WO2021199542A1 - 感光性転写材料、樹脂パターンの製造方法、及び回路配線の製造方法 - Google Patents

感光性転写材料、樹脂パターンの製造方法、及び回路配線の製造方法 Download PDF

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WO2021199542A1
WO2021199542A1 PCT/JP2020/048993 JP2020048993W WO2021199542A1 WO 2021199542 A1 WO2021199542 A1 WO 2021199542A1 JP 2020048993 W JP2020048993 W JP 2020048993W WO 2021199542 A1 WO2021199542 A1 WO 2021199542A1
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Prior art keywords
resin layer
photosensitive resin
layer
substrate
transferred
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PCT/JP2020/048993
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English (en)
French (fr)
Japanese (ja)
Inventor
晃男 片山
隆志 有冨
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富士フイルム株式会社
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Application filed by 富士フイルム株式会社 filed Critical 富士フイルム株式会社
Priority to JP2022511537A priority Critical patent/JPWO2021199542A1/ja
Priority to CN202080098703.6A priority patent/CN115335771B/zh
Publication of WO2021199542A1 publication Critical patent/WO2021199542A1/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
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/26—Processing photosensitive materials; Apparatus therefor
    • G03F7/40—Treatment after imagewise removal, e.g. baking
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/26—Processing photosensitive materials; Apparatus therefor
    • G03F7/42—Stripping or agents therefor
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/02—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding
    • H05K3/06—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding the conductive material being removed chemically or electrolytically, e.g. by photo-etch process

Definitions

  • the present disclosure relates to a photosensitive transfer material, a method for manufacturing a resin pattern, and a method for manufacturing a circuit wiring.
  • the electrode pattern corresponding to the sensor of the visual recognition part, the peripheral wiring part, and the wiring of the take-out wiring part are wired. Etc. is provided inside the touch panel.
  • a photosensitive resin composition that can be patterned by exposure and development is generally used for forming the patterned layer.
  • a method using a photosensitive transfer material having a photosensitive resin layer has also been proposed because the number of steps required to obtain a desired pattern shape is small.
  • the photosensitive transfer material is attached to the substrate to be transferred, the photosensitive layer is transferred onto the substrate to be transferred, and the photosensitive layer is formed into a pattern through a mask having a desired pattern.
  • a method of developing after irradiating with light is widely adopted. After development, it is common practice to form wiring by etching the substrate to be transferred using the formed cured pattern as a mask, and then peeling off the cured pattern to obtain a wiring pattern.
  • the processing speed due to filtration or the like tends to decrease significantly. Further, in some cases, a phenomenon may occur in which the piping in the filtration device or the like is blocked, or conversely, the peeled piece is deformed by the filtration pressure and passes through the filtration device or the like and is not filtered. Therefore, it is desirable that the peeled piece has a hardness sufficient to prevent it from adhering to the inside of the device. The hardness of the peeled piece is required to be stably maintained in the liquid regardless of process fluctuations and the like.
  • An object to be solved by one embodiment of the present disclosure is to provide a photosensitive transfer material in which the adhesiveness of the peeled pieces peeled off in the apparatus in the step of peeling the photosensitive transfer material after patterning is reduced.
  • a problem to be solved by another embodiment of the present disclosure is the production of a resin pattern using a photosensitive transfer material in which the adhesiveness of the peeled piece to be peeled off in an apparatus is reduced in the step of peeling the photosensitive transfer material after patterning.
  • the problem to be solved by the other embodiment of the present disclosure is the manufacture of circuit wiring using the photosensitive transfer material in which the adhesiveness of the peeled pieces to be peeled off in the apparatus in the step of peeling the photosensitive transfer material after patterning is reduced. To provide a method.
  • a photosensitive resin layer containing an alkali-soluble resin, a polymerizable compound, and a photopolymerization initiator is provided on the temporary support.
  • a photosensitive resin layer is attached to a substrate to be transferred, the photosensitive resin layer is exposed to an exposure amount of Ep, and then a 10% by mass aqueous solution of monoethanolamine at 50 ° C. is applied to the surface of the cured layer in a state where the temporary support is peeled off.
  • .. Ep 2 ⁇
  • Eb Ep represents the exposure amount in units of mJ / cm 2.
  • Eb has a unit of mJ / cm 2 , and after the photosensitive resin layer is attached to the substrate to be transferred, it is exposed to a mask having a 15-step step wedge at an illuminance of 20 mW / cm 2 with a high-pressure mercury lamp to temporarily support it.
  • the unit time t 50 and The unit is at least the time from the time when the cured layer and the substrate to be transferred are immersed in a 10% by mass aqueous solution of monoethanolamine at 25 ° C. after the exposure to the time when the peeling of the cured layer from the substrate to be transferred is completed.
  • a photosensitive resin layer containing an alkali-soluble resin, a polymerizable compound, and a photopolymerization initiator is provided on the temporary support.
  • a photosensitive resin layer is attached to the substrate to be transferred, the photosensitive resin layer is exposed to an exposure amount of Ep, and then the cured layer and the substrate to be transferred are at least monoethanolamine at 25 ° C. in a state where the temporary support is peeled off.
  • Ep 2 ⁇ Eb Ep represents the exposure amount in units of mJ / cm 2.
  • Eb has a unit of mJ / cm 2 , and after the photosensitive resin layer is attached to the substrate to be transferred, it is exposed to a mask having a 15-step step wedge at an illuminance of 20 mW / cm 2 with a high-pressure mercury lamp to temporarily support it. It represents the exposure amount indicating the number of steps in which the residual film after peeling and developing the body has a residual thickness of ⁇ 1% with respect to the thickness of the photosensitive resin layer.
  • the time from at least the time when the cured layer and the substrate to be transferred are immersed to the time when the cured layer autonomously starts peeling from the substrate to be transferred is within 300 seconds.
  • a photosensitive resin layer containing an alkali-soluble resin, a polymerizable compound, and a photopolymerization initiator is provided on the temporary support.
  • a photosensitive resin layer is attached to the substrate to be transferred, the photosensitive resin layer is exposed to an exposure amount of Ep, and then at least the cured layer and the substrate to be transferred are monoethanolamine at 50 ° C. in a state where the temporary support is peeled off.
  • the time t fr from the time of immersion in the 10% by mass aqueous solution until the peeling of the cured layer from the substrate to be transferred is completed, After the photosensitive resin layer is attached to the substrate to be transferred and the photosensitive resin layer is exposed to an exposure amount of Ep, at least the cured layer and the substrate to be transferred are subjected to 10 mass of monoethanolamine in a state where the temporary support is peeled off.
  • the time t fa from the time of immersion in the 50 ° C. aqueous solution in which carbon dioxide was blown into 1000 mL of the% aqueous solution at a flow rate of 46 mL / min for 160 seconds until the peeling of the cured layer from the substrate to be transferred was completed.
  • Is a photosensitive transfer material satisfying the following formula (B1). t fa ⁇ t fr x 1.5 (B1) Ep 2 ⁇ Eb Ep represents the exposure amount in units of mJ / cm 2. Eb has a unit of mJ / cm 2 , and after the photosensitive resin layer is attached to the substrate to be transferred, it is exposed to a mask having a 15-step step wedge at an illuminance of 20 mW / cm 2 with a high-pressure mercury lamp to temporarily support it. It represents the exposure amount indicating the number of steps in which the residual film after peeling and developing the body has a residual thickness of ⁇ 1% with respect to the thickness of the photosensitive resin layer.
  • the polymerizable compound is the photosensitive transfer material according to any one of ⁇ 1> to ⁇ 7>, which contains a bifunctional or higher compound having two or more ethylenically unsaturated groups in one molecule.
  • the polymerizable compound is a bifunctional ethylenically unsaturated compound having two ethylenically unsaturated groups in one molecule, and a trifunctional ethylenically unsaturated compound having three ethylenically unsaturated groups in one molecule.
  • the photosensitive compound according to ⁇ 8> or ⁇ 9>, wherein the bifunctional or higher functional compound having two or more ethylenically unsaturated groups in one molecule contains the compound represented by the following formula (1). It is a sex transfer material.
  • R 1 and R 2 independently represent a hydrogen atom or a methyl group
  • A represents C 2 H 4
  • B represents C 3 H 6
  • n 1 and n 3 independently represent integers from 1 to 39
  • n 1 + n 3 are integers from 2 to 40
  • n 2 and n 4 independently represent integers from 0 to 29, and n 2 + n 4 are integers from 0 to 30.
  • the sequence of repeating units of-(AO)-and-(BO)- may be random or block. When the sequence is a block, either ⁇ (A—O) ⁇ or ⁇ (BO) ⁇ may be on the bisphenyl group side.
  • ⁇ 11> The photosensitive transfer material according to ⁇ 9>, wherein the content ratio of the trifunctional ethylenically unsaturated compound to the total amount of the polymerizable compound is 30% by mass or more.
  • ⁇ 12> The photosensitive transfer material according to any one of ⁇ 1> to ⁇ 11>, wherein the thickness of the photosensitive resin layer is 5 ⁇ m or more.
  • This is a method for producing a resin pattern, which includes a step of pattern-exposing the photosensitive resin layer and a step of developing the photosensitive resin layer to form a resin pattern.
  • the photosensitive transfer material according to any one of ⁇ 1> to ⁇ 12> and the transfer base material having a conductive layer are bonded together, and a photosensitive resin layer is arranged on the transfer base material.
  • a photosensitive transfer material in which the adhesiveness of the peeled piece peeled off in the device in the step of peeling the photosensitive transfer material after patterning is reduced.
  • a method for producing a resin pattern using a photosensitive transfer material in which the adhesiveness of the peeled piece to be peeled off in an apparatus is reduced in the step of peeling the photosensitive transfer material after patterning.
  • NS there is provided a method for manufacturing a circuit wiring using a photosensitive transfer material in which the adhesiveness of the peeled piece to be peeled off in an apparatus is reduced in the step of peeling the photosensitive transfer material after patterning.
  • FIG. 1 is a schematic cross-sectional view showing an example of the configuration of a photosensitive transfer material.
  • FIG. 2 is a schematic plan view showing an example of a pattern of a mask for manufacturing a touch panel.
  • FIG. 3 is a schematic plan view showing another example of the pattern of the mask for manufacturing the touch panel.
  • the amount of each component in the composition when referred to, when a plurality of substances corresponding to each component are present in the composition, unless otherwise specified, the plurality of components present in the composition are present. Means the total amount of.
  • solid content in the present specification means a component excluding a solvent, and a liquid component such as a low molecular weight component other than a solvent is also included in the “solid content” in the present specification.
  • solvent is used to include water, an organic solvent, and a mixed solvent of water and an organic solvent.
  • acrylic and methacryl may be referred to as "(meth) acrylic".
  • (meth) acrylic acid contains both acrylic acid and methacrylic acid
  • (meth) acryloyl group contains both acryloyl group and methacrylic acid group.
  • (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.
  • alkali-soluble means that the solubility of sodium carbonate in 100 g of a 1% by mass aqueous solution at 22 ° C. is 0.1 g or more.
  • process is included in this term as long as the intended purpose of the process is achieved, not only in an independent process but also in the case where it cannot be clearly distinguished from other processes. Is done.
  • the weight average molecular weight (Mw) in the present disclosure shall be measured by gel permeation chromatography (GPC).
  • GPC gel permeation chromatography
  • HLC-8220GPC manufactured by Tosoh Co., Ltd.
  • TSKgeL Super HZ2000, TSKgeL Super HZ4000, and TSKgeL Super HZ-H are connected in series.
  • NMP N-methylpyrrolidone
  • the sample concentration is 0.3% by mass
  • the flow velocity is 0.35 ml / min
  • the sample injection amount is 10 ⁇ L
  • the measurement temperature is 40 ° C.
  • an RI (Refractive Index) detector differential refractive index detector
  • the photosensitive transfer material of the present disclosure has a photosensitive resin layer containing an alkali-soluble resin, a polymerizable compound, and a photopolymerization initiator on a temporary support.
  • a pattern-like cured portion that is, a resin pattern
  • a further formed resin pattern can be formed.
  • the photosensitive transfer material of the present disclosure is suitable as a material to be subjected to a process in which peeling is performed using a stripping liquid.
  • the cured layer formed by exposure-curing the photosensitive resin layer has the characteristics described in (1), (2) or (3) below.
  • (1) The swelling rate of the cured layer at the time of peeling is below a certain level.
  • the cured layer is autonomously peeled, and preferably the cured layer is autonomously peeled as, for example, a small piece of peeled piece.
  • (3) The change in peeling speed depending on the fatigue of the stripping liquid is small.
  • the photosensitive transfer material of the present disclosure may further have another layer such as a thermoplastic resin layer and an intermediate layer, if necessary.
  • the initial swelling rate, the final swelling rate, and the immersion time until the final swelling rate after immersing the cured resist after exposure in an aqueous sodium carbonate solution are specified.
  • a dry film having a layered photosensitive resin composition in the range has been proposed. For example, when wiring is formed on a substrate to be transferred using a dry film, as described above, a resist (resin pattern in a cured state) cured in a pattern that remains on the substrate to be transferred after wiring formation is used. Peel off.
  • the stripped resist When peeling the resist, a method is usually adopted in which the resist is swollen and peeled using a high-temperature alkaline solution as the stripping solution, and the stripped resist may remain in the stripping solution as a stripping piece. Depending on the properties of the stripped pieces remaining in the stripping liquid, they cannot be removed by filtration or the like and remain in the stripping liquid, and the remaining stripped pieces adhere to and accumulate in the device, thereby blocking the piping and filtering function. Invite a decline. There is also a concern that it will reattach to the manufactured wiring board. In particular, it appears remarkably when the peeled piece is, for example, a gel-like soft material.
  • a resin pattern having a small amount of swelling tends to be autonomously deformed into a wound shape or the like when peeled with a stripping liquid, and the resin pattern is easily gathered into small pieces to obtain a resin pattern having good filterability.
  • a resin pattern with a small amount of swelling is a process because the property change of the resin pattern itself is small even if the stripping liquid, which is an alkaline liquid, absorbs carbon dioxide and becomes neutralized (that is, in a fatigue state). A stable cured state can be maintained regardless of fluctuations in the amount of carbon dioxide, and the filterability is not impaired.
  • the process suitability is improved, and as a result, the adhesion of the peeled piece in the device can be suppressed to a small extent.
  • the photosensitive transfer material of the present disclosure includes three aspects (first aspect, second aspect, and third aspect) described below.
  • the first aspect corresponds to the above-mentioned feature (1)
  • the second aspect corresponds to the above-mentioned (2) feature
  • the third aspect corresponds to the above-mentioned (3) feature.
  • the photosensitive transfer material has a photosensitive resin layer containing an alkali-soluble resin, a polymerizable compound, and a photopolymerization initiator on a temporary support, and is photosensitive with a substrate to be transferred. After laminating the sex resin layers and exposing the photosensitive resin layers with an exposure amount of Ep, in a state where the temporary support is peeled off, monoethanolamine at 50 ° C.
  • MEA monoethanolamine
  • the cured layer refers to an exposed region of the photosensitive resin layer exposed at an exposure amount of Ep.
  • Ep represents the exposure amount in units of mJ / cm 2.
  • Eb has a unit of mJ / cm 2 , and after the photosensitive resin layer is attached to the substrate to be transferred, it is exposed to a mask having a 15-step step wedge at an illuminance of 20 mW / cm 2 with a high-pressure mercury lamp to temporarily support it.
  • An exposure amount indicating the number of steps in which the residual film after peeling and developing the body has a residual thickness of ⁇ 1% (that is, 0.99 to 1.01 t) with respect to the thickness (t) of the photosensitive resin layer. be.
  • the photosensitive transfer material according to the first aspect is less likely to be gelled, less likely to reattach after peeling, and less likely to be deposited in the apparatus.
  • the photosensitive transfer material of the present disclosure exhibits good process suitability when the resin pattern formed by exposing and developing the photosensitive transfer material is peeled off and removed.
  • the bonding of the photosensitive resin layer to the substrate to be transferred will be described in the “bonding step” in the method for manufacturing the resin pattern or circuit wiring described later.
  • the exposure of the photosensitive resin layer with the exposure amount Ep will be described in the "exposure step” in the method for manufacturing the resin pattern or the circuit wiring described later.
  • a step wedge is a concentration step in which a plurality of steps (regions) whose concentration changes stepwise with a constant concentration difference are arranged in one direction.
  • a step wedge having 15 steps is used.
  • the exposure amount Ep is determined by the exposure amount Eb.
  • the determination of Eb shall be made by the following method. That is, The substrate to be transferred and the photosensitive transfer material are bonded together, a step wedge is placed on a temporary support of the photosensitive transfer material bonded onto the substrate to be transferred, and the step wedge is placed by a high-pressure mercury lamp having an illuminance of 20 mW / cm 2.
  • the photosensitive resin layer is irradiated with ultraviolet rays at an exposure amount of 180 mJ / cm 2.
  • the temporary support after irradiation is peeled off and developed in a 0.9% by mass aqueous solution of sodium carbonate at 25 ° C. for 30 seconds.
  • the thickness (residual film thickness) of the cured layer in the region corresponding to each step of the step wedge is measured.
  • the number of step steps in which the residual film thickness (thickness of the cured layer) is within ⁇ 1% of the thickness of the photosensitive resin layer before development is determined, and the exposure amount corresponding to the determined number of step steps is defined as Eb.
  • the swelling rate in the normal direction of the substrate to be transferred in the cured layer is the ratio of the thick film formed in the normal direction of the cured layer parallel to the normal direction of the substrate to be transferred in the drip region of the MEA 10% by mass aqueous solution.
  • it refers to the ratio of the thickness of the cured layer (t 10s ) 10 seconds after the application of the aqueous solution to the thickness (t b ) of the cured layer after irradiation and before dropping the aqueous solution, and is calculated by the following formula. Be done.
  • the thickness (t b ) after irradiation and before dropping the aqueous solution the thickness is measured by selecting 5 arbitrary regions of the cured layer and taking the average value of the 5 thicknesses.
  • the thickness of the cured layer before and after the application of the MEA 10% by mass aqueous solution is a value measured by a non-contact three-dimensional surface shape measuring device, and can be measured using, for example, Zygo NewView 6300 manufactured by Zygo Corporation.
  • the swelling rate after 10 seconds is preferably 102% or less, more preferably 101% or less, for the same reason as described above.
  • the lower limit of the swelling rate after 10 seconds is 100%, preferably a range exceeding 100%.
  • the photosensitive transfer material according to the first aspect has a swelling rate in the normal direction of the substrate to be transferred in the cured layer 20 seconds after the droplet of the 10% by mass aqueous solution of monoethanolamine (hereinafter, "after 20 seconds".
  • the swelling rate is preferably 105% or less.
  • the swelling rate in the normal direction of the substrate to be transferred in the cured layer is the ratio of the thickened film in the normal direction of the cured layer parallel to the normal direction of the substrate to be transferred, that is, the MEA 10% by mass aqueous solution after irradiation.
  • the ratio of the thickness of the cured layer (t 20s ) 20 seconds after the application of the MEA 10% by mass aqueous solution to the thickness (t b ) of the cured layer before dropping For the thickness (t b ) after irradiation and before dropping the aqueous solution, the thickness is measured by selecting 5 arbitrary regions of the cured layer and taking the average value of the 5 thicknesses.
  • the thickness of the cured layer before and after the application of the MEA 10% by mass aqueous solution is a value measured by a non-contact three-dimensional surface shape measuring device, and can be measured using, for example, Zygo NewView 6300 manufactured by Zygo Corporation.
  • the swelling rate after 20 seconds is preferably 103% or less, more preferably 102% or less, for the same reason as described above.
  • the lower limit of the swelling rate after 20 seconds is 100%, preferably a range exceeding 100%.
  • a step of revealing the pattern according to the irradiation pattern (so-called development step) and a step of peeling and removing the pattern (so-called peeling step). Is exposed to alkaline solution at least twice.
  • alkaline development of the uncured portion is performed at a low temperature (about 25 ° C.)
  • peeling step alkaline peeling of the cured portion is performed at a high temperature (about 50 ° C.). Therefore, in each step, it is preferable that the cured layer has a large difference in swelling rate depending on the temperature.
  • From the time of immersion to the time when the peeling of the cured layer from the substrate to be transferred is completed means that at least the cured layer and the substrate to be transferred constituting the photosensitive transfer material after exposure are 10% by mass of MEA.
  • the starting point is the time when the film is completely immersed in the aqueous solution, and the period from the starting point to the time when the cured layer in the aqueous solution is completely separated from the substrate to be transferred (end point).
  • t 50 is 60 seconds or less, preferably 20 seconds or less, and more preferably 15 seconds or less. Further, t 50 is preferably more than 5 seconds.
  • t 25 is 180 seconds or less, preferably 120 seconds or less, and more preferably 60 seconds or less. Further, t 25 is preferably 10 seconds or longer.
  • t 50 and t 25 more preferably satisfy the following formula (A2-1) from the viewpoint of satisfactorily performing alkali development in a low temperature region and satisfactorily performing alkali peeling in a high temperature region. It is more preferable to satisfy the following formula (A2-2). 2 ⁇ t 25 / t 50 ⁇ 3 (A2-1) 2.5 ⁇ t 25 / t 50 ⁇ 3 (A2-2)
  • the photosensitive transfer material in order to reduce the swelling rate of the cured layer after 10 seconds to 103% or less, it is conceivable to control the degree of curing of the cured layer. Specific means for achieving the swelling rate after 10 seconds are listed below.
  • (2) The type and content of the polymerizable compound used in the photosensitive resin layer and the combination when two or more kinds of polymerizable compounds are used in combination are adjusted.
  • Use a chain transfer agent Use a chain transfer agent.
  • the alkali-soluble resin, the polymerizable compound, the photopolymerization initiator and the like, the temporary support, the photosensitive resin layer, the substrate to be transferred and the like are described. , Will be described later.
  • the photosensitive transfer material has a photosensitive resin layer containing an alkali-soluble resin, a polymerizable compound, and a photopolymerization initiator on a temporary support, and is photosensitive with a substrate to be transferred.
  • a photosensitive resin layer containing an alkali-soluble resin, a polymerizable compound, and a photopolymerization initiator on a temporary support, and is photosensitive with a substrate to be transferred.
  • Ep monoethanolamine
  • Ep represents the exposure amount in units of mJ / cm 2.
  • Eb has a unit of mJ / cm 2 , and after the photosensitive resin layer is attached to the substrate to be transferred, it is exposed to a mask having a 15-step step wedge at an illuminance of 20 mW / cm 2 with a high-pressure mercury lamp to temporarily support it.
  • An exposure amount indicating the number of steps in which the residual film after peeling and developing the body has a residual thickness of ⁇ 1% (that is, 0.99 to 1.01 t) with respect to the thickness (t) of the photosensitive resin layer. be.
  • Ep and Eb are the same as in the first aspect. Further, the details of the alkali-soluble resin, the polymerizable compound, the photopolymerization initiator and the like, the temporary support, the photosensitive resin layer, the substrate to be transferred and the like in the photosensitive transfer material according to the second aspect are described. , Will be described later.
  • the phenomenon of autonomous peeling is a phenomenon in the liquid when immersed in a 10% by mass aqueous solution of MEA, and is a phenomenon that occurs in the peeling step of peeling the cured layer from the substrate to be transferred.
  • the details of the peeling step will be described later.
  • the peeling step is a step after the photosensitive resin layer is attached to the substrate to be transferred and the photosensitive resin layer is exposed to an exposure amount of Ep.
  • the bonding of the photosensitive resin layer to the substrate to be transferred will be described in the “bonding step” in the method for manufacturing a resin pattern or circuit wiring described later.
  • the exposure of the photosensitive resin layer with the exposure amount Ep will be described in the "exposure step” in the method for manufacturing the resin pattern or the circuit wiring described later.
  • “Autonomous peeling” means that the cured layer itself does not receive an external force such as pulling when the substrate to be transferred to which the cured layer after exposure is attached is immersed in a 10% by mass aqueous solution of MEA at 25 ° C. It refers to the state of peeling away from the substrate to be transferred.
  • the photosensitive resin layer is a negative type photosensitive layer
  • the light on the side of the photosensitive resin layer bonded to the transfer substrate close to the transfer substrate is attenuated when exposed at the exposure amount Ep.
  • the degree of curing may be low, and it tends to swell when it comes into contact with a 10% by mass aqueous solution of MEA.
  • the transfer substrate side tends to be harder to cure than the side closer to the temporary support.
  • the cured layer formed by the exposure of the photosensitive resin layer has a degree of curing from the side farther from the substrate to be transferred (the side closer to the light source at the time of exposure) to the side closer to the substrate to be transferred in the layer thickness direction.
  • the cured layer When the cured layer is autonomously peeled from the substrate to be transferred, the cured layer may be peeled without major deformation or with deformation. In the former case, it is easy to obtain a peeled piece including a flat surface. In the latter, the side with large swelling of the cured layer (the side facing the transfer base material) faces outward, and the temporary support side with less swelling than the transfer base material side (the side not facing the transfer base material) faces inward. It is easy to obtain a peeled piece having a shape including a curved surface that is rolled toward and curled (that is, curled). Since the latter peeling piece is rolled up and formed into, for example, a cylinder, small pieces can be easily obtained. As in the latter case, when the peeled pieces are grouped into small pieces, the peeled pieces can be easily removed (sedimentation, filtration, etc.).
  • the cured layer in the second aspect of the present disclosure is one that autonomously peels off from the substrate to be transferred and curls the cured layer with the side opposite to the substrate to be transferred inside. preferable.
  • the cured layer when immersed in a 10% by mass aqueous solution of MEA, the cured layer is autonomously peeled from the substrate to be transferred, at least from the time of immersion of the cured layer and the substrate to be transferred. It is preferable that the time up to the time when the above is started (hereinafter, the autonomous peeling time) is 300 seconds or less. That is, it is preferable that the time until the autonomous peeling occurs after immersion is within 300 seconds. If the autonomous peeling time is 300 seconds or less, for example, when the degree of swelling differs between the side facing the substrate to be transferred and the side not facing the cured layer as described above, in-film stress is likely to occur. It can be said that the film has a film property in which small pieces of peeled pieces can be easily obtained.
  • At least at the time of immersion of the cured layer and the substrate to be transferred means that at least the entire cured layer and the substrate to be transferred constituting the photosensitive transfer material after exposure are completely immersed in the MEA 10% by mass aqueous solution. Point to the point in time.
  • the time when the cured layer starts to be autonomously peeled from the substrate to be transferred means that at least a part of the edge of the cured layer after exposure in a state of being immersed in a 10% by mass aqueous solution of MEA is the substrate to be transferred. It refers to the point when it rises away from.
  • the autonomous peeling time is preferably 280 seconds or less, preferably 230 seconds or less, or 200 seconds or less for the same reason as described above.
  • the autonomous peeling time is measured by adjusting the temperature of the 10% by mass MEA solution that has been allowed to stand in a water bath, immersing the measurement sample, and visually observing it until the cured layer first floats from the surface of the substrate to be transferred. Time was measured. The measurement was performed 3 times, and the average value was taken as the peeling time.
  • the photosensitive transfer material in order for the cured layer to be autonomously peeled from the transfer substrate, swelling of the cured layer on the side facing the transfer substrate and the side not facing the transfer substrate is required. It is conceivable to control so that the sex is different. Specific means for achieving autonomous exfoliation are listed below. (1) Adjust the thickness of the photosensitive resin layer (cured layer). (2) The type and content of the polymerizable compound used in the photosensitive resin layer and the combination when two or more kinds of polymerizable compounds are used in combination are adjusted. (3) Adjust the type and content of the polymerization initiator. (4) Use a chain transfer agent.
  • the photosensitive transfer material according to the third aspect of the present disclosure has a photosensitive resin layer containing an alkali-soluble resin, a polymerizable compound, and a photopolymerization initiator on a temporary support, and has a time t fr shown below. And the time t fa satisfy the following equation (B1). t fa ⁇ t fr x 1.5 (B1)
  • Time t fr is defined as at least the cured layer and the substrate to be transferred in a state where the photosensitive resin layer is attached to the substrate to be transferred, the photosensitive resin layer is exposed to an exposure amount Ep, and then the temporary support is peeled off.
  • the time (seconds) from the time when the cured layer was immersed in a 10% by mass aqueous solution of monoethanolamine at 50 ° C. to the completion of peeling of the cured layer from the substrate to be transferred is shown.
  • “Time t fa ” is defined as at least the cured layer and the substrate to be transferred in a state where the photosensitive resin layer is attached to the substrate to be transferred, the photosensitive resin layer is exposed to an exposure amount Ep, and then the temporary support is peeled off.
  • Eb Ep 2 ⁇
  • Eb Ep represents the exposure amount in units of mJ / cm 2.
  • Eb has a unit of mJ / cm 2 , and after the photosensitive resin layer is attached to the substrate to be transferred, it is exposed to a mask having a 15-step step wedge at an illuminance of 20 mW / cm 2 with a high-pressure mercury lamp to temporarily support it.
  • An exposure amount indicating the number of steps in which the residual film after peeling and developing the body has a residual thickness of ⁇ 1% (that is, 0.99 to 1.01 t) with respect to the thickness (t) of the photosensitive resin layer. be.
  • Ep and Eb are the same as in the first aspect. Further, the details of the alkali-soluble resin, the polymerizable compound, the photopolymerization initiator and the like, the temporary support, the photosensitive resin layer, the substrate to be transferred and the like in the photosensitive transfer material according to the third aspect are described. , Will be described later.
  • t fa and t fr satisfy the relationship of the above formula (B1) means that even when the cured resin pattern is peeled from the substrate to be transferred using a deteriorated alkaline liquid (stripping liquid), the stripping liquid is used.
  • the swelling property when touched and the time required for peeling (peeling time) are significantly higher than when the cured resin pattern is peeled from the substrate to be transferred using a new alkaline liquid (peeling liquid) before deterioration. Indicates that it does not change. That is, it is desirable that the change in the peeling time before and after the deterioration of the stripping liquid is small.
  • the photosensitive transfer material having a small change in swelling property and peeling time due to fatigue of the peeling liquid is good when the cured layer (resin pattern) formed by exposing and developing the photosensitive resin layer is peeled off. Exhibits process suitability. This is because the photosensitive transfer material having a large change in swelling property and peeling time due to fatigue of the peeling liquid impairs the adhesiveness of the peeling piece in the apparatus and makes stable operation difficult.
  • the peeling of the cured layer from the substrate to be transferred is a phenomenon that occurs in the peeling liquid and is a phenomenon that occurs in the peeling step described later.
  • the details of the peeling step will be described later.
  • the peeling step is a step after the photosensitive resin layer is attached to the substrate to be transferred and the photosensitive resin layer is exposed to an exposure amount of Ep.
  • the bonding of the photosensitive resin layer to the substrate to be transferred will be described in the “bonding step” in the method for manufacturing a resin pattern or circuit wiring described later.
  • the exposure of the photosensitive resin layer with the exposure amount Ep will be described in the "exposure step” in the method for manufacturing the resin pattern or the circuit wiring described later.
  • the time of immersing the at least cured layer and the transfer substrate to monoethanolamine 10% by weight aqueous solution of 50 ° C. is the time t fr, at least cured layer and the transfer substrate constituting the photosensitive transfer material after exposure Refers to the time when the whole of is completely immersed in the MEA 10% by mass aqueous solution (immersion completion point).
  • time t fr indicates the time from the immersion completion point to the peeling completion point, that is, the time required for peeling in a normal state when a new alkaline solution (peeling solution) before deterioration is used.
  • MEA fatigue solution An aqueous solution at 50 ° C. in which carbon dioxide is blown into 1000 mL of a 10 mass% monoethanolamine aqueous solution at a flow rate of 46 mL / min for 160 seconds
  • MEA fatigue solution imitates a stripping solution deteriorated by use. It is a fatigued liquid.
  • the alkaline solution used as the stripping solution may have a plurality of factors such as neutralization fatigue and pH decrease due to absorption of carbon dioxide in the atmosphere to generate carbonate, but in the present disclosure, it is a representative of the fatigue solution.
  • the above MEA fatigue liquid in which a certain amount of carbon dioxide is blown is used.
  • Time t fa By "at least a hardened layer and the transfer substrate, monoethanolamine time of the carbon dioxide with respect to the amine 10 wt% aqueous solution of 1000mL was immersed in an aqueous solution of 50 ° C. was blown for 160 seconds at a flow rate of 46 mL / min" Refers to the immersion completion point at which at least the cured layer and the entire substrate to be transferred, which constitute the photosensitive transfer material after exposure, are completely immersed in the MEA fatigue liquid.
  • time tfa means that the cured layer is peeled from the substrate to be transferred in the MEA fatigue liquid, and the cured layer and the substrate to be transferred are completely separated. It refers to "until the time when it becomes two solids (peeling completion point)".
  • Time t fa indicates the time from the immersion completion point to the peeling completion point when the MEA fatigue liquid is used, that is, the time required for peeling when the peeling liquid is fatigued.
  • the photosensitive transfer material according to the first aspect of the present disclosure is further preferred in the following aspects.
  • the photosensitive transfer material has a photosensitive resin layer containing an alkali-soluble resin, a polymerizable compound, and a photopolymerization initiator on a temporary support.
  • a photosensitive resin layer containing an alkali-soluble resin, a polymerizable compound, and a photopolymerization initiator on a temporary support.
  • 10 ⁇ L of a 10 ⁇ L MEA aqueous solution at 50 ° C. is dropped onto the surface of the cured layer to obtain monoethanolamine (MEA).
  • MEA monoethanolamine
  • Ep 2 ⁇ Eb The details of Ep and Eb are as described above.
  • the photosensitive transfer material has a photosensitive resin layer containing an alkali-soluble resin, a polymerizable compound, and a photopolymerization initiator on a temporary support.
  • a photosensitive resin layer containing an alkali-soluble resin, a polymerizable compound, and a photopolymerization initiator on a temporary support.
  • 10 ⁇ L of a 10 ⁇ L MEA aqueous solution at 50 ° C. is dropped onto the surface of the cured layer to obtain monoethanolamine (MEA).
  • MEA monoethanolamine
  • the swelling rate in the normal direction of the substrate to be transferred swelling rate after 10 seconds) in the cured layer 10 seconds after the drip of the 10 mass% aqueous solution is in the range of 103% or less, and the following formula (B1) is satisfied.
  • Ep 2 ⁇ Eb t fa ⁇ t fr x 1.5
  • the details of Ep, Eb, time t fr , and time t fa are as described above.
  • the photosensitive transfer material has a photosensitive resin layer containing an alkali-soluble resin, a polymerizable compound, and a photopolymerization initiator on a temporary support.
  • the photosensitive resin layer is attached to the substrate to be transferred, the photosensitive resin layer is exposed to an exposure amount of Ep, and then at least the cured layer and the substrate to be transferred are immersed in a 10% by mass aqueous solution of monoethanolamine at 25 ° C. , The cured layer is autonomously peeled from the substrate to be transferred and satisfies the following formula (B1).
  • Ep 2 ⁇ Eb t fa ⁇ t fr x 1.5
  • the details of Ep, Eb, time t fr , and time t fa are as described above.
  • the photosensitive transfer material has a photosensitive resin layer containing an alkali-soluble resin, a polymerizable compound, and a photopolymerization initiator on a temporary support. After the photosensitive resin layer is attached to the substrate to be transferred and the photosensitive resin layer is exposed to an exposure amount of Ep, 10 ⁇ L of a 10 ⁇ L MEA aqueous solution at 50 ° C. is dropped onto the surface of the cured layer to obtain monoethanolamine (MEA).
  • MEA monoethanolamine
  • the swelling rate in the normal direction of the substrate to be transferred (swelling rate after 10 seconds) in the cured layer 10 seconds after the drip of the 10 mass% aqueous solution is in the range of 103% or less, and at least the cured layer and
  • the cured layer is autonomously peeled from the substrate to be transferred and the following formula (B1) is satisfied.
  • Ep 2 ⁇ Eb t fa ⁇ t fr x 1.5 (B1)
  • the details of Ep, Eb, time t fr , and time t fa are as described above.
  • the photosensitive transfer material in the present disclosure includes at least a temporary support and a photosensitive resin layer provided on the temporary support and containing an alkali-soluble resin, a polymerizable compound, and a photopolymerization initiator.
  • the photosensitive transfer material in the present disclosure may have a structure having another layer such as a thermoplastic resin layer, an intermediate layer and a protective film (hereinafter, referred to as a cover film), if necessary.
  • the temporary support is a support that can be peeled off from the photosensitive transfer material.
  • the temporary support can support at least a photosensitive resin layer.
  • the structure of the temporary support may be either a single-layer structure or a multi-layer structure.
  • the layer structure of the temporary support having a multi-layer structure is not limited.
  • the temporary support having a multi-layer structure may have a coating layer or a functional layer.
  • Examples of the temporary support having a multi-layer structure include a temporary support having a base material and a coating layer or a functional layer.
  • the coating layer is a layer that covers a part or all of the surface of an arbitrary layer (for example, a base material).
  • Examples of the functional layer include an adhesive layer (adhesive layer) and a hard coat layer.
  • the coating layer may be a functional layer.
  • the temporary support preferably has light transmission. Since the temporary support has light transmission property, it is possible to perform pattern-like exposure (hereinafter, pattern exposure) on the photosensitive resin layer via the temporary support. “Having light transmittance” means that the transmittance of light having a wavelength used for pattern exposure is 50% or more. Regarding the light transmittance of the temporary support, from the viewpoint of increasing the exposure sensitivity of the photosensitive resin layer, the light transmittance at the wavelength (preferably wavelength 365 nm) used for pattern exposure is preferably 60% or more. More preferably, it is 70% or more.
  • Transmittance refers to the intensity of incident light when light is incident in a direction perpendicular to the main surface of the layer to be measured (that is, in the thickness direction), and is emitted through the layer to be measured. It is the ratio of the intensity of the emitted light.
  • the transmittance is measured using MCPD Series manufactured by Otsuka Electronics Co., Ltd.
  • Examples of the temporary support include a glass substrate, a resin film, and paper, and a resin film is preferable from the viewpoint of strength, flexibility, and light transmission.
  • the resin film examples include polyethylene terephthalate (PET) film, cellulose triacetate (TAC) film, polystyrene (PS) film, polycarbonate (PC) film and the like.
  • PET polyethylene terephthalate
  • TAC cellulose triacetate
  • PS polystyrene
  • PC polycarbonate
  • a PET film is preferable, and a biaxially stretched PET film which has been stretched in two directions on the XY axes is more preferable.
  • the thickness of the temporary support is not particularly limited, and is formed through the strength of the support, the flexibility required for bonding to the substrate to be transferred, and the exposure of the photosensitive resin layer via the temporary support. From the viewpoint of improving the resolution of the pattern to be formed, it may be selected according to the material.
  • the thickness of the temporary support is preferably in the range of 5 ⁇ m to 100 ⁇ m, more preferably in the range of 10 ⁇ m to 50 ⁇ m, and further preferably in the range of 10 ⁇ m to 30 ⁇ m from the viewpoint of ease of handling and versatility.
  • the average thickness of the temporary support is measured by the following method. That is, A scanning electron microscope (SEM) is used to observe the cross section in the direction perpendicular to the main surface of the temporary support (that is, in the thickness direction). Based on the obtained observation image, the thickness of the temporary support is measured at 10 points. The average thickness of the temporary support is obtained by arithmetically averaging the measured values.
  • the measuring method here is not limited to the temporary support having a single-layer structure, but is also applied to the temporary support having a multi-layer structure.
  • the temporary support does not have deformation such as wrinkles, scratches, defects, or the like.
  • the number of fine particles, foreign substances, defects, precipitates, etc. contained in the temporary support from the viewpoint of pattern formation when pattern exposure of the photosensitive resin layer is performed via the temporary support and transparency of the temporary support. Is preferably small.
  • the number of fine particles, foreign substances, and defects having a diameter of 1 ⁇ m or more is preferably 50 pieces / 10 mm 2 or less, more preferably 10 pieces / 10 mm 2 or less, and further preferably 3 pieces / 10 mm 2 or less. It is preferably 0 pieces / 10 mm 2 , and it is particularly preferable.
  • Preferred embodiments of the provisional support include, for example, paragraphs 0017 to 0018 of JP2014-85643, paragraphs 0019 to 0026 of JP2016-27363, and paragraphs 0041 to A1 of International Publication No. 2012/081680A1.
  • 0057, paragraphs 0029 to 0040 of International Publication No. 2018/179370 A1, paragraphs 0012 to paragraph 0032 of JP2019-101405, and the contents of these publications are incorporated herein by reference.
  • the photosensitive resin layer contains an alkali-soluble resin, a polymerizable compound, and a photopolymerization initiator.
  • the photosensitive resin layer is a negative type photosensitive layer in which the solubility of the exposed exposed area (exposed area) in the developing solution is reduced and the unexposed non-exposed area (non-exposed area) is removed by development. Can be configured. Further, the photosensitive resin layer may further contain an optional component such as a dye and a surfactant, if necessary.
  • the photosensitive resin layer may be laminated directly on the temporary support or via an arbitrary layer.
  • an arbitrary layer may be laminated on the photosensitive resin layer.
  • the photosensitive resin layer comprises 10% by mass to 90% by mass of an alkali-soluble resin, 5% by mass to 70% by mass of a polymerizable compound, and 0.
  • the composition preferably contains 01% by mass to 20% by mass of a photopolymerization initiator.
  • the photosensitive resin layer contains at least one kind of alkali-soluble resin (hereinafter, also referred to as polymer A).
  • the alkali-soluble resin contains a polymer that is easily dissolved in an alkaline substance.
  • the acid value of the polymer A can control the swelling of the photosensitive resin layer by an acrylic solution (for example, an alkaline developer at the time of development, an alkaline developer at the time of peeling, etc.). By controlling the acid value, it is possible to obtain excellent resolution.
  • the acid value of the polymer A is preferably 220 mgKOH / g or less, more preferably less than 200 mgKOH / g, and even more preferably less than 190 mgKOH / g.
  • the lower limit of the acid value of the polymer A is not particularly limited, and is preferably 60 mgKOH / g or more, more preferably 120 mgKOH / g or more, further preferably 150 mgKOH / g or more, and particularly preferably 170 mgKOH / g or more.
  • the acid value is the mass [mg] of potassium hydroxide required to neutralize 1 g of the sample, and has "mgKOH / g" as a unit.
  • the acid value can be calculated, for example, from the average content of acid groups in the compound.
  • the acid value of the polymer A can be adjusted by 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, the resolution and developability can be improved. From this point of view, the weight average molecular weight is more preferably 100,000 or less, further preferably 60,000 or less, and particularly preferably 50,000 or less. Further, when the weight average molecular weight is 5,000 or more, the hardness of the peeled piece to be peeled off at the time of peeling can be increased to improve the adhesiveness of the peeled piece. Further, from the viewpoint of controlling the properties of the developed aggregate, the edge fuse property, and the cut chip property, the weight average molecular weight is preferably 5,000 or more.
  • 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 to which the photosensitive resin layer easily protrudes from the end face of the roll when the photosensitive transfer material is wound into a roll.
  • the cut chip property refers to the degree of ease with which the chip flies when the unexposed film is cut with a cutter. For example, if the chip adheres to the surface of the photosensitive transfer material, the chip is transferred to the mask in the exposure process, which causes a defective product.
  • the dispersity of the polymer A is preferably 1.0 to 6.0, more preferably 1.0 to 5.0, and even more preferably 1.0 to 4.0. It is more preferably 0.0 to 3.0.
  • the degree of dispersion is the ratio of the weight average molecular weight to the number average molecular weight (weight average molecular weight / number average molecular weight).
  • the weight average molecular weight and the number average molecular weight are values measured using gel permeation chromatography.
  • the polymer A preferably contains a structural unit derived from a monomer having an aromatic hydrocarbon group, from the viewpoint of suppressing line width thickening and deterioration of resolution when a focal position shift occurs during exposure. ..
  • the aromatic hydrocarbon group include a substituted or unsubstituted phenyl group and a substituted or unsubstituted aralkyl group.
  • the content ratio of the structural unit derived from the monomer having an aromatic hydrocarbon group in the polymer A is preferably 20% by mass or more, preferably 30% by mass or more, based on the total mass of all the structural units. More preferably, it is more preferably 40% by mass or more, particularly preferably 45% by mass or more, and most preferably 50% by mass or more.
  • the upper limit of the content ratio of the structural unit derived from the monomer having an aromatic hydrocarbon group is not particularly limited, and is preferably 95% by mass or less, more preferably 85% by mass or less.
  • the content ratio of the structural unit derived from the monomer having an aromatic hydrocarbon group is determined as a mass average value.
  • Examples of the monomer having an aromatic hydrocarbon group include a monomer having an aralkyl group, styrene, and a polymerizable styrene derivative (for example, methylstyrene, vinyltoluene, tert-butoxystyrene, acetoxystyrene, 4-). Vinyl benzoic acid, styrene dimer, styrene trimmer, etc.) can be mentioned. 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.
  • the polymer A may include a structural unit derived from styrene as a structural unit derived from a monomer having an aromatic hydrocarbon group.
  • the content ratio of the styrene-derived constituent units is preferably 20% by mass to 50% by mass, more preferably 25% by mass to 45% by mass, and 30% by mass, based on the total mass of all the constituent units. It is more preferably from 40% by mass to 40% by mass, and particularly preferably from 30% by mass to 35% by mass.
  • Examples of the monomer having a benzyl group include a (meth) acrylate having a benzyl group (for example, benzyl (meth) acrylate, chlorobenzyl (meth) acrylate, etc.) and a vinyl monomer having a benzyl group (for example, vinylbenzyl chloride, vinyl). Benzyl alcohol, etc.) and the like. Of these, benzyl (meth) acrylate is preferable.
  • the polymer A may include a structural unit derived from benzyl (meth) acrylate as a structural unit derived from a monomer having an aromatic hydrocarbon group.
  • the content ratio of the constituent units derived from benzyl (meth) acrylate is preferably 50% by mass to 95% by mass, more preferably 60% by mass to 90% by mass, based on the total mass of all the constituent units. , 70% by mass to 90% by mass, more preferably 75% by mass to 90% by mass.
  • the polymer A containing a structural unit derived from 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 derived from a monomer having an aromatic hydrocarbon group is at least one kind of the first monomer (excluding the monomer having an aromatic hydrocarbon group) described later. It is preferable to obtain at least one of the first monomer (excluding the monomer having an aromatic hydrocarbon group) and the second monomer (aromatic hydrocarbon) described later. It is more preferable to obtain it by copolymerizing with at least one of (excluding monomers having a group).
  • the first monomer is a monomer having a carboxyl group and a polymerizable unsaturated group in the molecule.
  • the first monomer may be a monomer having no aromatic hydrocarbon group in the molecule.
  • Examples of the first monomer include (meth) acrylic acid, fumaric acid, cinnamic acid, crotonic acid, itaconic acid, 4-vinylbenzoic acid, maleic anhydride, maleic acid semiester and the like. Among these, (meth) acrylic acid is preferable.
  • the content ratio of the structural unit derived from the first monomer in the polymer A is preferably 5% by mass to 50% by mass, and 10% by mass to 40% by mass, based on the total mass of all the structural units. Is more preferable, and 15% by mass to 30% by mass is further preferable.
  • the copolymerization ratio of the first monomer is preferably 10% by mass to 50% by mass based on the total mass of all the copolymerized constituent units. When the copolymerization ratio is 10% by mass or more, it is preferable in that good developability can be exhibited and edge fuseability can be controlled.
  • the copolymerization ratio of the first monomer is more preferably 15% by mass or more, further preferably 20% by mass or more. When the copolymerization ratio of the first monomer is 50% by mass or less, the resolution of the pattern and the shape of the hem of the pattern are improved, and the chemical resistance of the pattern is also improved.
  • the copolymerization ratio of the first monomer is more preferably 35% by mass or less, further preferably 30% by mass or less, and particularly preferably 27% by mass or less.
  • 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.
  • the content ratio of the structural unit derived from the second monomer in the polymer A is preferably 5% by mass to 60% by mass, preferably 15% by mass to 50% by mass, based on the total mass of all the structural units. It is more preferably%, and further preferably 20% by mass to 45% by mass.
  • the polymer A preferably contains a structural unit derived from a monomer having an aralkyl group and / or a structural unit derived from styrene. It is possible to suppress the line width thickening and the deterioration of the resolution when the focal position shifts during exposure.
  • the preferable polymer A for example, a copolymer obtained by copolymerizing methacrylic acid, benzyl methacrylate and styrene, a copolymer obtained by copolymerizing methacrylic acid, methyl methacrylate, benzyl methacrylate and styrene, and the like are preferable.
  • the structural unit derived from the monomer having an aromatic hydrocarbon group is 25 to 40% by mass, and the structural unit derived from the first monomer is 20 to 35% by mass.
  • a polymer containing a structural unit derived from the second monomer of 30 to 45% by mass is a preferred embodiment.
  • the structural unit derived from the monomer having an aromatic hydrocarbon group is 70 to 90% by mass, and the structural unit derived from the first monomer is 10 to 25% by mass.
  • % And a polymer containing% is a preferred embodiment.
  • the polymer A may be contained alone or in combination of two or more.
  • two kinds of polymers A containing a structural unit derived from a monomer having an aromatic hydrocarbon group may be mixed, or a single amount having an aromatic hydrocarbon group may be mixed. It is preferable to mix the polymer A containing a structural unit derived from the body and the polymer A containing no structural unit derived from a monomer having an aromatic hydrocarbon group.
  • the content ratio of the polymer A containing the structural unit derived from the monomer having an aromatic hydrocarbon group is preferably 50% by mass or more with respect to the total structural units of the polymer A. It is more preferably 70% by mass or more, further preferably 80% by mass or more, and particularly preferably 90% by mass or more.
  • the polymer (A) may have any of a linear structure, a branched structure, and an alicyclic structure in the side chain.
  • the side chain of the polymer (A) has a branched structure, an alicyclic structure, or a branch. Structures and alicyclic structures can be introduced.
  • the group having an alicyclic structure may be monocyclic or polycyclic.
  • the monomer containing a group having a branched structure in the side chain include (meth) acrylic acid i-propyl, (meth) acrylic acid i-butyl, (meth) acrylic acid s-butyl, and (meth) acrylic acid.
  • t-butyl (meth) acrylate i-amyl, (meth) acrylate t-amyl, (meth) acrylate sec-iso-amyl, (meth) acrylate 2-octyl, (meth) acrylate 3-octyl , (Meta) t-octyl acrylate and the like.
  • i-propyl (meth) acrylate, i-butyl (meth) acrylate, and t-butyl methacrylate are preferable, and i-propyl methacrylate and t-butyl methacrylate are more preferable.
  • the monomer containing a group having an alicyclic structure in the side chain include (meth) acrylate having an alicyclic hydrocarbon group having 5 to 20 carbon atoms. More specific examples include (meth) acrylic acid (bicyclo [2.2.1] heptyl-2), (meth) acrylic acid-1-adamantyl, (meth) acrylic acid-2-adamantyl, (meth).
  • (meth) acrylic acid esters (meth) acrylic acid cyclohexyl, (meth) acrylic acid (nor) boronyl, (meth) acrylic acid isobornyl, (meth) acrylic acid-1-adamantyl, (meth) acrylic acid- 2-adamantyl, fentyl (meth) acrylate, 1-mentyl (meth) acrylate, tricyclodecane (meth) acrylate are preferred, cyclohexyl (meth) acrylate, (nor) bornyl (nor) acrylate, (meth). ) Isobornyl acrylate, -2-adamantyl (meth) acrylate, and tricyclodecane (meth) acrylate are more preferred.
  • a radical polymerization initiator such as benzoyl peroxide or azoisobutyronitrile is added to a solution obtained by diluting the above-mentioned single or multiple monomers with a solvent such as acetone, methyl ethyl ketone or isopropanol. It is preferably carried out by adding and heating and stirring. In some cases, the synthesis is carried out while dropping a part of the mixture into the reaction solution. 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 in the range of 30 ° C. or higher and 135 ° C. or lower.
  • Tg of the polymer A is 135 ° C. or lower, it is possible to suppress the line width thickening and the deterioration of the resolution when the focal position shift occurs when the photosensitive resin layer is exposed.
  • the Tg of the polymer A is more preferably 130 ° C. or lower, further preferably 120 ° C. or lower, and particularly preferably 110 ° C. or lower.
  • the Tg of the polymer A is 30 ° C. or higher, the edge fuse resistance can be improved.
  • 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 content of the polymer A in the photosensitive resin layer is preferably in the range of 10% by mass to 90% by mass, more preferably 30% by mass to 70% by mass, based on the total solid content of the photosensitive resin layer. It is more preferably 40% by mass to 60% by mass.
  • the content of the polymer A is 90% by mass or less, the development time can be easily controlled. Further, when the content of the polymer A is 10% by mass or more, the edge fuse resistance can be further improved.
  • the photosensitive resin layer contains at least one of the polymerizable compounds.
  • the polymerizable compound is a compound that polymerizes under the action of a polymerization initiator described later, and is a compound different from the above-mentioned polymer A.
  • the polymerizable group contained in the polymerizable compound is not particularly limited as long as it is a group that contributes to 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.
  • the photosensitive resin layer preferably contains a polymerizable compound B having an aromatic ring and two ethylenically unsaturated groups.
  • the polymerizable compound B is a bifunctional polymerizable compound having one or more aromatic rings in one molecule among the above-mentioned polymerizable compounds.
  • the content of the polymerizable compound B in the photosensitive resin layer with respect to the total amount of the polymerizable compound is preferably 40% by mass or more, more preferably 50% by mass or more, from the viewpoint of better resolution. , 55% by mass or more, and particularly preferably 60% by mass or more.
  • the upper limit of the content of the polymerizable compound B is not particularly limited, and is preferably 99% by mass or less, more preferably 95% by mass or less, further preferably 90% by mass or less, and 85% by mass or less from the viewpoint of peelability. Especially preferable.
  • Examples of the aromatic ring contained in the polymerizable compound B include an aromatic hydrocarbon ring such as a benzene ring, a naphthalene ring, and an anthracene ring; a thiophene ring, a furan ring, a pyrrole ring, an imidazole ring, a triazole ring, a pyridine ring, and the like. Aromatic heterocycles; as well as these fused rings. As the aromatic ring, an aromatic hydrocarbon ring is preferable, and a benzene ring is more preferable.
  • the aromatic ring may have a substituent.
  • the polymerizable compound B may be a compound having one aromatic ring or a compound having two or more aromatic rings.
  • the polymerizable compound B preferably has a bisphenol structure. Since the polymerizable compound B has a bisphenol structure, the swelling of the photosensitive resin layer due to the developing solution during development is suppressed, and as a result, the resolution can be improved.
  • Examples of 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 B 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.
  • alkyleneoxy group 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 preferably 4 to 16 per molecule, more preferably 6 to 14.
  • the polymerizable compound B having a bisphenol structure is described in paragraphs 0072 to 0080 of JP-A-2016-224162, and the contents described in the publication are incorporated in the present specification.
  • the polymerizable compound B 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) acryloxipolyalkoxy) phenyl) propane examples include 2,2-bis (4- (methacryloxydiethoxy) phenyl) propane (eg, Hitachi Chemical Co., Ltd.).
  • polymerizable compound B a compound represented by the following formula (1) is preferably mentioned.
  • R 1 and R 2 independently represent a hydrogen atom or a methyl group
  • A represents C 2 H 4
  • B represents C 3 H 6
  • n 1 and n 3 represent respectively.
  • Independently represents an integer from 1 to 39
  • n 1 + n 3 is an integer from 2 to 40
  • n 2 and n 4 independently represent an integer from 0 to 29, and n 2 + n 4 is an integer from 0 to 29. It is an integer from 0 to 30.
  • the sequence of repeating units of-(AO)-and-(BO)- may be random or block. When the sequence is a block, either ⁇ (A—O) ⁇ or ⁇ (BO) ⁇ may be on the bisphenyl group side.
  • n 1 + n 2 + n 3 + n 4 is preferably 2 to 40, more preferably 2 to 35. Further, n2 + n4 is preferably 0 to 10, more preferably 0 to 4.
  • the polymerizable compound B may be used alone or in combination of two or more.
  • the content of the polymerizable compound B in the photosensitive resin layer is preferably 10% by mass or more, more preferably 20% by mass or more, based on the solid content of the photosensitive resin layer, in that the resolution is more excellent.
  • the upper limit of the content of the polymerizable compound B is not particularly limited, and is preferably 70% by mass or less, preferably 60% by mass or less, in terms of transferability and edge fusion (a phenomenon in which the photosensitive resin exudes from the end of the transfer member). More preferably, it is by mass or less.
  • the photosensitive resin layer can contain a polymerizable compound other than the above-mentioned polymerizable compound B.
  • the polymerizable compound other than the polymerizable compound B is not particularly limited, and can be appropriately selected from known compounds.
  • a compound having one ethylenically unsaturated group in one molecule monoofunctional ethylenically unsaturated compound
  • a bifunctional ethylenically unsaturated compound having no aromatic ring and a trifunctional or higher ethylenically unsaturated compound. Examples include compounds.
  • Examples of the monofunctional ethylenically unsaturated compound include ethyl (meth) acrylate, ethylhexyl (meth) acrylate, 2- (meth) acryloyloxyethyl succinate, polyethylene glycol mono (meth) acrylate, and polypropylene glycol mono (meth) acrylate. , And phenoxyethyl (meth) acrylate.
  • bifunctional ethylenically unsaturated compound having no aromatic ring examples include alkylene glycol di (meth) acrylate, polyalkylene glycol di (meth) acrylate, urethane di (meth) acrylate, and trimethylolpropane diacrylate. Be done.
  • alkylene glycol di (meth) acrylate examples include tricyclodecanedimethanol diacrylate (eg, NK ester A-DCP of Shin-Nakamura Chemical Industry Co., Ltd.) and tricyclodecanedimethanol dimethacrylate (eg, Shin-Nakamura Chemical).
  • tricyclodecanedimethanol diacrylate eg, NK ester A-DCP of Shin-Nakamura Chemical Industry Co., Ltd.
  • tricyclodecanedimethanol dimethacrylate eg, Shin-Nakamura Chemical
  • polyalkylene glycol di (meth) acrylate examples include polyethylene glycol di (meth) acrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, and polypropylene glycol di (meth) acrylate (eg, Aronix of Toa Synthetic Co., Ltd.). M-270 etc.).
  • urethane di (meth) acrylate examples include propylene oxide-modified urethane di (meth) acrylate, and ethylene oxide and propylene oxide-modified urethane di (meth) acrylate.
  • Commercially available urethane di (meth) acrylate products on the market include, for example, 8UX-015A (manufactured by Taisei Fine Chemical Co., Ltd.), UA-32P (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), and UA-1100H (new). Nakamura Chemical Industry Co., Ltd.).
  • trimethylolpropane diacrylate examples include NK ester A-TMPT of 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, ditrimethylolpropane tetra (meth) acrylates, trimethylolethanetri (meth) acrylates, tri (meth) acrylates of isocyanurates, glycerintri (meth) acrylates, and modified alkylene oxides thereof.
  • Examples of the trimethylolpropane tri (meth) acrylate include ethoxylated trimethylolpropane tri (meth) acrylate, and examples of commercially available products on the market include Arkema Co., Ltd.'s Sartmer series (eg, Sartmer SR-). 454, Sartmer SR-502, etc.) and the like.
  • Examples of the above-mentioned tri (meth) acrylate of isocyanuric acid include tri (meth) acrylate of isocyanuric acid ethoxylated, ⁇ -caprolactone-modified tris- (2-acryloxyethyl) isocyanurate, and the like, and examples of commercially available products on the market. , A-9300-1CL manufactured by Shin-Nakamura Chemical Industry Co., Ltd. and the like.
  • 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 manufactured by Shin-Nakamura Chemical Industry Co., Ltd.). -9300-1CL, etc.), alkylene oxide-modified (meth) acrylate compound (KAYARAD RP-1040 manufactured by Nippon Kayaku Co., Ltd., ATM-35E and A-9300 manufactured by Shin-Nakamura Chemical Industry Co., Ltd., manufactured by Daicel Ornex Co., Ltd.
  • EBECRYL (registered trademark) 135, etc.), ethoxylated glycerin triacrylate (A-GLY-9E, etc. manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.), KAYARAD DPEA-12 (Nippon Kayaku Co., Ltd.)
  • Examples include Aronix (registered trademark) TO-2349 (manufactured by Toa Synthetic Co., Ltd.), Aronix M-520 (manufactured by Toa Synthetic Co., Ltd.), Aronix M-510 (manufactured by Toa Synthetic Co., Ltd.), and the like.
  • the polymerizable compound other than the polymerizable compound B the polymerizable compound having an acid group described in paragraphs 0025 to 0030 of JP-A-2004-239942 may be used.
  • the weight average molecular weight (Mw) of the polymerizable compound containing the polymerizable compound B is preferably 200 to 3,000, more preferably 280 to 2,200, and even more preferably 300 to 2,200.
  • the photosensitive resin layer preferably contains the above-mentioned polymerizable compound B and a trifunctional or higher functional ethylenically unsaturated compound as the polymerizable compound, and the above-mentioned polymerizable compound B and two or more kinds of trifunctional compounds. It is more preferable to contain the above ethylenically unsaturated compound.
  • the mass ratio of the polymerizable compound B to the trifunctional or higher ethylenically unsaturated compound is 1: 1 to 5.
  • the photosensitive resin layer preferably contains the above-mentioned polymerizable compound B and two or more trifunctional ethylenically unsaturated compounds as the polymerizable compound.
  • the photosensitive resin layer in the present disclosure has two or more ethylenically unsaturated substances in one molecule from the viewpoint of improving the balance between the photosensitivity of the photosensitive resin layer and the resolution and the peelability at the time of peeling. It is preferable to contain a bifunctional or higher functional compound having a saturated group (ethylenically unsaturated compound). Further, in the photosensitive resin layer in the present disclosure, the cured portion (that is, the resin pattern) formed by exposing the photosensitive resin layer is adjusted to a hardness suitable for peelability, and the peeled piece generated by peeling of the cured portion.
  • a bifunctional ethylenically unsaturated compound having two ethylenically unsaturated groups in one molecule and three ethylenically unsaturated groups in one molecule. It is preferable to contain at least one of the trifunctional ethylenically unsaturated compound having the above, and more preferably to contain the bifunctional ethylenically unsaturated compound and the trifunctional ethylenically unsaturated compound.
  • the content of the bifunctional ethylenically unsaturated compound in the photosensitive resin layer with respect to the total amount of the polymerizable compound is preferably 60% by mass or more, and may be more than 70% by mass from the viewpoint of excellent peelability.
  • the upper limit of the content of the bifunctional ethylenically unsaturated compound is not particularly limited and may be 100% by mass, but is preferably 70% by mass or less from the viewpoint of exfoliation piece adhesion.
  • a (meth) acrylate compound having a (meth) acryloyl group as a polymerizable group is preferable.
  • the photosensitive resin layer in the present disclosure has a cured portion (resin pattern) formed by exposing the photosensitive resin layer to be peelable in all of the first aspect, the second aspect and the third aspect described above. It contains a bifunctional ethylenically unsaturated compound and a trifunctional ethylenically unsaturated compound from the viewpoint of adjusting the hardness to an appropriate level and further reducing the adhesion of the peeled piece caused by the peeling of the cured portion in the device, and is photosensitive.
  • the content ratio of the trifunctional ethylenically unsaturated compound to the total amount of the polymerizable compound in the sex resin layer is preferably 10% by mass or more, more preferably 30% by mass or more, and 40% by mass or more.
  • the content ratio of the trifunctional ethylenically unsaturated compound to the total amount of the polymerizable compound is preferably 70% by mass or less, more preferably 60% by mass or less, still more preferably 50% by mass or less for the same reason as described above. ..
  • the thickness of the photosensitive resin layer is 5 ⁇ m or more, and the content ratio of the trifunctional ethylenically unsaturated compound to the total amount of the polymerizable compound in the photosensitive resin layer is 30. It is preferably mass% to 70% by mass, the thickness of the photosensitive resin layer is 10 ⁇ m or more, and the content ratio of the trifunctional ethylenically unsaturated compound to the total amount of the polymerizable compound in the photosensitive resin layer. Is preferably 40% by mass to 70% by mass.
  • the polymerizable compound may be used alone or in combination of two or more.
  • the total amount of the polymerizable compound in the photosensitive resin layer is preferably 10% by mass to 70% by mass, more preferably 20% by mass to 60% by mass, and 20% by mass to 20% by mass, based on the total solid content of the photosensitive resin layer. 50% by mass is more preferable.
  • the photosensitive resin layer contains at least one kind of 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 photoradical polymerization initiator preferably contains at least one selected from the group consisting of 2,4,5-triarylimidazole dimers and derivatives thereof. Thereby, the photosensitive, the visibility of the exposed portion and the non-exposed portion, and the resolvability can be further improved.
  • 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. (Methoxyphenyl) imidazole dimer, 2- (o-fluorophenyl) -4,5-diphenylimidazole dimer, 2- (o-methoxyphenyl) -4,5-diphenylimidazole dimer, and 2 -(P-methoxyphenyl) -4,5-diphenylimidazole dimer can be mentioned.
  • the photoradical polymerization initiator for example, the polymerization initiator described in paragraphs 0031 to 0042 of JP2011-95716A and paragraphs 0064 to 0081 of JP2015-14783 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:).
  • Midori Kagaku Co., Ltd. Benzoinone, TAZ-111 (trade name: Midori Kagaku Co., Ltd.), IrgacureOXE01, OXE02, OXE03, OXE04 (BASF), Omnirad 651 and 369 (trade name: IGM Resins B.V.) , And 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetraphenyl-1,2'-biimidazole (manufactured by Tokyo Kasei Kogyo Co., Ltd.) Be done.
  • Examples of commercially available photoradical polymerization initiators include 1- [4- (phenylthio)] -1,2-octanedione-2- (O-benzoyloxime) (trade name: IRGACURE® OXE-01). , BASF), 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-3-yl] etanone-1- (O-acetyloxime) (trade name: IRGACURE OXE-02, BASF) IRGACURE OXE-03 (BASF), IRGACURE OXE-04 (BASF), 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4) -Morphorinyl) phenyl] -1-butanone (trade name: Omnirad 379EG, manufactured by IGM Resins VV), 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane-1-one
  • a photocationic polymerization initiator is a compound that receives active light to generate an acid.
  • the photocationic polymerization initiator is preferably a compound that has no structural limitation and is sensitive to active light having a wavelength of 300 nm or more (preferably a wavelength of 300 to 450 nm) to generate an acid.
  • a photocationic polymerization initiator that is not directly sensitive to active light having a wavelength of 300 nm or more a compound capable of generating an acid by being sensitive to active light having a wavelength of 300 nm or more can be used by using a sensitizer in combination.
  • a photocationic polymerization initiator that generates an acid of pKa4 or less is preferable, a photocationic polymerization initiator that generates an acid of pKa3 or less is more preferable, and light that generates an acid of pKa2 or less.
  • Cationic polymerization initiators are particularly preferred.
  • the lower limit of pKa is not particularly limited, and is preferably -10.0 or more, for example.
  • Examples of the photocationic polymerization initiator include an ionic photocationic polymerization initiator and a nonionic photocationic polymerization initiator.
  • Examples of the ionic photocationic polymerization initiator include onium salt compounds such as diaryliodonium salts and triarylsulfonium salts, and quaternary ammonium salts.
  • the ionic photocationic polymerization initiator described in paragraphs 0114 to 0133 of JP-A-2014-85643 may be used.
  • nonionic photocationic polymerization initiator examples include trichloromethyl-s-triazine compounds, diazomethane compounds, imide sulfonate compounds, and oxime sulfonate compounds.
  • trichloromethyl-s-triazine compound the diazomethane compound and the imide sulfonate compound
  • the compounds described in paragraphs 0083 to 0088 of JP2011-221494 may be used.
  • the oxime sulfonate compound the compounds described in paragraphs 0084 to 0088 of International Publication No. 2018/179640 may be used.
  • the photosensitive resin 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 photosensitive resin layer may contain one type of photopolymerization initiator alone or two or more types.
  • the content of the photopolymerization initiator in the photosensitive resin layer is not particularly limited, and is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, based on the total solid content of the photosensitive resin layer. More preferably 1.0% by mass or more.
  • the upper limit of the content of the photopolymerization initiator is not particularly limited, and is preferably 10% by mass or less, more preferably 5% by mass or less, based on the total solid content of the photosensitive resin layer.
  • the photosensitive resin layer may contain components other than the above-mentioned alkali-soluble resin (polymer A), polymerizable compound, and photopolymerization initiator.
  • the photosensitive resin layer has a maximum absorption wavelength of 450 nm or more in the wavelength range of 400 nm to 780 nm at the time of color development from the viewpoints of visibility of exposed and unexposed areas, pattern visibility after development, and resolution. Moreover, it is preferable to contain a dye (also simply referred to as "dye N") whose maximum absorption wavelength is changed by an acid, a base, or a radical. When the dye N is contained, the detailed reason is unknown, but the adhesion to the adjacent layer (temporary support, intermediate layer, etc.) is improved, and the resolution is improved.
  • the maximum absorption wavelength changes depending on the acid, base or radical means that the dye in the color-developing state is decolorized by the acid, base or radical, and the dye in the decolorized state is colored by the acid, base or radical. It may mean any aspect of the above-mentioned aspect and the aspect in which the dye in the color-developing state changes to the color-developing state of another hue.
  • the dye N may be a compound that changes from the decolorized state by exposure to develop a color, or may be a compound that changes from the decolorized state by exposure to decolorize.
  • the dye may change the state of color development or decolorization due to the generation and action of acids, bases or radicals in the photosensitive resin layer by exposure, and the state in the photosensitive resin layer due to the acid, base or radicals. 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 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 resin layer may contain both a dye whose maximum absorption wavelength is changed by radicals as dye N and a photoradical polymerization initiator. preferable.
  • 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 resin layer, and a photoradical polymerization initiator is added after exposure.
  • a photoradical polymerization initiator examples thereof include a mode in which a radical-reactive dye, an acid-reactive dye or a base-reactive dye (for example, a leuco dye) is colored by a radical, an acid or a base generated from a photocationic polymerization initiator or a photobase generator.
  • the dye N preferably has a maximum absorption wavelength of 550 nm or more in the wavelength range of 400 nm to 780 nm at the time of color development, more preferably 550 nm to 700 nm. It is more preferably about 650 nm.
  • the dye N may have only one maximum absorption wavelength in the wavelength range of 400 nm to 780 nm at the time of color development, or may have two or more.
  • the maximum absorption wavelength having the highest absorbance among the two or more maximum absorption wavelengths may be 450 nm or more.
  • the transmission spectrum of a solution containing dye N was measured in the range of 400 nm to 780 nm using a spectrophotometer in an atmospheric atmosphere, and the light intensity was minimized. It is obtained by detecting the wavelength (maximum absorption wavelength).
  • the spectrophotometer for example, UV3100 manufactured by Shimadzu Corporation can be used.
  • Examples of the dye that develops or decolorizes by exposure include leuco compounds.
  • Examples of dyes that are decolorized by exposure include leuco compounds, diarylmethane dyes, oxazine dyes, xanthene dyes, iminonaphthoquinone dyes, azomethine dyes and anthraquinone dyes.
  • As the dye N a leuco compound is preferable from the viewpoint of 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 spiropylan skeleton (spiropylan dye), a leuco compound having a fluorane skeleton (fluorane dye), and a diarylmethane skeleton.
  • Leuco compounds diarylmethane dyes
  • leuco compounds having a rhodamine lactam skeleton (rodamine lactam dyes)
  • leuco compounds having an indrill phthalide skeleton indrill phthalide dyes
  • leuco auramine skeletons examples include a leuco compound having a triarylmethane skeleton (triarylmethane dye), a leuco compound having a spiropylan skeleton (spiropylan dye), a leuco compound having a fluorane skeleton (fluorane dye), and a
  • leuco compounds having leuco compounds include leuco auramine dyes.
  • leuco auramine dyes include leuco compounds having leuco compounds (leuco auramine dyes).
  • a triarylmethane dye or a fluorane dye is preferable, and a leuco compound having a triphenylmethane skeleton (triphenylmethane dye) or a fluorane dye is more preferable.
  • the leuco compound preferably has a lactone ring, a surujin ring, or a sultone ring from the viewpoint of visibility of the exposed portion and the non-exposed portion.
  • the lactone ring, sultin ring, or sulton ring of the leuco compound is reacted with the radical generated from the photoradical polymerization initiator or the acid generated from the photocationic polymerization initiator to change the leuco compound into a ring-closed 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 preferably has a lactone ring, a sultone ring, or a sultone ring, and the lactone ring, the sultone ring, or the sultone ring is opened by a radical or an acid to develop a color.
  • a compound in which the lactone ring is opened to develop color is more preferable.
  • Examples of the dye N include the following dyes and leuco compounds.
  • specific examples of the dyes include Brilliant Green, Ethyl Violet, Methyl Green, Crystal Violet, Basic Fuxin, Methyl Violet 2B, Kinaldine Red, Rose Bengal, Metanyl Yellow, Timor Sulfophthalene, Xylenol Blue, Methyl orange, paramethyl red, congofred, benzopurpurin 4B, ⁇ -naphthyl red, Nile blue 2B, Nile blue A, methyl violet, malakite green, parafuxin, Victoria pure blue-naphthalene sulfonate, Victoria pure blue BOH ( Hodoya Chemical Industry Co., Ltd.), Oil Blue # 603 (manufactured by Orient Chemical Industry Co., Ltd.), Oil Pink # 312 (manufactured by Orient Chemical Industry Co., Ltd.), Oil Red 5B (manufactured by Orient Chemical Industry Co., Ltd.)
  • the leuco compound examples include p, p', p "-hexamethyltriaminotriphenylmethane (leucocrystal violet), Pergascript Blue SRB (manufactured by Ciba Geigy), crystal violet lactone, and malakite green lactone.
  • the dye N is preferably a dye whose maximum absorption wavelength is changed by radicals from the viewpoints of visibility of exposed and unexposed areas, pattern visibility after development, and resolution, and is a dye that develops color by radicals. Is more preferable.
  • As the dye N leuco crystal violet, crystal violet lactone, brilliant green, or Victoria pure blue-naphthalene sulfonate is preferable.
  • the dye N may be used alone or in combination of two or more.
  • the content of the dye N is 0.1% by mass with respect to the total solid content of the photosensitive resin layer from the viewpoints of visibility of the exposed and non-exposed areas, pattern visibility after development, and resolution.
  • the above is preferable, 0.1% by mass to 10% by mass is more preferable, 0.1% by mass to 5% by mass is further preferable, and 0.1% by mass to 1% by mass is particularly preferable.
  • the content of the dye N means the content of the dye when all of the dye N contained in the photosensitive resin layer is in a colored state.
  • the content of dye N is determined as follows. Hereinafter, a method for quantifying the content of dye N will be described by taking a dye that develops color by radicals as an example.
  • the absorbance of the solution in which all the dyes are colored is measured by the same method as above except that 3 g of the photosensitive resin layer is dissolved in methyl ethyl ketone instead of the dye. From the absorbance of the obtained solution containing the photosensitive resin layer, the content of the dye contained in the photosensitive resin layer is calculated based on the calibration curve.
  • the photosensitive resin layer preferably contains a surfactant from the viewpoint of thickness uniformity.
  • the surfactant include anionic surfactants, cationic surfactants, nonionic (nonionic) surfactants, and amphoteric surfactants, and nonionic surfactants are preferable.
  • nonionic surfactant examples include a polyoxyethylene higher alkyl ether compound, a polyoxyethylene higher alkylphenyl ether compound, a higher fatty acid diester compound of polyoxyethylene glycol, a silicone-based nonionic surfactant, and a fluorine-based nonionic.
  • examples include sex surfactants.
  • the photosensitive resin layer preferably contains a fluorine-based nonionic surfactant from the viewpoint of being more excellent in resolution. When the photosensitive resin layer contains a fluorine-based nonionic surfactant, it is possible to suppress the penetration of the etching solution used in the etching step into the photosensitive resin layer and reduce side etching.
  • fluorine-based nonionic surfactants examples include Megafuck F-551, F-552 and F-554 (all manufactured by DIC Corporation).
  • 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.
  • a fluorine-based surfactant an acrylic compound having a molecular structure having a functional group containing a fluorine atom, and when heat is applied, a portion of the functional group containing a fluorine atom is cut and the fluorine atom volatilizes.
  • 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.
  • a block polymer can also be used as the fluorine-based surfactant.
  • the fluorine-based surfactant has a structural unit derived from a (meth) acrylate compound having a fluorine atom and 2 or more (preferably 5 or more) alkyleneoxy groups (preferably ethyleneoxy groups and propyleneoxy groups).
  • a fluorine-containing polymer compound containing a structural unit derived from a (meth) acrylate compound can also be preferably used.
  • fluorine-based surfactant a fluorine-containing polymer having an ethylenically unsaturated bond-containing group in the side chain can also be used.
  • Megafvck RS-101, RS-102, RS-718K, RS-72-K (all manufactured by DIC Corporation) and the like can be mentioned.
  • fluorine-based surfactant compounds having a linear perfluoroalkyl group having 7 or more carbon atoms, such as perfluorooctanoic acid (PFOA) and perfluorooctanesulfonic acid (PFOS), are used. It is preferably a surfactant derived from an alternative material.
  • Nonionic surfactants include glycerol, trimethylolpropane, trimethylolethane and their ethoxylates and propoxylates (eg, glycerol propoxylate, glycerol ethoxylate, etc.), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, etc.
  • silicone-based surfactant examples include a linear polymer composed of a siloxane bond and a modified siloxane polymer in which an organic group is introduced into a side chain or a terminal.
  • surfactant examples include DOWNSIL 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 (above, Toray Dow).
  • surfactant examples include the surfactant described in paragraphs 0120 to 0125 of International Publication No. 2018/179640, the surfactant described in paragraph 0017 of Japanese Patent No. 45027884, and JP-A-2009-237362.
  • the surfactants described in paragraphs 0060 to 0071 can also be used.
  • the photosensitive resin layer may contain one type of surfactant alone or two or more types.
  • the content of the surfactant is preferably 0.001% by mass to 10% by mass, more preferably 0.01% by mass to 3% by mass, based on the total solid content of the photosensitive resin layer.
  • the photosensitive resin layer may contain a known additive in addition to the above components, if necessary.
  • the additive include a polymerization inhibitor, a sensitizer, a plasticizer, a heterocyclic compound, a benzotriazole compound, a carboxybenzotriazole compound, a resin other than the polymer A, and a solvent.
  • the photosensitive resin layer may contain each additive alone or in combination of two or more.
  • the photosensitive resin layer may contain a polymerization inhibitor.
  • the polymerization inhibitor include radical polymerization inhibitors.
  • 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 nitrosophenylhydroxyamine aluminum salt as a radical polymerization inhibitor so as not to impair the sensitivity of the photosensitive resin composition.
  • Examples of the benzotriazole compound 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.
  • Examples of the carboxybenzotriazole compound 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) aminomethylene carboxybenzotriazole, N- (N, N-di-2-ethylhexyl) aminoethylene carboxybenzotriazole and the like.
  • carboxybenzotriazoles for example, a commercially available product such as CBT-1 (Johoku Chemical Industry Co., Ltd., trade name) can be used.
  • the total content of the polymerization inhibitor, the benzotriazole compound, and the carboxybenzotriazole compound is preferably 0.01% by mass to 3% by mass, more preferably 0.05, based on the total solid content of the photosensitive resin layer. It is 1% by mass by mass. When the total content is 0.01% by mass or more, the storage stability of the photosensitive resin layer becomes better. Further, when the total content is 3% by mass or less, the sensitivity can be maintained and the decolorization of the dye can be effectively suppressed.
  • the photosensitive resin 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), stillben compounds, triazine compounds, thiophene compounds, naphthalimide compounds, triarylamine compounds, and aminoaclydin compounds.
  • the photosensitive resin layer may contain one kind of sensitizer alone or two or more kinds.
  • 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 movement. Therefore, 0.01% by mass to 5% by mass is preferable, and 0.05% by mass to 1% by mass is more preferable with respect to the total mass of the photosensitive resin layer.
  • the photosensitive resin 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 resin layer may contain a resin other than the polymer A.
  • the photosensitive resin layer may contain, for example, a resin in which the content ratio of the constituent units derived from styrene is 40% by mass or less with respect to all the constituent units.
  • Resins other than polymer A include acrylic resin, styrene-acrylic copolymer (however, styrene content is 40% by mass or less), polyurethane, polyvinyl alcohol, polyvinylformal, polyamide, polyester, polyamide, and epoxy resin. , Polyacetal, polyhydroxystyrene, polyimide, polybenzoxazole, polysiloxane, polyethyleneimine, polyallylamine, and polyalkylene glycol.
  • the photosensitive resin layer may contain a solvent.
  • the solvent may remain in the photosensitive resin layer.
  • the photosensitive resin layer may further contain a known additive.
  • Known additives include metal oxide particles, antioxidants, dispersants, acid growth agents, development accelerators, conductive fibers, thermal radical polymerization initiators, thermal acid generators, ultraviolet absorbers, thickeners, etc. Examples thereof include a cross-linking agent and an organic or inorganic precipitation inhibitor. Additives contained in the photosensitive resin layer are described in paragraphs 0165 to 0184 of JP-A-2014-85643, and the contents described in JP-A-2014-85643 are incorporated in the present specification.
  • the photosensitive resin 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 content is preferably as follows.
  • the content of impurities in the photosensitive resin layer is preferably 80 ppm or less, more preferably 10 ppm or less, and further preferably 2 ppm or less on a mass basis.
  • the content of impurities in the photosensitive resin layer can be 1 ppb or more or 0.1 ppm or more on a mass basis.
  • a raw material having a low content of impurities is selected as a raw material of the photosensitive resin layer, prevention of impurities from being mixed in when forming the photosensitive resin layer, and cleaning of the manufacturing equipment. Removal of impurities can be mentioned. By such a method, the amount of impurities can be kept within the above range.
  • Impurities can be quantified by a known method, for example, ICP (Inductively Coupled Plasma) emission spectroscopy, atomic absorption spectroscopy, or ion chromatography.
  • ICP Inductively Coupled Plasma
  • the content of benzene, formaldehyde, trichlorethylene, 1,3-butadiene, carbon tetrachloride, chloroform, N, N-dimethylformamide, N, N-dimethylacetamide, and hexane in the photosensitive resin layer is preferably low.
  • the content of the above compound in the photosensitive resin 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 content of the above-mentioned compound in the photosensitive resin layer can be 10 ppb or more or 100 ppb or more on a mass basis.
  • the content of the above-mentioned compound can be suppressed in the same manner as the above-mentioned metal impurities. Moreover, it can be quantified by a known measurement method.
  • the water content in the photosensitive resin layer is preferably 0.01% by mass to 1.0% by mass, preferably 0.05% by mass to 0.5% by mass, from the viewpoint of improving reliability and laminateability. Is more preferable.
  • the thickness of the photosensitive resin layer is generally preferably 0.1 ⁇ m to 300 ⁇ m, more preferably 0.2 ⁇ m to 100 ⁇ m, further preferably 0.5 ⁇ m to 50 ⁇ m, still more preferably 0.5 ⁇ m to 15 ⁇ m.
  • the thickness of the photosensitive resin layer is within the above range, the developability of the photosensitive resin layer is improved, and the resolvability can be improved.
  • the thickness of the photosensitive resin layer is adjusted so that the cured portion (resin pattern) formed by exposing the photosensitive resin layer has a hardness suitable for peeling, and the inside of the peeling piece generated by peeling of the cured portion is inside the device.
  • the thickness of the photosensitive resin layer is preferably 50 ⁇ m or less, more preferably 30 ⁇ m or less, from the viewpoint of compatibility with resolution.
  • each layer in the photosensitive transfer material is determined by observing a cross section parallel to the main surface of the photosensitive transfer material with a scanning electron microscope (SEM) and based on the obtained observation image. The thickness of is measured at 10 points and calculated as the average value.
  • the main surfaces of the photosensitive transfer material refer to two surfaces facing each other, which have a larger area than the other surfaces.
  • the transmittance of light having a wavelength of 365 nm in the photosensitive resin layer is preferably 10% or more, more preferably 30% or more, still more preferably 50% or more, in that it is more excellent in adhesion.
  • the upper limit of the transmittance of light having a wavelength of 365 nm is not particularly limited and may be 99.9% or less.
  • the method for forming the photosensitive resin layer is not particularly limited as long as it is a method capable of forming a layer containing the above components.
  • a method for forming the photosensitive resin layer for example, a photosensitive resin composition containing an alkali-soluble resin, a polymerizable compound, a photopolymerization initiator, and a solvent is prepared, and the photosensitive resin composition is formed on the surface of a temporary support or the like. Examples thereof include a method of forming by applying an object and drying a coating film of the photosensitive resin composition.
  • Examples of the photosensitive resin composition used for forming the photosensitive resin layer include an alkali-soluble resin, a polymerizable compound, a photopolymerization initiator, and a composition containing a solvent and an optional component.
  • the photosensitive resin composition preferably contains a solvent in order to adjust the viscosity of the photosensitive resin composition and facilitate the formation of the photosensitive resin layer.
  • an alkali-soluble resin As the solvent contained in the photosensitive resin composition, an alkali-soluble resin, a polymerizable compound, a photopolymerization initiator, and a known solvent capable of dissolving or dispersing the solvent and arbitrary components can be used.
  • the solvent examples include an alkylene glycol ether solvent, an alkylene glycol ether acetate solvent, an alcohol solvent (methanol, ethanol, etc.), a ketone solvent (acetone, methyl ethyl ketone, etc.), an aromatic hydrocarbon solvent (toluene, etc.), and an aprotonic polar solvent.
  • examples thereof include (N, N-dimethylformamide, etc.), a cyclic ether solvent (tetrahydrofuran, etc.), an ester solvent, an amide solvent, a lactone solvent, and a mixed solvent containing two or more of these.
  • the photosensitive resin composition for forming the photosensitive resin layer is an alkylene glycol ether solvent and an alkylene glycol. It preferably contains at least one selected from the group consisting of ether acetate solvents. Among them, 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 cyclic ether solvents is more preferable.
  • alkylene glycol ether solvent examples include ethylene glycol monoalkyl ether, ethylene glycol dialkyl ether, propylene glycol monoalkyl ether, propylene glycol dialkyl ether, diethylene glycol dialkyl ether, dipropylene glycol monoalkyl ether and dipropylene glycol dialkyl ether. ..
  • alkylene glycol ether acetate solvent examples include ethylene glycol monoalkyl ether acetate, propylene glycol monoalkyl ether acetate, diethylene glycol monoalkyl ether acetate, and dipropylene glycol monoalkyl ether acetate.
  • the solvent described in paragraphs 0092 to 0094 of International Publication No. 2018/179640 and the solvent described in paragraph 0014 of JP-A-2018-177789 may be used, and the contents thereof are described in the present specification. Incorporated into the book.
  • the photosensitive resin composition may contain one type of solvent alone, or may contain two or more types of solvent.
  • the content of the solvent in the photosensitive resin composition is preferably 50% by mass to 1,900% by mass, more preferably 100% by mass to 900% by mass, based on the total solid content of the photosensitive resin composition.
  • the method for preparing the photosensitive resin composition is not particularly limited.
  • a solution in which each component is dissolved in the above solvent is prepared in advance, and the obtained solution is mixed in a predetermined ratio to prepare the photosensitive resin composition.
  • Examples include a method of preparing a product.
  • the photosensitive resin composition is preferably filtered using a filter having a pore size of 0.2 ⁇ m to 30 ⁇ m before forming the photosensitive resin layer.
  • the method for applying the photosensitive resin composition is not particularly limited, and the photosensitive resin composition may be applied by a known method.
  • the coating method include slit coating, spin coating, curtain coating and inkjet coating.
  • the photosensitive resin layer may be formed on the cover film by applying the photosensitive resin composition on a cover film described later and drying the composition.
  • the photosensitive transfer material may have a thermoplastic resin layer between the temporary support and the photosensitive resin layer.
  • the photosensitive transfer material preferably includes a thermoplastic resin layer between the temporary support and the photosensitive resin layer.
  • thermoplastic resin layer contains an alkali-soluble resin as the thermoplastic resin.
  • the alkali-soluble resin in the thermoplastic resin layer may be the same as or different from the alkali-soluble resin in the photosensitive resin layer.
  • alkali-soluble resin examples include acrylic resin, polystyrene resin, styrene-acrylic copolymer, polyurethane resin, polyvinyl alcohol, polyvinyl formal, polyamide resin, polyester resin, polyamide resin, epoxy resin, polyacetal resin, and polyhydroxystyrene resin.
  • alkali-soluble resin examples include acrylic resin, polystyrene resin, styrene-acrylic copolymer, polyurethane resin, polyvinyl alcohol, polyvinyl formal, polyamide resin, polyester resin, polyamide resin, epoxy resin, polyacetal resin, and polyhydroxystyrene resin.
  • examples thereof include polyimide resins, polybenzoxazole resins, polysiloxane resins, polyethyleneimines, polyallylamines and polyalkylene glycols.
  • an acrylic resin is preferable from the viewpoint of developability and adhesion to an adjacent layer.
  • the acrylic resin is at least one selected from the group consisting of a structural unit derived from (meth) acrylic acid, a structural unit derived from (meth) acrylic acid ester, and a structural unit derived from (meth) acrylic acid amide. It means a resin having a constituent unit of.
  • the total content of the structural unit derived from (meth) acrylic acid, the structural unit derived from (meth) acrylic acid ester, and the structural unit derived from (meth) acrylic acid amide is that of the acrylic resin. It is preferably 50% by mass or more with respect to the total mass. Above all, the total content of the structural unit derived from (meth) acrylic acid and the structural unit derived from (meth) acrylic acid ester is preferably 30% by mass to 100% by mass with respect to the total mass of the acrylic resin. , 50% by mass to 100% by mass, more preferably.
  • the alkali-soluble resin is preferably a polymer having an acid group.
  • the acid group include a carboxy group, a sulfo group, a phosphoric acid group and a phosphonic acid group, and a carboxy group is preferable.
  • the alkali-soluble resin is more preferably an alkali-soluble resin having an acid value of 60 mgKOH / g or more, and further preferably a carboxy group-containing acrylic resin having an acid value of 60 mgKOH / g or more.
  • the upper limit of the acid value of the alkali-soluble resin is not particularly limited, but is preferably 200 mgKOH / g or less, and more preferably 150 mgKOH / g or less.
  • the carboxy group-containing acrylic resin having an acid value of 60 mgKOH / g or more is not particularly limited, and can be appropriately selected from known resins and used.
  • an alkali-soluble resin which is a carboxy group-containing acrylic resin having an acid value of 60 mgKOH / g or more, described in paragraphs 0033 to 0052 of JP2010-237589.
  • Acrylic resin can be mentioned.
  • the copolymerization ratio of the structural unit having a carboxy group in the carboxy group-containing acrylic resin is preferably 5% by mass to 50% by mass, more preferably 10% by mass to 40% by mass, and 12 by mass, based on the total mass of the acrylic resin. More preferably, it is by mass% to 30% by mass.
  • an acrylic resin having a structural unit derived from (meth) acrylic acid is particularly preferable from the viewpoint of developability and adhesion to an adjacent layer.
  • the alkali-soluble resin may have a reactive group.
  • the reactive group may be any addition-polymerizable group, and an ethylenically unsaturated group; a polycondensable group such as a hydroxy group and a carboxy group; and a polyadditive reactive group such as an epoxy group and a (block) isocyanate group are used. Can be mentioned.
  • the weight average molecular weight (Mw) of the alkali-soluble resin is preferably 1,000 or more, more preferably 10,000 to 100,000, and even more preferably 20,000 to 50,000.
  • the alkali-soluble resin may be used alone or in combination of two or more.
  • the content of the alkali-soluble resin in the thermoplastic resin layer is preferably 10% by mass to 99% by mass, preferably 20% by mass, based on the total mass of the thermoplastic resin layer from the viewpoint of developability and adhesion to the adjacent layer. It is more preferably mass% to 90% by mass, further preferably 40% by mass to 80% by mass, and particularly preferably 50% by mass to 70% by mass.
  • thermoplastic resin layer contains a dye (also simply referred to as "dye B") having a maximum absorption wavelength of 450 nm or more in the wavelength range of 400 nm to 780 nm at the time of color development and whose maximum absorption wavelength is changed by an acid, a base, or a radical. It is preferable to do so.
  • the preferred embodiment of the dye B is the same as the preferred embodiment of the dye N except for the points described later.
  • the dye B is preferably a dye whose maximum absorption wavelength is changed by an acid or a radical, and more preferably a dye whose maximum absorption wavelength is changed by an acid. ..
  • the thermoplastic layer contains both a dye whose maximum absorption wavelength changes depending on the acid as the dye B and a compound that generates an acid by light, which will be described later. It is preferable to contain it.
  • the dye B may be used alone or in combination of two or more.
  • the content of the dye B is preferably 0.2% by mass or more, preferably 0.2% by mass to 6% by mass, based on the total mass of the thermoplastic resin layer from the viewpoint of visibility of the exposed part and the non-exposed part. More preferably, 0.2% by mass to 5% by mass is further preferable, and 0.25% by mass to 3.0% by mass is particularly preferable.
  • the content of the dye B means the content of the dye when all of the dye B contained in the thermoplastic resin layer is in a colored state.
  • a method for quantifying the content of dye B will be described by taking a dye that develops color by radicals as an example.
  • a solution prepared by dissolving 0.001 g and 0.01 g of the dye in 100 mL of methyl ethyl ketone is prepared.
  • Irradicure OXE01 (trade name, BASF Japan 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 colored is measured by the same method as above except that 0.1 g of the thermoplastic resin layer is dissolved in methyl ethyl ketone instead of the dye. From the absorbance of the obtained solution containing the thermoplastic resin layer, the amount of the dye contained in the thermoplastic resin layer is calculated based on the calibration curve.
  • the thermoplastic resin layer may contain a compound that generates an acid, a base, or a radical by light (also simply referred to as “Compound C”).
  • a compound that generates an acid, a base, or a radical by receiving active rays such as ultraviolet rays and visible rays is preferable.
  • a known photoacid generator, photobase generator, and photoradical polymerization initiator (photoradical generator) can be used. Of these, a photoacid generator is preferred.
  • thermoplastic resin layer can contain a photoacid generator from the viewpoint of resolution.
  • the photoacid generator include a photocationic polymerization initiator that may be contained in the above-mentioned photosensitive resin layer, and the same preferred embodiments are used except for the points described below.
  • the photoacid generator preferably contains at least one compound selected from the group consisting of an onium salt compound and an oxime sulfonate compound from the viewpoint of sensitivity and resolution, and preferably contains sensitivity, resolution and resolution. From the viewpoint of adhesion, it is more preferable to contain an oxime sulfonate compound. Further, as the photoacid generator, a photoacid generator having the following structure is also preferable.
  • the thermoplastic resin layer may contain a photoradical polymerization initiator.
  • the photoradical polymerization initiator include a photoradical polymerization initiator that may be contained in the photosensitive resin layer described above, and the preferred embodiment is also the same.
  • the thermoplastic resin layer may contain a photobase generator.
  • the photobase generator is not particularly limited as long as it is a known photobase generator, and for example, 2-nitrobenzylcyclohexylcarbamate, triphenylmethanol, O-carbamoyl hydroxylamide, O-carbamoyloxime, [[(2,2).
  • Compound C may be used alone or in combination of two or more.
  • the content of compound C in the thermoplastic resin layer is 0.1% by mass to 10% by mass with respect to the total solid content of the thermoplastic resin layer from the viewpoint of visibility and resolution of the exposed and unexposed areas. % Is preferable, and 0.5% by mass to 5% by mass is more preferable.
  • the thermoplastic resin layer preferably contains a plasticizer from the viewpoints of resolution, adhesion to adjacent layers, and developability.
  • the plasticizer preferably has a smaller molecular weight (weight average molecular weight (Mw) in the case of an oligomer or polymer) than the alkali-soluble resin.
  • the molecular weight (weight average molecular weight (Mw)) of the plasticizer is preferably 200 to 2,000.
  • the plasticizer is not particularly limited as long as it is a compound that exhibits plasticity by being compatible with an alkali-soluble resin.
  • the plasticizer preferably has an alkyleneoxy group in the molecule from the viewpoint of imparting plasticity, and a polyalkylene glycol compound is more preferable.
  • the alkyleneoxy group contained in the plasticizer more preferably has a polyethyleneoxy structure or a polypropyleneoxy structure.
  • the plasticizer preferably contains a (meth) acrylate compound from the viewpoint of resolution and storage stability. From the viewpoint of compatibility, resolution and adhesion to the adjacent layer, it is more preferable that the alkali-soluble resin is an acrylic resin and the plasticizer contains a (meth) acrylate compound.
  • thermoplastic resin layer and the photosensitive resin layer examples include the (meth) acrylate compound described as the polymerizable compound contained in the photosensitive resin layer described above.
  • both the thermoplastic resin layer and the photosensitive resin layer contain the same (meth) acrylate compound. .. This is because the thermoplastic resin layer and the photosensitive resin layer contain the same (meth) acrylate compound, respectively, so that the diffusion of components between the layers is suppressed and the storage stability is improved.
  • the thermoplastic resin layer contains a (meth) acrylate compound as a plasticizer
  • the (meth) acrylate compound used as a plasticizer is a polyfunctional compound having two or more (meth) acryloyl groups in one molecule from the viewpoints of resolution, adhesion to adjacent layers, and developability.
  • a (meth) acrylate compound is preferred.
  • a (meth) acrylate compound having an acid group or a urethane (meth) acrylate compound is also preferable.
  • the thermoplastic resin layer may contain one type of plasticizer alone, or may contain two or more types of plasticizer.
  • the content of the plastic agent is preferably 1% by mass to 70% by mass and 10% by mass to 60% by mass with respect to the total mass of the thermoplastic resin layer from the viewpoint of resolution, adhesion to the adjacent layer and developability. By mass% is more preferable, and 20% by mass to 50% by mass is particularly preferable.
  • thermoplastic resin layer preferably contains a surfactant from the viewpoint of thickness uniformity.
  • the surfactant include surfactants that may be contained in the above-mentioned photosensitive resin layer, and the preferred embodiment is the same.
  • the thermoplastic resin layer may contain one type of surfactant alone or two or more types.
  • the content of the surfactant is preferably 0.001% by mass to 10% by mass, more preferably 0.01% by mass to 3% by mass, based on the total mass of the thermoplastic resin layer.
  • the thermoplastic resin layer may contain a sensitizer.
  • the sensitizer is not particularly limited, and examples thereof include a sensitizer that may be contained in the above-mentioned photosensitive resin layer.
  • the thermoplastic resin layer may contain one type of sensitizer alone or two or more types.
  • 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 the visibility of the exposed and non-exposed areas, 0.01 mass with respect to the total mass of the thermoplastic resin layer.
  • the range of% to 5% by mass is preferable, and the range of 0.05% by mass to 1% by mass is more preferable.
  • thermoplastic resin layer may contain known additives, if necessary. Further, the thermoplastic resin layer is described in paragraphs 0189 to 0193 of Japanese Patent Application Laid-Open No. 2014-85643, and the contents described in this publication are incorporated in the present specification.
  • the thickness of the thermoplastic resin layer is not particularly limited, and is preferably 1 ⁇ m or more, more preferably 2 ⁇ m or more. When the thickness is in the above range, the adhesion with the adjacent layer becomes better.
  • the upper limit of the thickness of the thermoplastic resin layer is not particularly limited, and is preferably 20 ⁇ m or less, more preferably 10 ⁇ m or less, still more preferably 5 ⁇ m or less, from the viewpoint of developability and resolvability.
  • the method for forming the thermoplastic resin layer is not particularly limited as long as it is a method capable of forming a layer containing the above components.
  • a method for forming the thermoplastic resin layer for example, a thermoplastic resin composition containing the above components and a solvent is prepared, and the thermoplastic resin composition is applied to the surface of a temporary support or the like to form the thermoplastic resin composition. Examples thereof include a method of forming by drying a coating film of an object.
  • the thermoplastic resin composition preferably contains a solvent in order to adjust the viscosity of the thermoplastic resin composition and facilitate the formation of the thermoplastic resin layer.
  • the solvent contained in the thermoplastic resin composition is not particularly limited as long as the above-mentioned components contained in the thermoplastic resin layer can be dissolved or dispersed.
  • Examples of the solvent contained in the thermoplastic resin composition include solvents that can be used in the above-mentioned photosensitive resin composition, and preferred embodiments are also the same.
  • the solvent may be used alone or in combination of two or more.
  • the content of the solvent when the thermoplastic resin composition is applied is preferably 50% by mass to 1,900% by mass, preferably 100% by mass to 900% by mass, based on the total solid content in the thermoplastic resin composition. More preferred.
  • thermoplastic resin composition and the formation of the thermoplastic resin layer may be carried out according to the method for preparing the photosensitive resin composition and the method for forming the photosensitive resin layer described above.
  • a solution in which each component contained in the thermoplastic resin layer is dissolved in the above solvent is prepared in advance, and the obtained solution is mixed at a predetermined ratio to prepare a thermoplastic resin composition.
  • the thermoplastic resin layer is formed by applying the obtained thermoplastic resin composition to the surface of the temporary support and drying the coating film of the thermoplastic resin composition. Further, after forming the photosensitive resin layer and the intermediate layer on the cover film described later, the thermoplastic resin layer may be formed on the surface of the intermediate layer.
  • the photosensitive transfer material preferably has, for example, an intermediate layer between the thermoplastic resin layer and the photosensitive resin layer.
  • an intermediate layer By having the intermediate layer, it is possible to suppress the mixing of the components when the plurality of layers are applied and when the layers are stored after application.
  • the intermediate layer is preferably a water-soluble layer from the viewpoint of developability and suppressing mixing of components during application of the plurality of layers and storage after application.
  • 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.
  • the intermediate layer examples include an oxygen blocking layer having an oxygen blocking function, which is described as a “separation layer” in JP-A-5-72724.
  • the intermediate layer is an oxygen blocking layer, the sensitivity at the time of exposure is improved, the time load of the exposure machine is reduced, and the productivity is improved, which is preferable.
  • the oxygen blocking layer used as the intermediate layer may be appropriately selected from the known layers described in the above publications and the like. Of these, an oxygen blocking layer that exhibits low oxygen permeability and is dispersed or dissolved in water or an alkaline aqueous solution (1% by mass aqueous solution of sodium carbonate at 22 ° C.) is preferable.
  • the intermediate layer preferably contains a resin.
  • the resin contained in the intermediate layer include polyvinyl alcohol-based resin, polyvinylpyrrolidone-based resin, cellulose-based resin, acrylamide-based resin, polyethylene oxide-based resin, gelatin, vinyl ether-based resin, polyamide resin, and their common weights. Examples include resins such as coalescence.
  • a water-soluble resin is preferable.
  • the resin contained in the intermediate layer contains the polymer A contained in the photosensitive resin layer and the thermoplastic resin (alkali soluble) contained in the thermoplastic resin layer from the viewpoint of suppressing the mixing of the components between the plurality of layers. It is preferable that the resin is different from any of the resins).
  • the intermediate layer preferably contains polyvinyl alcohol from the viewpoint of oxygen blocking property and suppressing mixing of components during application of the plurality of layers and storage after application, and contains both polyvinyl alcohol and polyvinylpyrrolidone. It is more preferable to contain it.
  • the intermediate layer may contain the above resin alone or in combination of two or more.
  • the content of the resin in the intermediate layer is not particularly limited, but is based on the total mass of the intermediate layer from the viewpoint of oxygen blocking property and suppressing the mixing of components during application of the plurality of layers and storage after application. , 50% by mass to 100% by mass, more preferably 70% by mass to 100% by mass, further preferably 80 to 100% by mass, and particularly preferably 90% by mass to 100% by mass.
  • the intermediate layer may contain an additive such as a surfactant, if necessary.
  • the layer thickness of the intermediate layer is not particularly limited, but is preferably 0.1 ⁇ m to 5 ⁇ m, and more preferably 0.5 ⁇ m to 3 ⁇ m.
  • the thickness of the intermediate layer is within the above range, the oxygen blocking property is not lowered, the mixing of the components at the time of applying the plurality of layers and at the time of storage after application can be suppressed, and the intermediate layer at the time of development is intermediate. This is because an increase in layer removal time can be suppressed.
  • the method for forming the intermediate layer is not particularly limited, and for example, an intermediate layer composition containing the above resin and any additive is prepared and applied to the surface of the thermoplastic resin layer or the photosensitive resin layer to form the intermediate layer composition.
  • examples thereof include a method of forming an intermediate layer by drying a coating film of an object.
  • the intermediate layer composition preferably contains a solvent in order to adjust the viscosity of the thermoplastic resin composition and facilitate the formation of the thermoplastic resin layer.
  • the solvent contained in the intermediate layer composition is not particularly limited as long as the above resin can be dissolved or dispersed, and at least one selected from the group consisting of water and a water-miscible organic solvent is preferable, and water or water or water is preferable.
  • a mixed solvent of water and a water-miscible organic solvent is more preferable.
  • the water-miscible organic solvent include alcohols having 1 to 3 carbon atoms, acetone, ethylene glycol and glycerin, and alcohols having 1 to 3 carbon atoms are preferable, and methanol or ethanol is more preferable.
  • the photosensitive transfer material preferably has a cover film (protective film) on the side opposite to the side facing the temporary support of the photosensitive resin layer.
  • a cover film protecting film
  • the surface of the photosensitive resin layer on the side facing the temporary support is referred to as a "first surface”
  • the surface of the photosensitive resin layer on the side opposite to the first surface is also referred to as a "second surface”. ..
  • cover film examples include a resin film and paper, and a resin film is preferable from the viewpoint of strength and flexibility.
  • the resin film include a polyethylene film, a polypropylene film, a polyethylene terephthalate film, a cellulose triacetate film, a polystyrene film, and a polycarbonate film. Of these, polyethylene film, polypropylene film, or polyethylene terephthalate film is preferable.
  • the thickness of the cover film is not particularly limited, and is preferably 5 ⁇ m to 100 ⁇ m, more preferably 10 ⁇ m to 50 ⁇ m.
  • the arithmetic mean roughness Ra value of the surface of the cover film in contact with the photosensitive resin layer is preferably 0.3 ⁇ m or less, more preferably 0.1 ⁇ m or less, and 0. It is more preferably 05 ⁇ m or less.
  • the lower limit of the Ra value on the surface of the cover film is not particularly limited, and is preferably 0.001 ⁇ m or more.
  • the Ra value on the surface of the cover film is measured by the following method. Using a three-dimensional optical profiler (New View7300, manufactured by Zygo), the surface of the cover film is measured under the following conditions to obtain a surface profile of the optical film. As the measurement / analysis software, Microscope Application of MetroPro ver 8.3.2 is used. Next, the Surface Map screen is displayed by the analysis software, and the histogram data is obtained in the Surface Map screen. The arithmetic mean roughness is calculated from the obtained histogram data, and the Ra value of the surface of the cover film is obtained. When the cover film is attached to the photosensitive transfer material, the cover film is peeled from the photosensitive transfer material, and the Ra value of the peeled surface of the cover film is measured.
  • the photosensitive transfer material may have, for example, a contrast enhancement layer in addition to the above-mentioned layer.
  • the contrast enhancement layer is described in paragraph 0134 of WO 2018/179640. Further, it may have other layers described in paragraphs 0194 to 0196 of JP2014-85643, and the contents described in the gazette are incorporated in the present specification.
  • the photosensitive transfer material can be produced by a known production method.
  • a method for producing a photosensitive transfer material will be described with reference to FIG.
  • the photosensitive transfer material in the present disclosure is not limited to the one having the structure shown in FIG.
  • FIG. 1 is a schematic cross-sectional view showing an example of the configuration of a photosensitive transfer material.
  • a temporary support 10 a thermoplastic resin layer 12, an intermediate layer 14, a photosensitive resin layer 16, and a cover film 18 are laminated in this order. It has a configuration. Further, the structure may not have the thermoplastic resin layer 12 and the intermediate layer 14 in FIG. 1, and for example, the temporary support 10, the photosensitive resin layer 16, and the cover film 18 are laminated in this order. It may be.
  • the thermoplastic resin layer 12 is formed by applying the thermoplastic resin composition to the surface of the temporary support 10 and then drying the coating film of the thermoplastic resin composition.
  • the step, the step of applying the intermediate layer composition to the surface of the thermoplastic resin layer 12 and then drying the coating film of the intermediate layer composition to form the intermediate layer 14, and the step of forming the intermediate layer 14 and the polymer A and the polymer A on the surface of the intermediate layer 14 This can be performed by a method including a step of applying the photosensitive resin composition containing the polymerizable compound B and then drying the coating film of the photosensitive resin composition to form the photosensitive resin layer 16.
  • thermoplastic resin composition containing at least one selected from the group consisting of an alkylene glycol ether solvent and an alkylene glycol ether acetate solvent, and a water- and water-mixable organic solvent.
  • a photosensitive resin containing at least one selected from the group consisting of an intermediate layer composition containing at least one of the above, polymer A, polymerizable compound B, and an alkylene glycol ether solvent and an alkylene glycol ether acetate solvent. It is preferable to use with the composition.
  • thermoplastic resin layer 12 and the intermediate layer 14 during the application of the intermediate layer composition to the surface of the thermoplastic resin layer 12 and / or the storage period of the laminate having the coating film of the intermediate layer composition.
  • the photosensitive transfer material 100 is manufactured by pressing the cover film 18 onto the photosensitive resin layer 16 of the laminate.
  • the method for producing the photosensitive transfer material includes a step of providing a cover film 18 so as to be in contact with the second surface of the photosensitive resin layer 16, so that the temporary support 10, the thermoplastic resin layer 12, the intermediate layer 14, and the photosensitive resin layer 16 are photosensitive. It is preferable to manufacture the photosensitive transfer material 100 including the sex resin layer 16 and the cover film 18.
  • the photosensitive transfer material 100 in the form of a roll may be produced and stored by winding the photosensitive transfer material 100.
  • the photosensitive transfer material in the form of a roll can be provided as it is in the process of bonding with a substrate in a roll-to-roll method described later.
  • the method for producing a resin pattern of the present disclosure is a step of laminating the above-described photosensitive transfer material of the present disclosure and a substrate to be transferred and arranging a photosensitive resin layer on the substrate to be transferred (hereinafter, ""
  • a step of pattern-exposing the photosensitive resin layer hereinafter, also referred to as “exposure step”
  • a step of developing the photosensitive resin layer to form a resin pattern hereinafter, also referred to as “exposure step”.
  • development process also includes a step of peeling and removing the resin pattern.
  • the method for manufacturing a circuit wiring of the present disclosure is a step of laminating the above-described photosensitive transfer material of the present disclosure and a substrate to be transferred having a conductive layer, and arranging a photosensitive resin layer on the substrate to be transferred.
  • bonding step also referred to as “bonding step”
  • exposure step a step of pattern-exposing the photosensitive resin layer
  • development step a step of developing the photosensitive resin layer to form a resin pattern.
  • development process it is also referred to as "development process”.
  • etching process the process of forming the circuit wiring by etching the conductive layer in the region where the resin pattern is not arranged.
  • a peeling step may be provided after any of the exposure step, the developing step, and the etching processing step.
  • the method for producing the resin pattern is not particularly limited as long as it is the method for producing the resin pattern using the above-mentioned photosensitive transfer material.
  • the photosensitive transfer material and the substrate to be transferred are placed on the second surface of the photosensitive resin layer, that is, on the side not facing the temporary support.
  • a method including the steps (development steps) to be performed in this order is preferable.
  • the method for manufacturing the circuit wiring is not particularly limited as long as it is the method for manufacturing the circuit wiring using the above-mentioned photosensitive transfer material.
  • a method for manufacturing circuit wiring no resin pattern is arranged in a laminate in which a substrate to be transferred, a conductive layer, and a resin pattern manufactured by using the above-mentioned photosensitive transfer material are laminated in this order.
  • a method including a step of etching the conductive layer in the region (hereinafter, also referred to as an “etching step”) is preferable, and a resin produced by a manufacturing method including the bonding step, the exposure step, and the developing step. It is more preferable to use a pattern.
  • the method for producing a resin pattern includes a bonding step.
  • the substrate to be transferred (or the conductive layer when the conductive layer is provided on the surface of the substrate to be transferred) is brought into contact with the second surface of the photosensitive resin layer, and the photosensitive transfer material and the substrate to be transferred are transferred. It is preferable to crimp with the base material.
  • an etching resist for etching the patterned photosensitive resin layer conductive layer after exposure and development can be suitably used as.
  • the cover film may be removed from the surface of the photosensitive resin layer and then bonded. Further, in the bonding step, a layer other than the cover film (for example, a high refractive index layer and / or a low refractive index layer) is further formed on the surface of the photosensitive resin layer on the side where the photosensitive transfer material does not face the temporary support. In this case, the surface of the photosensitive resin layer on the side that does not have the temporary support and the substrate to be transferred are bonded to each other via the layer.
  • a layer other than the cover film for example, a high refractive index layer and / or a low refractive index layer
  • the method of pressure-bonding the substrate to be transferred and the photosensitive transfer material is not particularly limited, and a known transfer method or laminating method can be used.
  • the photosensitive transfer material is bonded to the transfer base material by stacking the transfer base material on the second surface side of the photosensitive resin layer and applying pressure and heat using a means such as a roll.
  • a known laminator such as a laminator, a vacuum laminator, and an auto-cut laminator capable of further increasing productivity can be used.
  • the resin pattern manufacturing method and the circuit wiring manufacturing method including the bonding step are preferably performed by a roll-to-roll method.
  • the roll-to-roll method uses a substrate that can be wound and unwound as a substrate to be transferred, and is a substrate or a substrate before any of the steps included in the resin pattern manufacturing method or the circuit wiring manufacturing method.
  • the unwinding method in the unwinding step and the winding method in the winding step are not particularly limited, and a known method may be used in the manufacturing method to which the roll-to-roll method is applied.
  • a known substrate to be transferred may be used, but a substrate having a conductive layer is preferable, and a conductive layer is formed on the surface of the substrate. It is more preferable to have.
  • the substrate to be transferred may have any layer other than the conductive layer, if necessary.
  • Examples of the base material to be transferred include glass, silicon and a film.
  • the substrate to be transferred is preferably transparent. “Transparent” refers to a property in which the transmittance of light having a wavelength of 400 nm to 700 nm is 80% or more.
  • the refractive index of the substrate to be transferred is preferably 1.50 to 1.52.
  • the transparent glass base material examples include tempered glass represented by Corning's gorilla glass. Further, as the transparent glass substrate, the materials used in JP-A-2010-86684, JP-A-2010-152809 and JP-A-2010-257492 can be used.
  • a film base material When a film base material is used as the base material, it is preferable to use a film base material having low optical distortion and / or high transparency.
  • a film substrate examples include polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polycarbonate (PC), triacetyl cellulose (TAC), and cycloolefin polymer (COP).
  • a film is preferable as the base material to be transferred when it is manufactured by the roll-to-roll method.
  • the transfer base material is preferably a sheet-like resin composition.
  • Examples of the conductive layer contained in the substrate to be transferred include a conductive layer used for general circuit wiring or touch panel wiring.
  • a conductive layer used for general circuit wiring or touch panel wiring.
  • the conductive layer at least one selected from the group consisting of a metal layer, a conductive metal oxide layer, a graphene layer, a carbon nanotube layer, a metal nanofiber layer and a conductive polymer layer from the viewpoint of conductivity and fine wire forming property. Layer is preferable, a metal layer is more preferable, and a copper layer or a silver layer is further preferable.
  • the substrate to be transferred may have one conductive layer alone, or may have two or more conductive layers. When having two or more conductive layers, it is preferable to have conductive layers made of different materials.
  • Examples of the material of the conductive layer include metals and conductive metal oxides.
  • Examples of the metal include Al, Zn, Cu, Fe, Ni, Cr, Mo, Ag and Au.
  • Examples of the conductive metal oxide include ITO (Indium Tin Oxide), IZO (Indium Zinc Oxide) and SiO 2 .
  • conductivity means that the volume resistivity is less than 1 ⁇ 10 6 ⁇ cm.
  • the volume resistivity of the conductive metal oxide is preferably less than 1 ⁇ 10 4 ⁇ cm.
  • a resin pattern is produced using a substrate to be transferred having a plurality of conductive layers
  • the conductive layer an electrode pattern corresponding to a sensor of a visual recognition portion used in a capacitive touch panel or wiring of a peripheral extraction portion is preferable.
  • the method for producing a resin pattern includes a step (exposure step) of pattern-exposing the photosensitive resin layer after the bonding step.
  • the detailed arrangement and specific size of the pattern in the pattern exposure are not particularly limited. At least a part of the pattern (preferably) so as to improve the display quality of a display device (for example, a touch panel) including an input device having a circuit wiring manufactured by a circuit wiring manufacturing method and to reduce the area occupied by the take-out wiring.
  • the electrode pattern and / or the portion of the take-out wiring of the touch panel preferably includes a thin wire having a width of 20 ⁇ m or less, and more preferably contains a thin wire having a width of 10 ⁇ m or less.
  • the light source used for exposure can be appropriately selected and used as long as it is a light source that irradiates the photosensitive resin layer with light having a wavelength that allows exposure (for example, 365 nm or 405 nm).
  • a light source that irradiates the photosensitive resin layer with light having a wavelength that allows exposure for example, 365 nm or 405 nm.
  • Specific examples thereof include ultra-high pressure mercury lamps, high pressure mercury lamps, metal halide lamps and LEDs (Light Emitting Diodes).
  • the exposure amount is preferably 5 mJ / cm 2 to 200 mJ / cm 2, more preferably 10 mJ / cm 2 to 100 mJ / cm 2 .
  • the temporary support may be peeled off from the photosensitive resin layer and then the pattern exposure may be performed. Before the temporary support is peeled off, the temporary support is exposed to the pattern through the temporary support, and then the temporary support is peeled off. You may.
  • the mask When the temporary support is peeled off before the exposure, the mask may be exposed in contact with the photosensitive layer, or may be exposed in close proximity without contact.
  • the temporary support When the temporary support is exposed without being peeled off, the mask may be exposed in contact with the temporary support, or may be exposed in close proximity without contact. In order to prevent mask contamination due to contact between the photosensitive resin layer and the mask and to avoid the influence of foreign matter adhering to the mask on the exposure, it is preferable to perform pattern exposure without peeling off the temporary support.
  • the exposure method may be a contact exposure method in the case of contact exposure, a proximity exposure method in the case of a non-contact exposure method, a lens-based or mirror-based projection exposure method, or a direct exposure method using an exposure laser or the like. It can be selected and used.
  • an exposure machine having an appropriate numerical aperture (NA) of the lens can be used according to the required resolving power and depth of focus.
  • drawing may be performed directly on the photosensitive layer, or reduced projection exposure may be performed on the photosensitive layer via a lens. Further, the exposure may be performed not only in the atmosphere but also under reduced pressure or vacuum, or may be exposed by interposing a liquid such as water between the light source and the photosensitive layer.
  • the method for producing a resin pattern includes, after the above-mentioned exposure step, a step (development step) of developing the exposed photosensitive resin layer to form a resin pattern.
  • a step (development step) of developing the exposed photosensitive resin layer to form a resin pattern When the photosensitive transfer material has a thermoplastic resin and an intermediate layer, the thermoplastic resin layer and the intermediate layer in the non-exposed portion are also removed together with the photosensitive resin layer in the non-exposed portion in the developing step. Further, in the developing step, the thermoplastic resin layer and the intermediate layer of the exposed portion may also be removed in a form of being dissolved or dispersed in the developing solution.
  • the exposed photosensitive resin layer in the developing step can be developed by using a developing solution.
  • the developing solution is not particularly limited as long as the non-image portion (non-exposed portion) of the photosensitive resin layer can be removed.
  • a known developing solution such as the developing solution described in JP-A-5-72724 can be used. Can be used.
  • the developer may contain a water-soluble organic solvent and / or a surfactant.
  • the developing solution the developing solution described in paragraph 0194 of International Publication No. 2015/093271 is also preferable.
  • the development method is not particularly limited, and may be any of paddle development, shower development, shower and spin development, and dip development.
  • Shower development is a development process for removing a non-exposed portion by spraying a developing solution on the photosensitive resin layer after exposure by a shower. After the developing step, it is preferable to spray the cleaning agent with a shower and rub with a brush to remove the developing residue.
  • the temperature of the developing solution is not particularly limited, but is preferably 20 to 40 ° C.
  • the circuit wiring is manufactured by the transfer base material, the conductive layer, and the resin pattern (more preferably, the resin pattern manufactured by the manufacturing method including the bonding step, the exposure step, and the developing step).
  • the step (etching step) of etching the conductive layer in the region where the resin pattern is not arranged is included.
  • the resin pattern formed from the photosensitive resin layer is used as an etching resist, and the conductive layer is etched.
  • a method of etching treatment a known method can be applied. Examples thereof include a wet etching method of immersing in an etching solution and a method of dry etching such as plasma etching.
  • an acidic or alkaline etching solution may be appropriately selected according to the etching target.
  • the acidic etching solution include an aqueous solution of an acidic component alone selected from hydrochloric acid, sulfuric acid, nitric acid, acetic acid, hydrofluoric acid, oxalic acid and phosphoric acid, an acidic component, ferric chloride, ammonium fluoride and Examples thereof include a mixed aqueous solution with a salt selected from potassium permanganate.
  • the acidic component may be a component in which a plurality of acidic components are combined.
  • an aqueous solution of an alkaline component alone selected from sodium hydroxide, potassium hydroxide, ammonia, an organic amine, and a salt of an organic amine (tetramethylammonium hydroxide, etc.), and an alkaline component and a salt. Examples thereof include a mixed aqueous solution with (potassium permanganate, etc.).
  • the alkaline component may be a component in which a plurality of alkaline components are combined.
  • the method for manufacturing the circuit wiring of the present disclosure includes a step (peeling step) of peeling and removing the cured portion (resin pattern) remaining on the substrate to be transferred. Further, the method for producing a resin pattern of the present disclosure may include the above-mentioned peeling step.
  • the peeling step can be provided after the above-mentioned exposure step, development step and etching step.
  • the resin pattern formed through the above-mentioned exposure step, development step and etching step using the above-mentioned photosensitive transfer material of the present disclosure is peeled off, so that the peeled-off piece is in the apparatus. It becomes difficult to adhere to. As a result, the peeled pieces are less likely to accumulate in the apparatus, and it is possible to avoid clogging of pipes and the like and deterioration of the filtration function. In addition, reattachment to the manufactured wiring board can be suppressed.
  • a method of removing the resin pattern which is a cured portion remaining in the pattern there is a method of peeling and removing the resin pattern by chemical treatment.
  • a method of removing by peeling a method of removing by using a peeling liquid is preferable.
  • the liquid temperature is preferably 30 ° C. to 80 ° C. (more preferably 40 ° C. to 70 ° C.), and the stripping liquid being stirred has a resin pattern to be transferred. Examples thereof include a method of immersing the base material for 1 to 30 minutes.
  • an alkaline liquid (also referred to as an alkaline stripping liquid) can be used.
  • the alkaline solution include a stripping solution in which an inorganic alkaline component or an organic alkaline component is dissolved in water, dimethyl sulfoxide, N-methylpyrrolidone, or a mixed solution thereof.
  • the inorganic alkaline component include sodium hydroxide and potassium hydroxide.
  • the organic alkali component include a primary amine compound, a secondary amine compound, a tertiary amine compound, and a quaternary ammonium salt compound.
  • the resin pattern may be removed by a known method such as a spray method using a stripping solution, a shower method, or a paddle method, in addition to the above dipping method.
  • the circuit wiring manufacturing method may include an arbitrary step (other steps) other than the above-mentioned steps. For example, the following steps can be mentioned, but the steps are not limited to these steps. Further, examples of the exposure step, the developing step, and other steps applicable to the method for manufacturing the circuit wiring include the steps described in paragraphs 0035 to 0051 of JP-A-2006-23696.
  • the method for producing the resin pattern preferably includes a step of peeling the cover film from the photosensitive transfer material.
  • the method of peeling the cover film is not limited, and a known method can be applied.
  • the method for manufacturing the circuit wiring may include a step of reducing the visible light reflectance of a part or all of the plurality of conductive layers of the substrate to be transferred.
  • the treatment for reducing the visible light reflectance include an oxidation treatment.
  • the visible light reflectance of the conductive layer can be reduced by oxidizing copper to copper oxide and blackening the conductive layer.
  • the treatment for lowering the visible light reflectance is described in paragraphs 0017 to 0025 of JP2014-150118, and paragraphs 0041, 0042, 0048 and 0058 of JP2013-206315. , The contents of these gazettes are incorporated herein by reference.
  • the method for manufacturing the circuit wiring preferably includes a step of forming an insulating film on the surface of the circuit wiring and a step of forming a new conductive layer on the surface of the insulating film.
  • the step of forming the insulating film is not particularly limited, and examples thereof include a known method of forming a permanent film. Further, 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 manufacturing method uses a transfer base material having a plurality of conductive layers on both surfaces of the base material, and sequentially or simultaneously forms a circuit on the conductive layers formed on both surfaces of the transfer base material. It is also preferable to do so. 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 to be transferred and a second conductive pattern is formed on the other surface. Further, it is also preferable to form the circuit wiring for the touch panel having such a configuration from both sides of the substrate to be transferred by roll-to-roll.
  • the circuit wiring manufactured by the method of manufacturing the circuit wiring can be applied to various devices.
  • Examples of the device provided with the circuit wiring manufactured by the above manufacturing method include an input device, a touch panel is preferable, and a capacitance type touch panel is more preferable.
  • the input device can be applied to a display device such as an organic EL display device and a liquid crystal display device.
  • the method for manufacturing the touch panel is not particularly limited as long as it is the method for manufacturing the touch panel using the above-mentioned photosensitive transfer material.
  • a method for manufacturing a touch panel a region in which a resin pattern is not arranged in a laminate in which a substrate to be transferred, a conductive layer, and a resin pattern manufactured by using the above-mentioned photosensitive transfer material are laminated in this order.
  • a method including a step of forming wiring for a touch panel by etching a conductive layer in the above is preferable, and a resin pattern manufactured by a manufacturing method including the bonding step, the exposure step, and the developing step is formed. It is more preferable to use it.
  • each step in the touch panel manufacturing method and the embodiment such as the order in which each step is performed are as described in the above-mentioned "Circuit wiring manufacturing method", and the preferred embodiments are also the same.
  • the method for manufacturing the touch panel a known method for manufacturing the touch panel may be referred to except that the wiring for the touch panel is formed by the above method.
  • the touch panel manufacturing method may include any process (other process) other than those described above.
  • FIGS. 2 and 3 An example of a mask pattern used in manufacturing a touch panel is shown in FIGS. 2 and 3.
  • SL and G are non-image parts (light-shielding parts)
  • DL is a virtual representation of the alignment frame.
  • a touch panel in which a circuit wiring having a pattern A corresponding to SL and G is formed is manufactured. can. Specifically, it can be produced by the method shown in FIG. 1 of International Publication No. 2016/190405.
  • G is a portion where a transparent electrode (touch panel electrode) is formed
  • SL is a portion where wiring of a peripheral take-out portion is formed.
  • a touch panel having at least touch panel wiring is manufactured.
  • the touch panel preferably has a transparent substrate, electrodes, and an insulating layer or a protective layer.
  • Examples of the detection method on the touch panel include known methods such as a resistive film method, a capacitance method, an ultrasonic method, an electromagnetic induction method, and an optical method. Above all, the capacitance method is preferable.
  • the touch panel type includes a so-called in-cell type (for example, those shown in FIGS. 5, 6, 7, and 8 of Japanese Patent Application Laid-Open No. 2012-517501), and a so-called on-cell type (for example, Japanese Patent Application Laid-Open No. 2013-168125).
  • in-cell type for example, those shown in FIGS. 5, 6, 7, and 8 of Japanese Patent Application Laid-Open No. 2012-517501
  • on-cell type for example, Japanese Patent Application Laid-Open No. 2013-168125.
  • OGS One Glass Solution
  • TOR Touch-on-Lens
  • A-5 Kuraray Poval PVA-205 (Kuraray Co., Ltd.)
  • A-6 Polyvinylpyrrolidone K-30 (Nippon Shokubai Co., Ltd.)
  • B Polymerizable compound B-1: NK ester BPE-500 (Ethoxylated bisphenol A dimethacrylate (molecular weight 804), Shin Nakamura Chemical Industry Co., Ltd.)
  • C-1 B-CIM (2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetraphenyl-1,2'-biimidazole, black gold Kasei Co., Ltd.
  • C-2 SB-PI 701 (4,4'-bis (diethylamino) benzophenone, Sanyo Trading Co., Ltd.)
  • D Dyes and additives
  • D-1 Leuco crystal violet (Tokyo Chemical Industry Co., Ltd.)
  • D-2 N-Phenylglycine (Tokyo Chemical Industry Co., Ltd.)
  • D-3 Brilliant Green (Tokyo Chemical Industry Co., Ltd.)
  • D-4 CBT-1 (carboxybenzotriazole, Johoku Chemical Industry Co., Ltd.) 1: 1 (mass ratio) of D-5: 1- (2-di-n-butylaminomethyl) -5-carboxybenzotriazole and 1- (2-di-n-butylaminomethyl) -6-carboxybenzotriazole )
  • D-6 TDP-G (phenothiazine, Kawaguchi Chemical Industry Co., Ltd .; polymerization inhibitor)
  • D-7 Irganox245 (BASF; Antioxidant)
  • D-8 N-nitrosophenylhydroxylamine aluminum salt (Fujifilm Wako Pure Chemical Industries, Ltd .; polymer
  • F Solvent
  • F-1 Methyl ethyl ketone (Sankyo Chemical Co., Ltd.)
  • F-2 Propylene glycol monomethyl ether acetate (Showa Denko KK)
  • F-3 Ion-exchanged water
  • F-4 Methanol (Mitsubishi Gas Chemical Company, Inc.)
  • Example 1-1 First, an example corresponding to the invention according to the first aspect described above will be shown.
  • thermoplastic resin composition The following components were mixed to prepare a thermoplastic resin composition.
  • -A-4 42.85 parts by mass-B-9: 4.63 parts by mass-B-10: 2.31 parts by mass-B-11: 0.77 parts by mass-E-1: 0.03 parts by mass ⁇ F-1: 39.50 parts by mass ⁇ F-2: 9.51 parts by mass
  • a compound having the following structure (a photoacid generator, a compound synthesized according to the method described in paragraph 0227 of JP2013-47765A): 0.32 parts by mass.
  • thermoplastic resin composition was applied to the surface of the temporary support so that the coating width was 1.0 m and the thickness after drying was 4.0 ⁇ m.
  • the coating film of the thermoplastic resin composition was dried at 80 ° C. for 40 seconds to form a thermoplastic resin layer.
  • the above intermediate layer composition was applied to the surface of the thermoplastic resin layer so that the coating width was 1.0 m and the layer thickness after drying was 1.2 ⁇ m.
  • the coating film of the intermediate layer composition was dried at 80 ° C. for 40 seconds to form an intermediate layer.
  • the photosensitive resin composition 1-1 was applied to the surface of the intermediate layer so that the coating width was 1.0 m and the layer thickness after drying was 3.0 ⁇ m.
  • the coating film of the photosensitive resin composition 1-1 was dried at 80 ° C. for 40 seconds to form a photosensitive resin layer.
  • a PET film Limirror 16KS40, Toray Industries, Inc.
  • a 15-step step wedge (manufactured by FUJIFILM Corporation) is placed on the temporary support of the photosensitive transfer material 1-1 bonded on the substrate with a copper layer, and the illuminance is 20 mW / cm 2 .
  • the photosensitive resin layer was irradiated with ultraviolet rays (UV) at an exposure amount of 180 mJ / cm 2 via a 15-step step wedge with a high-pressure mercury lamp. After irradiation, the temporary support was peeled off and developed in a 0.9% by mass aqueous solution of sodium carbonate at 25 ° C. for 30 seconds.
  • UV ultraviolet rays
  • the thickness (residual film thickness) of the cured layer in the region corresponding to each step was measured, and the number of step steps in which the residual film thickness was in the range of ⁇ 1% of the thickness of the photosensitive resin layer before development was determined.
  • the exposure amount corresponding to the determined number of step steps was defined as Eb.
  • the Eb in Example 1-1 was 46 mJ / cm 2 .
  • the entire surface was irradiated with UV light by the high-pressure mercury lamp of No. 2.
  • the temporary support was peeled off from the photosensitive transfer material 1-1 after irradiation, and 10 ⁇ L of a 10% by mass aqueous solution of monoethanolamine at 50 ° C. was added dropwise to the surface of the exposed cured layer after exposure.
  • the droplets were removed at the time when 10 seconds had passed since the drop of the monoethanolamine 10% by mass aqueous solution and at the time when 20 seconds had passed since the drop of the monoethanolamine 10% by mass aqueous solution, and at the time when 10 seconds had passed.
  • the temporary support is peeled off from the photosensitive transfer material 1-1 after irradiation, and the peeled laminate (layer of cured layer / intermediate layer / thermoplastic resin layer) is stirred together with the base material with a copper layer 50.
  • the laminate was peeled off from the base material with a copper layer by immersing it in a 10% by mass aqueous solution of monoethanolamine at ° C. Then, a peeling liquid containing the peeled strip was poured onto a SUS screen (Manabe Kogyo Co., Ltd.) of 150 mesh / 18B wire, and the stripped piece was filtered off. By repeating this operation, the peeled pieces were deposited until the amount of the peeled pieces was 1.0 g per square centimeter of the SUS mesh. Then, by turning the SUS screen upside down by 180 °, the deposit surface side of the filter medium of the SUS screen was directed vertically downward, and the weight of the peeled pieces that naturally fell from the SUS screen was measured.
  • SUS screen Manabe Kogyo Co., Ltd.
  • the adhesion rate of the peeled pieces was calculated from the following formula.
  • the adhesion rate is the ratio of the amount of the peeled pieces remaining on the SUS screen without falling to the amount of the peeled pieces deposited before the front and back inversion.
  • Adhesion rate of peeled pieces (%) (1-W f / W t ) x 100 W f : Mass of the peeled piece that fell W t : Total mass of the separated peeled piece
  • the adhesiveness of the peeled piece was evaluated according to the following evaluation criteria from the value of the adhesion rate. The evaluation was performed in four stages of A (excellent)>B>C> D (inferior).
  • the adhesion rate is B or higher. It can be evaluated that the smaller the value of the adhesion rate, the less likely it is that the peeled pieces are deposited on the apparatus for peeling the cured layer, and the higher the process suitability as a photosensitive transfer material.
  • the photosensitive transfer material 1-1 after irradiation was cut into 10 cm squares, and the temporary support was peeled off to obtain a test piece.
  • the test piece is immersed in 1 liter of a stirring 50 ° C. monoethanolamine 10% by mass aqueous solution, and the laminate is completely peeled off from the copper layered substrate from the time of immersion (start of immersion) (peeling completed).
  • Time to time was measured. Separately, 1 liter of a 10% by mass aqueous solution of monoethanolamine at 50 ° C. was replaced with 1 liter of a 10% by mass aqueous solution of monoethanolamine at 25 ° C., and the same measurement was performed.
  • Example 1-1 the photosensitive resin composition 1-1 is selected from the photosensitive resin compositions 1-2 to 1-11 and the photosensitive resin compositions A to C shown in Tables 1 and 2 below.
  • Photosensitive transfer materials 1-2 to 1-11 and photosensitive transfer materials A to C were prepared in the same manner as in Example 1-1 except that the layer thickness of the photosensitive resin layer was changed instead of any of them. Then, the same measurement and evaluation were performed. The measurement and evaluation results are shown in Tables 1 and 2 below.
  • the photosensitive transfer materials produced in the examples had a small amount of swelling at the time of peeling, and the adhesiveness to the peeled pieces was also reduced. Therefore, it is considered that the photosensitive transfer material of the example exhibits good process suitability when the resin pattern formed through exposure and development is peeled off.
  • the amount of swelling at the time of peeling was larger than in each of the examples, and the peeled pieces were more likely to adhere.
  • Example 2 The photosensitive transfer material 2-1 prepared in Example 2-1 was used, and measurement and evaluation were carried out in the same manner as in Example 1-1. The results of measurement and evaluation are shown in Table 3.
  • the Eb in Example 2-1 was 58 mJ / cm 2 .
  • the photosensitive transfer material 2-1 after irradiation was cut into 5 cm squares, and the temporary support was peeled off to obtain a test piece.
  • the test piece was held horizontally and immersed in a 10% by mass aqueous solution of monoethanolamine at 25 ° C. without stirring.
  • the test piece was allowed to stand in this state, and the peeled form of the test piece and the time from the time of immersion (start of immersion) to the complete peeling of the laminate from
  • Example 2-1 the photosensitive resin composition 2-1 is replaced with any one selected from the photosensitive resin compositions 2-2 to 2-6 shown in Table 3 below, and the layer thickness of the photosensitive resin layer is changed.
  • Photosensitive transfer materials 2-2 to 2-6 were prepared in the same manner as in Example 2-1 except that the above was changed, and the same measurement and evaluation were performed. The results of measurement and evaluation are shown in Table 3 below. The details of Comparative Examples 1 to 3 are as described above.
  • the laminate was autonomously peeled off from the base material with the copper layer. No curl of the peeled piece was observed.
  • the time required for the laminate to autonomously complete the peeling from the base material with the copper layer was 320 seconds.
  • Table 3 in each of the photosensitive transfer materials prepared in Examples 2-2 to 2-6, the peeled pieces were curled, and the peeled pieces were autonomously peeled as small pieces. Was done. Therefore, it is considered that the photosensitive transfer material of the example exhibits good process suitability when the resin pattern formed through exposure and development is peeled off.
  • Comparative Examples 1 to 3 no independent peeling was observed as compared with each of the Examples.
  • Example 3 The photosensitive transfer material 3-1 prepared in Example 3-1 was used, and measurement and evaluation were carried out in the same manner as in Example 1-1. The results of measurement and evaluation are shown in Table 4.
  • the Eb in Example 3-1 was 46 mJ / cm 2 .
  • Example 3-1 the photosensitive resin composition 3-1 was replaced with any one selected from the photosensitive resin compositions 3-2 to 3-6 shown in Table 4 below, and the layer thickness of the photosensitive resin layer was changed.
  • Photosensitive transfer materials 3-2 to 3-6 were prepared in the same manner as in Example 3-1 except that the above was changed, and the same measurement and evaluation were performed. The results of measurement and evaluation are shown in Table 4 below. The details of Comparative Examples 1 to 3 are as described above.
  • the peeling time (t fa ) when the photosensitive transfer material 3-1 was peeled off with the fatigue liquid was 15 seconds. Further, the t fa when the fatigue liquid was used was less than 1.5 t fr when the unused liquid was used.
  • the photosensitive transfer material produced in the examples does not significantly change the peelability even when the peeling liquid is CO 2 fatigued and the basicity is lowered, and the peeling piece adhesion is reduced. It had been. Therefore, it is considered that the photosensitive transfer material of the example exhibits good process suitability when the resin pattern formed through exposure and development is peeled off.
  • Comparative Examples 1 to 3 the peelability when the stripping liquid was CO 2 fatigued was inferior to that of each Example, and the amount of swelling at the time of stripping tended to be large. Therefore, the peeled pieces tend to adhere.
  • the photosensitive transfer material of the example is at the time of peeling.
  • the amount of swelling was suppressed to a small level, autonomous peeling from the base material with a copper layer was observed, and the adhesiveness of the peeled pieces was reduced.
  • the photosensitive transfer material of the example has a copper layer. Autonomous peeling from the base material was observed, and the peelability did not change significantly even with the fatigue stripping solution with reduced basicity, and the peeling piece adhesion was reduced.
  • the photosensitive transfer material of Example has a small amount of swelling at the time of peeling, and the peelability does not change significantly even with a fatigue stripping solution having reduced basicity, and stripping is performed. One-sided adhesion was reduced.
  • the photosensitive transfer material of Example is at the time of peeling. The amount of swelling is suppressed to a small level, autonomous peeling from the base material with a copper layer is observed, and the peelability does not change significantly even with a fatigue stripping solution with reduced basicity, and the peeling piece adhesion is good. It was reduced.
  • the photosensitive transfer material of the present disclosure can be suitably used for various applications requiring precision microfabrication by photolithography.
  • the photosensitive resin layer may be used as a coating for etching, or electroforming may be performed mainly by electroplating.
  • the cured film obtained by patterning the photosensitive resin layer may be used as a permanent film, or may be used as, for example, an interlayer insulating film, a wiring protective film, a wiring protective film having an index matching layer, or the like. good.
  • the photosensitive transfer material of the present disclosure is used for various wiring formation of semiconductor packages, printed circuit boards, sensor substrates; touch panels, electromagnetic wave shielding materials, conductive films such as film heaters, liquid crystal sealing materials, micromachine fields or microelectronics fields. It can be suitably used for applications such as the formation of a structure in.

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PCT/JP2020/048993 2020-03-30 2020-12-25 感光性転写材料、樹脂パターンの製造方法、及び回路配線の製造方法 WO2021199542A1 (ja)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2024070650A1 (ja) * 2022-09-30 2024-04-04 富士フイルム株式会社 多層メタサーフェス構造体の製造方法および多層メタサーフェス構造体

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002357901A (ja) * 2001-05-31 2002-12-13 Fuji Photo Film Co Ltd 感光性樹脂組成物、転写材料、及び画像形成方法
JP2008058636A (ja) * 2006-08-31 2008-03-13 Fujifilm Corp パターン形成材料及びパターン形成方法
WO2020031958A1 (ja) * 2018-08-09 2020-02-13 東レ株式会社 感光性樹脂組成物、感光性シート、ならびにそれらの硬化膜およびその製造方法、電子部品

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4515123B2 (ja) * 2004-03-18 2010-07-28 旭化成イーマテリアルズ株式会社 感光性樹脂積層体及びその用途
JP5875345B2 (ja) * 2011-11-28 2016-03-02 ニッコー・マテリアルズ株式会社 ソルダーレジスト用感光性樹脂組成物、及びこれを用いたソルダーレジスト用フォトレジストフィルム
US10338468B2 (en) * 2014-09-24 2019-07-02 Asahi Kasei Kabushiki Kaisha Photosensitive resin composition, photosensitive resin laminate, resin pattern production method, cured film, and display device
JP6782417B2 (ja) * 2015-07-29 2020-11-11 昭和電工マテリアルズ株式会社 感光性樹脂組成物、感光性エレメント、レジストパターンの形成方法及びプリント配線板の製造方法

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002357901A (ja) * 2001-05-31 2002-12-13 Fuji Photo Film Co Ltd 感光性樹脂組成物、転写材料、及び画像形成方法
JP2008058636A (ja) * 2006-08-31 2008-03-13 Fujifilm Corp パターン形成材料及びパターン形成方法
WO2020031958A1 (ja) * 2018-08-09 2020-02-13 東レ株式会社 感光性樹脂組成物、感光性シート、ならびにそれらの硬化膜およびその製造方法、電子部品

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2024070650A1 (ja) * 2022-09-30 2024-04-04 富士フイルム株式会社 多層メタサーフェス構造体の製造方法および多層メタサーフェス構造体

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