skeleton (fluorane dye), and a diarylmethane skeleton.
  • triarylmethane dye a leuco compound having a triarylmethane skeleton
  • spiropyran skeleton a leuco compound having a spiropyran skeleton
  • fluorane dye fluorane skeleton
  • diarylmethane skeleton examples include a diarylmethane skeleton having a diarylmethane skeleton.
  • leuco compound (diarylmethane dye) having a leuco compound (diarylmethane dye), a leuco compound having a rhodamine lactam skeleton (lodamine lactam dye), a leuco compound having an indrill phthalide skeleton (indrill phthalide dye), and a leuco auramine skeleton.
  • leuco compounds (leuco auramine-based dyes) examples thereof include leuco compounds (leuco auramine-based dyes).
  • triarylmethane-based dyes or fluorane-based dyes are preferable, and leuco compounds (triphenylmethane-based dyes) or fluorane-based dyes having a triphenylmethane skeleton are more preferable.
  • the leuco compound preferably has a lactone ring, a surujin ring, or a sultone ring from the viewpoint of visibility of the exposed portion and the non-exposed portion.
  • the lactone ring, sultin ring, or sulton ring of the leuco compound is reacted with the radical generated from the photoradical polymerization initiator or the acid generated from the photocationic polymerization initiator to change the leuco compound into a closed ring state.
  • the color can be decolorized, or the leuco compound can be changed to an open ring state to develop a color.
  • the leuco compound has a lactone ring, a sultone ring, or a sultone ring, and a compound in which the lactone ring, the sultone ring, or the sultone ring is opened by a radical or an acid to develop color is preferable, and the compound has a lactone ring and is a radical or a radical.
  • a compound in which the lactone ring is opened by an acid to develop a color is more preferable.
  • dye N examples include the following dyes and leuco compounds. Specific examples of dyes among dyes N include Brilliant Green, Ethyl Violet, Methyl Green, Crystal Violet, Basic Fuxin, Methyl Violet 2B, Kinaldine Red, Rose Bengal, Metanyl Yellow, Timor Sulfophthalein, Xylenol Blue, and Methyl.
  • leuco compound among the dyes N include p, p', p "-hexamethyltriaminotriphenylmethane (leucocrystal violet), Pergascript Blue SRB (manufactured by Ciba Geigy), crystal violet lactone, and malakite green lactone.
  • the dye N is preferably a dye whose maximum absorption wavelength is changed by radicals from the viewpoints of visibility of exposed and unexposed areas, pattern visibility after development, and resolution, and is a dye that develops color by radicals. It is more preferable to have.
  • As the dye N leuco crystal violet, crystal violet lactone, brilliant green, or Victoria pure blue-naphthalene sulfonate is preferable.
  • the dye N may be used alone or in combination of two or more.
  • the content of the dye N is preferably 0.1% by mass or more with respect to the total mass of the photosensitive layer from the viewpoints of visibility of the exposed and non-exposed areas, pattern visibility after development, and resolution. , 0.1 to 10% by mass is more preferable, 0.1 to 5% by mass is further preferable, and 0.1 to 1% by mass is particularly preferable.
  • the content of the dye N means the content of the dye when all of the dye N contained in the total mass of the photosensitive layer is in a colored state.
  • a method for quantifying the content of dye N will be described by taking a dye that develops color by radicals as an example.
  • a solution in which 0.001 g and 0.01 g of the dye are dissolved in 100 mL of methyl ethyl ketone is prepared.
  • Irradicure OXE01 (trade name, BASF Japan Co., Ltd.), a photoradical polymerization initiator, is added to each of the obtained solutions, and radicals are generated by irradiating with light of 365 nm to bring all the dyes into a colored state.
  • the absorbance of each solution having a liquid temperature of 25 ° C. is measured using a spectrophotometer (UV3100, manufactured by Shimadzu Corporation), and a calibration curve is prepared.
  • UV3100 UV3100, manufactured by Shimadzu Corporation
  • the absorbance of the solution in which all the dyes are developed is measured by the same method as above except that 3 g of the photosensitive layer is dissolved in methyl ethyl ketone instead of the dye. From the absorbance of the obtained solution containing the photosensitive layer, the content of the dye contained in the photosensitive layer is calculated based on the calibration curve.
  • the photosensitive layer 3 g is the same as the total solid content of 3 g in the photosensitive composition.
  • Thermally crosslinkable compound When the photosensitive layer is a negative photosensitive layer, it is preferable to contain a thermally crosslinkable compound from the viewpoint of the strength of the obtained cured film and the adhesiveness of the obtained uncured film.
  • the thermally crosslinkable compound having an ethylenically unsaturated group described later is not treated as a polymerizable compound, but is treated as a thermally crosslinkable compound.
  • the heat-crosslinkable compound include a methylol compound and a blocked isocyanate compound. Of these, a blocked isocyanate compound is preferable from the viewpoint of the strength of the obtained cured film and the adhesiveness of the obtained uncured film.
  • the blocked isocyanate compound reacts with a hydroxy group and a carboxy group, for example, when the resin and / or the polymerizable compound has at least one of the hydroxy group and the carboxy group, the hydrophilicity of the formed film decreases.
  • the function tends to be enhanced.
  • the blocked isocyanate compound refers to "a compound having a structure in which the isocyanate group of isocyanate is protected (so-called masked) with a blocking agent".
  • the dissociation temperature of the blocked isocyanate compound is not particularly limited, but is preferably 100 to 160 ° C, more preferably 130 to 150 ° C.
  • the dissociation temperature of the blocked isocyanate means "the temperature of the endothermic peak associated with the deprotection reaction of the blocked isocyanate when measured by DSC (Differential scanning calorimetry) analysis using a differential scanning calorimeter".
  • DSC Different scanning calorimeter
  • a differential scanning calorimeter model: DSC6200 manufactured by Seiko Instruments Inc. can be preferably used.
  • the differential scanning calorimeter is not limited to this.
  • the blocking agent having a dissociation temperature of 100 to 160 ° C. for example, at least one selected from oxime compounds is preferable from the viewpoint of storage stability.
  • the blocked isocyanate compound preferably has an isocyanurate structure, for example, from the viewpoint of improving the brittleness of the membrane and improving the adhesion to the transferred body.
  • the blocked isocyanate compound having an isocyanurate structure can be obtained, for example, by subjecting hexamethylene diisocyanate to isocyanurate to protect it.
  • a compound having an oxime structure using an oxime compound as a blocking agent is more likely to have a dissociation temperature in a preferable range than a compound having no oxime structure, and has less development residue. It is preferable from the viewpoint of easy operation.
  • the blocked isocyanate compound may have a polymerizable group.
  • the polymerizable group is not particularly limited, and a known polymerizable group can be used, and a radically polymerizable group is preferable.
  • the polymerizable group include an ethylenically unsaturated group such as a (meth) acryloxy group, a (meth) acrylamide group, and a styryl group, and a group having an epoxy group such as a glycidyl group.
  • an ethylenically unsaturated group is preferable, a (meth) acryloxy group is more preferable, and an acryloxy group is further preferable.
  • blocked isocyanate compound a commercially available product can be used.
  • examples of commercially available blocked isocyanate compounds include Karenz (registered trademark) AOI-BM, Karenz (registered trademark) MOI-BM, Karenz (registered trademark) MOI-BP (all manufactured by Showa Denko KK), and block type.
  • examples thereof include the Duranate series (for example, Duranate (registered trademark) TPA-B80E, Duranate (registered trademark) WT32-B75P, etc., manufactured by Asahi Kasei Chemicals Co., Ltd.).
  • the blocked isocyanate compound a compound having the following structure can also be used.
  • the heat-crosslinkable compound may be used alone or in combination of two or more.
  • the content of the heat-crosslinkable compound is preferably 1 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 known additives in addition to the above components, if necessary.
  • the additive include a radical polymerization inhibitor, a sensitizer, a plasticizer, a heterocyclic compound (triazole, etc.), benzotriazoles, carboxybenzotriazoles, pyridines (isonicotinamide, etc.), a purine base (adenine, etc.). ), And a surfactant.
  • a radical polymerization inhibitor e.g., a radical polymerization inhibitor, etc.
  • benzotriazoles e.g., benzotriazoles, carboxybenzotriazoles, pyridines (isonicotinamide, etc.), a purine base (adenine, etc.).
  • a surfactant e.g., etc., etc., etc.
  • Each additive may be used alone or in combination of two or more.
  • the photosensitive layer may contain a radical polymerization inhibitor.
  • the radical polymerization inhibitor include the thermal polymerization inhibitor described in paragraph 0018 of Japanese Patent No. 4502784. Of these, phenothiazine, phenoxazine, or 4-methoxyphenol is preferable.
  • examples of other radical polymerization inhibitors include naphthylamine, cuprous chloride, nitrosophenylhydroxyamine aluminum salt, diphenylnitrosamine and the like. It is preferable to use a nitrosophenylhydroxylamine aluminum salt as a radical polymerization inhibitor so as not to impair the sensitivity of the photosensitive layer.
  • the preferable content of the radical polymerization inhibitor is the same as the content of the same component in the photosensitive layer of the transfer film X2 of the second embodiment.
  • benzotriazoles include 1,2,3-benzotriazole, 1-chloro-1,2,3-benzotriazole, bis (N-2-ethylhexyl) aminomethylene-1,2,3-benzotriazole, and the like. Examples thereof include bis (N-2-ethylhexyl) aminomethylene-1,2,3-tolyltriazole and bis (N-2-hydroxyethyl) aminomethylene-1,2,3-benzotriazole.
  • carboxybenzotriazoles examples include 4-carboxy-1,2,3-benzotriazole, 5-carboxy-1,2,3-benzotriazole, and N- (N, N-di-2-ethylhexyl) aminomethylene. Examples thereof include carboxybenzotriazole, N- (N, N-di-2-hydroxyethyl) aminomethylenecarboxybenzotriazole, and N- (N, N-di-2-ethylhexyl) aminoethylenecarboxybenzotriazole.
  • a commercially available product such as CBT-1 (Johoku Chemical Industry Co., Ltd., trade name) can be used.
  • the total content of benzotriazols and carboxybenzotriazols 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.
  • 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 the suppression of dye decolorization are more excellent.
  • a hindered phenol compound is also preferable.
  • the hindered phenol compound include bis [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionic acid] [ethylene bis (oxyethylene)] 2,4-bis [(laurylthio) methyl.
  • 1,3,5-tris (3,5-di-t-butyl-4-hydroxybenzyl), 1,3,5-tris (4-t-butyl-3-hydroxy-2, 6-Dimethylbenzyl), 2,4-bis- (n-octylthio) -6- (4-hydroxy-3,5-di-t-butylanilino) -1,3,5-triazine, and pentaerythritol tetrakis 3 -(3,5-Di-tert-butyl-4-hydroxyphenyl) propionate and the like can be mentioned.
  • the photosensitive layer may contain a sensitizer.
  • the sensitizer is not particularly limited, and known sensitizers, dyes and pigments can be used.
  • Examples of the sensitizer include dialkylaminobenzophenone compounds, pyrazoline compounds, anthracene compounds, coumarin compounds, xanthone compounds, thioxanthone compounds, acridone compounds, oxazole compounds, benzoxazole compounds, thiazole compounds, benzothiazole compounds, and triazole compounds (for example,). 1,2,4-triazole), stylben compounds, triazine compounds, thiophene compounds, naphthalimide compounds, triarylamine compounds, and aminoacridin compounds.
  • Examples of commercially available sensitizers include "SB-PI 701"(4,4'-bis (diethylamino) benzophenone) manufactured by Sanyo Trading Co., Ltd.
  • the sensitizer may be used alone or in combination of two or more.
  • the content of the sensitizer can be appropriately selected depending on the purpose, but from the viewpoint of improving the sensitivity to the light source and improving the curing rate by balancing the polymerization rate and the chain transfer, the photosensitive layer is photosensitive. It is preferably 0.01 to 5% by mass, more preferably 0.05 to 1% by mass, based on the total mass of the sex layer.
  • the photosensitive layer may contain at least one selected from the group consisting of a plasticizer and a heterocyclic compound.
  • a plasticizer and a heterocyclic compound include the compounds described in paragraphs 097 to 0103 and 0111 to 0118 of International Publication No. 2018/179640.
  • the photosensitive layer preferably contains a surfactant.
  • the surfactant include the same surfactants that may be contained in the photosensitive layer of the transfer film X2 of the second embodiment described later, and the preferred embodiments are also the same.
  • the photosensitive layer includes metal oxide particles, antioxidants, rust inhibitors, dispersants, acid growth agents, development accelerators, conductive fibers, ultraviolet absorbers, thickeners, cross-linking agents, and organic or inorganic materials. It may further contain known additives such as anti-precipitation agents. It is also preferable to include N-phenylcarbamoylmethyl-N-carboxymethylaniline and / or N, N-tetraethyl-4,4-diaminobenzophenone as the chain transfer agent. Additives contained in the photosensitive layer are described in paragraphs 0165 to 0184 of JP-A-2014-085643, and the contents of this publication are incorporated in the present specification.
  • 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 laminating property.
  • the transmittance of light having a wavelength of 365 nm in the photosensitive layer is preferably 10% or more, more preferably 30% or more, still more preferably 50% or more.
  • the upper limit is not particularly limited, but is preferably 99.9% or less.
  • the photosensitive layer may contain a predetermined amount of impurities.
  • impurities include sodium, potassium, magnesium, calcium, iron, manganese, copper, aluminum, titanium, chromium, cobalt, nickel, zinc, tin, halogen and ions thereof.
  • halide ions, sodium ions, and potassium ions are likely to be mixed as impurities, so the following content is preferable.
  • the content of impurities in the photosensitive layer is preferably 80 ppm or less, more preferably 10 ppm or less, and even more preferably 2 ppm or less on a mass basis.
  • the content of impurities may be 1 ppb or more, or 0.1 ppm or more, on a mass basis.
  • Examples of the method for keeping impurities within the above range include selecting a raw material for the composition having a low content of impurities, preventing contamination of the photosensitive layer at the time of producing the photosensitive layer, and cleaning and removing the impurities. .. By such a method, the amount of impurities can be kept within the above range.
  • Impurities can be quantified by known methods such as ICP (Inductively Coupled Plasma) emission spectroscopy, atomic absorption spectroscopy, and ion chromatography.
  • ICP Inductively Coupled Plasma
  • the content of compounds such as benzene, formaldehyde, trichlorethylene, 1,3-butadiene, carbon tetrachloride, chloroform, N, N-dimethylformamide, N, N-dimethylacetamide, and hexane in the photosensitive layer may be low. preferable.
  • the content of these compounds with respect to the total mass of the photosensitive layer is preferably 100 ppm or less, more preferably 20 ppm or less, still more preferably 4 ppm or less on a mass basis.
  • the lower limit can be 10 ppb or more and 100 ppb or more with respect to the total mass of the photosensitive layer on a mass basis.
  • the content of these compounds can be suppressed in the same manner as the above-mentioned metal impurities. Further, it can be quantified by a known measurement method.
  • the water content in the photosensitive layer is preferably 0.01 to 1.0% by mass, more preferably 0.05 to 0.5% by mass, from the viewpoint of improving reliability and laminating property.
  • the pigment photosensitive layer may be a colored resin layer containing a pigment.
  • the liquid crystal display window of an electronic device may have a cover glass having a black frame-shaped light-shielding layer formed on the peripheral edge of the back surface of a transparent glass substrate or the like to protect the liquid crystal display window. be.
  • a colored resin layer can be used to form such a light-shielding layer.
  • the pigment may be appropriately selected according to the desired hue, and can be selected from black pigments, white pigments, and chromatic pigments other than black and white. Among them, when forming a black pattern, a black pigment is preferably selected as the pigment.
  • the black pigment a known black pigment (organic pigment, inorganic pigment, etc.) can be appropriately selected as long as the effect of the present invention is not impaired.
  • the black pigment for example, carbon black, titanium oxide, titanium carbide, iron oxide, titanium oxide, graphite and the like are preferably mentioned from the viewpoint of optical density, and carbon black is particularly preferable.
  • carbon black from the viewpoint of surface resistance, carbon black having at least a part of the surface coated with a resin is preferable.
  • the particle size of the black pigment is preferably 0.001 to 0.1 ⁇ m, more preferably 0.01 to 0.08 ⁇ m in terms of number average particle size.
  • the particle size refers to the diameter of the circle when the area of the pigment particles is obtained from the photographic image of the pigment particles taken with an electronic microscope and the circle having the same area as the area of the pigment particles is considered, and the number average particle size. Is an average value obtained by obtaining the above particle size for any 100 particles and averaging the obtained 100 particle sizes.
  • the white pigment described in paragraphs 0015 and 0114 of JP-A-2005-007765 can be used as the white pigment.
  • the white pigments as the inorganic pigment, titanium oxide, zinc oxide, lithopone, light calcium carbonate, white carbon, aluminum oxide, aluminum hydroxide, or barium sulfate are preferable, and titanium oxide or zinc oxide is more preferable. Titanium oxide is preferable, and titanium oxide is more preferable.
  • rutile-type or anatase-type titanium oxide is more preferable, and rutile-type titanium oxide is particularly preferable.
  • the surface of titanium oxide may be treated with silica, alumina, titania, zirconia, or an organic substance, or may be subjected to two or more treatments.
  • the catalytic activity of titanium oxide is suppressed, and heat resistance, fading and the like are improved.
  • at least one of alumina treatment and zirconia treatment is preferable as the surface treatment of the surface of titanium oxide, and both alumina treatment and zirconia treatment are particularly preferable.
  • the photosensitive layer is a colored resin layer
  • the photosensitive layer further contains a chromatic pigment other than the black pigment and the white pigment from the viewpoint of transferability.
  • a chromatic pigment is contained, the particle size of the chromatic pigment is preferably 0.1 ⁇ m or less, more preferably 0.08 ⁇ m or less, in that the dispersibility is more excellent.
  • chromatic pigments include Victoria Pure Blue BO (Color Index (hereinafter CI) 42595), Auramine (CI41000), Fat Black HB (CI26150), and Monolite.
  • Pigment Red 180 C.I. I. Pigment Red 192, C.I. I. Pigment Red 215, C.I. I. Pigment Green 7, C.I. I. Pigment Blue 15: 1, C.I. I. Pigment Blue 15: 4, C.I. I. Pigment Blue 22, C.I. I. Pigment Blue 60, C.I. I. Pigment Blue 64, and C.I. I. Pigment Violet 23 and the like. Above all, C.I. I. Pigment Red 177 is preferred.
  • the content of the pigment is preferably more than 3% by mass and 40% by mass or less, more preferably more than 3% by mass and 35% by mass or less, based on the total mass of the photosensitive layer. It is more preferably more than mass% and 35% by mass or less, and particularly preferably 10% by mass or more and 35% by mass or less.
  • the content of the pigment other than the black pigment is preferably 30% by mass or less, preferably 1 to 20% by mass, based on the black pigment. Is more preferable, and 3 to 15% by mass is further preferable.
  • the black pigment (preferably carbon black) is introduced into the photosensitive composition in the form of a pigment dispersion.
  • the dispersion liquid may be prepared by adding a mixture obtained by previously mixing a black pigment and a pigment dispersant to an organic solvent (or vehicle) and dispersing it with a disperser.
  • the pigment dispersant may be selected depending on the pigment and the solvent, and for example, a commercially available dispersant can be used.
  • the vehicle refers to a portion of the medium in which the pigment is dispersed when the pigment is dispersed, and is a liquid, a binder component that holds the black pigment in a dispersed state, and a solvent component that dissolves and dilutes the binder component. (Organic solvent) and.
  • the disperser is not particularly limited, and examples thereof include known dispersers such as a kneader, a roll mill, an attritor, a super mill, a dissolver, a homomixer, and a sand mill. Further, it may be finely pulverized by mechanical grinding using frictional force.
  • disperser and fine pulverization the description of "Encyclopedia of Pigments" (Kunizo Asakura, First Edition, Asakura Shoten, 2000, 438, 310) can be referred to.
  • the thickness of the photosensitive layer is not particularly limited, but is often 30 ⁇ m or less, and is preferably 20 ⁇ m or less, more preferably 15 ⁇ m or less, still more preferably 10 ⁇ m or less, and further preferably 5.0 ⁇ m in that the effect of the present invention is more excellent.
  • the following are particularly preferred.
  • As the lower limit 0.60 ⁇ m or more is preferable, 1.5 ⁇ m or more is more preferable, and 2.0 ⁇ m or more is further preferable, in that the strength of the film obtained by curing the photosensitive layer is excellent.
  • the thickness of the photosensitive layer is calculated as an average value of any five points measured by cross-sectional observation with an SEM (Scanning Electron Microscope).
  • the protective film transfer film X1 may have a protective film.
  • a resin film having heat resistance and solvent resistance can be used, and examples thereof include a polyolefin film such as a polypropylene film and a polyethylene film, a polyester film such as a polyethylene terephthalate film, a polycarbonate film, and a polystyrene film. Be done.
  • a resin film made of the same material as the above-mentioned temporary support may be used.
  • a polyolefin film is preferable, a polypropylene film or a polyethylene film is more preferable, and a polyethylene film is further preferable.
  • the thickness of the protective film is preferably 1 to 100 ⁇ m, more preferably 5 to 50 ⁇ m, further preferably 5 to 40 ⁇ m, and particularly preferably 15 to 30 ⁇ m.
  • the thickness of the protective film is preferably 1 ⁇ m or more in terms of excellent mechanical strength, and preferably 100 ⁇ m or less in terms of relatively low cost.
  • the number of fish eyes having a diameter of 80 ⁇ m or more contained in the protective film is 5 / m 2 or less.
  • fisheye refers to foreign substances, undissolved substances, oxidative deterioration substances, etc. of the material when the material is thermally melted, kneaded, extruded, and used to produce a film by a biaxial stretching method, a casting method, or the like. Was incorporated into the film.
  • 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 further preferably 5 particles / mm 2 or less. As a result, it is possible to suppress defects caused by the unevenness caused by the particles contained in the protective film being transferred to the photosensitive layer or the conductive layer.
  • the arithmetic average roughness Ra of the surface of the protective film opposite to the surface in contact with the composition layer is preferably 0.01 ⁇ m or more, more preferably 0.02 ⁇ m or more, and more preferably 0.03 ⁇ m from the viewpoint of imparting windability.
  • the above is more preferable.
  • less than 0.50 ⁇ m is preferable, 0.40 ⁇ m or less is more preferable, and 0.30 ⁇ m or less is further preferable.
  • the protective film has a surface roughness Ra of the surface in contact with the composition layer of preferably 0.01 ⁇ m or more, more preferably 0.02 ⁇ m or more, still more preferably 0.03 ⁇ m or more, from the viewpoint of suppressing defects during transfer.
  • the arithmetic average roughness Ra of each surface of the protective film is carried out in the same manner as the above-mentioned method for measuring "arithmetic mean roughness Ra on the intermediate layer side of the temporary support".
  • the transfer film X1 shows the following aspects of the physical properties of the temporary support, the photosensitive layer, and the protective film. Is preferable.
  • the transfer film X1 preferably satisfies one or more of the preferred embodiment 1, the preferred embodiment 2, the preferred embodiment 3, the preferred embodiment 4, and the preferred embodiment 5, and more preferably all of them.
  • the photosensitive layer having a thickness of 20 ⁇ m was exposed to 120 mJ / cm 2 with an ultra-high pressure mercury lamp and cured, and then further added at 400 mJ / cm 2 with a high-pressure mercury lamp.
  • the cured film after exposure and heating at 145 ° C. for 30 minutes is measured by a tensile test.
  • the method for measuring the "arithmetic mean roughness Ra on the intermediate layer side of the temporary support" is as described above.
  • the method for measuring "arithmetic mean roughness Ra on the surface of the protective film on the photosensitive layer side” is carried out in the same manner as the above-mentioned measuring method for "arithmetic mean roughness Ra on the intermediate layer side of the temporary support". ..
  • the physical characteristics of the temporary support, the photosensitive layer, and the protective film satisfy all of the following conditions (P1) to (P3).
  • P1 The breaking elongation of the cured film obtained by curing the photosensitive layer at 120 ° C. is 15% or more.
  • P2 The arithmetic average roughness Ra of the surface of the temporary support on the intermediate layer side is 50 nm or less.
  • P3 The arithmetic average roughness Ra of the surface of the protective film on the photosensitive layer side is 150 nm or less.
  • the physical characteristics of the temporary support and the photosensitive layer of the transfer film X1 preferably satisfy the following formula (1).
  • X ⁇ Y ⁇ 1500 formula (1) X represents the value (%) of the elongation at break at 120 ° C. of the cured film obtained by curing the photosensitive layer, and Y is the arithmetic mean roughness of the surface of the temporary support on the intermediate layer side. Represents the value (nm) of Ra.
  • the value represented by X ⁇ Y is preferably 750 or less.
  • the physical characteristics of the photosensitive layer of the transfer film X1 preferably satisfy the following conditions (P4).
  • P4 The breaking elongation at 120 ° C. is more than twice as large as the breaking elongation at 23 ° C. of the cured film obtained by curing the photosensitive layer.
  • the physical characteristics of the temporary support and the photosensitive layer of the transfer film X1 preferably satisfy the following formula (2).
  • Y represents the arithmetic average roughness Ra value (nm) of the surface of the temporary support on the intermediate layer side
  • Z is the arithmetic mean of the surface of the protective film on the photosensitive layer side. Represents the value (nm) of roughness Ra.
  • the method for producing the transfer film X1 of the first embodiment is not particularly limited, and a known method can be used.
  • a method for producing the transfer film 10 for example, a composition for forming an intermediate layer is applied to the surface of the temporary support 1 to form a coating film, and the coating film is further dried to form the intermediate layer 3.
  • drying means removing at least a part of the solvent contained in a composition. Examples of the drying method include natural drying, heat drying, and vacuum drying. The above methods can be applied alone or in combination.
  • the transfer film 10 is manufactured by crimping the protective film 9 onto the photosensitive layer 5 of the laminate manufactured by the above-mentioned manufacturing method.
  • the method for producing the transfer film of the first embodiment includes a step of providing the protective film 9 so as to be in contact with the surface of the photosensitive layer 5 opposite to the side having the temporary support 1. It is preferable to manufacture the transfer film 10 including the intermediate layer 3, the photosensitive layer 5, and the protective film 9.
  • the transfer film 10 may be wound up to prepare and store the transfer film in the form of a roll.
  • the roll-type transfer film can be provided as it is in the bonding process with the substrate in the roll-to-roll method described later.
  • composition for forming an intermediate layer preferably contains the above-mentioned various components forming the intermediate layer and a solvent.
  • the preferable range of the content of each component with respect to the total solid content of the composition is the same as the preferable range of the content of each component with respect to the total mass of the intermediate layer described above.
  • the solvent is not particularly limited as long as it can dissolve or disperse the water-soluble resin, and at least one selected from the group consisting of water and water-miscible organic solvents is preferable, and water or water-miscible organic. A mixed solvent with a solvent is more preferable.
  • water-miscible organic solvent examples include alcohols having 1 to 3 carbon atoms, acetone, ethylene glycol, and glycerin, and alcohols having 1 to 3 carbon atoms are preferable, and methanol or ethanol is more preferable.
  • the solvent may be used alone or in combination of two or more.
  • 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 with respect to 100 parts by mass of the total solid content of the composition.
  • the method for forming the intermediate layer is not particularly limited as long as it can form a layer containing the above components, and examples thereof include known coating methods (slit coating, spin coating, curtain coating, inkjet coating, etc.). ..
  • the drying temperature is preferably 80 ° C. or higher, more preferably 90 ° C. or higher.
  • the upper limit thereof is preferably 130 ° C. or lower, more preferably 120 ° C. or lower. It can also be dried by continuously changing the temperature.
  • the drying time is preferably 20 seconds or longer, more preferably 40 seconds or longer, and even more preferably 60 seconds or longer.
  • the upper limit is not particularly limited, but is preferably 600 seconds or less, and more preferably 300 seconds or less.
  • the components constituting the above-mentioned photosensitive layer for example, a binder polymer, a polymerizable compound, a polymerization initiator, etc.), and a solvent. It is desirable that it be formed by a coating method using a photosensitive composition containing.
  • the photosensitive composition preferably contains the above-mentioned various components forming the photosensitive layer and a solvent.
  • the preferable range of the content of each component with respect to the total solid content of the composition is the same as the preferable range of the content of each component with respect to the total mass of the photosensitive layer described above.
  • the solvent is not particularly limited as long as each component other than the solvent can be dissolved or dispersed, and a known solvent can be used.
  • alkylene glycol ether solvent for example, alkylene glycol ether solvent, alkylene glycol ether acetate solvent, alcohol solvent (methanol, ethanol, etc.), ketone solvent (acetone, methyl ethyl ketone, etc.), aromatic hydrocarbon solvent (toluene, etc.), aprotonic polarity.
  • examples thereof include a solvent (N, N-dimethylformamide, etc.), a cyclic ether solvent (tetratetra, etc.), an ester solvent (npropyl acetate, etc.), an amide solvent, a lactone solvent, and a mixed solvent containing two or more of these.
  • the solvent preferably contains at least one selected from the group consisting of an alkylene glycol ether solvent and an alkylene glycol ether acetate solvent.
  • a mixed solvent containing at least one selected from the group consisting of an alkylene glycol ether solvent and an alkylene glycol ether acetate solvent and at least one selected from the group consisting of a ketone solvent and a cyclic ether solvent is more preferable.
  • a mixed solvent containing at least one selected from the group consisting of an alkylene glycol ether solvent and an alkylene glycol ether acetate solvent, a ketone solvent, and at least three types of a cyclic ether solvent is more preferable.
  • alkylene glycol ether solvent examples include ethylene glycol monoalkyl ether, ethylene glycol dialkyl ether, propylene glycol monoalkyl ether (propylene glycol monomethyl ether acetate, etc.), propylene glycol dialkyl ether, diethylene glycol dialkyl ether, and dipropylene glycol monoalkyl ether. And dipropylene glycol dialkyl ether.
  • alkylene glycol ether acetate solvent include ethylene glycol monoalkyl ether acetate, propylene glycol monoalkyl ether acetate, diethylene glycol monoalkyl ether acetate, and dipropylene glycol monoalkyl ether acetate.
  • the solvent described in paragraphs 0092 to 0094 of International Publication No. 2018/179640 and the solvent described in paragraph 0014 of JP-A-2018-177789 may be used, and the contents thereof are described in the present specification. Incorporated in.
  • the solvent may be used alone or in combination of two or more.
  • the content of the solvent is preferably 50 to 1,900 parts by mass, more preferably 100 to 1200 parts by mass, still more preferably 100 to 900 parts by mass with respect to 100 parts by mass of the total solid content of the composition.
  • Examples of the method for applying the photosensitive composition 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 (that is, a slit coating method).
  • the drying temperature is preferably 80 ° C. or higher, more preferably 90 ° C. or higher.
  • the upper limit thereof is preferably 130 ° C. or lower, more preferably 120 ° C. or lower. It can also be dried by continuously changing the temperature.
  • the drying time is preferably 20 seconds or longer, more preferably 40 seconds or longer, and even more preferably 60 seconds or longer.
  • the upper limit is not particularly limited, but is preferably 600 seconds or less, and more preferably 300 seconds or less.
  • the transfer film X1 of the first embodiment can be manufactured by adhering the protective film to the photosensitive layer.
  • the method of attaching the protective film to the photosensitive layer is not particularly limited, and known methods can be mentioned.
  • Examples of the device for adhering the protective film to the photosensitive layer include a vacuum laminator and a known laminator such as an auto-cut laminator. It is preferable that the laminator is provided with an arbitrary heatable roller such as a rubber roller and can be pressurized and heated.
  • the transfer film X1 of the first embodiment is a circuit wiring arranged on a support substrate such as a sheet, a metal substrate, a ceramic substrate, and glass in a manufacturing process film of a semiconductor package, a printed circuit board, and an interposer rewiring layer, for example. It is preferably used for the formation of.
  • the transfer film 20 shown in FIG. 2 has a temporary support 11, a composition layer 19 including an intermediate layer 13, a photosensitive layer 15, and a refractive index adjusting layer 17, and a protective film 21 in this order.
  • the transfer film 20 shown in FIG. 2 has a form in which the protective film 21 is arranged, but the protective film 21 may not be arranged.
  • the transfer film 20 shown in FIG. 2 has a form in which the refractive index adjusting layer 17 is arranged, but the refractive index adjusting layer 17 may not be arranged.
  • FIG. 1 the transfer film 20 shown in FIG. 2 has a form in which the refractive index adjusting layer 17 is arranged, but the refractive index adjusting layer 17 may not be arranged.
  • each layer excluding the protective film 21 that can be arranged on the temporary support 11 is referred to as a composition layer 17.
  • a composition layer 17 each element constituting the transfer film X2 will be described.
  • the configurations of the intermediate layer and the temporary support constituting the transfer film X2 are as described above.
  • the structure of the protective film is the same as that of the transfer film X1.
  • Photosensitive layer The transfer film X2 of the second embodiment has a photosensitive layer.
  • a pattern can be formed on the transferred object by transferring the photosensitive layer onto the transferred object and then exposing and developing the photosensitive layer.
  • the photosensitive layer is preferably a negative photosensitive layer.
  • the negative photosensitive layer is a photosensitive layer whose solubility in a developing solution is reduced by exposure.
  • the formed pattern corresponds to a cured layer.
  • Binder polymer The photosensitive layer may contain a binder polymer.
  • the binder polymer include (meth) acrylic resin, styrene resin, epoxy resin, amide resin, amide epoxy resin, alkyd resin, phenol resin, ester resin, urethane resin, and the reaction of epoxy resin with (meth) acrylic acid.
  • examples thereof include the obtained epoxy acrylate resin and the acid-modified epoxy acrylate resin obtained by reacting the epoxy acrylate resin with the acid anhydride.
  • the binder polymer is a (meth) acrylic resin in that it is excellent in alkali developability and film forming property.
  • the (meth) acrylic resin means a resin having a structural unit derived from the (meth) acrylic compound.
  • the content of the structural unit derived from the (meth) acrylic compound is preferably 50% by mass or more, more preferably 70% by mass or more, still more preferably 90% by mass or more, based on all the structural units of the (meth) acrylic resin. ..
  • the (meth) acrylic resin may be composed of only a structural unit derived from the (meth) acrylic compound, or may have a structural unit derived from a polymerizable monomer other than the (meth) acrylic compound. .. That is, the upper limit of the content of the structural unit derived from the (meth) acrylic compound is 100% by mass or less with respect to all the structural units of the (meth) acrylic resin.
  • Examples of the (meth) acrylic compound include (meth) acrylic acid, (meth) acrylic acid ester, (meth) acrylamide, and (meth) acrylonitrile.
  • Examples of the (meth) acrylic acid ester include (meth) acrylic acid alkyl ester, (meth) acrylic acid tetrahydrofurfuryl ester, (meth) acrylic acid dimethylaminoethyl ester, (meth) acrylic acid diethylaminoethyl ester, and (meth) acrylic acid ester.
  • Acrylic acid glycidyl ester (meth) acrylic acid benzyl ester, 2,2,2-trifluoroethyl (meth) acrylate, and 2,2,3,3-tetrafluoropropyl (meth) acrylate.
  • Meta) Acrylic acid alkyl esters are preferred.
  • the (meth) acrylamide include acrylamide such as diacetone acrylamide.
  • the alkyl group of the (meth) acrylic acid alkyl ester may be linear or may have a branch. Specific examples include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, ( Heptyl acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, undecyl (meth) acrylate, and (meth) acrylate.
  • Examples thereof include (meth) acrylic acid alkyl esters having an alkyl group having 1 to 12 carbon atoms such as dodecyl.
  • As the (meth) acrylic acid ester a (meth) acrylic acid alkyl ester having an alkyl group having 1 to 4 carbon atoms is preferable, and methyl (meth) acrylate or ethyl (meth) acrylate is more preferable.
  • the (meth) acrylic resin may have a structural unit other than the structural unit derived from the (meth) acrylic compound.
  • the polymerizable monomer forming the structural unit is not particularly limited as long as it is a compound other than the (meth) acrylic compound copolymerizable with the (meth) acrylic compound, and is, for example, styrene, vinyltoluene, and ⁇ . -Methylstyrene or the like may have a substituent at the ⁇ -position or an aromatic ring.
  • Vinyl alcohol esters such as styrene compounds, acrylonitrile and vinyl-n-butyl ether, maleic acid, maleic acid anhydride, monomethyl maleate, monoethyl maleate, and monoester maleic acid such as monoisopropyl maleate, fumaric acid, cinnamic acid. Acids, ⁇ -cyanocinnamic acid, esteric acid, and crotonic acid can be mentioned. These polymerizable monomers may be used alone or in combination of two or more.
  • the (meth) acrylic resin preferably has a structural unit having an acid group from the viewpoint of improving the alkali developability.
  • the acid group include a carboxy group, a sulfo group, a phosphoric acid group, and a phosphonic acid group.
  • the (meth) acrylic resin more preferably has a structural unit having a carboxy group, and further preferably has a structural unit derived from the above-mentioned (meth) acrylic acid.
  • the content of the structural unit having an acid group (preferably the structural unit derived from (meth) acrylic acid) in the (meth) acrylic resin is excellent in developability, and is based on the total mass of the (meth) acrylic resin. 10% by mass or more is preferable.
  • the upper limit is not particularly limited, but is preferably 50% by mass or less, more preferably 40% by mass or less, in terms of excellent alkali resistance.
  • the (meth) acrylic resin has a structural unit derived from the above-mentioned (meth) acrylic acid alkyl ester.
  • the content of the constituent units derived from the (meth) acrylic acid alkyl ester in the (meth) acrylic resin is preferably 50 to 90% by mass, preferably 60 to 90% by mass, based on all the constituent units of the (meth) acrylic resin. More preferably, 65 to 90% by mass is further preferable.
  • the (meth) acrylic resin a resin having both a structural unit derived from (meth) acrylic acid and a structural unit derived from (meth) acrylic acid alkyl ester is preferable, and the structural unit derived from (meth) acrylic acid and the structural unit derived from (meth) acrylic acid are preferable.
  • a resin composed only of structural units derived from the (meth) acrylic acid alkyl ester is more preferable.
  • an acrylic resin having a structural unit derived from methacrylic acid, a structural unit derived from methyl methacrylate, and a structural unit derived from ethyl acrylate is also preferable.
  • the (meth) acrylic resin may have at least one selected from the group consisting of a structural unit derived from methacrylic acid and a structural unit derived from methacrylic acid alkyl ester from the viewpoint that the effect of the present invention is more excellent. It is preferable to have both a structural unit derived from methacrylic acid and a structural unit derived from an alkyl methacrylate ester.
  • the total content of the constituent units derived from methacrylic acid and the constituent units derived from methacrylic acid alkyl ester in the (meth) acrylic resin is higher than that of all the constituent units of the (meth) acrylic resin because the effect of the present invention is more excellent.
  • 40% by mass or more is preferable, and 60% by mass or more is more preferable.
  • the upper limit is not particularly limited, and may be 100% by mass or less, preferably 80% by mass or less.
  • the (meth) acrylic resin is at least one selected from the group consisting of a structural unit derived from methacrylic acid and a structural unit derived from methacrylic acid, and acrylic acid, because the effect of the present invention is more excellent. It is also preferable to have at least one selected from the group consisting of the structural unit derived from the acrylic acid alkyl ester and the structural unit derived from the acrylic acid alkyl ester. From the viewpoint that the effect of the present invention is more excellent, the total content of the structural unit derived from methacrylic acid and the structural unit derived from methacrylic acid alkyl ester is the structural unit derived from acrylic acid and the structural unit derived from acrylic acid alkyl ester. The mass ratio is preferably 60/40 to 80/20 with respect to the total content of the ester.
  • the (meth) acrylic resin preferably has an ester group at the terminal in that the photosensitive layer after transfer is excellent in developability.
  • the terminal portion of the (meth) acrylic resin is composed of a site derived from the polymerization initiator used in the synthesis.
  • a (meth) acrylic resin having an ester group at the terminal can be synthesized by using a polymerization initiator that generates a radical having an ester group.
  • the binder polymer is preferably, for example, a binder polymer having an acid value of 60 mgKOH / g or more from the viewpoint of developability.
  • the binder polymer is, for example, a resin having a carboxy group having an acid value of 60 mgKOH / g or more (so-called carboxy group-containing resin) from the viewpoint that it is easily crosslinked with the crosslinked component by heating to form a strong film. More preferably, it is a (meth) acrylic resin having a carboxy group having an acid value of 60 mgKOH / g or more (so-called carboxy group-containing (meth) acrylic resin).
  • the binder polymer is a resin having a carboxy group
  • the three-dimensional crosslink density can be increased by adding a thermally crosslinkable compound such as a blocked isocyanate compound and thermally crosslinking the binder polymer.
  • a thermally crosslinkable compound such as a blocked isocyanate compound
  • the carboxy group of the resin having a carboxy group is made anhydrous and hydrophobic, the wet heat resistance can be improved.
  • the carboxy group-containing (meth) acrylic resin having an acid value of 60 mgKOH / g or more is not particularly limited as long as the above acid value conditions are satisfied, and can be appropriately selected from known (meth) acrylic resins.
  • carboxy group-containing acrylic resins having an acid value of 60 mgKOH / g or more paragraphs [0033] to [0052] of JP-A-2010-237589.
  • a carboxy group-containing acrylic resin having an acid value of 60 mgKOH / g or more can be preferably used.
  • the binder polymer is a styrene-acrylic copolymer.
  • the styrene-acrylic copolymer refers to a resin having a structural unit derived from a styrene compound and a structural unit derived from a (meth) acrylic compound, and is a structural unit derived from the styrene compound.
  • the total content of the structural units derived from the (meth) acrylic compound is preferably 30% by mass or more, more preferably 50% by mass or more, based on all the structural units of the copolymer.
  • the content of the structural unit derived from the styrene compound is preferably 1% by mass or more, more preferably 5% by mass or more, still more preferably 5 to 80% by mass, based on all the structural units of the copolymer.
  • the content of the structural unit derived from the (meth) acrylic compound is preferably 5% by mass or more, more preferably 10% by mass or more, and 20 to 95% by mass, based on all the structural units of the copolymer. Is more preferable.
  • the binder polymer preferably has an aromatic ring structure, and more preferably has a structural unit having an aromatic ring structure, from the viewpoint that the effect of the present invention is more excellent.
  • the monomers forming the structural unit having an aromatic ring structure include a monomer having an aralkyl group, styrene, and a polymerizable styrene derivative (for example, methylstyrene, vinyltoluene, tert-butoxystyrene, acetoxystyrene, 4-vinylbenzoic acid). , Styrene dimer, styrene trimmer, etc.). Of these, a monomer having an aralkyl group or styrene is preferable.
  • aralkyl group examples include a substituted or unsubstituted phenylalkyl group (excluding a benzyl group), a substituted or unsubstituted benzyl group and the like, and a substituted or unsubstituted benzyl group is preferable.
  • Examples of the monomer having a phenylalkyl group include phenylethyl (meth) acrylate and the like.
  • Examples of the monomer having a benzyl group include (meth) acrylate having a benzyl group, for example, benzyl (meth) acrylate, and chlorobenzyl (meth) acrylate; a vinyl monomer having a benzyl group, for example, vinylbenzyl chloride, and the like. Examples include vinylbenzyl alcohol. Of these, benzyl (meth) acrylate is preferable.
  • the binder polymer has a structural unit (constituent unit derived from styrene) represented by the following formula (S) from the viewpoint that the effect of the present invention is more excellent.
  • the content of the structural unit having an aromatic ring structure is 5 to 90 mass with respect to all the structural units of the binder polymer because the effect of the present invention is more excellent.
  • % Is preferred, more preferably 10 to 70% by mass, still more preferably 20 to 60% by mass.
  • the content of the structural unit having an aromatic ring structure in the binder polymer is preferably 5 to 70 mol%, preferably 10 to 60 mol%, based on all the structural units of the binder polymer, from the viewpoint of further excellent effect of the present invention. Is more preferable, and 20 to 60 mol% is further preferable.
  • the content of the structural unit represented by the above formula (S) in the binder polymer is preferably 5 to 70 mol% with respect to all the structural units of the binder polymer from the viewpoint of further excellent effect of the present invention. From 20 to 60 mol% is more preferable, 20 to 60 mol% is further preferable, and 20 to 50 mol% is particularly preferable.
  • the above “constituent unit” shall be synonymous with the "monomer unit”.
  • the above-mentioned "monomer unit” may be modified after polymerization by a polymer reaction or the like. The same applies to the following.
  • the binder polymer preferably has an aliphatic hydrocarbon ring structure from the viewpoint that the effect of the present invention is more excellent. That is, the binder polymer preferably has a structural unit having an aliphatic hydrocarbon ring structure.
  • the aliphatic hydrocarbon ring structure may be monocyclic or polycyclic. Above all, it is more preferable that the binder polymer has a ring structure in which two or more aliphatic hydrocarbon rings are fused.
  • Examples of the ring constituting the aliphatic hydrocarbon ring structure in the structural unit having the aliphatic hydrocarbon ring structure include a tricyclodecane ring, a cyclohexane ring, a cyclopentane ring, a norbornane ring, and an isoborone ring.
  • a ring in which two or more aliphatic hydrocarbon rings are condensed is preferable because the effect of the present invention is more excellent, and a tetrahydrodicyclopentadiene ring (tricyclo [5.2.1.0 2,6 ] decane) is preferable. Ring) is more preferred.
  • the monomer forming a structural unit having an aliphatic hydrocarbon ring structure examples include dicyclopentanyl (meth) acrylate, cyclohexyl (meth) acrylate, and isobornyl (meth) acrylate.
  • the binder polymer more preferably has a structural unit represented by the following formula (Cy), and the structural unit represented by the above formula (S) and the following formula. It is more preferable to have a structural unit represented by (Cy).
  • RM represents a hydrogen atom or a methyl group
  • RCy represents a monovalent group having an aliphatic hydrocarbon ring structure.
  • the RM in the formula ( Cy ) is preferably a methyl group.
  • the RCy in the formula ( Cy ) is preferably a monovalent group having an aliphatic hydrocarbon ring structure having 5 to 20 carbon atoms, and a fat having 6 to 16 carbon atoms, because the effect of the present invention is more excellent. It is more preferably a monovalent group having a group hydrocarbon ring structure, and even more preferably a monovalent group having an aliphatic hydrocarbon ring structure having 8 to 14 carbon atoms.
  • the aliphatic hydrocarbon ring structure in RCy of the formula ( Cy ) has a cyclopentane ring structure, a cyclohexane ring structure, a tetrahydrodicyclopentadiene ring structure, a norbornane ring structure, or a norbornane ring structure, because the effect of the present invention is more excellent. It is preferably an isoborone ring structure, more preferably a cyclohexane ring structure or a tetrahydrodicyclopentadiene ring structure, and even more preferably a tetrahydrodicyclopentadiene ring structure.
  • the aliphatic hydrocarbon ring structure in RCy of the formula ( Cy ) is preferably a ring structure in which two or more aliphatic hydrocarbon rings are fused, from the viewpoint that the effect of the present invention is more excellent. It is more preferable that the ring is a condensed ring of ⁇ 4 aliphatic hydrocarbon rings.
  • the binder polymer may have one type of structural unit having an aliphatic hydrocarbon ring structure alone, or may have two or more types.
  • the content of the structural unit having an aliphatic hydrocarbon ring structure is higher than that of all the structural units of the binder polymer because the effect of the present invention is more excellent. 5 to 90% by mass is preferable, 10 to 80% by mass is more preferable, and 20 to 70% by mass is further preferable.
  • the content of the constituent unit having an aliphatic hydrocarbon ring structure in the binder polymer is preferably 5 to 70 mol% with respect to all the constituent units of the binder polymer from the viewpoint of further excellent effect of the present invention, and is preferably 10 to 70 mol%. 60 mol% is more preferable, and 20 to 50 mol% is further preferable. Further, the content of the structural unit represented by the above formula (Cy) in the binder polymer is preferably 5 to 70 mol% with respect to all the structural units of the binder polymer from the viewpoint of further excellent effect of the present invention. -60 mol% is more preferred, and 20-50 mol% is even more preferred.
  • the binder polymer has a structural unit having an aromatic ring structure and a structural unit having an aliphatic hydrocarbon ring structure
  • the total content of the structural unit having an aromatic ring structure and the structural unit having an aliphatic hydrocarbon ring structure is the present.
  • 10 to 90% by mass is preferable, 20 to 80% by mass is more preferable, and 40 to 75% by mass is further preferable, based on all the structural units of the binder polymer.
  • the total content of the structural unit having an aromatic ring structure and the structural unit having an aliphatic hydrocarbon ring structure in the binder polymer is 10 with respect to all the structural units of the binder polymer because the effect of the present invention is more excellent.
  • the total content of the structural unit represented by the above formula (S) and the structural unit represented by the above formula (Cy) in the binder polymer is the total structural unit of the binder polymer from the viewpoint that the effect of the present invention is more excellent.
  • 10 to 80 mol% is preferable, 20 to 70 mol% is more preferable, and 40 to 60 mol% is further preferable.
  • the molar amount nS of the structural unit represented by the above formula (S) and the molar amount nCy of the structural unit represented by the above formula (Cy) in the binder polymer are given by the following formulas because the effects of the present invention are more excellent. It is preferable to satisfy the relationship shown in (SCy), more preferably to satisfy the following formula (SCy-1), and further preferably to satisfy the following formula (SCy-2).
  • the binder polymer preferably has a structural unit having an acid group because the effect of the present invention is more excellent.
  • the acid group include a carboxy group, a sulfo group, a phosphonic acid group, and a phosphoric acid group, and a carboxy group is preferable.
  • the structural unit having the acid group the structural unit derived from (meth) acrylic acid shown below is preferable, and the structural unit derived from methacrylic acid is more preferable.
  • the binder polymer may have one type of structural unit having an acid group alone or two or more types.
  • the content of the structural unit having an acid group is 5 to 50% by mass with respect to all the structural units of the binder polymer because the effect of the present invention is more excellent. It is preferable, 5 to 40% by mass is more preferable, and 10 to 30% by mass is further preferable.
  • the content of the constituent unit having an acid group in the binder polymer is preferably 5 to 70 mol%, preferably 10 to 50 mol%, based on all the constituent units of the binder polymer, from the viewpoint of further excellent effect of the present invention. More preferably, 20-40 mol% is even more preferable.
  • the content of the structural unit derived from (meth) acrylic acid in the binder polymer is preferably 5 to 70 mol% with respect to all the structural units of the binder polymer from the viewpoint of further excellent effect of the present invention, and is preferably 10 to 50. More preferably, mol%, more preferably 20-40 mol%.
  • the binder polymer preferably has a reactive group, and more preferably has a structural unit having a reactive group, from the viewpoint that the effect of the present invention is more excellent.
  • a reactive group a radically polymerizable group is preferable, and an ethylenically unsaturated group is more preferable.
  • the binder polymer preferably has a structural unit having an ethylenically unsaturated group in the side chain.
  • the "main chain” represents a relatively longest binding chain among the molecules of the polymer compound constituting the resin, and the "side chain” refers to an atomic group branched from the main chain. show.
  • an ethylenically unsaturated group an allyl group or a (meth) acryloxy group is more preferable. Examples of structural units having a reactive group include, but are not limited to, those shown below.
  • the binder polymer may have one type of structural unit having a reactive group alone or two or more types.
  • the content of the structural unit having a reactive group is 5 to 70 mass by mass with respect to all the structural units of the binder polymer because the effect of the present invention is more excellent. % Is preferable, 10 to 50% by mass is more preferable, and 20 to 40% by mass is further preferable.
  • the content of the structural unit having a reactive group in the binder polymer is preferably 5 to 70 mol%, preferably 10 to 60 mol%, based on all the structural units of the binder polymer, from the viewpoint of further excellent effect of the present invention. Is more preferable, and 20 to 50 mol% is further preferable.
  • a functional group such as a hydroxy group, a carboxy group, a primary amino group, a secondary amino group, an acetoacetyl group, and a sulfo group, an epoxy compound, and a blocked isocyanate are used.
  • a functional group such as a hydroxy group, a carboxy group, a primary amino group, a secondary amino group, an acetoacetyl group, and a sulfo group, an epoxy compound, and a blocked isocyanate.
  • examples thereof include a method of reacting a compound such as a compound, an isocyanate compound, a vinyl sulfone compound, an aldehyde compound, a methylol compound, and a carboxylic acid anhydride.
  • a preferred example of a means for introducing a reactive group into a binder polymer is that a polymer having a carboxy group is synthesized by a polymerization reaction and then glycidyl (meth) acrylate is added to a part of the carboxy group of the obtained polymer by the polymer reaction.
  • a means for introducing a (meth) acryloxy group into a polymer by reacting with the polymer By this means, a binder polymer having a (meth) acryloxy group in the side chain can be obtained.
  • the polymerization reaction is preferably carried out under a temperature condition of 70 to 100 ° C., and more preferably carried out under a temperature condition of 80 to 90 ° C.
  • an azo-based initiator is preferable, and for example, V-601 (trade name) or V-65 (trade name) manufactured by Wako Pure Chemical Industries, Ltd. is more preferable.
  • the polymer reaction is preferably carried out under temperature conditions of 80 to 110 ° C. In the above polymer reaction, it is preferable to use a catalyst such as an ammonium salt.
  • the polymers X1 to X4 shown below are preferable from the viewpoint that the effect of the present invention is more excellent.
  • the content ratios (a to d) and the weight average molecular weight Mw of each structural unit shown below can be appropriately changed depending on the intended purpose, but the following configuration is particularly effective in that the effect of the present invention is more excellent. Is preferable.
  • Polymer X3 a: 30 to 65% by mass, b: 1.0 to 20% by mass, c: 5.0 to 25% by mass, d: 10 to 50% by mass.
  • Polymer X4 a: 1.0 to 20% by mass, b: 20 to 60% by mass, c: 5.0 to 25% by mass, d: 10 to 50% by mass.
  • the binder polymer may contain a polymer having a structural unit having a carboxylic acid anhydride structure (hereinafter, also referred to as “polymer X”).
  • the carboxylic acid anhydride structure may be either a chain carboxylic acid anhydride structure or a cyclic carboxylic acid anhydride structure, but a cyclic carboxylic acid anhydride structure is preferable.
  • a cyclic carboxylic acid anhydride structure As the ring having a cyclic carboxylic acid anhydride structure, a 5- to 7-membered ring is preferable, a 5-membered ring or a 6-membered ring is more preferable, and a 5-membered ring is further preferable.
  • the structural unit having a carboxylic acid anhydride structure is a structural unit containing a divalent group obtained by removing two hydrogen atoms from the compound represented by the following formula P-1 in the main chain, or the following formula P-1. It is preferable that the monovalent group obtained by removing one hydrogen atom from the represented compound is a structural unit bonded directly to the main chain or via a divalent linking group.
  • RA1a represents a substituent
  • n1a RA1a may be the same or different
  • Examples of the substituent represented by RA1a include an alkyl group.
  • Z 1a an alkylene group having 2 to 4 carbon atoms is preferable, an alkylene group having 2 or 3 carbon atoms is more preferable, and an alkylene group having 2 carbon atoms is further preferable.
  • n 1a represents an integer of 0 or more.
  • Z 1a represents an alkylene group having 2 to 4 carbon atoms
  • n 1a is preferably an integer of 0 to 4, more preferably an integer of 0 to 2, and even more preferably 0.
  • a plurality of RA1a may be the same or different. Further, although a plurality of RA1a may be bonded to each other to form a ring, it is preferable that the RA1a are not bonded to each other to form a ring.
  • a structural unit derived from an unsaturated carboxylic acid anhydride is preferable, a structural unit derived from an unsaturated cyclic carboxylic acid anhydride is more preferable, and an unsaturated aliphatic cyclic carboxylic acid is preferable.
  • a structural unit derived from an acid anhydride is more preferable, a structural unit derived from maleic anhydride or an itaconic acid anhydride is particularly preferable, and a structural unit derived from maleic anhydride is most preferable.
  • Rx represents a hydrogen atom, a methyl group, a CH 2 OH group, or CF 3 groups
  • Me represents a methyl group.
  • the structural unit having a carboxylic acid anhydride structure in the polymer X may be one kind alone or two or more kinds.
  • the total content of the structural units having a carboxylic acid anhydride structure is preferably 0 to 60 mol%, more preferably 5 to 40 mol%, and further preferably 10 to 35 mol% with respect to all the structural units of the polymer X. preferable.
  • the photosensitive layer may contain only one type of polymer X, or may contain two or more types of polymer X.
  • the content of the polymer X is preferably 0.1 to 30% by mass, preferably 0, based on the total mass of the photosensitive layer, because the effect of the present invention is more excellent. .2 to 20% by mass is more preferable, 0.5 to 20% by mass is further preferable, and 1 to 20% by mass is further preferable.
  • the weight average molecular weight (Mw) of the binder polymer is preferably 5,000 or more, more preferably 10,000 or more, still more preferably 10,000 to 50,000, and even more preferably 20,000, because the effect of the present invention is more excellent. ⁇ 30,000 is particularly preferable.
  • the acid value of the binder polymer is preferably 10 to 200 mgKOH / g, more preferably 60 mg to 200 mgKOH / g, even more preferably 60 to 150 mgKOH / g, and particularly preferably 70 to 125 mgKOH / g.
  • the acid value of the binder polymer can be measured, for example, according to the method described in JIS K0070: 1992.
  • the dispersity of the binder polymer is preferably 1.0 to 6.0, more preferably 1.0 to 5.0, further preferably 1.0 to 4.0, and 1.0 to 3 from the viewpoint of developability. .0 is particularly preferred.
  • the photosensitive layer may contain only one kind of binder polymer, or may contain two or more kinds of binder polymers.
  • the content of the binder polymer is preferably 10 to 90% by mass, more preferably 20 to 80% by mass, and 30 to 70% by mass with respect to the total mass of the photosensitive layer because the effect of the present invention is more excellent. More preferred.
  • the photosensitive layer may contain a polymerizable compound.
  • the polymerizable compound is a compound having a polymerizable group. Examples of the polymerizable group include a radically polymerizable group and a cationically polymerizable group, and a radically polymerizable group is preferable.
  • the polymerizable compound preferably contains a radically polymerizable compound having an ethylenically unsaturated group (hereinafter, also simply referred to as “ethylenically unsaturated compound”).
  • ethylenically unsaturated compound a (meth) acryloxy group is preferable.
  • the ethylenically unsaturated compound in the present specification is a compound other than the binder polymer, and preferably has a molecular weight of less than 5,000.
  • a compound represented by the following formula (M) (simply referred to as “Compound M”) can be mentioned.
  • Q2 - R1 - Q1 formula (M) Q 1 and Q 2 each independently represent a (meth) acryloyloxy group, and R 1 represents a divalent linking group having a chain structure.
  • Q 1 and Q 2 in the formula (M) have the same group as Q 1 and Q 2 from the viewpoint of ease of synthesis. Further, Q 1 and Q 2 in the formula (M) are preferably acryloyloxy groups from the viewpoint of reactivity.
  • R 1 in the formula (M) an alkylene group, an alkyleneoxyalkylene group (-L 1 -OL 1- ), or a polyalkylene oxyalkylene group (-(L)" is used because the effect of the present invention is more excellent.
  • a hydrocarbon group having 2 to 20 carbon atoms or a polyalkyleneoxyalkylene group is more preferable, an alkylene group having 4 to 20 carbon atoms is further preferable, and an alkylene group having 6 to 20 carbon atoms is more preferable. Eighteen linear alkylene groups are particularly preferred.
  • the hydrocarbon group may have a chain structure at least partially, and the portion other than the chain structure is not particularly limited, and is, for example, a branched chain, cyclic, or having 1 to 1 to carbon atoms.
  • the alkylene group is more preferable, and the linear alkylene group is further preferable.
  • the above L 1 independently represents an alkylene group, and an ethylene group, a propylene group, or a butylene group is preferable, and an ethylene group or a 1,2-propylene group is more preferable.
  • p represents an integer of 2 or more, and is preferably an integer of 2 to 10.
  • the number of atoms of the shortest connecting chain connecting between Q1 and Q2 in the compound M is preferably 3 to 50, more preferably 4 to 40, from the viewpoint of further excellent effect of the present invention. 6 to 20 are more preferable, and 8 to 12 are particularly preferable.
  • the number of atoms in the shortest connecting chain connecting between Q1 and Q2 means the atoms in R1 connected to Q1 to the atoms in R1 connected to Q2 . The shortest number of atoms.
  • the compound M examples include 1,3-butanediol di (meth) acrylate, tetramethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, and 1,6-hexanediol di (meth) acrylate.
  • the ester monomer can also be used as a mixture.
  • 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, and 1,10-decanediol di (meth) acrylate are more excellent in the effect of the present invention.
  • a bifunctional or higher functional ethylenically unsaturated compound can be mentioned.
  • the term "bifunctional or higher functional ethylenically unsaturated compound” means a compound having two or more ethylenically unsaturated groups in one molecule.
  • a (meth) acryloyl group is preferable.
  • a (meth) acrylate compound is preferable.
  • the bifunctional ethylenically unsaturated compound is not particularly limited and may be appropriately selected from known compounds.
  • Examples of the bifunctional ethylenically unsaturated compound other than the compound M include tricyclodecanedimethanol di (meth) acrylate and 1,4-cyclohexanediol di (meth) acrylate.
  • NK ester A-DCP tricyclodecanedimethanol diacrylate
  • NK ester A-DCP tricyclodecanedimenanol dimethacrylate
  • NK ester DCP manufactured by Shin Nakamura Chemical Industry Co., Ltd.
  • 1,9-nonanediol diacrylate (trade name: NK ester A-NOD-N, manufactured by Shin Nakamura Chemical Industry Co., Ltd.)
  • 1,6 -Hexanediol diacrylate (trade name: NK ester A-HD-N, manufactured by Shin Nakamura Chemical Industry Co., Ltd.)
  • the trifunctional or higher functional ethylenically unsaturated compound is not particularly limited and may be appropriately selected from known compounds.
  • Examples of the trifunctional or higher functional ethylenically unsaturated compound include dipentaerythritol (tri / tetra / penta / hexa) (meth) acrylate, pentaerythritol (tri / tetra) (meth) acrylate, and trimethylolpropane tri (meth) acrylate.
  • Examples thereof include ditrimethylolpropane tetra (meth) acrylate, isocyanuric acid (meth) acrylate, and (meth) acrylate compound having a glycerintri (meth) acrylate skeleton.
  • (tri / tetra / penta / hexa) (meth) acrylate is a concept including tri (meth) acrylate, tetra (meth) acrylate, penta (meth) acrylate, and hexa (meth) acrylate.
  • (tri / tetra) (meth) acrylate” is a concept that includes tri (meth) acrylate and tetra (meth) acrylate.
  • Examples of the polymerizable compound include caprolactone-modified compounds of (meth) acrylate compounds (KAYARAD (registered trademark) DPCA-20 manufactured by Nippon Kayaku Co., Ltd., A-9300-1CL manufactured by Shin-Nakamura Chemical Industry Co., Ltd., etc.), (Meta). ) Alkylene oxide-modified compound of acrylate compound (KAYARAD (registered trademark) RP-1040 manufactured by Nippon Kayaku Co., Ltd., ATM-35E, A-9300 manufactured by Shin-Nakamura Chemical Industry Co., Ltd., EBECRYL (registered trademark) manufactured by Daicel Ornex Co., Ltd. ) 135, etc.), ethoxylated glycerin triacrylate (NK ester A-GLY-9E, etc. manufactured by Shin-Nakamura Chemical Industry Co., Ltd.) can also be mentioned.
  • KAYARAD registered trademark
  • DPCA-20 Alkylene oxide-modified compound of acrylate compound
  • Examples of the polymerizable compound include urethane (meth) acrylate compounds.
  • Examples of the urethane (meth) acrylate include urethane di (meth) acrylate, and examples thereof include propylene oxide-modified urethane di (meth) acrylate, and ethylene oxide and propylene oxide-modified urethane di (meth) acrylate.
  • a urethane (meth) acrylate having trifunctionality or higher can also be mentioned.
  • As the lower limit of the number of functional groups 6-functionality or more is more preferable, and 8-functionality or more is further preferable.
  • the upper limit of the number of functional groups is preferably 20 or less.
  • trifunctional or higher functional urethane (meth) acrylates examples include 8UX-015A (manufactured by Taisei Fine Chemical Co., Ltd.), UA-32P (manufactured by Shin Nakamura Chemical Industry Co., Ltd.), and U-15HA (manufactured by Shin Nakamura Chemical Industry Co., Ltd.). ), UA-1100H (manufactured by Shin Nakamura Chemical Industry Co., Ltd.), AH-600 (trade name) manufactured by Kyoeisha Chemical Co., Ltd., and UA-306H, UA-306T, UA-306I, UA-510H. , And UX-5000 (both manufactured by Nippon Kayaku Co., Ltd.) and the like.
  • One of the preferred embodiments of the polymerizable compound is an ethylenically unsaturated compound having an acid group.
  • the acid group include a phosphoric acid group, a sulfo group, and a carboxy group.
  • the carboxy group is preferable as the acid group.
  • the ethylenically unsaturated compound having an acid group a 3- to 4-functional ethylenically unsaturated compound having an acid group [pentaerythritol tri and a tetraacrylate (PETA) skeleton introduced with a carboxy group (acid value: 80 to 80).
  • the ethylenically unsaturated compound having an acid group at least one selected from the group consisting of a bifunctional or higher functional ethylenically unsaturated compound having a carboxy group and a carboxylic acid anhydride thereof is preferable.
  • the ethylenically unsaturated compound having an acid group is at least one selected from the group consisting of a bifunctional or higher functional ethylenically unsaturated compound having a carboxy group and a carboxylic acid anhydride thereof, the developability and film strength are further improved. It will increase.
  • the bifunctional or higher functional unsaturated compound having a carboxy group is not particularly limited and can be appropriately selected from known compounds.
  • Examples of the bifunctional or higher functional unsaturated compound having a carboxy group include Aronix (registered trademark) TO-2349 (manufactured by Toagosei Co., Ltd.), Aronix (registered trademark) M-520 (manufactured by Toagosei Co., Ltd.), and the like.
  • Aronix (registered trademark) M-510 manufactured by Toagosei Co., Ltd. can be mentioned.
  • the polymerizable compound having an acid group described in paragraphs [0025] to [0030] of JP-A-2004-239942 is preferable, and the content described in this publication is described in this publication. Incorporated in the specification.
  • Examples of the polymerizable compound include a compound obtained by reacting a polyhydric alcohol with an ⁇ , ⁇ -unsaturated carboxylic acid, a compound obtained by reacting a glycidyl group-containing compound with an ⁇ , ⁇ -unsaturated carboxylic acid, and a urethane.
  • Urethane monomers such as (meth) acrylate compounds having a bond, ⁇ -chloro- ⁇ -hydroxypropyl- ⁇ '-(meth) acryloyloxyethyl-o-phthalate, ⁇ -hydroxyethyl- ⁇ '-(meth) acryloyloxyethyl Examples thereof include phthalic acid compounds such as -o-phthalate and ⁇ -hydroxypropyl- ⁇ '-(meth) acryloyloxyethyl-o-phthalate, and (meth) acrylic acid alkyl esters. These may be used alone or in combination of two or more.
  • Examples of the compound obtained by reacting a polyvalent alcohol with an ⁇ , ⁇ -unsaturated carboxylic acid include 2,2-bis (4-((meth) acrylamide polyethoxy) phenyl) propane and 2,2-bis.
  • Bisphenol A-based (meth) acrylate compounds such as (4-((meth) acrylamide polypropoxy) phenyl) propane and 2,2-bis (4-((meth) acrylamide polyethoxypolypropoxy) phenyl) propane , Polyethylene glycol di (meth) acrylate having 2 to 14 ethylene oxide groups, polypropylene glycol di (meth) acrylate having 2 to 14 propylene oxide groups, and 2 to 14 ethylene oxide groups.
  • an ethylene unsaturated compound having a tetramethylolmethane structure or a trimethylolpropane structure is preferable, and a tetramethylolmethanetri (meth) acrylate, a tetramethylolmethanetetra (meth) acrylate, a trimethylolpropanetri (meth) acrylate, or a trimethylolpropane tri (meth) acrylate is preferable.
  • Di (trimethylolpropane) tetraacrylate is more preferred.
  • Examples of the polymerizable compound include caprolactone-modified compounds of ethylenically unsaturated compounds (for example, KAYARAD® DPCA-20 manufactured by Nippon Kayaku Co., Ltd., A-9300-1CL manufactured by Shin-Nakamura Chemical Industry Co., Ltd., etc.).
  • An alkylene oxide-modified compound of an ethylenically unsaturated compound for example, KAYARAD RP-1040 manufactured by Nippon Kayaku Co., Ltd., ATM-35E, A-9300 manufactured by Shin-Nakamura Chemical Industry Co., Ltd., EBECRYL manufactured by Daicel Ornex Co., Ltd. (registered trademark). ) 135, etc.), ethoxylated glycerin triacrylate (A-GLY-9E, etc. manufactured by Shin-Nakamura Chemical Industry Co., Ltd.) and the like.
  • a compound containing an ester bond is preferable in that the photosensitive layer after transfer is excellent in developability.
  • the ethylenically unsaturated compound containing an ester bond is not particularly limited as long as it contains an ester bond in the molecule, but is not ethylene-free having a tetramethylolmethane structure or a trimethylolpropane structure in that the effect of the present invention is excellent.
  • the ethylenically unsaturated compound includes an ethylenically unsaturated compound having an aliphatic group having 6 to 20 carbon atoms and the above-mentioned ethylene unsaturated compound having a tetramethylol methane structure or a trimethylol propane structure. It is preferable to contain a compound.
  • Examples of the ethylenically unsaturated compound having an aliphatic structure having 6 or more carbon atoms include 1,9-nonanediol di (meth) acrylate, 1,10-decanediol di (meth) acrylate, and tricyclodecanedimethanoldi. Examples include (meth) acrylate.
  • One of the preferred embodiments of the polymerizable compound is a polymerizable compound having an aliphatic hydrocarbon ring structure (preferably a bifunctional ethylenically unsaturated compound).
  • a polymerizable compound having a ring structure in which two or more aliphatic hydrocarbon rings are condensed preferably a structure selected from the group consisting of a tricyclodecane structure and a tricyclodecene structure
  • a bifunctional ethylenically unsaturated compound having a ring structure in which two or more aliphatic hydrocarbon rings are fused is more preferable, and tricyclodecanedimethanol di (meth) acrylate is further preferable.
  • a cyclopentane structure, a cyclohexane structure, a tricyclodecane structure, a tricyclodecene structure, a norbornane structure, or an isoborone structure is preferable from the viewpoint that the effect of the present invention is more excellent.
  • the molecular weight of the polymerizable compound is preferably 200 to 3,000, more preferably 250 to 2,600, still more preferably 280 to 2,200, and particularly preferably 300 to 2,200.
  • the ratio of the content of the polymerizable compound having a molecular weight of 300 or less among the polymerizable compounds contained in the photosensitive layer is preferably 30% by mass or less with respect to the content of all the polymerizable compounds contained in the photosensitive layer. , 25% by mass or less is more preferable, and 20% by mass or less is further preferable.
  • the photosensitive layer preferably contains a bifunctional or higher functional ethylenically unsaturated compound, more preferably a trifunctional or higher functional ethylenically unsaturated compound. It is more preferable to contain a tetrafunctional ethylenically unsaturated compound.
  • the photosensitive layer comprises a bifunctional ethylenically unsaturated compound having an aliphatic hydrocarbon ring structure and a binder polymer having a structural unit having an aliphatic hydrocarbon ring. It is preferable to include it.
  • the photosensitive layer preferably contains a compound represented by the formula (M) and an ethylenically unsaturated compound having an acid group, and 1,9-nonane. It is more preferable to contain a diol diacrylate, a tricyclodecanedimethanol diacrylate, and a polyfunctional ethylenically unsaturated compound having a carboxylic acid group, preferably 1,9-nonanediol diacrylate and tricyclodecanedimethanol diacrylate. More preferably, it contains an acrylate and a succinic acid-modified form of dipentaerythritol pentaacrylate.
  • the photosensitive layer contains a compound represented by the formula (M), an ethylenically unsaturated compound having an acid group, and a thermally crosslinkable compound described later. It is more preferable to contain a compound represented by the formula (M), an ethylenically unsaturated compound having an acid group, and a blocked isocyanate compound described later.
  • the photosensitive layer is a bifunctional ethylenically unsaturated compound (preferably bifunctional (meth)) from the viewpoint of suppressing development residue and preventing rust. It is preferable to include an acrylate compound) and a trifunctional or higher functional ethylenically unsaturated compound (preferably a trifunctional or higher (meth) acrylate compound).
  • the mass ratio of the content of the bifunctional ethylenically unsaturated compound and the trifunctional or higher functional ethylenically unsaturated compound is preferably 10:90 to 90:10, more preferably 30:70 to 70:30.
  • the content of the bifunctional ethylenically unsaturated compound is preferably 20 to 80% by mass, more preferably 30 to 70% by mass, based on the total amount of all the ethylenically unsaturated compounds.
  • the bifunctional ethylenically unsaturated compound in the photosensitive layer is preferably 10 to 60% by mass, more preferably 15 to 40% by mass.
  • the photosensitive layer preferably contains compound M and a bifunctional ethylenically unsaturated compound having an aliphatic hydrocarbon ring structure from the viewpoint of rust resistance. .. Further, as one of the preferred embodiments of the photosensitive layer, the photosensitive layer is a compound M and an ethylenically unsaturated compound having an acid group from the viewpoints of substrate adhesion, development residue inhibitory property, and rust resistance.
  • compound M a bifunctional ethylenically unsaturated compound having an aliphatic hydrocarbon ring structure, and an ethylenically unsaturated compound having an acid group, and more preferably compound M, an aliphatic hydrocarbon. It is more preferable to contain a bifunctional ethylenically unsaturated compound having a ring structure, a trifunctional or higher functional ethylenically unsaturated compound, and an ethylenically unsaturated compound having an acid group, and the compound M has an aliphatic hydrocarbon ring structure.
  • the photosensitive layer is a 1,9-nonanediol diacrylate, from the viewpoint of substrate adhesion, development residue inhibitory property, and rust resistance.
  • a polyfunctional ethylenically unsaturated compound having a carboxylic acid group 1,9-nonanediol diacrylate, tricyclodecanedimethanol diacrylate, and a polyfunctional ethylenically unsaturated compound having a carboxylic acid group. It preferably contains a compound, more preferably 1,9-nonanediol diacrylate, tricyclodecanedimethanol diacrylate, dipentaerythritol hexaacrylate, and an ethylenically unsaturated compound having a carboxylic acid group.
  • 9-Nonandiol diacrylate 9-Nonandiol diacrylate, tricyclodecanedimethanol diacrylate, an ethylenically unsaturated compound having a carboxylic acid group, and a urethane acrylate compound are particularly preferable.
  • the photosensitive layer may contain a monofunctional ethylenically unsaturated compound as the ethylenically unsaturated compound.
  • the content of the bifunctional or higher functional ethylenically unsaturated compound in the ethylenically unsaturated compound is preferably 60 to 100% by mass, preferably 80 to 100% by mass, based on the total content of all the ethylenically unsaturated compounds contained in the photosensitive layer. It is more preferably from 100% by mass, still more preferably from 90 to 100% by mass.
  • the polymerizable compound (particularly, the ethylenically unsaturated compound) may be used alone or in combination of two or more.
  • the content of the polymerizable compound (particularly, the ethylenically unsaturated compound) in the photosensitive layer is preferably 1 to 70% by mass, more preferably 5 to 70% by mass, and 5 to 5 to 70% by mass with respect to the total mass of the photosensitive layer. 60% by mass is more preferable, and 5 to 50% by mass is particularly preferable.
  • the photosensitive layer may contain a polymerization initiator.
  • a photopolymerization initiator is preferable.
  • the photopolymerization initiator is not particularly limited, and a known photopolymerization initiator can be used.
  • Examples of the photopolymerization initiator include a photopolymerization initiator having an oxime ester structure (hereinafter, also referred to as “oxym-based photopolymerization initiator”) and a photopolymerization initiator having an ⁇ -aminoalkylphenone structure (hereinafter, “ ⁇ -”.
  • Photopolymerization initiator hereinafter, also referred to as “acylphosphine oxide-based photopolymerization initiator”
  • photopolymerization initiator having an N-phenylglycine structure hereinafter, “N-phenylglycine-based photopolymerization initiator”. Also referred to as "agent").
  • the photopolymerization initiator is selected from the group consisting of an oxime-based photopolymerization initiator, an ⁇ -aminoalkylphenone-based photopolymerization initiator, an ⁇ -hydroxyalkylphenone-based polymerization initiator, and an N-phenylglycine-based photopolymerization initiator. It is preferable to contain at least one selected from the group consisting of an oxime-based photopolymerization initiator, an ⁇ -aminoalkylphenone-based photopolymerization initiator, and an N-phenylglycine-based photopolymerization initiator. Is more preferable.
  • photopolymerization initiator is described in, for example, paragraphs [0031] to [0042] of JP-A-2011-95716 and paragraphs [0064]-[0081] of JP-A-2015-014783.
  • a polymerization initiator may be used.
  • photopolymerization initiators include 1- [4- (phenylthio) phenyl] -1,2-octanedione-2- (O-benzoyloxime) [trade name: IRGACURE (registered trademark) OXE-01, BASF.
  • the photopolymerization initiator may be used alone or in combination of two or more. When two or more kinds are used in combination, an oxime-based photopolymerization initiator and at least one selected from an ⁇ -aminoalkylphenone-based photopolymerization initiator and an ⁇ -hydroxyalkylphenone-based polymerization initiator may be used. preferable.
  • the content of the photopolymerization initiator is preferably 0.1% by mass or more, preferably 0.5% by mass or more, based on the total mass of the photosensitive layer. It is more preferably present, and further preferably 1.0% by mass or more. The upper limit thereof is preferably 10% by mass or less, more preferably 5% by mass or less, based on the total mass of the photosensitive layer.
  • the photosensitive layer may contain a heterocyclic compound.
  • the heterocycle contained in the heterocyclic compound may be either a monocyclic or polycyclic complex.
  • Examples of the hetero atom contained in the heterocyclic compound include a nitrogen atom, an oxygen atom, and a sulfur atom.
  • the heterocyclic compound preferably has at least one atom selected from the group consisting of a nitrogen atom, an oxygen atom, and a sulfur atom, and more preferably has a nitrogen atom.
  • heterocyclic compound examples include a triazole compound, a benzotriazole compound, a tetrazole compound, a thiadiazol compound, a triazine compound, a rhonin compound, a thiazole compound, a benzothiazole compound, a benzoimidazole compound, a benzoxazole compound, and a pyrimidine compound.
  • the heterocyclic compound is at least one selected from the group consisting of a triazole compound, a benzotriazole compound, a tetrazole compound, a thiadiazol compound, a triazine compound, a rhonin compound, a thiazole compound, a benzoimidazole compound, and a benzoxazole compound.
  • Species compounds are preferred, and at least one compound selected from the group consisting of triazole compounds, benzotriazole compounds, tetrazole compounds, thiadiazol compounds, thiazole compounds, benzothiazole compounds, benzoimidazole compounds, and benzoxazole compounds is more preferred.
  • heterocyclic compound A preferable specific example of the heterocyclic compound is shown below.
  • examples of the triazole compound and the benzotriazole compound include the following compounds.
  • Examples of the tetrazole compound include the following compounds.
  • Examples of the thiadiazole compound include the following compounds.
  • Examples of the triazine compound include the following compounds.
  • Examples of the loadonine compound include the following compounds.
  • Examples of the thiazole compound include the following compounds.
  • benzothiazole compound examples include the following compounds.
  • Examples of the benzimidazole compound include the following compounds.
  • benzoxazole compound examples include the following compounds.
  • the heterocyclic compound may be used alone or in combination of two or more.
  • the content of the heterocyclic compound is preferably 0.01 to 20.0% by mass, preferably 0.10 to 10.0% by mass, based on the total mass of the photosensitive layer. Is more preferable, 0.30 to 8.0% by mass is further preferable, and 0.50 to 5.0% by mass is particularly preferable.
  • Aliphatic thiol compound The photosensitive layer may contain an aliphatic thiol compound.
  • the photosensitive layer contains an aliphatic thiol compound, the aliphatic thiol compound undergoes an en-thiol reaction with a radically polymerizable compound having an ethylenically unsaturated group, thereby suppressing the curing shrinkage of the formed film. And the stress is relieved.
  • aliphatic thiol compound a monofunctional aliphatic thiol compound or a polyfunctional aliphatic thiol compound (that is, a bifunctional or higher functional aliphatic thiol compound) is preferable.
  • aliphatic thiol compound a polyfunctional aliphatic thiol compound is preferable from the viewpoint of adhesion of the formed pattern (particularly, adhesion after exposure).
  • polyfunctional aliphatic thiol compound means an aliphatic compound having two or more thiol groups (also referred to as “mercapto groups”) in the molecule.
  • the polyfunctional aliphatic thiol compound a low molecular weight compound having a molecular weight of 100 or more is preferable. Specifically, the molecular weight of the polyfunctional aliphatic thiol compound is more preferably 100 to 1,500, and even more preferably 150 to 1,000.
  • the number of functional groups of the polyfunctional aliphatic thiol compound for example, 2 to 10 functionalities are preferable, 2 to 8 functionalities are more preferable, and 2 to 6 functionalities are further preferable, from the viewpoint of adhesion of the formed pattern.
  • polyfunctional aliphatic thiol compound examples include trimethylolpropanetris (3-mercaptobutylate), 1,4-bis (3-mercaptobutylyloxy) butane, pentaerythritol tetrakis (3-mercaptobutyrate), and the like.
  • the polyfunctional aliphatic thiol compounds include trimethylolpropane tris (3-mercaptobutyrate), 1,4-bis (3-mercaptobutylyloxy) butane, and 1,3,5-. At least one compound selected from the group consisting of tris (3-mercaptobutylyloxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione is preferred.
  • Examples of the monofunctional aliphatic thiol compound include 1-octanethiol, 1-dodecanethiol, ⁇ -mercaptopropionic acid, methyl-3-mercaptopropionate, 2-ethylhexyl-3-mercaptopropionate, and n-. Examples thereof include octyl-3-mercaptopropionate, methoxybutyl-3-mercaptopropionate, and stearyl-3-mercaptopropionate.
  • the photosensitive layer may contain one kind of aliphatic thiol compound alone, or may contain two or more kinds of aliphatic thiol compounds.
  • the content of the aliphatic thiol compound is preferably 5% by mass or more, more preferably 5 to 50% by mass, and 5 to 30% by mass with respect to the total mass of the photosensitive layer.
  • the mass% is more preferable, and 8 to 20% by mass is particularly preferable.
  • Thermally crosslinkable compound The photosensitive layer preferably contains a thermally crosslinkable compound from the viewpoint of the strength of the obtained cured film and the adhesiveness of the obtained uncured film.
  • the thermally crosslinkable compound having an ethylenically unsaturated group described later is not treated as an ethylenically unsaturated compound, but is treated as a thermally crosslinkable compound.
  • the heat-crosslinkable compound include an epoxy compound, an oxetane compound, a methylol compound, and a blocked isocyanate compound. Among them, the blocked isocyanate compound is preferable from the viewpoint of the strength of the obtained cured film and the adhesiveness of the obtained uncured film.
  • the blocked isocyanate compound reacts with a hydroxy group and a carboxy group, for example, when at least one of the binder polymer and the radically polymerizable compound having an ethylenically unsaturated group has at least one of the hydroxy group and the carboxy group, The hydrophilicity of the formed film tends to decrease, and the function as a protective film tends to be strengthened.
  • the blocked isocyanate compound refers to "a compound having a structure in which the isocyanate group of isocyanate is protected (so-called masked) with a blocking agent".
  • the dissociation temperature of the blocked isocyanate compound is not particularly limited, but is preferably 100 to 160 ° C, more preferably 130 to 150 ° C.
  • the dissociation temperature of the blocked isocyanate means "the temperature of the endothermic peak associated with the deprotection reaction of the blocked isocyanate when measured by DSC (Differential scanning calorimetry) analysis using a differential scanning calorimeter".
  • DSC Different scanning calorimeter
  • a differential scanning calorimeter model: DSC6200 manufactured by Seiko Instruments Inc. can be preferably used.
  • the differential scanning calorimeter is not limited to this.
  • the blocking agent having a dissociation temperature of 100 to 160 ° C. for example, at least one selected from oxime compounds is preferable from the viewpoint of storage stability.
  • the blocked isocyanate compound preferably has an isocyanurate structure, for example, from the viewpoint of improving the brittleness of the membrane and improving the adhesion to the transferred body.
  • the blocked isocyanate compound having an isocyanurate structure can be obtained, for example, by subjecting hexamethylene diisocyanate to isocyanurate to protect it.
  • a compound having an oxime structure using an oxime compound as a blocking agent is more likely to have a dissociation temperature in a preferable range than a compound having no oxime structure, and has less development residue. It is preferable because it is easy to do.
  • the blocked isocyanate compound may have a polymerizable group.
  • the polymerizable group is not particularly limited, and a known polymerizable group can be used, and a radically polymerizable group is preferable.
  • the polymerizable group include a (meth) acryloxy group, a (meth) acrylamide group, an ethylenically unsaturated group such as a styryl group, and a group having an epoxy group such as a glycidyl group.
  • an ethylenically unsaturated group is preferable
  • a (meth) acryloxy group is more preferable
  • an acryloxy group is further preferable.
  • blocked isocyanate compound a commercially available product can be used.
  • examples of commercially available blocked isocyanate compounds include Karenz (registered trademark) AOI-BM, Karenz (registered trademark) MOI-BM, Karenz (registered trademark) MOI-BP (all manufactured by Showa Denko KK), and blocks.
  • Examples thereof include the Duranate series of molds (for example, Duranate (registered trademark) TPA-B80E, Duranate (registered trademark) WT32-B75P, etc., manufactured by Asahi Kasei Chemicals Co., Ltd.).
  • the heat-crosslinkable compound may be used alone or in combination of two or more.
  • the content of the heat-crosslinkable compound is preferably 1 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 a surfactant.
  • the surfactant include the surfactants described in paragraph [0017] of Japanese Patent No. 4502784 and paragraphs [0060] to [0071] of JP-A-2009-237362.
  • a nonionic surfactant a fluorine-based surfactant or a silicone-based surfactant is preferable. Further, as the surfactant, a nonionic surfactant is preferable.
  • Commercially available products of fluorine-based surfactants include, for example, Megafuck F-171, F-172, F-173, F-176, F-177, F-141, F-142, F-143, F-144.
  • the fluorine-based surfactant has a molecular structure having a functional group containing a fluorine atom, and when heat is applied, the portion of the functional group containing the fluorine atom is cut off and the fluorine atom volatilizes. Can also be suitably used.
  • fluorine-based surfactants include the Megafuck DS series manufactured by DIC Corporation (The Chemical Daily (February 22, 2016), Nikkei Sangyo Shimbun (February 23, 2016)), for example, Megafuck. DS-21 can be mentioned.
  • the fluorine-based surfactant it is also preferable to use a polymer of a fluorine atom-containing vinyl ether compound having a fluorinated alkyl group or a fluorinated alkylene ether group and a hydrophilic vinyl ether compound. Further, as the fluorine-based surfactant, a block polymer can also be used.
  • the fluorine-based surfactant has a structural unit derived from a (meth) acrylate compound having a fluorine atom and 2 or more (preferably 5 or more) alkyleneoxy groups (preferably ethyleneoxy groups and propyleneoxy groups).
  • a fluorine-containing polymer compound containing a structural unit derived from a (meth) acrylate compound can also be preferably used.
  • a fluorine-based surfactant a fluorine-containing polymer having an ethylenically unsaturated bond-containing group in the side chain can also be used. Examples thereof include Megafuck RS-101, RS-102, RS-718K, RS-72-K (all manufactured by DIC Corporation) and the like.
  • the compound having a linear perfluoroalkyl group having 7 or more carbon atoms is preferably a compound using a substitute material of PFOA or PFOS as the fluorine-based surfactant from the viewpoint of improving environmental suitability.
  • nonionic surfactant examples include glycerol, trimethylolpropane, trimethylolethane, their ethoxylates and propoxylates (eg, glycerol propoxylate, glycerol ethoxylate, etc.), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, and the like.
  • examples thereof include polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, and sorbitan fatty acid ester.
  • silicone-based surfactant examples include a linear polymer composed of a siloxane bond and a modified siloxane polymer having an organic group introduced into a side chain or a terminal.
  • surfactants include EXP. S-309-2, EXP. S-315, EXP. S-503-2, EXP. S-505-2 (all manufactured by DIC Co., Ltd.), DOWSIL 8032 ADDITIVE, Torre Silicone DC3PA, Torre Silicone SH7PA, Torre Silicone DC11PA, Torre Silicone SH21PA, Torre Silicone SH28PA, Torre Silicone SH29PA, Torre Silicone SH30PA, Torre Silicone SH8400 ( (Made by Toray Dow Corning Co., Ltd.), 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-101KP-103, KP-104, KP-105, KP
  • the surfactant may be used alone or in combination of two or more.
  • the content of the surfactant is preferably 0.01 to 3.0% by mass, preferably 0.01 to 1.0% by mass, based on the total mass of the photosensitive layer. Is more preferable, and 0.05 to 0.80% by mass is further preferable.
  • the photosensitive layer may contain a polymerization inhibitor.
  • the polymerization inhibitor means a compound having a function of delaying or prohibiting a polymerization reaction.
  • a known compound used as a polymerization inhibitor can be used.
  • polymerization inhibitor examples include phenothiazine compounds such as phenothiazine, bis- (1-dimethylbenzyl) phenothiazine, and 3,7-dioctylphenothiazine; bis [3- (3-tert-butyl-4-hydroxy-5-.
  • Methylphenyl) propionic acid [ethylene bis (oxyethylene)] 2,4-bis [(laurylthio) methyl] -o-cresol, 1,3,5-tris (3,5-di-t-butyl-4-) Hydroxybenzyl), 1,3,5-tris (4-t-butyl-3-hydroxy-2,6-dimethylbenzyl), 2,4-bis- (n-octylthio) -6- (4-hydroxy-3) , 5-Di-t-butylanilino) -1,3,5-triazine, and hindered phenolic compounds such as pentaerythritol tetrakis 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate; 4 -Nitroso compounds such as nitrosophenol, N-nitrosodiphenylamine, N-nitrosocyclohexylhydroxylamine, and N-nitrosophenylhydroxylamine or salts thereof
  • At least one selected from the group consisting of a phenothiazine compound, a nitroso compound or a salt thereof, and a hindered phenol compound is preferable as the polymerization inhibitor because the effect of the present invention is more excellent, and phenothiazine and bis [ 3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionic acid], [ethylenebis (oxyethylene)] 2,4-bis [(laurylthio) methyl] -o-cresol, 1,3 5-Tris (3,5-di-t-butyl-4-hydroxybenzyl), p-methoxyphenol, and N-nitrosophenylhydroxylamine aluminum salts are more preferred.
  • the polymerization inhibitor may be used alone or in combination of two or more.
  • the content of the polymerization inhibitor is preferably 0.001 to 5.0% by mass, preferably 0.01 to 3.0% by mass, based on the total mass of the photosensitive layer. Is more preferable, and 0.02 to 2.0% by mass is further preferable.
  • the content of the polymerization inhibitor is preferably 0.005 to 5.0% by mass, more preferably 0.01 to 3.0% by mass, and 0.01 to 1.0 with respect to the total mass of the polymerizable compound. Mass% is more preferred.
  • the photosensitive layer may contain a hydrogen-donating compound.
  • the hydrogen donating compound has an action of further improving the sensitivity of the photopolymerization initiator to active light rays and suppressing the inhibition of the polymerization of the polymerizable compound by oxygen.
  • Examples of the hydrogen donating compound include amines and amino acid compounds.
  • Examples of amines include M.I. R. "Journal of Polymer Society" by Sander et al., Vol. 10, pp. 3173 (1972), Japanese Patent Application Laid-Open No. 44-020189, Japanese Patent Application Laid-Open No. 51-082102, Japanese Patent Application Laid-Open No. 52-134692, Japanese Patent Application Laid-Open No. 59-138205. Examples thereof include the compounds described in Japanese Patent Application Laid-Open No. 60-0843305, Japanese Patent Application Laid-Open No. 62-018537, Japanese Patent Application Laid-Open No. 64-033104, and Research Disclosure No. 33825.
  • examples thereof include dimethylaniline and p-methylthiodimethylaniline.
  • at least one selected from the group consisting of 4,4'-bis (diethylamino) benzophenone and tris (4-dimethylaminophenyl) methane is used as amines because the effect of the present invention is more excellent. preferable.
  • amino acid compound examples include N-phenylglycine, N-methyl-N-phenylglycine, and N-ethyl-N-phenylglycine.
  • N-phenylglycine is preferable as the amino acid compound because the effect of the present invention is more excellent.
  • Examples of the hydrogen donor compound include an organometallic compound (tributyltin acetate, etc.) described in JP-A-48-042965, a hydrogen donor described in JP-A-55-0344414, and JP-A-6.
  • a sulfur compound (Trithian and the like) described in JP-A-308727 can also be mentioned.
  • the hydrogen donating compound may be used alone or in combination of two or more.
  • the content of the hydrogen donating compound is 0 with respect to the total mass of the photosensitive layer in terms of improving the curing rate due to the balance between the polymerization growth rate and the chain transfer. It is preferably 0.01 to 10.0% by mass, more preferably 0.01 to 8.0% by mass, still more preferably 0.03 to 5.0% by mass.
  • the photosensitive layer may contain a predetermined amount of impurities.
  • impurities include sodium, potassium, magnesium, calcium, iron, manganese, copper, aluminum, titanium, chromium, cobalt, nickel, zinc, tin, halogen and ions thereof.
  • halide ions, sodium ions, and potassium ions are easily mixed as impurities, so the following content is preferable.
  • the content of impurities in the photosensitive layer is preferably 80 ppm or less, more preferably 10 ppm or less, and even more preferably 2 ppm or less on a mass basis.
  • the content of impurities in the photosensitive layer can be 1 ppb or more or 0.1 ppm or more on a mass basis.
  • Impurities can be quantified by known methods such as ICP (Inductively Coupled Plasma) emission spectroscopy, atomic absorption spectroscopy, and ion chromatography.
  • ICP Inductively Coupled Plasma
  • the content of compounds such as benzene, formaldehyde, trichlorethylene, 1,3-butadiene, carbon tetrachloride, chloroform, N, N-dimethylformamide, N, N-dimethylacetamide, and hexane in the photosensitive layer is low. Is preferable.
  • the content of these compounds in the photosensitive layer is preferably 100 ppm or less, more preferably 20 ppm or less, still more preferably 4 ppm or less on a mass basis.
  • the lower limit is based on mass and can be 10 ppb or more, and can be 100 ppb or more.
  • the content of these compounds can be suppressed in the same manner as the above-mentioned metal impurities. Further, it can be quantified by a known measurement method.
  • the water content in the photosensitive layer is preferably 0.01 to 1.0% by mass, more preferably 0.05 to 0.5% by mass, from the viewpoint of improving reliability and laminating property.
  • the photosensitive layer may contain the residual monomer of each structural unit of the alkali-soluble resin described above.
  • the content of the residual monomer is preferably 5,000 mass ppm or less, more preferably 2,000 mass ppm or less, and 500 mass ppm or less with respect to the total mass of the alkali-soluble resin from the viewpoint of patterning property and reliability. Is more preferable.
  • the lower limit is not particularly limited, but 1 mass ppm or more is preferable, and 10 mass ppm or more is more preferable.
  • the residual monomer of each structural unit of the alkali-soluble resin is preferably 3,000 mass ppm or less, more preferably 600 mass ppm or less, based on the total mass of the photosensitive layer from the viewpoint of patterning property and reliability. More preferably, it is 100 mass ppm or less.
  • the lower limit is not particularly limited, but is preferably 0.1 mass ppm or more, and more preferably 1 mass ppm or more.
  • the amount of residual monomer of the monomer when synthesizing the alkali-soluble resin by the polymer reaction is also preferably in the above range.
  • the content of glycidyl acrylate is preferably in the above range.
  • the amount of the residual monomer can be measured by a known method such as liquid chromatography and gas chromatography.
  • the photosensitive layer may contain components other than the components described above (hereinafter, also referred to as “other components”).
  • Other components include, for example, colorants, antioxidants, and particles (eg, metal oxide particles).
  • other additives described in paragraphs [0058] to [0071] of JP-A-2000-310706 can also be mentioned.
  • metal oxide particles are preferable.
  • the metal in the metal oxide particles also includes metalloids such as B, Si, Ge, As, Sb, and Te.
  • the average primary particle diameter of the particles is, for example, preferably 1 to 200 nm, more preferably 3 to 80 nm, from the viewpoint of transparency of the cured film.
  • the average primary particle size of the particles is calculated by measuring the particle size of 200 arbitrary particles using an electron microscope and arithmetically averaging the measurement results. If the shape of the particle is not spherical, the longest side is the particle diameter.
  • the photosensitive layer may contain only one kind of metal type and particles having different sizes, etc., or may contain two or more kinds of particles.
  • the photosensitive layer does not contain particles, or when the photosensitive layer contains particles, the content of the particles is preferably more than 0% by mass and 35% by mass or less with respect to the total mass of the photosensitive layer. It is more preferable that the particles are not contained or the content of the particles is more than 0% by mass and 10% by mass or less with respect to the total mass of the photosensitive composition, and the particles are not contained or the content of the particles is photosensitive.
  • it is more than 0% by mass and 5% by mass or less based on the total mass of the layer, and it does not contain particles or the content of particles is more than 0% by mass and 1% by mass or less based on the total mass of the photosensitive layer. It is more preferable, and it is particularly preferable that it does not contain particles.
  • the photosensitive layer may contain a trace amount of a colorant (pigment, dye, etc.), but for example, from the viewpoint of transparency, it is preferable that the photosensitive layer contains substantially no colorant.
  • the content of the colorant is preferably less than 1% by mass, more preferably less than 0.1% by mass, based on the total mass of the photosensitive layer.
  • the antioxidant examples include 1-phenyl-3-pyrazolidone (also known as phenidone), 1-phenyl-4,4-dimethyl-3-pyrazolidone, and 1-phenyl-4-methyl-4-hydroxymethyl-.
  • 3-Pyrazoridones such as 3-pyrazolidone; polyhydroxybenzenes such as hydroquinone, catechol, pyrogallol, methylhydroquinone, and chlorhydroquinone; paramethylaminophenol, paraaminophenol, parahydroxyphenylglycine, and paraphenylenediamine. Be done.
  • 3-pyrazolidones are preferable, and 1-phenyl-3-pyrazolidone is more preferable as the antioxidant because the effect of the present invention is more excellent.
  • the content of the antioxidant is preferably 0.001% by mass or more, more preferably 0.005% by mass or more, and 0. 01% by mass or more is more preferable.
  • the upper limit is not particularly limited, but is preferably 1% by mass or less.
  • the thickness of the photosensitive layer is not particularly limited, but is often 30 ⁇ m or less, and is preferably 20 ⁇ m or less, more preferably 15 ⁇ m or less, and 10 ⁇ m or less in that the effect of the present invention is more excellent. Is more preferable, and 5.0 ⁇ m or less is particularly preferable. As the lower limit, 0.60 ⁇ m or more is preferable, 1.5 ⁇ m or more is more preferable, and 2.0 ⁇ m or more is further preferable, in that the strength of the film obtained by curing the photosensitive layer is excellent.
  • the thickness of the photosensitive layer is calculated as an average value of any five points measured by cross-sectional observation with an SEM (Scanning Electron Microscope).
  • the refractive index of the photosensitive layer is preferably 1.47 to 1.56, more preferably 1.49 to 1.54.
  • the photosensitive layer is preferably achromatic.
  • the total reflection (incident angle 8 °, light source: D-65 (2 ° field)) has an L * value of 10 to 90 in the CIE1976 (L *, a *, b *) color space.
  • the a * value is preferably ⁇ 1.0 to 1.0
  • the b * value is preferably ⁇ 1.0 to 1.0.
  • the pattern (cured film of the photosensitive layer) obtained by curing the photosensitive layer is preferably achromatic.
  • the total reflection (incident angle 8 °, light source: D-65 (2 ° field)) has a pattern L * value of 10 to 90 in the CIE1976 (L *, a *, b *) color space.
  • the a * value of the pattern is preferably ⁇ 1.0 to 1.0
  • the b * value of the pattern is preferably ⁇ 1.0 to 1.0.
  • the moisture permeability of the pattern (cured film of the photosensitive layer) obtained by curing the photosensitive layer at a film thickness of 40 ⁇ m is 500 g / m 2/24 hr or less from the viewpoint of rust prevention. It is preferably 300 g / m 2/24 hr or less, and even more preferably 100 g / m 2/24 hr or less.
  • the moisture permeability is measured with a cured film obtained by curing the photosensitive layer by exposing the photosensitive layer with an i-line at an exposure amount of 300 mJ / cm 2 and then post-baking at 145 ° C. for 30 minutes. do.
  • the transfer film X2 of the second embodiment preferably has a refractive index adjusting layer.
  • a refractive index adjusting layer a known refractive index adjusting layer can be applied.
  • the material contained in the refractive index adjusting layer include a binder polymer, a polymerizable compound, a metal salt, and particles.
  • the method for controlling the refractive index of the refractive index adjusting layer is not particularly limited, and for example, a method using a resin having a predetermined refractive index alone, a method using a resin and particles, and a composite of a metal salt and a resin are used. Is mentioned.
  • binder polymer and the polymerizable compound examples include the binder polymer and the polymerizable compound described in the above section “Photosensitive layer”.
  • the particles include metal oxide particles and metal particles.
  • the type of the metal oxide particles is not particularly limited, and examples thereof include known metal oxide particles.
  • the metal in the metal oxide particles also includes metalloids such as B, Si, Ge, As, Sb, and Te.
  • the average primary particle diameter of the particles is, for example, preferably 1 to 200 nm, more preferably 3 to 80 nm, from the viewpoint of transparency of the cured film.
  • the average primary particle size of the particles is calculated by measuring the particle size of 200 arbitrary particles using an electron microscope and arithmetically averaging the measurement results. If the shape of the particle is not spherical, the longest side is the particle diameter.
  • the metal oxide particles include zirconium oxide particles (ZrO 2 particles), Nb 2 O 5 particles, titanium oxide particles (TIO 2 particles), silicon dioxide particles (SiO 2 particles), and a composite thereof. At least one selected from the group consisting of particles is preferred. Among these, as the metal oxide particles, for example, at least one selected from the group consisting of zirconium oxide particles and titanium oxide particles is more preferable because the refractive index can be easily adjusted.
  • metal oxide particles include calcined zirconium oxide particles (manufactured by CIK Nanotech Co., Ltd., product name: ZRPGM15WT% -F04), calcined zirconium oxide particles (manufactured by CIK Nanotech Co., Ltd., product name: ZRPGM15WT% -F74).
  • Fired zirconium oxide particles (CIK Nanotech Co., Ltd., product name: ZRPGM15WT% -F75), fired zirconium oxide particles (CIK Nanotech Co., Ltd., product name: ZRPGM15WT% -F76), zirconium oxide particles (Nano Teen OZ-S30M, Nissan) Examples include (manufactured by Chemical Industry Co., Ltd.) and zirconium oxide particles (Nano Teen OZ-S30K, manufactured by Nissan Chemical Industry Co., Ltd.).
  • the particles may be used alone or in combination of two or more.
  • the content of the particles in the refractive index adjusting layer is preferably 1 to 95% by mass, more preferably 20 to 90% by mass, still more preferably 40 to 85% by mass, based on the total mass of the refractive index adjusting layer.
  • the content of the titanium oxide particles is preferably 1 to 95% by mass, more preferably 20 to 90% by mass, and 40 to 85% by mass with respect to the total mass of the refractive index adjusting layer. % Is more preferable.
  • the refractive index of the refractive index adjusting layer is preferably higher than that of the photosensitive layer.
  • the refractive index of the refractive index adjusting layer is preferably 1.50 or more, more preferably 1.55 or more, further preferably 1.60 or more, and particularly preferably 1.65 or more.
  • the upper limit of the refractive index of the refractive index adjusting layer is preferably 2.10 or less, more preferably 1.85 or less, and even more preferably 1.78 or less.
  • the thickness of the refractive index adjusting layer is preferably 50 to 500 nm, more preferably 55 to 110 nm, and even more preferably 60 to 100 nm.
  • the thickness of the refractive index adjusting layer is calculated as an average value of any five points measured by cross-sectional observation with a scanning electron microscope (SEM).
  • the method for producing the transfer film of the second embodiment is not particularly limited, and a known method can be used.
  • a method for producing the transfer film 20 for example, a composition for forming an intermediate layer is applied to the surface of the temporary support 11 to form a coating film, and the coating film is further dried to form the intermediate layer 13.
  • Examples thereof include a step of applying a composition for forming an adjusting layer to form a coating film, and further drying the coating film to form a refractive index adjusting layer 17.
  • the transfer film 20 is manufactured by crimping the protective film 21 onto the refractive index adjusting layer 17 of the laminate manufactured by the above-mentioned manufacturing method.
  • the method for producing the transfer film of the second embodiment includes a step of providing the protective film 21 so as to be in contact with the surface of the refractive index adjusting layer 17 opposite to the side having the temporary support 11. It is preferable to manufacture a transfer film 20 including 11, an intermediate layer 13, a photosensitive layer 15, a refractive index adjusting layer 17, and a protective film 21.
  • the transfer film 20 may be wound up to prepare and store the transfer film in the form of a roll.
  • the roll-type transfer film can be provided as it is in the bonding process with the substrate in the roll-to-roll method described later.
  • the intermediate layer 13 and the photosensitive layer 15 are formed on the temporary support 11, and the refractive index adjusting layer 17 is separately formed on the protective film 21 to be photosensitive.
  • a method may be used in which the refractive index adjusting layer 17 is bonded to the layer 15 to form the layer 15.
  • compositions for forming the intermediate layer and the intermediate layer for forming the intermediate layer As the method for forming the composition for forming the intermediate layer and the intermediate layer, the composition for forming the intermediate layer and the method for forming the intermediate layer of the transfer film X1 of the first embodiment. Is similar to.
  • the photosensitive layer in the transfer film X2 is composed of the above-mentioned components constituting the photosensitive layer (for example, a binder polymer, a polymerizable compound, and , Polymerization initiator, etc.), and it is desirable to form by a coating method using a photosensitive composition containing a solvent.
  • a photosensitive composition is applied onto a temporary support to form a coating film, and the coating film is dried at a predetermined temperature.
  • a method of forming a photosensitive layer is preferable.
  • an organic solvent is preferable.
  • the organic solvent include methyl ethyl ketone, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate (also known as 1-methoxy-2-propyl acetate), diethylene glycol ethyl methyl ether, cyclohexanone, methyl isobutyl ketone, ethyl lactate, methyl lactate, and caprolactam. , N-propanol, and 2-propanol.
  • an organic solvent having a boiling point of 180 to 250 ° C. can be used, if necessary.
  • the solvent may be used alone or in combination of two or more.
  • the total solid content of the photosensitive composition is preferably 5 to 80% by mass, more preferably 5 to 40% by mass, still more preferably 5 to 30% by mass, based on the total mass of the photosensitive composition. That is, the content of the solvent in the photosensitive composition is preferably 20 to 95% by mass, more preferably 60 to 95% by mass, and further preferably 70 to 95% by mass with respect to the total mass of the photosensitive composition. preferable.
  • the viscosity of the photosensitive composition at 25 ° C. is, for example, preferably 1 to 50 mPa ⁇ s, more preferably 2 to 40 mPa ⁇ s, and even more preferably 3 to 30 mPa ⁇ s from the viewpoint of coatability. Viscosity is measured using a viscometer.
  • a viscometer for example, a viscometer manufactured by Toki Sangyo Co., Ltd. (trade name: VISCOMETER TV-22) can be preferably used.
  • the viscometer is not limited to the above-mentioned viscometer.
  • the surface tension of the photosensitive composition at 25 ° C. is, for example, preferably 5 to 100 mN / m, more preferably 10 to 80 mN / m, and even more preferably 15 to 40 mN / m from the viewpoint of coatability.
  • Surface tension is measured using a tensiometer.
  • a surface tension meter manufactured by Kyowa Interface Science Co., Ltd. (trade name: Automatic Surface Tensiometer CBVP-Z) can be preferably used.
  • the tensiometer is not limited to the above-mentioned tensiometer.
  • Examples of the method for applying the photosensitive composition 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 (that is, a slit coating method).
  • the drying temperature is preferably 80 ° C. or higher, more preferably 90 ° C. or higher.
  • the upper limit thereof is preferably 130 ° C. or lower, more preferably 120 ° C. or lower. It can also be dried by continuously changing the temperature.
  • the drying time is preferably 20 seconds or longer, more preferably 40 seconds or longer, and even more preferably 60 seconds or longer.
  • the upper limit is not particularly limited, but is preferably 600 seconds or less, and more preferably 300 seconds or less.
  • composition for forming a refractive index adjusting layer preferably contains the above-mentioned various components forming the refractive index adjusting layer and a solvent.
  • the preferable range of the content of each component with respect to the total solid content of the composition is the same as the preferable range of the content of each component with respect to the total mass of the refractive index adjusting layer described above. be.
  • the solvent is not particularly limited as long as it can dissolve or disperse the components contained in the refractive index adjusting layer, and at least one selected from the group consisting of water and a water-miscible organic solvent is preferable, with water or water.
  • a mixed solvent with a water-miscible organic solvent is more preferable.
  • the water-miscible organic solvent include alcohols having 1 to 3 carbon atoms, acetone, ethylene glycol, and glycerin, and alcohols having 1 to 3 carbon atoms are preferable, and methanol or ethanol is more preferable.
  • the solvent may be used alone or in combination of two or more.
  • 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 with respect to 100 parts by mass of the total solid content of the composition.
  • the method for forming the refractive index adjusting layer is not particularly limited as long as it can form a layer containing the above components, and for example, known coating methods (slit coating, spin coating, curtain coating, inkjet coating, etc.) can be used. Can be mentioned.
  • the drying temperature is preferably 80 ° C. or higher, more preferably 90 ° C. or higher.
  • the upper limit thereof is preferably 130 ° C. or lower, more preferably 120 ° C. or lower. It can also be dried by continuously changing the temperature.
  • the drying time is preferably 20 seconds or longer, more preferably 40 seconds or longer, and even more preferably 60 seconds or longer.
  • the upper limit is not particularly limited, but is preferably 600 seconds or less, and more preferably 300 seconds or less.
  • the transfer film of the second embodiment can be manufactured by adhering the protective film to the refractive index adjusting layer.
  • the method of attaching the protective film to the refractive index adjusting layer is not particularly limited, and known methods can be mentioned.
  • Examples of the device for adhering the protective film to the refractive index adjusting layer include a vacuum laminator and a known laminator such as an auto-cut laminator. It is preferable that the laminator is provided with an arbitrary heatable roller such as a rubber roller and can be pressurized and heated.
  • the transfer film X2 of the second embodiment also has the same temporary support and photosensitive as the transfer film X1 of the first embodiment described above. It is preferable that each of the physical properties of the sex layer and the protective film satisfies one or more of the preferred embodiment 1, the preferred embodiment 2, the preferred embodiment 3, the preferred embodiment 4, and the preferred embodiment 5, and it is more preferable to satisfy all of them.
  • Each aspect of the preferred embodiment 1, the preferred embodiment 2, the preferred embodiment 3, the preferred embodiment 4, and the preferred embodiment 5 is as described above.
  • the present invention also relates to a method for manufacturing a circuit wiring.
  • the pattern formed by the above-mentioned method for manufacturing a laminate of the present invention can be used as a protection pattern for a seed layer during a plating process in the manufacture of circuit wiring using a semi-additive method (SAP).
  • SAP semi-additive method
  • the method for manufacturing the circuit wiring of the present invention is as follows.
  • a step of forming a seed layer on a substrate to form a substrate with a seed layer (hereinafter, also referred to as a “seed layer forming step”).
  • the transfer film and the substrate with the seed layer are bonded so that the side opposite to the temporary support side of the transfer film having the temporary support, the intermediate layer, and the photosensitive layer is in contact with the substrate with the seed layer.
  • a step of obtaining a substrate with a photosensitive layer having the substrate, the seed layer, the photosensitive layer, the intermediate layer, and the temporary support in this order (transfer film bonding step).
  • a step of peeling the temporary support between the temporary support and the intermediate layer (temporary support peeling step) and An exposure process is performed by bringing the exposed intermediate layer into contact with the mask, and a development process is further performed after the exposure to form a pattern (pattern formation step).
  • a step of forming a metal plating layer by a plating process on the seed layer in a region where the pattern is not arranged (hereinafter, also referred to as a “metal plating layer forming step”).
  • a step of forming a protective layer on the metal plating layer (hereinafter, also referred to as a “protective layer forming step”) and The step of removing the pattern (hereinafter, also referred to as “pattern removing step”) and It has a step of removing the exposed seed layer to obtain a conductive thin wire (hereinafter, also referred to as a “conductive thin wire forming step”).
  • the surface free energy of the surface of the intermediate layer on the temporary support side is 68.0 mJ / m 2 or less.
  • the first embodiment of the method for manufacturing a circuit wiring includes a seed layer forming step, a transfer film bonding step, a temporary support peeling step, a pattern forming step, a metal plating layer forming step, a protective layer forming step, a pattern removing step, and conductivity.
  • the fine wire forming steps are performed in this order, and the surface free energy of the surface of the intermediate layer on the temporary support side is 68.0 mJ / m 2 or less.
  • the transfer film bonding step, the temporary support peeling step, and the pattern forming step are the same as those in the first embodiment of the above-described laminated body manufacturing method except that the substrate is a substrate with a seed layer. , The preferred embodiment is also the same.
  • the seed layer forming step is a step of forming a seed layer on the substrate.
  • the substrate used in this step include the substrate described in the transfer film bonding step in the first embodiment of the above-mentioned method for manufacturing a laminate.
  • the metal contained in the seed layer is not particularly limited, and known metals can be used.
  • Examples of the main component (so-called main metal) contained in the seed layer include copper, chromium, lead, nickel, gold, silver, tin, zinc and the like.
  • the main component is intended to be the metal having the highest content among the metals contained in the seed layer.
  • the thickness of the seed layer is not particularly limited, and is preferably 50 nm or more, more preferably 100 nm or more.
  • the upper limit is not particularly limited, but is preferably 2 ⁇ m or less.
  • the method for forming the seed layer is not particularly limited, and examples thereof include known methods such as a method of applying a dispersion liquid in which metal fine particles are dispersed and sintering a coating film, a sputtering method, and a vapor deposition method.
  • the metal plating layer forming step is a step of forming a metal plating layer by a plating process on a seed layer in a region where a pattern is not arranged.
  • Examples of the plating treatment include an electrolytic plating method and an electroless plating method, and the electrolytic plating method is preferable from the viewpoint of productivity.
  • the metal contained in the metal plating layer is not particularly limited, and known metals can be used.
  • the metal plating layer may contain metals such as copper, chromium, lead, nickel, gold, silver, tin, and zinc, as well as alloys of these metals.
  • the metal plating layer preferably contains copper or an alloy thereof in that the conductive thin wire is more excellent in conductivity.
  • the main component of the metal plating layer is preferably copper in that the conductive thin wire is more excellent in conductivity.
  • the lower limit of the thickness of the metal plating layer is not particularly limited, but is preferably 0.1 ⁇ m or more, and more preferably 1 ⁇ m.
  • the upper limit is not particularly limited, but is preferably 20 ⁇ m or less.
  • the protective layer laminating step is a step of forming a protective layer on the metal plating layer.
  • a material having resistance to the removing liquid or the etching liquid in the removing step or the conductive fine wire forming step is preferable.
  • examples thereof include metals such as nickel, chromium, tin, zinc, magnesium, gold and silver, alloys thereof, and resins.
  • nickel or chromium is preferable as the material of the protective layer.
  • Examples of the method for forming the protective layer include an electroless plating method, an electroplating method, and the like, and the electroplating method is preferable.
  • the lower limit of the thickness of the protective layer is not particularly limited, but is preferably 0.3 ⁇ m or more, and more preferably 0.5 ⁇ m or more.
  • the upper limit is not particularly limited, but is preferably 3.0 ⁇ m or less, and more preferably 2.0 ⁇ m or less.
  • the pattern removing step is a step of removing the pattern.
  • the method for removing the pattern is not particularly limited, and examples thereof include a method for removing by chemical treatment, and a method for removing with a removing liquid is preferable.
  • the liquid temperature of the removing liquid is preferably 30 to 80 ° C, preferably 50 to 80 ° C.
  • a preferred embodiment of the removal method is a method of immersing a substrate having a pattern to be removed in a stirring liquid having a liquid temperature of 50 to 80 ° C. for 1 to 30 minutes.
  • the removing liquid examples include a removing liquid in which an inorganic alkaline component or an organic alkaline component is dissolved in water, dimethyl sulfoxide, N-methylpyrrolidone, or a mixed solution thereof.
  • examples of the inorganic alkaline component include sodium hydroxide and potassium hydroxide.
  • examples of the organic alkali component include a primary amine compound, a secondary amine compound, a tertiary amine compound and a quaternary ammonium salt compound.
  • the removing liquid may be used and removed by a known method such as a spray method, a shower method and a paddle method.
  • the seed layer removing step is a step of removing the exposed seed layer to obtain a conductive thin wire.
  • the metal plating layer formed by the metal plating layer forming step is used as an etching resist, and the seed layer is located in a non-pattern forming region (in other words, a region not protected by the metal plating layer). Etching process is performed.
  • the method for removing a part of the seed layer is not particularly limited, but it is preferable to use a known etching solution.
  • a known etching solution for example, ferric chloride solution, ferric chloride solution, ammonia alkaline solution, sulfuric acid-hydrogen hydrogen mixture, phosphoric acid-hydrogen mixture and the like can be mentioned. ..
  • the upper limit of the line width of the formed conductive thin wire is preferably 8 ⁇ m or less, more preferably 6 ⁇ m or less.
  • the lower limit is not particularly limited, but is often 2 ⁇ m or more.
  • the first embodiment of the method for manufacturing a circuit wiring may include any process (other process) other than the above-mentioned process.
  • a step of reducing the visible light reflectance described in paragraph [0172] of International Publication No. 2019/022089 a new conductive layer is provided on the insulating film described in paragraph [0172] of International Publication No. 2019/022089. Examples thereof include steps of forming, but the process is not limited to these steps.
  • the first embodiment of the method for manufacturing a circuit wiring may include a step of performing a process of reducing the visible light reflectance of a part or all of a plurality of conductive layers included in the substrate.
  • the treatment for reducing the visible light reflectance include an oxidation treatment.
  • the visible light reflectance of the conductive layer can be lowered by oxidizing copper to obtain copper oxide and blackening the conductive layer.
  • the treatment for reducing the visible light reflectance is described in paragraphs 0017 to 0025 of JP-A-2014-150118 and paragraphs 0041, 0042, 0048 and 0058 of JP-2013-206315. , The contents of these publications are incorporated herein.
  • the first embodiment of the method for manufacturing a circuit wiring includes a step of forming an insulating film on the surface of the circuit wiring and a step of forming a new conductive layer on the surface of the insulating film.
  • a second electrode pattern insulated from the first electrode pattern can be formed.
  • the step of forming the insulating film is not particularly limited, and examples thereof include a known method of forming a permanent film.
  • an insulating film having a desired pattern may be formed by photolithography using a photosensitive material having an insulating property.
  • the step of forming the new conductive layer on the insulating film is not particularly limited, and for example, a new conductive layer having a desired pattern may be formed by photolithography using a photosensitive material having conductivity.
  • the circuit wiring manufactured by the first embodiment of the circuit wiring manufacturing method supports, for example, a sheet, a metal substrate, a ceramic substrate, glass, etc. in a manufacturing process film of a semiconductor package, a printed circuit board, and an interposer rewiring layer. It is preferably used as a circuit wiring arranged on a substrate.
  • Circuit wiring manufacturing method (Circuit wiring manufacturing method 2)
  • a method of forming a conductive fine wire pattern on a substrate by a semi-additive method has been described, but the method of manufacturing a circuit wiring to which the method of manufacturing a laminated body of the present invention is applied is not limited to this.
  • a method for manufacturing a circuit wiring including the above-mentioned method for manufacturing a laminate of the present invention is a conductive substrate (the conductive substrate is a support substrate as described above.
  • the transfer film and the substrate are bonded so as to be in contact with the substrate having at least the conductive layer arranged on the support substrate), and the conductive substrate and the photosensitive substrate are photosensitive.
  • a substrate with a photosensitive layer having a sex layer, the intermediate layer, and the temporary support in this order (however, the conductive substrate is arranged so that the conductive layer faces the photosensitive layer).
  • the process of obtaining (transfer film bonding process) and A step of peeling the temporary support between the temporary support and the intermediate layer temporary support peeling step
  • An exposure process is performed by bringing the exposed intermediate layer into contact with the mask, and a development process is further performed after the exposure to form a pattern (pattern formation step).
  • etching step of etching a conductive layer in a region where the above pattern is not arranged.
  • the transfer film bonding step, the temporary support peeling step, and the pattern forming step are the same as those of the first embodiment of the above-mentioned method for manufacturing a laminated body, except that the substrate is a substrate having a conductive layer. The same is true, and the preferred embodiment thereof is also the same.
  • the etching step is a step of etching the conductive layer in the region where the pattern is not arranged.
  • a method of etching treatment a known method can be applied. For example, the methods described in paragraphs [0209] to [0210] of JP-A-2017-120435, paragraphs [0048] to JP-A-2010-152155. Examples thereof include the method described in [0054], a wet etching method of immersing in an etching solution, and a dry etching method such as plasma etching.
  • Examples of the device provided with the circuit wiring manufactured by the above manufacturing method include an input device, a touch panel is preferable, and a capacitive touch panel is more preferable. Further, the input device can be applied to a display device such as an organic EL display device and a liquid crystal display device.
  • the second embodiment of the method for manufacturing a circuit wiring it is also preferable to form a circuit sequentially or simultaneously on both surfaces of the substrate. With such a configuration, it is possible to form a circuit wiring for a touch panel in which a first conductive pattern is formed on one surface of a substrate and a second conductive pattern is formed on the other surface. It is also preferable to form the touch panel circuit wiring having such a configuration from both sides of the substrate by roll-to-roll.
  • the present invention also relates to a transfer film.
  • the transfer film of the present invention will be described.
  • the transfer film of the present invention is A transfer film having a temporary support, an intermediate layer, and a photosensitive layer.
  • the surface free energy of the surface of the intermediate layer on the temporary support side is 68.0 mJ / m 2 or less.
  • the arithmetic average roughness Ra of the surface of the intermediate layer on the temporary support side is 50 nm or less.
  • the transfer film is suitable for an exposure method in which the temporary support is peeled off and then exposed, and excessive adhesion between the photosensitive layer and the photomask after exposure can be suppressed, and the resolution is also excellent.
  • the transfer film of the present invention corresponds to one aspect of the transfer film X described above.
  • the configuration and preferred embodiments of the transfer film X are as described above.
  • the present invention will be described in more detail based on examples.
  • the materials, amounts, ratios, treatment contents, treatment procedures, etc. shown in the following examples can be appropriately changed as long as they do not deviate from the gist of the present invention. Therefore, the scope of the present invention should not be construed as limiting by the examples shown below.
  • “part” and “%” are based on mass.
  • the weight average molecular weight of the resin is the weight average molecular weight obtained in terms of polystyrene by gel permeation chromatography (GPC).
  • GPC gel permeation chromatography
  • the theoretical acid value was used as the acid value.
  • composition for forming an intermediate layer After mixing each component according to the description in Table 4, the solvent (solvent: ion-exchanged water and methanol (manufactured by Mitsubishi Gas Chemical Company, Inc.) are mixed so as to have a mixing ratio (mass ratio) of 40/60). Was added to prepare a composition for forming an intermediate layer.
  • the numerical value corresponding to each component described in the "Composition of the intermediate layer (type and blending amount (% by mass)" column of the intermediate layer in Table 4 represents the content of each component with respect to the total mass of the intermediate layer.
  • Each component of the photosensitive layer shown in Table 2 is as follows.
  • ⁇ Polymer> As the polymer P-1 and the polymer P-2, those synthesized by a known method were used. The weight average molecular weight (Mw) of the synthesized polymer was measured by gel permeation chromatography (GPC) under the following conditions.
  • the types of each monomer used for synthesizing each polymer, and the content (mass%) and weight average molecular weight of the structural units derived from each monomer in each polymer are shown below.
  • the polymers P-1 to P-2 all correspond to alkali-soluble resins.
  • Antioxidant ⁇ 4-Hydroxymethyl-4-methyl-1-phenyl-3-pyrazolidone (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.)
  • Surfactant -Megafuck F-552: Surfactant, manufactured by DIC Corporation
  • Photosensitive Compositions 1 to 4 After mixing each component according to the description in Table 2, photosensitive compositions 1 to 4 having a solid content concentration of 25% by mass were prepared by adding methyl ethyl ketone.
  • the numerical value corresponding to each component described in the component column in Table 2 represents the mass part of the solid content. That is, each of the above numerical values is intended to be a blending amount that does not contain a solvent such as a diluting solvent.
  • Temporary support The temporary supports (temporary supports A to F) in Table 4 are shown below.
  • Temporary support A Lumirer 16KS40 (manufactured by Toray Industries, Inc.)
  • Temporary support B A product manufactured by the method described later was used.
  • Temporary support C Toyobo ester film E5000 (manufactured by Toyobo Co., Ltd.)
  • Temporary support D Unitika TR-1 (manufactured by Unitika Ltd.)
  • Temporary support E Therapy 25WZ (manufactured by Toray Industries, Inc.)
  • Temporary support F Cosmo Shine A4300 (manufactured by Toyobo Co., Ltd.)
  • a photosensitive transfer film composed of a temporary support, an intermediate layer, and a photosensitive layer was prepared so as to have the configuration shown in Table 4. Specifically, it is as follows. First, the composition for forming an intermediate layer for forming the intermediate layer shown in Table 4 is dried on the temporary support shown in Table 4 using a slit-shaped nozzle, and the coating width is 1.0 m. The film was applied so that the film thickness was as shown in Table 4, and the mixture was passed through a drying zone at 80 ° C. for 40 seconds to form an intermediate layer.
  • the photosensitive composition for forming the photosensitive layer shown in Table 4 on the intermediate layer is dried using a slit-shaped nozzle, and the coating width is 1.0 m and the film thickness is Table 4. It was applied so as to have the numerical value described in 1 and passed through a drying zone at 80 ° C. for 40 seconds to form a negative photosensitive layer.
  • a polyethylene film (OSM-N manufactured by Tredegar Co., Ltd.) was pressure-bonded onto this as a protective film to prepare a photosensitive transfer film, which was wound into a roll form.
  • a photosensitive transfer film composed of a temporary support and a photosensitive layer was prepared so as to have the configuration shown in Table 4. It was produced by the same method as the transfer film used in Example 1 except that the intermediate layer was not formed.
  • a copper layer having a thickness of 200 nm was provided on a PET substrate having a thickness of 0.1 mm by a vapor deposition method, and a PET substrate with a copper layer was prepared. After peeling off the protective film of the produced transfer film, the copper layer is attached so that the copper layer and the photosensitive layer come into contact with each other under laminating conditions of a roll temperature of 100 ° C., a linear pressure of 1.0 MPa, and a linear velocity of 4.0 m / min. It was laminated on a PET substrate. Next, a photomask having a predetermined line ( ⁇ m) / space ( ⁇ m) pattern was used, and the temporary support was peeled off and then brought into contact with the mask for exposure.
  • a high-pressure mercury lamp having an i-line (365 nm) as the exposure main wavelength was used.
  • the exposure amount was arbitrarily set so that the top shape of each pattern matched the mask opening.
  • shower development was carried out with a 1% sodium carbonate aqueous solution having a liquid temperature of 25 ° C., washing with water was carried out, and a predetermined pattern was formed on copper.
  • the resolution was evaluated based on the following evaluation criteria. Table 4 shows the measurement results.
  • "resolving without residue between patterns” means that resolution can be performed without residue in the recessed region (position corresponding to the unexposed portion) of the pattern.
  • C Resolvability is B evaluation
  • mask non-adhesiveness and temporary support peeling property are evaluations of either A or B.
  • D Resolvability is rated C, or mask non-adhesiveness is rated C.
  • the provisional support evaluation may be any evaluation.
  • Table 4 is shown below.
  • type of photosensitive layer corresponds to the number of the photosensitive layer shown in Table 2 as described above.
  • whether or not the temporary support peeling step is carried out indicates whether or not the temporary support peeling step is carried out.
  • “A” represents the case where the temporary support peeling step is performed in the method for manufacturing the laminated body, and “B” represents the case where the temporary support peeling step is not carried out in the method for manufacturing the laminated body.
  • the surface free energy in the "Type and physical properties of temporary support” column indicates the surface free energy on the surface of the temporary support on the photosensitive layer side.
  • Comparative Examples 1 to 7 the desired effect was not obtained.
  • Comparative Examples 1 and 3 when the photosensitive layer and the mask were directly adhered to each other for exposure without forming the intermediate layer, the non-adhesiveness of the mask was inferior.
  • Comparative Examples 3 and 4 when the exposure is performed through the temporary support without forming the intermediate layer and without performing the temporary support peeling step, the result is that the resolution is inferior. became.
  • Comparative Example 5 when the intermediate layer was formed but the exposure was performed through the temporary support without performing the temporary support peeling step, the resolution was inferior.
  • the resolution was more excellent when the thickness of the photosensitive layer was 2.0 to 20 ⁇ m (preferably 2.0 to 10 ⁇ m). Further, from the results of Examples 1, 7, 8, 10, 11, 21 to 23, the upper limit of the content of the compound X in the intermediate layer is less than 30% by mass (preferably) with respect to the total mass of the intermediate layer. It was confirmed that the resolution was more excellent in the case of (15% by mass or less). Further, it was confirmed that when the upper limit of the content of the compound X in the intermediate layer is 0.5% by mass or more with respect to the total mass of the intermediate layer, the temporary support peeling property is more excellent.
  • the intermediate layer contains polyvinyl alcohol and polyvinylpyrrolid, and the compounding ratio (mass ratio) of polyvinyl alcohol and polyvinylpyrrolidone is 5/95 to 95/5. In this case, it was confirmed that the non-adhesiveness of the mask and the peelability of the temporary support were better. From the comparison between Examples 1 and 43 and 44, when the surface free energy of the surface of the temporary support on the intermediate layer side is 25.0 to 50.0 mJ / m 2 , the temporary support peelability is more excellent. It was confirmed that.
  • the resolution is more excellent when the material of the photosensitive layer contains at least one selected from the group consisting of 2,4,5-triarylimidazole dimer and its derivative. It was confirmed that. Further, from the results of Example 47, it was confirmed that the resolution is more excellent when the content of the styrene-based structural unit in the polymer is 30% by mass or more with respect to the total mass of the polymer. ..
  • Example 49 Manufacturing method of printed wiring board
  • the transfer film of Example 48 shown in Table 4 was used as the resist pattern forming material in paragraph 0050 of JP-A-2019-121740, the printed wiring board manufacturing method disclosed in the above-mentioned patent gazette was carried out, and there was no erosion. A substrate with good wiring was obtained. It was confirmed that the transfer film of the example was also suitable for the purpose of obtaining a resist pattern for the semi-additive method.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Architecture (AREA)
  • Structural Engineering (AREA)
  • Materials For Photolithography (AREA)
  • Laminated Bodies (AREA)
  • Manufacturing Of Printed Wiring (AREA)
  • Manufacturing Of Printed Circuit Boards (AREA)
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