WO2022163301A1 - Matériau de transfert photosensible, procédé de fabrication de motif de résine, procédé de fabrication de câblage de circuit, et procédé de fabrication de panneau tactile - Google Patents

Matériau de transfert photosensible, procédé de fabrication de motif de résine, procédé de fabrication de câblage de circuit, et procédé de fabrication de panneau tactile Download PDF

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Publication number
WO2022163301A1
WO2022163301A1 PCT/JP2021/048963 JP2021048963W WO2022163301A1 WO 2022163301 A1 WO2022163301 A1 WO 2022163301A1 JP 2021048963 W JP2021048963 W JP 2021048963W WO 2022163301 A1 WO2022163301 A1 WO 2022163301A1
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Prior art keywords
resin layer
mass
photosensitive resin
meth
photosensitive
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PCT/JP2021/048963
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English (en)
Japanese (ja)
Inventor
隆志 有冨
浩二 新田
英宏 望月
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富士フイルム株式会社
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Priority to CN202180091894.8A priority Critical patent/CN116745697A/zh
Priority to JP2022578198A priority patent/JPWO2022163301A1/ja
Publication of WO2022163301A1 publication Critical patent/WO2022163301A1/fr

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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G03F7/031—Organic compounds not covered by group G03F7/029
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/20—Exposure; Apparatus therefor
    • G—PHYSICS
    • G06—COMPUTING; CALCULATING OR COUNTING
    • G06F—ELECTRIC DIGITAL DATA PROCESSING
    • G06F3/00—Input arrangements for transferring data to be processed into a form capable of being handled by the computer; Output arrangements for transferring data from processing unit to output unit, e.g. interface arrangements
    • G06F3/01—Input arrangements or combined input and output arrangements for interaction between user and computer
    • G06F3/03—Arrangements for converting the position or the displacement of a member into a coded form
    • G06F3/041—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means

Definitions

  • the present disclosure relates to a photosensitive transfer material, a resin pattern manufacturing method, a circuit wiring manufacturing method, and a touch panel manufacturing method.
  • a display device with a touch panel such as a capacitive input device (organic electroluminescence (EL) display device, liquid crystal display device, etc.)
  • the electrode pattern corresponding to the sensor in the visible part the wiring of the peripheral wiring part and the lead-out wiring part
  • a conductive layer pattern such as is provided inside the touch panel.
  • the formation of a patterned layer requires a small number of steps to obtain the required pattern shape.
  • a method of developing after exposure through a mask having a desired pattern is widely used.
  • JP-A-2001-356493 As a conventional photosensitive resin composition, one described in JP-A-2001-356493 is known.
  • JP-A-2001-356493 after proceeding with the exposure curing reaction so that the reaction rate of the ethylenically unsaturated compound contained as a photosensitive component on the exposed surface is 70%, when stored in a dark place, substantially describes a photosensitive resin composition characterized in that the reaction rate of unsaturated compounds in the entire plate does not change, and the difference in local reaction rate between the exposed surface and the non-exposed surface is maintained at 20% or more even after 24 hours. It is
  • a problem to be solved by an embodiment of the present disclosure is to provide a photosensitive transfer material in which the variation in line width in the resulting resin pattern is small.
  • Another problem to be solved by another embodiment of the present disclosure is to provide a resin pattern manufacturing method, a circuit wiring manufacturing method, and a touch panel manufacturing method using the photosensitive transfer material.
  • Means for solving the above problems include the following aspects.
  • a temporary support, an alkali-soluble resin, an ethylenically unsaturated compound, and a photosensitive resin layer containing a photopolymerization initiator, and the photosensitive resin layer is measured in units of mJ/cm 2
  • the line and space pattern of 10 ⁇ m / 10 ⁇ m at Ep - 10% A photosensitive transfer material having a double bond reactive region width difference (W+) ⁇ (W ⁇ ) of 1.45 ⁇ m or less when the double bond reactive region width W ⁇ after exposure at an exposure dose is defined as W ⁇ .
  • Each of W+ and W ⁇ cuts the exposed photosensitive transfer material to form a cross section, exposes the sample having the cross section to a staining agent, forms a stained cross section, and electrons the sample having the stained cross section. It is a value calculated from an image obtained by colliding a beam, detecting backscattered electrons, and from the backscattered electrons.
  • the exposure amount indicate the step number that gives the thickness.
  • the ethylenically unsaturated compound contains an ethylenically unsaturated compound having a bisphenol structure.
  • the photopolymerization initiator contains a biimidazole compound and a benzophenone compound.
  • ⁇ 5> The photosensitive transfer material according to ⁇ 4>, wherein the polymerization inhibitor contains at least one compound selected from the group consisting of phenothiazine, phenoxazine, and compounds having a hindered phenol structure.
  • ⁇ 6> The photosensitive transfer material according to any one of ⁇ 1> to ⁇ 5>, wherein the double bond reactive region width difference (W+) ⁇ (W ⁇ ) is 1.20 ⁇ m or less.
  • ⁇ 7> The photosensitive transfer material according to any one of ⁇ 1> to ⁇ 6>, wherein the double bond reactive region width difference (W+) ⁇ (W ⁇ ) is 1.00 ⁇ m or less.
  • ⁇ 8> The photosensitive transfer material according to any one of ⁇ 1> to ⁇ 7>, wherein the Eb value is 35 mJ/cm 2 to 100 mJ/cm 2 .
  • the outermost layer on the side having the photosensitive resin layer with respect to the temporary support is brought into contact with the substrate and bonded together. a step of exposing the photosensitive resin layer in a pattern; and a step of developing the exposed photosensitive resin layer to form a resin pattern, in this order.
  • ⁇ 10> The resin pattern according to ⁇ 9>, wherein at least part of the resin pattern includes a line-and-space pattern, and the total width of at least one pair of lines and spaces in the line-and-space pattern is 20 ⁇ m or less.
  • Production method. ⁇ 11> In the photosensitive transfer material according to any one of ⁇ 1> to ⁇ 8>, the outermost layer on the side having the photosensitive resin layer with respect to the temporary support is brought into contact with a substrate having a conductive layer. exposing the photosensitive resin layer to pattern exposure; developing the exposed photosensitive resin layer to form a resin pattern; A circuit wiring manufacturing method comprising, in this order, the step of etching the substrate.
  • the outermost layer on the side having the photosensitive resin layer with respect to the temporary support is brought into contact with a substrate having a conductive layer.
  • a touch panel manufacturing method comprising, in this order, the step of etching the substrate.
  • a photosensitive transfer material with small line width variations in the resulting resin pattern. Further, according to another embodiment of the present disclosure, it is possible to provide a resin pattern manufacturing method, a circuit wiring manufacturing method, and a touch panel manufacturing method using the photosensitive transfer material.
  • FIG. 1 is a schematic diagram showing an example of the configuration of the photosensitive transfer material of the first embodiment.
  • FIG. 2 is a schematic diagram showing an example of the configuration of the photosensitive transfer material of the second embodiment.
  • FIG. 3 is a schematic plan view showing pattern A.
  • FIG. 4 is a schematic plan view showing Pattern B.
  • FIG. 1 is a schematic diagram showing an example of the configuration of the photosensitive transfer material of the first embodiment.
  • FIG. 2 is a schematic diagram showing an example of the configuration of the photosensitive transfer material of the second embodiment.
  • FIG. 3 is a schematic plan view showing pattern A.
  • FIG. FIG. 4 is a schematic plan view showing Pattern B.
  • symbol may be abbreviate
  • a numerical range represented by “to” means a range including the numerical values before and after "to” as lower and upper limits.
  • (meth)acryl represents both or either acrylic and methacrylic
  • (meth)acrylate represents both or either acrylate and methacrylate
  • (meth) ) acryloyl refers to either or both acryloyl and methacryloyl.
  • the amount of each component in the composition refers to the sum of the corresponding substances present in the composition when there are multiple substances corresponding to each component in the composition, unless otherwise specified. means quantity.
  • the term "process” includes not only independent processes but also processes that cannot be clearly distinguished from other processes as long as the intended purpose of the process is achieved.
  • a description that does not describe substitution or unsubstituted includes not only those having no substituents but also those having substituents.
  • alkyl group includes not only alkyl groups having no substituents (unsubstituted alkyl groups) but also alkyl groups having substituents (substituted alkyl groups).
  • exposure includes not only exposure using light but also drawing using particle beams such as electron beams and ion beams, unless otherwise specified.
  • the light used for exposure generally includes the emission line spectrum of a mercury lamp, far ultraviolet rays represented by excimer lasers, extreme ultraviolet rays (EUV light), X-rays, and active rays (active energy rays) such as electron beams. mentioned.
  • chemical structural formulas in this specification may be described as simplified structural formulas in which hydrogen atoms are omitted.
  • “% by mass” and “% by weight” are synonymous, and “parts by mass” and “parts by weight” are synonymous.
  • the weight average molecular weight (Mw) and number average molecular weight (Mn) in the present disclosure use columns of TSKgel GMHxL, TSKgel G4000HxL, and TSKgel G2000HxL (all trade names manufactured by Tosoh Corporation). It is a molecular weight converted using polystyrene as a standard substance detected with a solvent THF (tetrahydrofuran) and a differential refractometer using a gel permeation chromatography (GPC) analyzer.
  • THF tetrahydrofuran
  • total solid content refers to the total mass of components excluding the solvent from the total composition of the composition.
  • solid content is the component excluding the solvent, and may be solid or liquid at 25° C., for example.
  • the photosensitive transfer material according to the present disclosure has a temporary support and a photosensitive resin layer containing an alkali-soluble resin, an ethylenically unsaturated compound, and a photopolymerization initiator, and the photosensitive resin layer is The double bond reaction region width W+ and the line and space of 10 ⁇ m/10 ⁇ m after exposing the line and space pattern of 10 ⁇ m/10 ⁇ m at an exposure dose of Ep + 10% with respect to the exposure dose Ep in units of /cm 2
  • the value of the double bond reaction region width difference (W+)-(W-) is 1.45 ⁇ m or less when the double bond reaction region width W- after the pattern is exposed at an exposure dose of Ep-10%. is.
  • Each of W+ and W ⁇ cuts the exposed photosensitive transfer material to form a cross section, exposes the sample having the cross section to a staining agent, forms a stained cross section, and electrons the sample having the stained cross section. It is a value calculated from an image obtained by colliding a beam, detecting backscattered electrons, and from the backscattered electrons.
  • width difference (W+) ⁇ (W ⁇ ) is 1.45 ⁇ m or less
  • the photosensitive resin layer in which the width of the double bond reaction region changes little due to the difference (variation) in the amount of exposure as described above is , the reaction is sufficiently suppressed in the half-exposed portion at the edge of the exposed region, and the difference between the degree of polymerization reactivity in the exposed region and the degree of polymerization reactivity in the unexposed region is large. Therefore, even if there are some fluctuations in the exposure conditions, dissolution of the region where the polymerization reaction is sufficiently progressing is suppressed during development, and the shape of the obtained resin pattern is stabilized. It is presumed that the width variation is suppressed (also referred to as “line width variation suppression property”).
  • the elapsed time from the completion of exposure to the development of each photosensitive resin layer when exposing a photosensitive resin layer bonded to a substrate having a conductive layer, the elapsed time from the completion of exposure to the development of each photosensitive resin layer. difference, which in some cases can be of the order of several hours.
  • the exposed photosensitive resin layer may be left for a certain period of time without being developed immediately, and in this case, the elapsed time from the completion of exposure is further extended.
  • the post-exposure lay-off time as described above tends to be long, particularly in the case of a roll-to-roll process, because it takes time to transport the roll from the unwinding portion to the core portion. Since the photosensitive transfer material according to the present disclosure is in the above aspect, the change in line width of the resin pattern over time after exposure (also referred to as “change in line width during drawing time”) is small.
  • the resolution and the cross-sectional shape of the resin pattern are also excellent.
  • the photosensitive transfer material according to the present disclosure is obtained by exposing the photosensitive resin layer to a line and space pattern of 10 ⁇ m / 10 ⁇ m with an exposure amount of Ep + 10% with respect to the exposure amount Ep in mJ / cm 2 and the double bond reaction region width W ⁇ after exposing a line and space pattern of 10 ⁇ m/10 ⁇ m with an exposure dose of Ep ⁇ 10%.
  • the value of width difference (W+)-(W-) is 1.45 ⁇ m or less.
  • the value of the double bond reaction region width difference (W+)-(W-) should be 1.30 ⁇ m or less from the viewpoints of line width variation suppressing property, line width change over time, and cross-sectional shape of the resin pattern. , more preferably 1.20 ⁇ m or less, even more preferably 1.00 ⁇ m or less, particularly preferably 0.75 ⁇ m or less, and most preferably 0.50 ⁇ m or less.
  • a method for measuring Eb and a method for calculating Ep in the present disclosure are shown below.
  • the protective film is peeled off from the photosensitive transfer material, and the peeled photosensitive transfer material is laminated on a substrate (100 ⁇ m PET film coated with a 300 nm thick copper layer by sputtering) with a sheet laminator.
  • the lamination conditions are a roll temperature of 110° C., a lamination speed of 3 m/min, and a lamination pressure of 0.5 MPa.
  • a 15-stage step wedge manufactured by Fuji Film Co., Ltd. was placed on the temporary support of the laminated photosensitive transfer material, and exposure was performed at 180 mJ/cm 2 with a high pressure mercury lamp of 20 mW/cm 2 .
  • a photosensitive transfer material exposed to a line and space pattern of 10 ⁇ m/10 ⁇ m at an exposure amount of Ep+10% or Ep ⁇ 10% with respect to the exposure amount Ep in units of mJ/cm 2 calculated by the above method is cut.
  • a cross section of the sample having the above cross section is formed, vapor phase dyeing is performed for 1 hour with a staining agent using a 2% OsO 4 aqueous solution, and carbon deposition is performed on the sample having the above dye cross section to impart conductivity.
  • a backscattered electron image is obtained at an accelerating voltage of 5 kV, and the image contrast difference obtained from the backscattered electrons is W + (unit: ⁇ m). and W- (unit: ⁇ m) are calculated respectively. Also, the value of (W+)-(W-) (unit: ⁇ m) is calculated. If the exposure boundary is unclear, image analysis software such as Image J is used to calculate the above value using the position where the contrast change is maximum as the boundary.
  • the value of Eb in the photosensitive transfer material according to the present disclosure is 20 mJ/cm 2 to 200 mJ/cm 2 from the viewpoints of line width variation suppressing property, line width change over time, cross-sectional shape of the resin pattern, and sensitivity. is preferably 30 mJ/cm 2 to 150 mJ/cm 2 , more preferably 35 mJ/cm 2 to 100 mJ/cm 2 , and preferably 35 mJ/cm 2 to 70 mJ/cm 2 Especially preferred.
  • a preferable numerical range of the value of Ep is a value obtained by multiplying the preferable numerical range of the value of Eb by 1.4.
  • the value of W+ in the photosensitive transfer material according to the present disclosure is preferably 9.80 ⁇ m to 11.00 ⁇ m from the viewpoint of the line width variation suppressing property, line width change over time, and the cross-sectional shape of the resin pattern. , more preferably 9.90 ⁇ m to 10.70 ⁇ m, still more preferably 10.00 ⁇ m to 10.60 ⁇ m, particularly preferably 10.00 ⁇ m to 10.50 ⁇ m, 10.00 ⁇ m to 10.40 ⁇ m is most preferred.
  • the value of W- in the photosensitive transfer material according to the present disclosure is 9.00 ⁇ m to 10.20 ⁇ m from the viewpoint of the line width variation suppressing property, the line width change during the holding time, and the cross-sectional shape of the resin pattern. is preferably 9.30 ⁇ m to 10.10 ⁇ m, more preferably 9.40 ⁇ m to 10.00 ⁇ m, particularly preferably 9.50 ⁇ m to 10.00 ⁇ m, and 9.70 ⁇ m to Most preferably it is 10.00 ⁇ m.
  • the photosensitive transfer material according to the present disclosure should be capable of resolving a 10 ⁇ m/10 ⁇ m line-and-space pattern. It is preferably resolvable, more preferably capable of resolving a 5 ⁇ m/5 ⁇ m line and space pattern, and preferably capable of resolving a 4 ⁇ m/4 ⁇ m line and space pattern. Especially preferred.
  • a photosensitive transfer material has a temporary support and a photosensitive resin layer containing an alkali-soluble resin, an ethylenically unsaturated compound, and a photopolymerization initiator.
  • the temporary support and the photosensitive resin layer may be directly laminated with no other layer interposed therebetween, or may be laminated with another layer interposed therebetween.
  • Another layer may be laminated on the surface of the photosensitive resin layer opposite to the surface facing the temporary support.
  • Layers other than the temporary support and the photosensitive resin layer include, for example, a thermoplastic resin layer, a water-soluble resin layer and a protective film.
  • the photosensitive transfer material according to the present disclosure is shown below.
  • the photosensitive resin layer is preferably a negative photosensitive resin layer. It is also preferable that the photosensitive resin layer is a colored resin layer.
  • the photosensitive transfer material according to the present disclosure may be used as a photosensitive transfer material for a wiring protective film as described later, or may be used as a photosensitive transfer material for an etching resist.
  • the configuration of the photosensitive transfer material is preferably the configuration (1) or (2) described above, for example.
  • the configuration of the photosensitive transfer material is preferably, for example, the configurations (2) to (4) described above.
  • the photosensitive transfer material in the case of a configuration in which another layer is further provided on the side opposite to the temporary support side of the photosensitive resin layer, the sum of the other layers arranged on the side opposite to the temporary support side of the photosensitive resin layer.
  • the thickness is preferably 0.1% to 30%, more preferably 0.1% to 20%, of the layer thickness of the photosensitive resin layer.
  • the photosensitive transfer material according to the present disclosure will be described below with an example of a specific embodiment.
  • the photosensitive transfer material of the first embodiment below has a configuration that can be suitably used as a photosensitive transfer material for etching resist, and the photosensitive transfer material of the second embodiment below is a photosensitive transfer material for a wiring protective film. This configuration is suitable for use in transfer materials.
  • the photosensitive transfer material 20 shown in FIG. have in order.
  • the photosensitive transfer material 20 shown in FIG. 1 has a form in which the protective film 19 is arranged, the protective film 19 may not be arranged.
  • the photosensitive transfer material 20 shown in FIG. 1 has a form in which the thermoplastic resin layer 13 and the water-soluble resin layer 15 are arranged, but the thermoplastic resin layer 13 and the water-soluble resin layer 15 may not be arranged.
  • Each element constituting the photosensitive transfer material of the first embodiment will be described below.
  • the photosensitive transfer material used in the present disclosure has a temporary support.
  • the temporary support is a support that supports a photosensitive resin layer or a laminate containing a photosensitive resin layer and that can be peeled off.
  • the temporary support preferably has light transmittance from the viewpoint that the photosensitive resin layer can be exposed through the temporary support when the photosensitive resin layer is pattern-exposed.
  • “having light transmittance” means having a transmittance of 50% or more for light having a wavelength used for pattern exposure.
  • the temporary support preferably has a light transmittance of 60% or more, more preferably 70% or more, at a wavelength (more preferably a wavelength of 365 nm) used for pattern exposure. is more preferable.
  • the transmittance of a layer included in a photosensitive transfer material is defined as the intensity of the light emitted through the layer relative to the intensity of the incident light when the light is incident in the direction perpendicular to the main surface of the layer (thickness direction). It is the ratio of the intensity of incident light, and is measured using MCPD Series manufactured by Otsuka Electronics Co., Ltd.
  • Materials constituting the temporary support include, for example, a glass substrate, a resin film, and paper, and a resin film is preferable from the viewpoint of strength, flexibility, and light transmittance.
  • Resin films include polyethylene terephthalate (PET) films, cellulose triacetate films, polystyrene films and polycarbonate films. Among them, a PET film is preferable, and a biaxially stretched PET film is more preferable.
  • the thickness (layer thickness) of the temporary support is not particularly limited, and the strength as a support, the flexibility required for bonding with the substrate for forming circuit wiring, and the light required in the first exposure step From the viewpoint of permeability, the material 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, still more preferably in the range of 10 ⁇ m to 20 ⁇ m, even more preferably in the range of 10 ⁇ m to 16 ⁇ m, from the viewpoint of ease of handling and versatility. Especially preferred.
  • the thickness of the temporary support is preferably 50 ⁇ m or less, more preferably 25 ⁇ m or less, from the viewpoint of resolution and linearity in exposure through the temporary support.
  • the film used as the temporary support does not have deformation such as wrinkles, flaws, or defects.
  • the number of fine particles, foreign matter, defects, precipitates, etc. contained in the temporary support is preferably as small as possible.
  • the number of fine particles, foreign substances, and defects with a diameter of 1 ⁇ m or more is preferably 50/10 mm 2 or less, more preferably 10/10 mm 2 or less, and even more preferably 3/10 mm 2 or less. , 0/10 mm 2 .
  • Preferred embodiments of the temporary support include, for example, paragraphs 0017 to 0018 of JP-A-2014-85643, paragraphs 0019-0026 of JP-A-2016-27363, and paragraphs 0041 to 0057 of WO 2012/081680. , paragraphs 0029 to 0040 of International Publication No. WO 2018/179370, and paragraphs 0012 to 0032 of JP 2019-101405, and the contents of these publications are incorporated herein.
  • a photosensitive transfer material according to the present disclosure has a photosensitive resin layer.
  • the photosensitive resin layer is preferably a negative type photosensitive resin layer in which the solubility in the developer of the exposed portion is reduced by exposure and the non-exposed portion is removed by development.
  • the photosensitive resin layer contains an alkali-soluble resin, an ethylenically unsaturated compound, and a photopolymerization initiator. It preferably contains an ethylenically unsaturated compound, a biimidazole compound, and a benzophenone compound, and more preferably contains an alkali-soluble resin, an ethylenically unsaturated compound, a hexaarylbiimidazole compound, and a benzophenone compound. Moreover, it is preferable that the photosensitive resin layer further contains a polymerization inhibitor from the viewpoints of line width change over time, development temperature line width change, and sensitivity.
  • the photosensitive resin layer contains, based on the total weight of the photosensitive resin layer, an alkali-soluble resin: 10% to 90% by weight; an ethylenically unsaturated compound: 5% to 70% by weight; and a photopolymerization initiator: 0 0.01% to 20% by weight.
  • an alkali-soluble resin 10% to 90% by weight
  • an ethylenically unsaturated compound 5% to 70% by weight
  • a photopolymerization initiator 0 0.01% to 20% by weight.
  • the photosensitive resin layer contains an alkali-soluble resin.
  • alkali-soluble means that the solubility in 100 g of a 1% by mass aqueous solution of sodium carbonate at 22° C. is 0.1 g or more.
  • Alkali-soluble resins are not particularly limited, and suitable examples include known alkali-soluble resins used in etching resists.
  • the alkali-soluble resin is preferably a binder polymer.
  • the alkali-soluble resin is preferably an alkali-soluble resin having an acid group. Among them, as the alkali-soluble resin, a polymer A described later is preferable.
  • the polymer A is included as the alkali-soluble resin.
  • the acid value of the polymer A is preferably 220 mgKOH/g or less, more preferably less than 200 mgKOH/g, more preferably 190 mgKOH/g, from the viewpoint of better resolution by suppressing swelling of the photosensitive resin layer due to the developer. Less than is more preferred.
  • the lower limit of the acid value of polymer A is not particularly limited, but from the viewpoint of better developability, it is preferably 60 mgKOH/g or more, more preferably 120 mgKOH/g or more, still more preferably 150 mgKOH/g or more, and 170 mgKOH/g or more. Especially preferred.
  • the acid value is the mass [mg] of potassium hydroxide required to neutralize 1 g of the sample. In this specification, the unit is described as mgKOH/g.
  • the acid value can be calculated, for example, from the average content of acid groups in the compound.
  • the acid value of the polymer A may be adjusted according to the type of structural units constituting the polymer A and the content of structural units containing an acid group.
  • the weight average molecular weight of polymer A is preferably from 5,000 to 500,000.
  • a weight average molecular weight of 500,000 or less is preferable from the viewpoint of improving resolution and developability.
  • the weight average molecular weight is more preferably 100,000 or less, even more preferably 60,000 or less, and particularly preferably 50,000 or less.
  • setting the weight-average molecular weight to 5,000 or more is from the viewpoint of controlling the properties of development aggregates and the properties of unexposed films such as edge-fuse properties and cut-chip properties when formed into photosensitive resin laminates.
  • the weight average molecular weight is more preferably 10,000 or more, even more preferably 20,000 or more, and particularly preferably 30,000 or more.
  • Edge fuseability refers to the degree of ease with which the photosensitive resin layer 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 easiness of chip flying when the unexposed film is cut with a cutter. If this chip adheres to the upper surface of the photosensitive resin laminate, etc., it will be transferred to the mask in the subsequent exposure process or the like, resulting in defective products.
  • the dispersity of polymer A is preferably 1.0 to 6.0, more preferably 1.0 to 5.0, even more preferably 1.0 to 4.0, and 1 .0 to 3.0 is more preferable.
  • molecular weight is a value measured using gel permeation chromatography.
  • 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 photosensitive resin layer preferably contains, as the polymer A, a monomer component having an aromatic hydrocarbon group, from the viewpoint of suppressing line width thickening and deterioration of resolution when the focal point shifts during exposure.
  • a monomer component having an aromatic hydrocarbon group examples include substituted or unsubstituted phenyl groups and substituted or unsubstituted aralkyl groups.
  • the content of the monomer component 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 monomer components. 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 is not particularly limited, it is preferably 95% by mass or less, more preferably 85% by mass or less.
  • the content rate of the monomer component which has an aromatic-hydrocarbon group in the case where the polymer A contains multiple types was calculated
  • Examples of the monomer having an aromatic hydrocarbon group include monomers having an aralkyl group, styrene, and polymerizable styrene derivatives (e.g., methylstyrene, vinyltoluene, tert-butoxystyrene, acetoxystyrene, 4-vinyl benzoic acid, styrene dimer, styrene trimer, etc.).
  • a monomer having an aralkyl group or styrene is preferred.
  • the content of the styrene monomer component is 20% by mass based on the total mass of all monomer components. It is preferably 50% by mass, more preferably 25% by mass to 45% by mass, even more preferably 30% by mass to 40% by mass, particularly 30% by mass to 35% by mass. preferable.
  • Aralkyl groups include substituted or unsubstituted phenylalkyl groups (excluding benzyl groups), substituted or unsubstituted benzyl groups, and the like, with substituted or unsubstituted benzyl groups being preferred.
  • Examples of monomers having a phenylalkyl group include phenylethyl (meth)acrylate.
  • benzyl group-containing monomers examples include benzyl group-containing (meth)acrylates such as benzyl (meth)acrylate and chlorobenzyl (meth)acrylate; benzyl group-containing vinyl monomers such as vinylbenzyl chloride and vinylbenzyl Alcohol etc. are mentioned. Among them, benzyl (meth)acrylate is preferred.
  • the content of the benzyl (meth) acrylate monomer component is the total of all monomer components Based on the mass, it is preferably 50% by mass to 95% by mass, more preferably 60% by mass to 90% by mass, even more preferably 70% by mass to 90% by mass, 75% by mass to 90% by mass is particularly preferred.
  • Polymer A containing a monomer component having an aromatic hydrocarbon group includes a monomer having an aromatic hydrocarbon group and at least one of the first monomer described later and / or the second monomer described later. is preferably obtained by polymerizing at least one of the monomers of
  • Polymer A containing no monomer component having an aromatic hydrocarbon group is preferably obtained by polymerizing at least one of the first monomers described later, and at least More preferably, it is obtained by copolymerizing one of the monomers with at least one of the second monomers described below.
  • a 1st monomer is a monomer which has a carboxy group in a molecule
  • the first monomer include (meth)acrylic acid, fumaric acid, cinnamic acid, crotonic acid, itaconic acid, 4-vinylbenzoic acid, maleic anhydride, and maleic acid half ester. .
  • (meth)acrylic acid is preferred.
  • the content of the first monomer in the polymer A is preferably 5% by mass to 50% by mass, based on the total mass of all monomer components, and 10% by mass to 40% by mass. is more preferable, and 15% by mass to 30% by mass is even more preferable.
  • the copolymerization ratio of the first monomer is preferably 10% by mass to 50% by mass based on the total mass of all monomer components.
  • the copolymerization ratio of 10% by mass or more is preferable from the viewpoint of developing good developability and controlling edge fuse properties, more preferably 15% by mass or more, and even more preferably 20% by mass or more.
  • Setting the copolymerization ratio to 50% by mass or less is preferable from the viewpoint of the high resolution and groove shape of the resist pattern, and further from the viewpoint of the chemical resistance of the resist pattern. The following is more preferable, 30% by mass or less is even more preferable, and 27% by mass or less is particularly preferable.
  • tert-butyl (meth)acrylate 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate and other (meth)acrylates; vinyl acetate esters of vinyl alcohol such as; and (meth)acrylonitrile.
  • methyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, and n-butyl (meth)acrylate are preferred, and methyl (meth)acrylate is particularly preferred.
  • the content of the second monomer in the polymer A is preferably 5% by mass to 60% by mass, based on the total mass of all monomer components, and 15% by mass to 50% by mass. is more preferable, and 20% by mass to 45% by mass is even more preferable.
  • Containing a monomer having an aralkyl group and/or styrene as a monomer is preferable from the viewpoint of suppressing widening of line width and deterioration of resolution when the focal position during exposure is shifted.
  • a copolymer containing methacrylic acid, benzyl methacrylate and styrene, a copolymer containing methacrylic acid, methyl methacrylate, benzyl methacrylate and styrene, and the like are preferable.
  • the polymer A contains 25% to 40% by mass of the monomer component having an aromatic hydrocarbon group, 20% to 35% by mass of the first monomer component, and the second monomer It is preferably a polymer containing 30% by mass to 45% by mass of the solid component. In another aspect, the polymer preferably contains 70% by mass to 90% by mass of the monomer component having an aromatic hydrocarbon group and 10% by mass to 25% by mass of the first monomer component. .
  • the polymer A can be used singly or in combination of two or more. When two or more types are mixed and used, two types of polymer A containing a monomer component having an aromatic hydrocarbon group are mixed and used, or a monomer component having an aromatic hydrocarbon group is used. It is preferable to use a mixture of the polymer A containing the aromatic hydrocarbon group and the polymer A containing no monomer component having an aromatic hydrocarbon group. In the latter case, the use ratio of the polymer A containing a monomer component having an aromatic hydrocarbon group is preferably 50% by mass or more, preferably 70% by mass or more, based on the total amount of the polymer A. is more preferably 80% by mass or more, and more preferably 90% by mass or more.
  • the polymer A may have either a linear structure, a branched structure, or an alicyclic structure in its side chain.
  • the side chain of the polymer (A) can have a branched structure or an alicyclic structure. Structure can be introduced.
  • a group having an alicyclic structure may be monocyclic or polycyclic.
  • Examples of the monomer containing a group having a branched structure in the side chain include isopropyl (meth)acrylate, isobutyl (meth)acrylate, sec-butyl (meth)acrylate, tert-butyl (meth)acrylate, ( Isoamyl meth)acrylate, tert-amyl (meth)acrylate, sec-amyl (meth)acrylate, 2-octyl (meth)acrylate, 3-octyl (meth)acrylate and tert-octyl (meth)acrylate is mentioned.
  • isopropyl (meth)acrylate, isobutyl (meth)acrylate, and tert-butyl methacrylate are preferred, and isopropyl methacrylate and tert-butyl methacrylate are more preferred.
  • the monomer containing a group having an alicyclic structure in its side chain include a monomer having a monocyclic aliphatic hydrocarbon group and a monomer having a polycyclic aliphatic hydrocarbon group.
  • (Meth)acrylates having an alicyclic hydrocarbon group with 5 to 20 carbon atoms are also included.
  • Examples of the monomer containing a group having an alicyclic structure in the side chain include (meth)acrylic acid (bicyclo[2.2.1]heptyl-2), (meth)acrylic acid-1-adamantyl, (meth)acrylic acid (bicyclo[2.2.1]heptyl-2), )-2-adamantyl acrylate, (meth)-3-methyl-1-adamantyl acrylate, (meth)-3,5-dimethyl-1-adamantyl acrylate, (meth)-3-ethyladamantyl acrylate, ( 3-Methyl-5-ethyl-1-adamantyl meth)acrylate, 3,5,8-triethyl-1-adamantyl (meth)acrylate, 3,5-dimethyl-8-ethyl (meth)acrylate -1-adamantyl, 2-methyl-2-adamantyl (meth) acrylate, 2-ethyl-2-adamantyl (
  • cyclohexyl (meth) acrylate, (nor) bornyl (meth) acrylate, isobornyl (meth) acrylate, 1-adamantyl (meth) acrylate, 2-adamantyl (meth) acrylate, (meth) ) fenchyl acrylate, 1-menthyl (meth)acrylate and tricyclodecane (meth)acrylate are preferred, cyclohexyl (meth)acrylate, (nor)bornyl (meth)acrylate, isobornyl (meth)acrylate, ( More preferred are 2-adamantyl meth)acrylate and tricyclodecane (meth)acrylate.
  • Synthesis of polymer A is carried out by adding a radical polymerization initiator such as benzoyl peroxide and azoisobutyronitrile to a solution obtained by diluting one or more of the monomers described above with a solvent such as acetone, methyl ethyl ketone, or isopropanol. is preferably added in an appropriate amount and heated and stirred. In some cases, the synthesis is performed while part of the mixture is added dropwise to the reaction solution. After completion of the reaction, a solvent may be further added to adjust the desired concentration. As a means of synthesis, bulk polymerization, suspension polymerization, or emulsion polymerization may be used in addition to solution polymerization.
  • a radical polymerization initiator such as benzoyl peroxide and azoisobutyronitrile
  • the glass transition temperature Tg of polymer A is preferably 30°C or higher and 135°C or lower.
  • the Tg of polymer A is more preferably 130° C. or lower, still more preferably 120° C. or lower, and particularly preferably 110° C. or lower.
  • the polymer A having a Tg of 30° C. or more from the viewpoint of improving the edge fuse resistance.
  • the Tg of the polymer A is more preferably 40° C. or higher, still more preferably 50° C. or higher, particularly preferably 60° C. or higher, and most preferably 70° C. or higher. .
  • the photosensitive resin layer may contain a resin other than the alkali-soluble resin.
  • Resins other than alkali-soluble resins include acrylic resins, styrene-acrylic copolymers (with a styrene content of 40% by mass or less), polyurethane resins, polyvinyl alcohol, polyvinyl formal, polyamide resins, polyester resins, and polyamides.
  • Alkali-soluble resins may be used singly or in combination of two or more.
  • the ratio of the alkali-soluble resin to the total weight of 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, and still more preferably 40% by mass to 60% by mass. From the viewpoint of controlling the development time, it is preferable to set the ratio of the alkali-soluble resin to 90% by mass or less with respect to the photosensitive resin layer. On the other hand, it is preferable from the viewpoint of improving the edge fuse resistance that the ratio of the alkali-soluble resin to the photosensitive resin layer is 10% by mass or more.
  • the photosensitive resin layer contains an ethylenically unsaturated compound.
  • ethylenically unsaturated compound means a compound that polymerizes under the action of a photopolymerization initiator, which will be described later, and that is different from the alkali-soluble resin described above.
  • an ethylenically unsaturated compound is preferred.
  • the ethylenically unsaturated compound is a component that contributes to the photosensitivity (that is, photocurability) of the negative photosensitive resin layer and the strength of the cured film.
  • an ethylenically unsaturated compound is a compound having one or more ethylenically unsaturated groups.
  • the photosensitive resin layer preferably contains a bifunctional or higher ethylenically unsaturated compound as the ethylenically unsaturated compound.
  • the bifunctional or higher ethylenically unsaturated compound means a compound having two or more ethylenically unsaturated groups in one molecule.
  • a (meth)acryloyl group is more preferable as the ethylenically unsaturated group.
  • a (meth)acrylate compound is preferable as the ethylenically unsaturated compound.
  • the ethylenically unsaturated compound preferably contains an ethylenically unsaturated compound having a bisphenol structure from the viewpoints of line width variation suppressing property, line width change over time, cross-sectional shape of the resin pattern, and sensitivity.
  • an ethylenically unsaturated compound B1 having a bisphenol structure which will be described later, is preferably exemplified.
  • the photosensitive resin layer preferably contains an ethylenically unsaturated compound having a polymerizable group.
  • the polymerizable group possessed by the ethylenically unsaturated compound is not particularly limited as long as it is a group that participates in the polymerization reaction. and groups having cationic polymerizable groups such as epoxy groups and oxetane groups.
  • a group having an ethylenically unsaturated group is preferable, and an acryloyl group or a methacryloyl group is more preferable.
  • the ethylenically unsaturated compound a compound having two or more ethylenically unsaturated groups in one molecule (polyfunctional ethylenically unsaturated compound) may be included in order to improve the photosensitivity of the photosensitive resin layer.
  • the number of ethylenically unsaturated groups that the ethylenically unsaturated compound has in one molecule is preferably 6 or less, more preferably 3 or less, and 2 or less. More preferred.
  • the photosensitive resin layer is bifunctional or trifunctional having two or three ethylenically unsaturated groups in one molecule, in that the photosensitive resin layer has a better balance between photosensitivity, resolution, and releasability. It preferably contains an ethylenically unsaturated compound, and more preferably contains a bifunctional ethylenically unsaturated compound having two ethylenically unsaturated groups in one molecule.
  • the content of the bifunctional ethylenically unsaturated compound with respect to the content of the ethylenically unsaturated compound is preferably 60% by mass or more, more preferably more than 70% by mass, from the viewpoint of excellent peelability. More than % by mass is more preferable.
  • the upper limit is not particularly limited, and may be 100% by mass. That is, all the ethylenically unsaturated compounds contained in the photosensitive resin layer may be bifunctional ethylenically unsaturated compounds. Moreover, as the ethylenically unsaturated compound, a (meth)acrylate compound having a (meth)acryloyl group as a polymerizable group is preferable.
  • the photosensitive resin layer preferably contains an ethylenically unsaturated compound B1 having an aromatic ring and two ethylenically unsaturated groups.
  • the ethylenically unsaturated compound B1 is a bifunctional ethylenically unsaturated compound having one or more aromatic rings in one molecule among the ethylenically unsaturated compounds described above.
  • the mass ratio of the content of the ethylenically unsaturated compound B1 to the content of the ethylenically unsaturated compound is preferably 40% by mass or more, and 50% by mass, from the viewpoint of better resolution. % or more, more preferably 55 mass % or more, and particularly preferably 60 mass % or more. Although the upper limit is not particularly limited, it is preferably 99% by mass or less, more preferably 95% by mass or less, even more preferably 90% by mass or less, and particularly preferably 85% by mass or less, from the viewpoint of releasability.
  • aromatic ring of the ethylenically unsaturated compound B1 examples include aromatic hydrocarbon rings such as benzene ring, naphthalene ring and anthracene ring, thiophene ring, furan ring, pyrrole ring, imidazole ring, triazole ring and pyridine ring.
  • Aromatic heterocycles and condensed rings thereof are included, with aromatic hydrocarbon rings being preferred, and benzene rings being more preferred.
  • the said aromatic ring may have a substituent.
  • Ethylenically unsaturated compound B1 may have only one aromatic ring, or may have two or more aromatic rings.
  • the ethylenically unsaturated compound B1 preferably has a bisphenol structure from the viewpoint of improving the resolution by suppressing swelling of the photosensitive resin layer due to the developer.
  • 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).
  • the F structure and the bisphenol B structure derived from bisphenol B (2,2-bis(4-hydroxyphenyl)butane) can be mentioned, with the bisphenol A structure being preferred.
  • Examples of the ethylenically unsaturated compound B1 having a bisphenol structure include compounds having a bisphenol structure and two polymerizable groups (preferably (meth)acryloyl groups) bonded to both ends of the bisphenol structure. Both ends of the bisphenol structure and the two polymerizable groups may be directly bonded or bonded via one or more alkyleneoxy groups.
  • the alkyleneoxy group added to both ends of the bisphenol structure is preferably an ethyleneoxy group or a propyleneoxy group, more preferably an ethyleneoxy group.
  • the number of alkyleneoxy groups added to the bisphenol structure is not particularly limited, but is preferably 4 to 16, more preferably 6 to 14 per molecule.
  • the ethylenically unsaturated compound B1 is preferably a bifunctional ethylenically unsaturated compound having a bisphenol A structure, more preferably 2,2-bis(4-((meth)acryloxypolyalkoxy)phenyl)propane.
  • Examples of 2,2-bis(4-((meth)acryloxypolyalkoxy)phenyl)propane examples include 2,2-bis(4-(methacryloxydiethoxy)phenyl)propane (FA-324M, Hitachi Chemical ( Co., Ltd.), 2,2-bis(4-(methacryloxyethoxypropoxy)phenyl)propane, 2,2-bis(4-(methacryloxypentaethoxy)phenyl)propane (BPE-500, Shin-Nakamura Chemical Industry ( Ltd.), 2,2-bis(4-(methacryloxydodecaethoxytetrapropoxy)phenyl)propane (FA-3200MY, manufactured by Hitachi Chemical Co., Ltd.), 2,2-bis(4-(methacryloxypentadeca Ethoxy)phenyl)propane (BPE-1300, manufactured by Shin-Nakamura Chemical Co., Ltd.), 2,2-bis(4-(methacryloxydiethoxy)phenyl)propan
  • the ethylenically unsaturated compound B1 preferably contains a compound represented by the following formula (Bis) from the viewpoint of line width change over time, development temperature line width change, and sensitivity.
  • R 1 and R 2 each independently represent a hydrogen atom or a methyl group
  • A is C 2 H 4
  • B is C 3 H 6
  • n 1 and n 3 are each independently , an integer of 1 to 39
  • n 1 + n 3 is an integer of 2 to 40
  • n 2 and n 4 are each independently an integer of 0 to 29, and n 2 + n 4 is 0 to It is an integer of 30, and the arrangement of repeating units of -(AO)- and -(B-O)- may be random or block. In the case of a block, either -(AO)- or -(B-O)- may be on the bisphenol structure side.
  • n 1 +n 2 +n 3 +n 4 is preferably an integer of 2-20, more preferably an integer of 2-16, and even more preferably an integer of 4-12. Also, n 2 +n 4 is preferably an integer of 0 to 10, more preferably an integer of 0 to 4, even more preferably an integer of 0 to 2, and particularly preferably 0.
  • Ethylenically unsaturated compound B1 may be used alone or in combination of two or more.
  • the content of the ethylenically unsaturated compound B1 in the photosensitive resin layer is preferably 10% by mass or more, more preferably 20% by mass or more, with respect to the total mass of the photosensitive resin layer, from the viewpoint of better resolution.
  • the upper limit is not particularly limited, it is preferably 70% by mass or less, more preferably 60% by mass or less, from the viewpoint of transferability and edge fusion (a phenomenon in which components in the photosensitive resin layer ooze out from the edges of the photosensitive transfer material). preferable.
  • the photosensitive resin layer may contain an ethylenically unsaturated compound other than the ethylenically unsaturated compound B1 described above.
  • Ethylenically unsaturated compounds other than the ethylenically unsaturated compound B1 are not particularly limited and can be appropriately selected from known compounds. For example, a compound having one ethylenically unsaturated group in one molecule (monofunctional ethylenically unsaturated compound), a bifunctional ethylenically unsaturated compound having no aromatic ring, and a trifunctional or higher ethylenically unsaturated compound.
  • Examples of monofunctional ethylenically unsaturated compounds include ethyl (meth) acrylate, ethylhexyl (meth) acrylate, 2-(meth) acryloyloxyethyl succinate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate. , and phenoxyethyl (meth)acrylate.
  • Examples of bifunctional ethylenically unsaturated compounds having no aromatic ring include alkylene glycol di(meth)acrylate, polyalkylene glycol di(meth)acrylate, urethane di(meth)acrylate, and trimethylolpropane diacrylate. be done.
  • Alkylene glycol di(meth)acrylates include, for example, tricyclodecanedimethanol diacrylate (A-DCP, manufactured by Shin-Nakamura Chemical Co., Ltd.), tricyclodecanedimethanol dimethacrylate (DCP, Shin-Nakamura Chemical Co., Ltd.
  • Polyalkylene glycol di(meth)acrylates include, for example, polyethylene glycol di(meth)acrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, and polypropylene glycol di(meth)acrylate.
  • Urethane di(meth)acrylates include, for example, propylene oxide-modified urethane di(meth)acrylates, and ethylene oxide and propylene oxide-modified urethane di(meth)acrylates.
  • Commercially available products include, for example, 8UX-015A (manufactured by Taisei Fine Chemical Co., Ltd.), UA-32P (manufactured by Shin-Nakamura Chemical Co., Ltd.), and UA-1100H (manufactured by Shin-Nakamura Chemical Co., Ltd.). mentioned.
  • trifunctional or higher ethylenically unsaturated compounds include dipentaerythritol (tri/tetra/penta/hexa) (meth) acrylate, pentaerythritol (tri/tetra) (meth) acrylate, trimethylolpropane tri(meth) Acrylate, ditrimethylolpropane tetra(meth)acrylate, trimethylolethane tri(meth)acrylate, isocyanurate tri(meth)acrylate, glycerin tri(meth)acrylate, and alkylene oxide modified products thereof.
  • (tri/tetra/penta/hexa) (meth)acrylate is a concept including tri(meth)acrylate, tetra(meth)acrylate, penta(meth)acrylate, and hexa(meth)acrylate.
  • (tri/tetra)(meth)acrylate” is a concept including tri(meth)acrylate and tetra(meth)acrylate.
  • the photosensitive resin layer preferably contains the above-described ethylenically unsaturated compound B1 and a trifunctional or higher ethylenically unsaturated compound, and the above-described ethylenically unsaturated compound B1 and two or more trifunctional or higher functional of ethylenically unsaturated compounds.
  • the mass ratio of the ethylenically unsaturated compound B1 and the tri- or higher functional ethylenically unsaturated compound is (total mass of the ethylenically unsaturated compound B1):(total mass of the tri- or higher functional ethylenically unsaturated compound).
  • the photosensitive resin layer preferably contains the ethylenically unsaturated compound B1 and two or more trifunctional ethylenically unsaturated compounds.
  • alkylene oxide-modified tri- or higher ethylenically unsaturated compounds examples include caprolactone-modified (meth)acrylate compounds (KAYARAD (registered trademark) DPCA-20 manufactured by Nippon Kayaku Co., Ltd., A manufactured by Shin-Nakamura Chemical Co., Ltd.
  • alkylene oxide-modified (meth)acrylate compounds (KAYARAD RP-1040 manufactured by Nippon Kayaku Co., Ltd., ATM-35E and A-9300 manufactured by Shin-Nakamura Chemical Co., Ltd., EBECRYL manufactured by Daicel Allnex) (registered trademark) 135, etc.), ethoxylated glycerin triacrylate (A-GLY-9E, etc.
  • an ethylenically unsaturated compound having an acid group described in paragraphs 0025 to 0030 of JP-A-2004-239942 may be used.
  • the ratio Mm/Mb between the content Mm of the ethylenically unsaturated compound and the content Mb of the alkali-soluble resin in the photosensitive resin layer is preferably 1.0 or less from the viewpoint of resolution and linearity. It is preferably 0.9 or less, and particularly preferably 0.5 or more and 0.9 or less.
  • the ethylenically unsaturated compound in the photosensitive resin layer preferably contains a (meth)acrylic compound from the viewpoint of curability and resolution.
  • the ethylenically unsaturated compound in the photosensitive resin layer contains a (meth)acrylic compound, and the (meth)acrylic compound contained in the photosensitive resin layer. More preferably, the content of the acrylic compound with respect to the total mass is 60% by mass or less.
  • the molecular weight of the ethylenically unsaturated compound containing the ethylenically unsaturated compound B1 is preferably 200 to 3,000, more preferably 280 to 2,200, and 300 ⁇ 2,200 is more preferred.
  • An ethylenically unsaturated compound may be used individually by 1 type, or may use 2 or more types together.
  • the content of the ethylenically unsaturated 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 the total mass of the photosensitive resin layer. 50% by mass is more preferred.
  • the photosensitive resin layer contains a photopolymerization initiator.
  • a photopolymerization initiator is a compound that initiates polymerization of an ethylenically unsaturated compound upon exposure to actinic rays such as ultraviolet rays, visible rays, and X-rays.
  • the photopolymerization initiator is not particularly limited, and known photopolymerization initiators can be used. Further, the photopolymerization initiator in the present disclosure shall also include a sensitizer. Examples of photopolymerization initiators include radical photopolymerization initiators and cationic photopolymerization initiators, and radical photopolymerization initiators are preferred.
  • photoradical polymerization initiators examples include photopolymerization initiators having an oxime ester structure, photopolymerization initiators having an ⁇ -aminoalkylphenone structure, photopolymerization initiators having an ⁇ -hydroxyalkylphenone structure, and acylphosphine oxide. structure, a photopolymerization initiator having an N-phenylglycine structure, and a biimidazole compound.
  • the photopolymerization initiator preferably contains a biimidazole compound from the viewpoint of line width variation suppressing property, line width change over time, cross-sectional shape of the resin pattern, and sensitivity, and the biimidazole compound and benzophenone More preferably, it contains a compound.
  • a biimidazole compound a hexaarylbiimidazole compound is preferably exemplified.
  • biimidazole compounds include 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 dimers.
  • the photosensitive resin layer may contain one type of biimidazole compound as a photopolymerization initiator, or may contain two or more types thereof.
  • the content of the biimidazole compound is 1% by mass or more with respect to the total mass of the photosensitive resin layer, from the viewpoint of line width variation suppression property, line width change over time, cross-sectional shape of the resin pattern, and sensitivity. is preferably 2% by mass or more, more preferably 3% by mass to 10% by mass, and particularly preferably 5% by mass to 10% by mass.
  • the photopolymerization initiator preferably contains a benzophenone compound, and more preferably contains a dialkylaminobenzophenone compound, from the viewpoints of line width variation suppression property, line width change over time, cross-sectional shape of the resin pattern, and sensitivity. .
  • Benzophenone compounds include, for example, benzophenone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 4-methoxybenzophenone, 2-chlorobenzophenone, 4-chlorobenzophenone, 4-bromobenzophenone, 2-carboxybenzophenone, 2 -ethoxycarbonylbenzophenone, benzophenone tetracarboxylic acid or its tetramethyl ester, 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(dicyclohexylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, 4,4′-bis(dihydroxyethylamino)benzophenone, 4-methoxy-4′-dimethylaminobenzophenone, 4,4′-dimethoxybenzophenone, 4-dimethylaminobenzophenone, 4-phenylbenzophenone, isophthalophen
  • the photosensitive resin layer may contain one kind of benzophenone compound alone or two or more kinds thereof as a photopolymerization initiator.
  • the content of the benzophenone compound is 0.05% by mass with respect to the total mass of the photosensitive resin layer, from the viewpoints of line width variation suppression property, line width change over time, cross-sectional shape of the resin pattern, and sensitivity. It is preferably 5% by mass, more preferably 0.1% by mass to 2% by mass, even more preferably 0.2% by mass to 1.5% by mass, and 0.4% by mass to 0.8% by weight is particularly preferred.
  • the content of the benzophenone compound is used to control line width variation, line width change over time, cross-sectional shape of the resin pattern, and sensitivity. from the point of view, it is preferably less than the content of the biimidazole compound.
  • radical photopolymerization initiator for example, polymerization initiators described in paragraphs 0031 to 0042 of JP-A-2011-95716 or paragraphs 0064-0081 of JP-A-2015-14783 may be used.
  • photoradical polymerization initiators examples include ethyl dimethylaminobenzoate (DBE, CAS No. 10287-53-3), benzoin methyl ether, anisyl (p,p'-dimethoxybenzyl), TAZ-110 (trade name: Midori Chemical Co., Ltd.), benzophenone, TAZ-111 (trade name: Midori Chemical Co., Ltd.), Irgacure OXE01, OXE02, OXE03, OXE04 (manufactured by BASF), Omnirad 651 and 369 (trade name: IGM Resins BV (manufactured by Tokyo Chemical Industry Co., Ltd.), and 2,2′-bis(2-chlorophenyl)-4,4′,5,5′-tetraphenyl-1,2′-biimidazole (manufactured by Tokyo Chemical Industry Co., Ltd.). be done.
  • DBE ethyl dimethylaminobenzoate
  • photoradical polymerization initiators include, for example, 1-[4-(phenylthio)phenyl]-1,2-octanedione-2-(O-benzoyloxime) (trade name: IRGACURE (registered trademark) OXE- 01, manufactured by BASF), 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone-1-(O-acetyloxime) (trade name: IRGACURE OXE-02, BASF), IRGACURE OXE-03 (BASF), 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone (trade name: Omnirad 379EG, manufactured by IGM Resins B.V.), 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one (trade name: Omnirad 907, IGM Resins
  • a photocationic polymerization initiator is a compound that generates an acid upon receiving an actinic ray.
  • the photocationic polymerization initiator is preferably a compound that responds to an actinic ray with a wavelength of 300 nm or more, preferably 300 to 450 nm, and generates an acid, but its chemical structure is not limited.
  • the sensitizer can be used. It can be preferably used in combination with.
  • the photocationic polymerization initiator is preferably a photocationic polymerization initiator that generates an acid with a pKa of 4 or less, more preferably a photocationic polymerization initiator that generates an acid with a pKa of 3 or less, and an acid with a pKa of 2 or less.
  • Photocationic polymerization initiators generated are particularly preferred.
  • the lower limit of pKa is not particularly defined, it is preferably -10.0 or more, for example.
  • photocationic polymerization initiators examples include ionic photocationic polymerization initiators and nonionic photocationic polymerization initiators.
  • Ionic photocationic polymerization initiators include, for example, onium salt compounds such as diaryliodonium salts and triarylsulfonium salts, and quaternary ammonium salts.
  • the ionic photocationic polymerization initiator the ionic photocationic polymerization initiators described in paragraphs 0114 to 0133 of JP-A-2014-85643 may be used.
  • nonionic photocationic polymerization initiators include trichloromethyl-s-triazines, diazomethane compounds, imidosulfonate compounds, and oximesulfonate compounds.
  • trichloromethyl-s-triazines, diazomethane compounds and imidosulfonate compounds compounds described in paragraphs 0083 to 0088 of JP-A-2011-221494 may be used.
  • oxime sulfonate compound compounds described in paragraphs 0084 to 0088 of WO 2018/179640 may be used.
  • the sensitizer is not particularly limited, and known sensitizers, dyes and pigments can be used.
  • Sensitizers include, for example, dialkylaminobenzophenone compounds, pyrazoline compounds, anthracene compounds, coumarin compounds, xanthone compounds, thioxanthone compounds, acridone compounds, oxazole compounds, benzoxazole compounds, thiazole compounds, benzothiazole compounds, and triazole compounds (e.g., 1,2,4-triazole), stilbene compounds, triazine compounds, thiophene compounds, naphthalimide compounds, triarylamine compounds, and aminoacridine compounds.
  • the photosensitive resin layer may contain one type of photopolymerization initiator alone, or two or more types thereof.
  • the content of the photopolymerization initiator in the photosensitive resin layer is not particularly limited. 0% by mass or more is more preferable. Although the upper limit is not particularly limited, it is preferably 10% by mass or less, more preferably 5% by mass or less, relative to the total mass of the photosensitive resin layer.
  • the photosensitive resin layer preferably contains a dye from the viewpoint of the visibility of the exposed and unexposed areas, the visibility of the pattern after development, and the resolution. It is more preferable to contain a dye whose absorption wavelength is 450 nm or more and whose maximum absorption wavelength is changed by an acid, a base, or a radical (also simply referred to as "dye N"). Although the detailed mechanism is unknown, when the dye N is contained, the adhesion to the adjacent layers (for example, the temporary support and the water-soluble resin layer) is improved, and the resolution is improved.
  • the term "the maximum absorption wavelength of a dye changes with an acid, a base, or a radical” means that the dye in a colored state is decolored by an acid, a base, or a radical, the dye in a decolored state is an acid, It may mean either a mode in which a color is developed by a base or a radical, or a mode in which a dye in a coloring state changes to a coloring state of another hue.
  • the dye N may be a compound that changes from a decolored state to develop color upon exposure, or may be a compound that changes from a colored state to decolor upon exposure.
  • it may be a dye whose coloring or decoloring state is changed by the action of an acid, a base, or a radical generated in the photosensitive resin layer by exposure, and the state in the photosensitive resin layer by the acid, the base, or the radical. It may also be a dye that changes its coloring or decoloring state with a change in pH (eg, pH). Further, it may be a dye that changes its coloring or decoloring state by directly receiving an acid, a base or a radical as a stimulus without being exposed to light.
  • the dye N is preferably a dye whose maximum absorption wavelength is changed by acid or radicals, more preferably a dye whose maximum absorption wavelength is changed by radicals.
  • the photosensitive resin layer may contain both a dye whose maximum absorption wavelength is changed by radicals as dye N and a radical photopolymerization initiator. preferable.
  • the dye N is preferably a dye that develops color with 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 photoradical polymerization is performed after exposure.
  • Radical-reactive dyes, acid-reactive dyes, or base-reactive dyes develop colors with radicals, acids, or bases generated from an initiator, 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 during color development, more preferably 550 nm to 700 nm, and 550 nm. More preferably ⁇ 650 nm.
  • the dye N may have only one maximum absorption wavelength in the wavelength range of 400 nm to 780 nm during color development, or may have two or more.
  • the maximum absorption wavelength with the highest absorbance among the two or more maximum absorption wavelengths may be 450 nm or more.
  • the maximum absorption wavelength of Dye N is measured in the range of 400 nm to 780 nm using a spectrophotometer: UV3100 (manufactured by Shimadzu Corporation) in an air atmosphere. It is obtained by measuring the spectrum and detecting the wavelength (maximum absorption wavelength) at which the intensity of light is minimal.
  • Examples of dyes that develop or decolorize upon exposure include leuco compounds.
  • Examples of dyes that are decolorized by exposure include leuco compounds, diarylmethane dyes, oxazine dyes, xanthene dyes, iminonaphthoquinone dyes, azomethine dyes, and anthraquinone dyes.
  • As the dye N a leuco compound is preferable from the viewpoint of the visibility of the exposed area and the non-exposed area.
  • leuco compounds examples include leuco compounds having a triarylmethane skeleton (triarylmethane dyes), leuco compounds having a spiropyran skeleton (spiropyran dyes), leuco compounds having a fluorane skeleton (fluoran dyes), and diarylmethane skeletons.
  • triarylmethane dyes triarylmethane dyes
  • spiropyran dyes spiropyran dyes
  • fluorane skeleton fluorane skeleton
  • diarylmethane skeletons examples include leuco compounds having a triarylmethane skeleton (triarylmethane dyes), leuco compounds having a spiropyran skeleton (spiropyran dyes), leuco compounds having a fluorane skeleton (fluoran dyes), and diarylmethane skeletons.
  • a leuco compound (diarylmethane dye), a leuco compound having a rhodamine lactam skeleton (rhodamine lactam dye), a leuco compound having an indolylphthalide skeleton (indolylphthalide dye), and a leuco auramine skeleton leuco compounds (leuco auramine dyes) having Among them, triarylmethane-based dyes or fluoran-based dyes are preferable, and leuco compounds having a triphenylmethane skeleton (triphenylmethane-based dyes) or fluoran-based dyes are more preferable.
  • the leuco compound preferably has a lactone ring, a sultine ring, or a sultone ring from the viewpoint of the visibility of the exposed and non-exposed areas.
  • the lactone ring, sultine ring, or sultone ring of the leuco compound is reacted with a radical generated from a radical photopolymerization initiator or an acid generated from a photocationic polymerization initiator to change the leuco compound into a ring-closed state. It can be decolored, or it can be colored by changing the leuco compound into a ring-opened state.
  • the leuco compound is preferably a compound that has a lactone ring, a sultine ring or a sultone ring and develops a color when the lactone ring, sultine ring or sultone ring is opened by a radical or an acid.
  • a compound that develops color by ring-opening of the lactone ring is more preferred.
  • dye N examples include the following dyes and leuco compounds. Specific examples of dyes among dyes N include brilliant green, ethyl violet, methyl green, crystal violet, basic fuchsine, methyl violet 2B, quinaldine red, rose bengal, methanyl yellow, thymolsulfophtalein, xylenol blue, methyl Orange, Paramethyl Red, Congo Fred, Benzopurpurin 4B, ⁇ -Naphthyl Red, Nile Blue 2B, Nile Blue A, Methyl Violet, Malachite Green, Parafuchsin, Victoria Pure Blue-Naphthalene Sulfonate, Victoria Pure Blue BOH (protective Tsuchiya Chemical Industry Co., Ltd.), Oil Blue #603 (Orient Chemical Industry Co., Ltd.), Oil Pink #312 (Orient Chemical Industry Co., Ltd.), Oil Red 5B (Orient Chemical Industry Co., Ltd.), Oil Scarlet #308 (manufactured by Orient Chemical Industry Co., Ltd.), Oil
  • leuco compound of the dye N include p,p′,p′′-hexamethyltriaminotriphenylmethane (leuco crystal violet), Pergascript Blue SRB (manufactured by Ciba-Geigy), crystal violet lactone, malachite green lactone, benzoyl leucomethylene blue, 2-(N-phenyl-N-methylamino)-6-(Np-tolyl-N-ethyl)aminofluorane, 2-anilino-3-methyl-6-(N-ethyl-p -toluidino)fluorane, 3,6-dimethoxyfluorane, 3-(N,N-diethylamino)-5-methyl-7-(N,N-dibenzylamino)fluorane, 3-(N-cyclohexyl-N-methyl amino)-6-methyl-7-anilinofluorane, 3-(N,N-diethylamino)-6-
  • Dye N is preferably a dye whose maximum absorption wavelength is changed by radicals from the viewpoint 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.
  • Preferred dyes N are leuco crystal violet, crystal violet lactone, brilliant green, or victoria pure blue-naphthalene sulfonate.
  • a dye may be used individually by 1 type, or may use 2 or more types.
  • the content of the dye is preferably 0.1% by mass or more based on the total mass of the photosensitive resin layer, from the viewpoints of visibility of exposed and unexposed areas, pattern visibility after development, and resolution. , more preferably 0.1% by mass to 10% by mass, still more preferably 0.1% by mass to 5% by mass, and particularly preferably 0.1% by mass to 1% by mass.
  • the content of the dye N is 0.1% by mass with respect to the total mass of the photosensitive resin layer from the viewpoint of the visibility of the exposed area and the non-exposed area, the pattern visibility after development, and the resolution.
  • 0.1% by mass to 10% by mass is more preferable
  • 0.1% by mass to 5% by mass is still more preferable
  • 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 the dyes N contained in the photosensitive resin layer are in a colored state.
  • a method for quantifying the content of dye N will be described below using a dye that develops color by radicals as an example.
  • Two solutions are prepared by dissolving 0.001 g or 0.01 g of dye in 100 mL of methyl ethyl ketone.
  • a radical photopolymerization initiator Irgacure OXE01 (trade name, BASF Japan Co., Ltd.) is added to each of the obtained solutions, and radicals are generated by irradiation with light of 365 nm to make all the dyes develop colors. After that, the absorbance of each solution having a liquid temperature of 25° C.
  • the absorbance of the solution in which all the dyes are developed is measured in the same manner as described above except that 3 g of the photosensitive resin layer is dissolved in methyl ethyl ketone instead of the dyes. 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 further contains a polymerization inhibitor from the viewpoints of storage stability, suppression of line width variation, change in line width during storage, and cross-sectional shape of the resin pattern.
  • the polymerization inhibitor preferably contains a radical polymerization inhibitor.
  • the polymerization inhibitor is not particularly limited, and known polymerization inhibitors can be used.
  • Polymerization inhibitors include phenothiazine, phenoxazine, hydroquinone, chloranil, sodium phenolindophenol, m-aminophenol, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4 ,4'-thiobis(3-methyl-6-t-butylphenol), 2,2'-methylenebis(4-methyl-6-t-butylphenol), N-nitrosophenyl hydroxylamine salts (ammonium salts, cerous salts etc.), and 2,2,6,6-tetramethylpiperidine-1-oxyl and the like.
  • the polymerization inhibitor may function as an antioxidant.
  • examples of the polymerization inhibitor include thermal polymerization inhibitors described in paragraph 0018 of Japanese Patent No. 4502784.
  • Other polymerization inhibitors include naphthylamine, cuprous chloride, nitrosophenylhydroxyamine aluminum salt, and diphenylnitrosamine.
  • a nitrosophenylhydroxyamine aluminum salt is preferred as a radical polymerization inhibitor.
  • the polymerization inhibitor is composed of phenothiazine, phenoxazine, and a compound having a hindered phenol structure, from the viewpoint of line width variation suppressing property, line width change over time, cross-sectional shape of resin pattern, and sensitivity. It preferably contains at least one compound selected from the group, more preferably contains at least one compound selected from the group consisting of phenothiazine and phenoxazine, and particularly preferably contains phenothiazine.
  • a polymerization inhibitor may be used individually by 1 type, and may be used in combination of 2 or more types.
  • the content of the polymerization inhibitor is, from the viewpoints of storage stability, suppression of line width variation, change in line width over time, cross-sectional shape of the resin pattern, and sensitivity, 0.00% with respect to the total mass of the photosensitive resin layer. 005% by mass to 2% by mass is preferable, 0.01% by mass to 1% by mass is more preferable, 0.05% by mass to 0.5% by mass is even more preferable, and 0.2% by mass to 0.4% by mass is Especially preferred.
  • the value of the mass ratio Rd/Rc is the line width variation suppressing property, pulling From the viewpoints of change in line width over time, cross-sectional shape of the resin pattern, and sensitivity, it is preferably 0.01 or more and 0.2 or less, and more preferably 0.02 or more and 0.1 or less.
  • the photosensitive resin layer preferably contains a thermally crosslinkable compound from the viewpoint of the strength of the resulting cured film and the adhesiveness of the resulting uncured film.
  • a thermally crosslinkable compound having an ethylenically unsaturated group which will be described later, is not treated as an ethylenically unsaturated compound, but as a thermally crosslinkable compound.
  • Thermally crosslinkable compounds include methylol compounds and blocked isocyanate compounds. Among them, a blocked isocyanate compound is preferable from the viewpoint of the strength of the cured film to be obtained and the adhesiveness of the uncured film to be obtained.
  • the blocked isocyanate compound reacts with a hydroxy group and a carboxy group, for example, when the alkali-soluble resin and/or the ethylenically unsaturated compound or the like has at least one of a hydroxy group and a carboxy group, Hydrophilicity tends to decrease, and the function when a film obtained by curing a photosensitive resin layer is used as a protective film tends to be enhanced.
  • the blocked isocyanate compound refers to "a compound having a structure in which the isocyanate group of isocyanate is protected (so-called masked) with a blocking agent".
  • the dissociation temperature of the blocked isocyanate compound is not particularly limited, but is preferably 100°C to 160°C, more preferably 130°C to 150°C.
  • the dissociation temperature of the blocked isocyanate means "the temperature of the endothermic peak associated with the deprotection reaction of the blocked isocyanate as measured by DSC (Differential Scanning Calorimetry) analysis using a differential scanning calorimeter".
  • DSC Different Scanning Calorimetry
  • a differential scanning calorimeter for example, a differential scanning calorimeter (model: DSC6200) manufactured by Seiko Instruments Inc. can be preferably used. However, the differential scanning calorimeter is not limited to this.
  • Blocking agents having a dissociation temperature of 100° C. to 160° C. include active methylene compounds [malonic acid diesters (dimethyl malonate, diethyl malonate, di-n-butyl malonate, di-2-ethylhexyl malonate, etc.)] and oxime compounds.
  • malonic acid diesters dimethyl malonate, diethyl malonate, di-n-butyl malonate, di-2-ethylhexyl malonate, etc.
  • the blocking agent having a dissociation temperature of 100° C. to 160° C. preferably contains an oxime compound, for example, from the viewpoint of storage stability.
  • the blocked isocyanate compound preferably has an isocyanurate structure from the viewpoint of, for example, improving the brittleness of the film and improving the adhesion to the transferred material.
  • a blocked isocyanate compound having an isocyanurate structure can be obtained, for example, by converting hexamethylene diisocyanate into an isocyanurate for protection.
  • compounds having an oxime structure using an oxime compound as a blocking agent tend to have a dissociation temperature within a preferred range and can reduce development residues more easily than compounds having no oxime structure. This is preferable from the viewpoint of ease of use.
  • the blocked isocyanate compound may have a polymerizable group.
  • the polymerizable group is not particularly limited, and any known polymerizable group can be used, and a radically polymerizable group is preferred.
  • Polymerizable groups include groups having ethylenically unsaturated groups such as (meth)acryloxy groups, (meth)acrylamide groups and styryl groups, and epoxy groups such as glycidyl groups. Among them, the polymerizable group is preferably an ethylenically unsaturated group, more preferably a (meth)acryloxy group, and still more preferably an acryloxy group.
  • a commercial item can be used as a blocked isocyanate compound.
  • blocked isocyanate compounds include Karenz (registered trademark) AOI-BM, Karenz (registered trademark) MOI-BM, Karenz (registered trademark) MOI-BP, etc. (manufactured by Showa Denko K.K.), block type Duranate series (eg, Duranate (registered trademark) TPA-B80E, Duranate (registered trademark) WT32-B75P, etc., manufactured by Asahi Kasei Chemicals Corporation).
  • the compound of the following structure can also be used as a blocked isocyanate compound.
  • the thermally crosslinkable compounds may be used singly or in combination of two or more.
  • the content of the heat-crosslinkable compound is preferably 1% by mass to 50% by mass, and 5% by mass to 30% by mass, based on the total mass of the photosensitive resin layer. is more preferred.
  • the photosensitive resin layer may contain components other than the alkali-soluble resin, the ethylenically unsaturated compound, the photopolymerization initiator, the dye, the polymerization inhibitor and the thermally crosslinkable compound described above.
  • the photosensitive resin layer preferably contains a surfactant.
  • surfactants include anionic surfactants, cationic surfactants, nonionic (nonionic) surfactants, and amphoteric surfactants, with nonionic surfactants being preferred.
  • surfactants include surfactants described in paragraph 0017 of Japanese Patent No. 4502784 and paragraphs 0060 to 0071 of JP-A-2009-237362.
  • a fluorine-based surfactant or a silicone-based surfactant is preferable.
  • fluorosurfactants include MEGAFACE F-171, F-172, F-173, F-176, F-177, F-141, F-142, F-143, and F-144. , F-437, F-444, F-475, F-477, F-479, F-482, F-551-A, F-552, F-554, F-555-A, F-556, F -557, F-558, F-559, F-560, F-561, F-565, F-563, F-568, F-575, F-780, EXP. MFS-330, EXP.
  • MFS-578 EXP. MFS-578-2, EXP. MFS-579, EXP. MFS-586, EXP. MFS-587, EXP. MFS-628, EXP. MFS-631, EXP.
  • 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 is also preferable to use as the fluorosurfactant.
  • a block polymer can also be used as the fluorosurfactant.
  • the fluorosurfactant 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) (meta).
  • a fluorine-containing polymer compound containing structural units derived from an acrylate compound can also be preferably used.
  • a fluoropolymer having an ethylenically unsaturated group in a side chain can also be used as the fluorosurfactant.
  • Megafac (trade name) RS-101, RS-102, RS-718K, RS-72-K (manufactured by DIC Corporation) and the like.
  • Nonionic surfactants include glycerol, trimethylolpropane, trimethylolethane and their ethoxylates and propoxylates (e.g., glycerol propoxylate, glycerol ethoxylate, etc.), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, Polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester, Pluronic (trade name) L10, L31, L61, L62, 10R5, 17R2 , 25R2 (manufactured by BASF), Tetronic (trade name) 304, 701, 704, 901, 904, 150R1, HYDROPALAT WE 3323 (manufactured by BASF), Solsperse (trade name) 20000 (manufactured by Nippon
  • silicone-based surfactants include linear polymers composed of siloxane bonds, and modified siloxane polymers in which organic groups are introduced into side chains or terminals.
  • Specific examples of silicone surfactants include EXP. S-309-2, EXP. S-315, EXP. S-503-2, EXP.
  • the photosensitive resin layer may contain one type of surfactant alone, or may contain two or more types.
  • the content of the surfactant is preferably 0.001% by mass to 10% by mass, more preferably 0.01% by mass to 3% by mass, based on the total mass of the photosensitive resin layer.
  • the photosensitive resin layer may contain known additives, if necessary, in addition to the above components.
  • additives include plasticizers, heterocyclic compounds, benzotriazoles, carboxybenzotriazoles, pyridines (such as isonicotinamide), purine bases (such as adenine), and solvents.
  • the photosensitive resin layer may contain each additive singly or in combination of two or more.
  • benzotriazoles include 1,2,3-benzotriazole, 1-chloro-1,2,3-benzotriazole, bis(N-2-ethylhexyl)aminomethylene-1,2,3-benzotriazole, bis(N-2-ethylhexyl)aminomethylene-1,2,3-tolyltriazole, bis(N-2-hydroxyethyl)aminomethylene-1,2,3-benzotriazole and the like.
  • Carboxybenzotriazoles include, for example, 4-carboxy-1,2,3-benzotriazole, 5-carboxy-1,2,3-benzotriazole, N-(N,N-di-2-ethylhexyl)aminomethylene Carboxybenzotriazole, N-(N,N-di-2-hydroxyethyl)aminomethylene carboxybenzotriazole, N-(N,N-di-2-ethylhexyl)aminoethylene carboxybenzotriazole and the like.
  • carboxybenzotriazoles for example, commercial products such as CBT-1 (manufactured by Johoku Chemical Industry Co., Ltd., trade name) can be used.
  • the total content of benzotriazoles and carboxybenzotriazoles is preferably 0.01% by mass to 3% by mass, more preferably 0.05% by mass to 1% by mass, based on the total mass of the photosensitive resin layer. is more preferable.
  • the above content of 0.01% by mass or more is preferable from the viewpoint of imparting storage stability to the photosensitive resin layer.
  • setting the content to 3% by mass or less is preferable from the viewpoint of maintaining sensitivity and suppressing decolorization of the dye.
  • the photosensitive resin layer may contain at least one selected from the group consisting of plasticizers and heterocyclic compounds.
  • Plasticizers and heterocyclic compounds include compounds described in paragraphs 0097-0103 and 0111-0118 of WO2018/179640.
  • the photosensitive resin layer may contain a solvent.
  • the solvent may remain in the photosensitive resin layer.
  • the photosensitive resin layer contains metal oxide particles, antioxidants, dispersants, acid multipliers, development accelerators, conductive fibers, thermal radical polymerization initiators, thermal acid generators, ultraviolet absorbers, and thickeners. , a cross-linking agent, and an organic or inorganic suspending agent. Additives contained in the photosensitive resin layer are described in paragraphs 0165 to 0184 of JP-A-2014-85643, and the contents of this publication are incorporated herein.
  • 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, halogens and ions thereof.
  • halide ions, sodium ions, and potassium ions are likely to be mixed as impurities, so the following contents are preferable.
  • the content of impurities in the photosensitive resin layer is preferably 80 ppm or less, more preferably 10 ppm or less, and even more preferably 2 ppm or less on a mass basis.
  • the content of impurities can be 1 ppb or more, and may be 0.1 ppm or more, on a mass basis.
  • the amount of impurities can be made within the above range.
  • Impurities can be quantified by known methods such as ICP (Inductively Coupled Plasma) emission spectroscopy, atomic absorption spectroscopy, and ion chromatography.
  • ICP Inductively Coupled Plasma
  • the content of compounds such as benzene, formaldehyde, trichlorethylene, 1,3-butadiene, carbon tetrachloride, chloroform, N,N-dimethylformamide, N,N-dimethylacetamide, and hexane in the photosensitive resin layer should be small. is preferred.
  • the content of these compounds with respect to the total mass of the photosensitive resin layer is preferably 100 ppm or less, more preferably 20 ppm or less, and even more preferably 4 ppm or less, based on mass.
  • the lower limit can be 10 ppb or more, and can be 100 ppb or more based on the total weight of the photosensitive resin layer.
  • the content of these compounds can be suppressed in the same manner as the metal impurities described above. Moreover, it can quantify by a well-known measuring method.
  • the water content in the photosensitive resin layer is preferably 0.01% by mass to 1.0% by mass, more preferably 0.05% by mass to 0.5% by mass, from the viewpoint of improving reliability and lamination properties. .
  • the photosensitive resin layer may contain residual monomers corresponding to the constituent units of the alkali-soluble resin described above.
  • the content of the residual monomer is preferably 5,000 ppm by mass or less, more preferably 2,000 ppm by mass or less, and 500 ppm by mass or less, relative to the total mass of the alkali-soluble resin, from the viewpoints of patterning properties and reliability. is more preferred.
  • the lower limit is not particularly limited, it is preferably 1 mass ppm or more, more preferably 10 mass ppm or more.
  • the residual monomer of each structural unit of the alkali-soluble resin is preferably 3,000 ppm by mass or less, more preferably 600 ppm by mass or less, relative to the total mass of the photosensitive resin layer, from the viewpoints of patterning properties and reliability. , 100 ppm by mass or less is more preferable. Although the lower limit is not particularly limited, it is preferably 0.1 mass ppm or more, more preferably 1 mass ppm or more.
  • the amount of residual monomers when synthesizing an alkali-soluble resin by a polymer reaction is also within the above range.
  • the content of glycidyl acrylate is preferably within the above range.
  • the amount of residual monomers can be measured by known methods such as liquid chromatography and gas chromatography.
  • the layer thickness of the photosensitive resin layer is preferably 20 ⁇ m or less, more preferably 10 ⁇ m or less, even more preferably 8 ⁇ m or less, and 1 ⁇ m or more and 5 ⁇ m.
  • the layer thickness of each layer included in the photosensitive transfer material is based on an observation image obtained by observing a cross section in a direction perpendicular to the main surface of the photosensitive transfer material with a scanning electron microscope (SEM). It is measured by measuring the thickness of each layer at 10 points or more and calculating the average value.
  • SEM scanning electron microscope
  • the transmittance of the photosensitive resin layer for light with a wavelength of 365 nm is preferably 10% or more, preferably 30% or more, and more preferably 50% or more. Although the upper limit is not particularly limited, 99.9% or less is preferable.
  • 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 a photosensitive resin layer for example, a photosensitive resin composition containing an alkali-soluble resin, an ethylenically unsaturated compound, a photopolymerization initiator, a solvent, etc. is prepared, and a photosensitive layer is formed on the surface of a temporary support or the like.
  • a method of forming by applying a resin composition and drying a coating film of the photosensitive resin composition may be mentioned.
  • the photosensitive resin composition used for forming the photosensitive resin layer includes, for example, a composition containing an alkali-soluble resin, an ethylenically unsaturated compound, a photopolymerization initiator, the above optional components, and a solvent.
  • the photosensitive resin composition preferably contains a solvent in order to adjust the viscosity of the photosensitive resin composition and facilitate the formation of the photosensitive resin layer.
  • the solvent contained in the photosensitive resin composition is not particularly limited as long as it is capable of dissolving or dispersing the alkali-soluble resin, the ethylenically unsaturated compound, the photopolymerization initiator and the above optional components, and known solvents are used. can.
  • solvents include alkylene glycol ether solvents, alkylene glycol ether acetate solvents, alcohol solvents (methanol, ethanol, etc.), ketone solvents (acetone, methyl ethyl ketone, etc.), aromatic hydrocarbon solvents (toluene, etc.), aprotic polar solvents.
  • the photosensitive resin composition is selected from the group consisting of alkylene glycol ether solvents and alkylene glycol ether acetate solvents. It is preferable to contain at least one selected.
  • a mixed solvent containing at least one selected from the group consisting of alkylene glycol ether solvents and alkylene glycol ether acetate solvents and at least one selected from the group consisting of ketone solvents and cyclic ether solvents is more preferable.
  • a mixed solvent containing at least one selected from the group consisting of a glycol ether solvent and an alkylene glycol ether acetate solvent, a ketone solvent, and a cyclic ether solvent is more preferable.
  • Alkylene glycol ether solvents include, for example, ethylene glycol monoalkyl ether, ethylene glycol dialkyl ether, propylene glycol monoalkyl ether, propylene glycol dialkyl ether, diethylene glycol dialkyl ether, dipropylene glycol monoalkyl ether and dipropylene glycol dialkyl ether.
  • Alkylene glycol ether acetate solvents include, for example, ethylene glycol monoalkyl ether acetate, propylene glycol monoalkyl ether acetate, diethylene glycol monoalkyl ether acetate and dipropylene glycol monoalkyl ether acetate.
  • the solvent described in paragraphs 0092 to 0094 of WO 2018/179640, and the solvent described in paragraph 0014 of JP 2018-177889 may be used, the contents of which are herein incorporated into the book.
  • the photosensitive resin composition may contain one type of solvent alone, or may contain two or more types.
  • the content of the solvent when applying the photosensitive resin composition is preferably 50 parts by mass to 1,900 parts by mass, and 100 parts by mass to 900 parts by mass with respect to 100 parts by mass of the total solid content in the photosensitive resin composition. part is more preferred.
  • the method of preparing the photosensitive resin composition is not particularly limited, for example, by preparing a solution in which each component is dissolved in the solvent in advance and mixing the obtained solution in a predetermined ratio, the photosensitive resin composition and a method for preparing the
  • the photosensitive resin composition is preferably filtered using a filter with a pore size of 0.2 ⁇ m to 30 ⁇ m before forming the photosensitive resin layer.
  • the method of applying the photosensitive resin composition is not particularly limited, and a known method may be used.
  • coating methods include a printing method, a spray method, a roll coating method, a bar coating method, a curtain coating method, a spin coating method, and a die coating method (that is, a slit coating method).
  • the photosensitive resin layer may be formed by applying a photosensitive resin composition onto a protective film described below and drying the composition.
  • Heat drying and reduced pressure drying are preferable as a method for drying the coating film of the photosensitive resin composition.
  • the drying temperature is preferably 80° C. or higher, more preferably 90° C. or higher.
  • the upper limit thereof is preferably 130° C. or lower, more preferably 120° C. or lower. Drying can also be performed by changing the temperature continuously.
  • the drying time is preferably 20 seconds or longer, more preferably 40 seconds or longer, and even more preferably 60 seconds or longer.
  • the upper limit is not particularly limited, it is preferably 600 seconds or less, more preferably 300 seconds or less.
  • the photosensitive transfer material may comprise a thermoplastic resin layer.
  • the photosensitive transfer material preferably has a thermoplastic resin layer between the temporary support and the photosensitive resin layer. Since the photosensitive transfer material is provided with a thermoplastic resin layer between the temporary support and the photosensitive resin layer, the followability to the substrate in the step of bonding with the substrate is improved, and the substrate and the photosensitive transfer material are separated. This is because inclusion of air bubbles between the layers is suppressed, and adhesion with an adjacent layer (for example, a temporary support) is improved.
  • the thermoplastic resin layer preferably contains an alkali-soluble resin as the thermoplastic resin.
  • alkali-soluble resins include acrylic resins, polystyrene resins, styrene-acrylic copolymers, polyurethane resins, polyvinyl alcohol, polyvinyl formal, polyamide resins, polyester resins, polyamide resins, epoxy resins, polyacetal resins, polyhydroxystyrene resins, Polyimide resins, polybenzoxazole resins, polysiloxane resins, polyethyleneimines, polyallylamines and polyalkylene glycols.
  • an acrylic resin is preferable from the viewpoint of developability and adhesion to adjacent layers.
  • the acrylic resin is selected from the group consisting of structural units derived from (meth)acrylic acid, structural units derived from (meth)acrylic acid esters, and structural units derived from (meth)acrylic acid amides. It means a resin having at least one structural unit.
  • the acrylic resin the total content of structural units derived from (meth) acrylic acid, structural units derived from (meth) acrylic acid ester, and structural units derived from (meth) acrylic acid amide is It is preferably at least 50% by mass with respect to the total mass.
  • the total content of structural units derived from (meth)acrylic acid and structural units derived from (meth)acrylic ester is preferably 30% by mass to 100% by mass with respect to the total mass of the acrylic resin. , more preferably 50% by mass to 100% by mass.
  • the alkali-soluble resin is preferably a polymer having an acid group.
  • the acid group includes a carboxy group, a sulfo group, a phosphoric acid group and a phosphonic acid group, with the carboxy group being preferred.
  • the alkali-soluble resin is more preferably an alkali-soluble resin having an acid value of 60 mgKOH/g or more, and more 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, it is preferably 200 mgKOH/g or less, 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 that is a carboxy group-containing acrylic resin having an acid value of 60 mgKOH/g or more, described in paragraphs 0033 to 0052 of JP-A-2010-237589 A carboxy group-containing acrylic resin having an acid value of 60 mgKOH/g or more among the polymers, and a carboxy group having an acid value of 60 mgKOH/g or more among the alkali-soluble resins described in paragraphs 0053 to 0068 of JP-A-2016-224162.
  • 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, based on the total mass of the acrylic resin. % to 30% by mass is more preferred.
  • 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 group capable of addition polymerization, and includes an ethylenically unsaturated group; a polycondensable group such as a hydroxy group and a carboxyl group; a polyaddition reactive group such as an epoxy group and a (blocked) isocyanate group. 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 thermoplastic resin layer may contain one type of alkali-soluble resin alone, or may contain two or more types.
  • the content of the alkali-soluble resin is preferably 10% to 99% by mass, preferably 20% to 90% by mass, based on the total mass of the thermoplastic resin layer, from the viewpoint of developability and adhesion to adjacent layers. is more preferable, 40% by mass to 80% by mass is more preferable, and 50% by mass to 70% by mass is particularly preferable.
  • thermoplastic resin layer has a maximum absorption wavelength of 450 nm or more in a wavelength range of 400 nm to 780 nm when colored, and contains a dye whose maximum absorption wavelength is changed by an acid, a base, or a radical (also simply referred to as "dye B"). preferably.
  • Preferred embodiments of the dye B are the same as preferred embodiments of the dye N, except for the points described below.
  • Dye B is preferably a dye whose maximum absorption wavelength changes with acid or radicals, more preferably a dye whose maximum absorption wavelength changes with acid, from the viewpoint of visibility and resolution of exposed and unexposed areas.
  • the thermoplastic resin layer contains both a dye whose maximum absorption wavelength is changed by an acid as the dye B and a compound that generates an acid by light, which will be described later. It is preferable to contain
  • the dye B may be used singly or in combination of two or more.
  • the content of the dye B is preferably 0.2% by mass or more, and 0.2% to 6% by mass, based on the total mass of the thermoplastic resin layer, from the viewpoint of visibility of the exposed and unexposed areas. It is more preferably 0.2% by mass to 5% by mass, and particularly preferably 0.25% by mass to 3.0% by mass.
  • 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 the dye B will be described below using a dye that develops color by radicals as an example.
  • a solution of 0.001 g and 0.01 g of dye in 100 mL of methyl ethyl ketone is prepared.
  • a radical photopolymerization initiator Irgacure OXE01 (trade name, BASF Japan Co., Ltd.) is added to each of the solutions obtained, and radicals are generated by irradiation with light of 365 nm to bring all the dyes into a colored state. After that, the absorbance of each solution having a liquid temperature of 25° C.
  • thermoplastic resin layer is dissolved in methyl ethyl ketone instead of the dyes. From the absorbance of the obtained solution containing the thermoplastic resin layer, the amount of 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 upon exposure to light (also simply referred to as "compound C").
  • Compound C is preferably a compound that generates an acid, a base, or a radical upon receiving actinic rays such as ultraviolet rays and visible rays.
  • known photoacid generators, photobase generators, and photoradical polymerization initiators (photoradical generators) can be used. Among them, a photoacid generator is preferable.
  • thermoplastic resin layer preferably contains a photoacid generator.
  • the photoacid generator include photocationic polymerization initiators that may be contained in the photosensitive resin layer described above, and preferred embodiments are also the same except for the points described later.
  • the photoacid generator preferably contains at least one compound selected from the group consisting of onium salt compounds and oxime sulfonate compounds. From the viewpoint of adhesion, it is more preferable to contain an oxime sulfonate compound.
  • a photoacid generator having the following structure is also preferable.
  • the thermoplastic resin layer may contain a radical photopolymerization initiator (radical photopolymerization initiator).
  • radical photopolymerization initiator include the radical photopolymerization initiators that may be contained in the photosensitive resin layer described above, and preferred embodiments are 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 examples thereof include 2-nitrobenzylcyclohexylcarbamate, triphenylmethanol, O-carbamoylhydroxylamide, O-carbamoyloxime, 6-dinitrobenzyl)oxy]carbonyl ⁇ cyclohexylamine, bis ⁇ [(2-nitrobenzyl)oxy]carbonyl ⁇ hexane-1,6-diamine, 4-(methylthiobenzoyl)-1-methyl-1-morpholinoethane, ( 4-morpholinobenzoyl)-1-benzyl-1-dimethylaminopropane, N-(2-nitrobenzyloxycarbonyl)pyrrolidine, hexaamminecobalt (III) tris(triphenylmethylborate), 2-benzyl-2-dimethylamino -1-(4-morpholinophenyl)butanone,
  • the thermoplastic resin layer may contain compound C singly or in combination of two or more.
  • the content of compound C is preferably 0.1% by mass to 10% by mass, and 0.5% by mass, based on the total mass of the thermoplastic resin layer, from the viewpoint of visibility and resolution of exposed and unexposed areas. % by mass to 5% by mass is more preferred.
  • the thermoplastic resin layer preferably contains a plasticizer from the viewpoints of resolution, adhesion to adjacent layers, and developability.
  • the plasticizer preferably has a lower molecular weight (weight average molecular weight (Mw) if it is 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 the alkali-soluble resin, but from the viewpoint of imparting plasticity, the plasticizer preferably has an alkyleneoxy group in the molecule, and polyalkylene glycol Compounds are more preferred.
  • 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.
  • the alkali-soluble resin is an acrylic resin and the plasticizer contains a (meth)acrylate compound.
  • the (meth)acrylate compound used as the plasticizer include the (meth)acrylate compounds described as the ethylenically unsaturated compounds contained in the photosensitive resin layer.
  • both the thermoplastic resin layer and the photosensitive resin layer preferably contain the same (meth)acrylate compound. . This is because when the same (meth)acrylate compound is contained in the thermoplastic resin layer and the photosensitive resin layer, the diffusion of components between 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 viewpoint of resolution, adhesion with adjacent layers, and developability.
  • (Meth)acrylate compounds are 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 two or more types thereof.
  • the content of the plasticizer is preferably 1% by mass to 70% by mass, preferably 10% by mass to 60% by mass, based on the total mass of the thermoplastic resin layer, from the viewpoints of resolution, adhesion with adjacent layers, and developability. % by mass is more preferred, and 20% to 50% by mass is particularly preferred.
  • the thermoplastic resin layer preferably contains a surfactant.
  • surfactants include surfactants that may be contained in the above-described photosensitive resin layer, and preferred embodiments are also the same.
  • the thermoplastic resin layer may contain one type of surfactant alone, or may contain 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 includes sensitizers that may be contained in the photosensitive resin layer described above.
  • the thermoplastic resin layer may contain one type of sensitizer alone, or may contain 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 visibility of the exposed area and the non-exposed area, it is 0.01 mass with respect to the total mass of the thermoplastic resin layer. % to 5% by mass, more preferably 0.05% to 1% by mass.
  • thermoplastic resin layer may contain known additives, if necessary, in addition to the above components. Further, the thermoplastic resin layer is described in paragraphs 0189 to 0193 of JP-A-2014-85643, and the contents described in this publication are incorporated herein.
  • the layer thickness of the thermoplastic resin layer is not particularly limited, it is preferably 1 ⁇ m or more, more preferably 2 ⁇ m or more, from the viewpoint of adhesion to adjacent layers.
  • the upper limit is not particularly limited, it is preferably 20 ⁇ m or less, more preferably 10 ⁇ m or less, and even more preferably 5 ⁇ m or less from the viewpoint of developability and resolution.
  • 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 a thermoplastic resin layer for example, a thermoplastic resin composition containing the above components and a solvent is prepared, the thermoplastic resin composition is applied to the surface of a temporary support or the like, and the thermoplastic resin composition is formed. A method of forming by drying a coating film of a product can be mentioned.
  • 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.
  • thermoplastic resin composition is not particularly limited as long as it can dissolve or disperse the above components contained in the thermoplastic resin layer.
  • examples of the solvent contained in the thermoplastic resin composition include the solvent that may be contained in the photosensitive resin composition described above, and preferred embodiments are also the same.
  • the solvent contained in the thermoplastic resin composition may be of one type alone, or may be of two or more types.
  • the content of the solvent when applying the thermoplastic resin composition is preferably 50 parts by mass to 1,900 parts by mass, and 100 parts by mass to 900 parts by mass with respect to 100 parts by mass of the total solid content in the thermoplastic resin composition. part is more preferred.
  • thermoplastic resin composition and formation of the thermoplastic resin layer may be carried out according to the method of preparing the photosensitive resin composition and the method of forming the photosensitive resin layer described above.
  • the thermoplastic resin composition is prepared by previously preparing a solution in which each component contained in the thermoplastic resin layer is dissolved in the solvent, and mixing the resulting solution in a predetermined ratio, A thermoplastic resin layer is formed by applying the obtained thermoplastic resin composition to the surface of a temporary support and drying the coating film of the thermoplastic resin composition.
  • a thermoplastic resin layer may be formed on the surface of the water-soluble resin layer.
  • the photosensitive transfer material preferably has a water-soluble resin layer between the thermoplastic resin layer and the photosensitive resin layer.
  • the water-soluble resin layer is preferably a water-soluble layer from the viewpoint of developability and suppression of mixing of components during coating of multiple layers and storage after coating.
  • 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 water-soluble resin layer examples include an oxygen-blocking layer having an oxygen-blocking function, which is described as a "separation layer" in JP-A-5-72724. It is preferable that the water-soluble resin layer is an oxygen-blocking layer, because the sensitivity at the time of exposure is improved, the time load of the exposure machine is reduced, and the productivity is improved.
  • the oxygen barrier layer used as the water-soluble resin layer may be appropriately selected from known layers described in the above publications. Among them, 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 preferred.
  • the water-soluble resin layer preferably contains a resin.
  • resins contained in the water-soluble resin layer include polyvinyl alcohol-based resins, polyvinylpyrrolidone-based resins, cellulose-based resins, acrylamide-based resins, polyethylene oxide-based resins, gelatin, vinyl ether-based resins, polyamide resins, and these resins. Resins, such as a copolymer, are mentioned.
  • a water-soluble resin is preferable as the resin contained in the water-soluble resin layer.
  • the resin contained in the water-soluble resin layer includes the polymer A contained in the photosensitive resin layer and the thermoplastic resin (for example, it is preferably a resin different from any of the alkali-soluble resins).
  • the water-soluble resin layer preferably contains polyvinyl alcohol from the viewpoint of oxygen barrier properties and suppression of mixing of components during coating of multiple layers and storage after coating. It is more preferable to contain both.
  • the water-soluble resin layer may contain one of the above resins, or may contain two or more of them.
  • the content of the resin in the water-soluble resin layer is not particularly limited, but from the viewpoint of oxygen barrier properties and suppression of mixing of components during coating of multiple layers and storage after coating, the amount of the water-soluble resin layer is It is preferably 50% to 100% by mass, more preferably 70% to 100% by mass, still more preferably 80% to 100% by mass, and particularly preferably 90% to 100% by mass, based on the total mass.
  • the water-soluble resin layer may contain an additive such as a surfactant as necessary.
  • the layer thickness of the water-soluble resin layer is not particularly limited, it is preferably 0.1 ⁇ m to 5 ⁇ m, more preferably 0.5 ⁇ m to 3 ⁇ m.
  • the thickness of the water-soluble resin layer is within the above range, it is possible to suppress mixing of components during coating of multiple layers and during storage after coating without lowering the oxygen barrier properties, and during development. This is because an increase in the water-soluble resin layer removal time can be suppressed.
  • the method for forming the water-soluble resin layer is not particularly limited.
  • a water-soluble resin layer composition containing the above resin and optional additives is prepared and applied to the surface of the thermoplastic resin layer or photosensitive resin layer. and a method of forming a water-soluble resin layer by drying a coating film of a water-soluble resin layer composition.
  • the water-soluble resin layer composition preferably contains a solvent in order to adjust the viscosity of the water-soluble resin layer composition and facilitate the formation of the water-soluble resin layer.
  • the solvent contained in the water-soluble resin layer composition is not particularly limited as long as it can dissolve or disperse the resin, and is preferably at least one selected from the group consisting of water and water-miscible organic solvents.
  • Water or a mixed solvent of water and a water-miscible organic solvent is more preferable.
  • water-miscible organic solvents include alcohols having 1 to 3 carbon atoms, acetone, ethylene glycol and glycerin, with alcohols having 1 to 3 carbon atoms being preferred, and methanol or ethanol being more preferred.
  • the photosensitive transfer material preferably has a protective film in contact with the surface of the photosensitive resin layer not facing the temporary support.
  • Resin films include polyethylene films, polypropylene films, polyethylene terephthalate films, cellulose triacetate films, polystyrene films, and polycarbonate films. Among them, polyethylene film, polypropylene film, or polyethylene terephthalate film is preferable.
  • the thickness (layer thickness) of the protective film is not particularly limited, but is preferably 5 ⁇ m to 100 ⁇ m, more preferably 10 to 50 ⁇ m.
  • the arithmetic mean roughness Ra value of the surface of the protective film in contact with the photosensitive resin layer (hereinafter also simply referred to as "the surface of the protective film") is preferably 0.3 ⁇ m or less, and 0.3 ⁇ m or less from the viewpoint of better resolution. 1 ⁇ m or less is more preferable, and 0.05 ⁇ m or less is even more preferable. It is considered that the thickness uniformity of the photosensitive resin layer and the formed resin pattern is improved when the Ra value of the surface of the protective film is within the above range.
  • the lower limit of the Ra value of the surface of the protective film is not particularly limited, it is preferably 0.001 ⁇ m or more.
  • the Ra value of the surface of the protective film is measured by the following method. Using a three-dimensional optical profiler (New View 7300, manufactured by Zygo), the surface of the protective film is measured under the following conditions to obtain the surface profile of the optical film. As measurement/analysis software, Microscope Application of MetroPro ver 8.3.2 is used. Next, a Surface Map screen is displayed using the analysis software, and histogram data is obtained on the Surface Map screen. From the obtained histogram data, the arithmetic average roughness is calculated to obtain the surface Ra value of the protective film. When the protective film is attached to the photosensitive transfer material, the protective film may be peeled off from the photosensitive transfer material and the Ra value of the peeled surface may be measured.
  • a three-dimensional optical profiler As measurement/analysis software, Microscope Application of MetroPro ver 8.3.2 is used.
  • a Surface Map screen is displayed using the analysis software, and histogram data is obtained on the Surface Map screen. From the obtained histogram data, the arithmetic average roughness is calculated to obtain
  • the method of bonding the protective film to the photosensitive resin layer or the like is not particularly limited, and known methods can be used.
  • Apparatuses for bonding the protective film to the photosensitive resin layer or the like include known laminators such as a vacuum laminator and an autocut laminator.
  • the laminator is equipped with any heatable roller, such as a rubber roller, and can be applied with pressure and heat.
  • the photosensitive transfer material may include layers other than the layers described above (hereinafter also referred to as "other layers”).
  • Other layers include, for example, a contrast enhancement layer. Contrast enhancement layers are described in paragraph 0134 of WO2018/179640. Other layers are described in paragraphs 0194 to 0196 of JP-A-2014-85643. The contents of these publications are incorporated herein.
  • the total thickness of each layer excluding the temporary support and the protective film in the photosensitive transfer material is preferably 20 ⁇ m or less, more preferably 10 ⁇ m or less, and 8 ⁇ m or less from the viewpoint of exhibiting the effects of the present disclosure. more preferably, and particularly preferably 2 ⁇ m or more and 8 ⁇ m or less.
  • the total thickness of the photosensitive resin layer, the water-soluble resin layer and the thermoplastic resin layer in the photosensitive transfer material is preferably 20 ⁇ m or less, more preferably 10 ⁇ m or less, from the viewpoint of exhibiting the effects of the present disclosure. is more preferably 8 ⁇ m or less, and particularly preferably 2 ⁇ m or more and 8 ⁇ m or less.
  • the photosensitive transfer material according to the present disclosure can be suitably used for various applications requiring precision microfabrication by photolithography.
  • etching may be performed using the photosensitive resin layer as a film, or electroforming, which is mainly electroplating, may be performed.
  • the cured film obtained by patterning may be used as a permanent film, for example, as an interlayer insulating film, a wiring protective film, a wiring protective film having an index matching layer, and the like.
  • the photosensitive transfer material according to the present disclosure is used for various wiring formation applications of semiconductor packages, printed circuit boards, sensor substrates, touch panels, electromagnetic shielding materials, conductive films such as film heaters, liquid crystal sealing materials, micromachines and microelectronics fields It can be suitably used for applications such as the formation of structures in
  • the method for producing the photosensitive transfer material used in the present disclosure is not particularly limited, and known production methods such as known methods for forming each layer can be used.
  • a method for manufacturing a photosensitive transfer material according to the present disclosure will be described with reference to FIG.
  • the photosensitive transfer material according to the present disclosure is not limited to those having the configuration shown in FIG.
  • FIG. 1 is a schematic cross-sectional view showing an example of a layer structure in one embodiment of a photosensitive transfer material according to the present disclosure.
  • the photosensitive transfer material 20 shown in FIG. 1 has a structure in which a temporary support 11, a thermoplastic resin layer 13, a water-soluble resin layer 15, a photosensitive resin layer 17, and a protective film 19 are laminated in this order. have.
  • thermoplastic resin layer As a method for producing the photosensitive transfer material 20, for example, after applying a thermoplastic resin composition to the surface of the temporary support 11, by drying the coating film of the thermoplastic resin composition, the thermoplastic resin layer a step of forming a water-soluble resin layer 15 by applying a water-soluble resin layer composition to the surface of the thermoplastic resin layer 13 and then drying the coating film of the water-soluble resin layer composition; After applying a photosensitive resin composition containing an alkali-soluble resin and an ethylenically unsaturated compound to the surface of the water-soluble resin layer 15, the coating film of the photosensitive resin composition is dried to form a photosensitive resin layer 17.
  • thermoplastic resin composition containing at least one selected from the group consisting of alkylene glycol ether solvents and alkylene glycol ether acetate solvents, and selected from the group consisting of water and water-miscible organic solvents and an alkali-soluble resin, an ethylenically unsaturated compound, and at least one selected from the group consisting of alkylene glycol ether solvents and alkylene glycol ether acetate solvents. It is preferable to use a photosensitive resin composition.
  • the water-soluble resin layer composition is applied to the surface of the thermoplastic resin layer 13 and / or contained in the thermoplastic resin layer 13 during the storage period of the laminate having the coating film of the water-soluble resin layer composition. It is possible to suppress mixing of the component contained in the water-soluble resin layer 15 with the component contained in the water-soluble resin layer 15, and the application of the photosensitive resin composition to the surface of the water-soluble resin layer 15 and / or the photosensitive resin composition mixing of the components contained in the water-soluble resin layer 15 and the components contained in the photosensitive resin layer 17 during the storage period of the laminate having the coating film can be suppressed.
  • the photosensitive transfer material 20 is manufactured by pressing the protective film 19 onto the photosensitive resin layer 17 of the laminate manufactured by the manufacturing method described above.
  • a method for producing the photosensitive transfer material used in the present disclosure by including a step of providing a protective film 19 so as to be in contact with the second surface of the photosensitive resin layer 17, the temporary support 11, the thermoplastic resin layer 13, It is preferable to manufacture a photosensitive transfer material 20 comprising a water-soluble resin layer 15 , a photosensitive resin layer 17 and a protective film 19 .
  • the photosensitive transfer material 20 may be wound up to produce and store a roll-shaped photosensitive transfer material.
  • the photosensitive transfer material in roll form can be provided as it is to the lamination step with a substrate in a roll-to-roll system, which will be described later.
  • the photosensitive transfer material according to the present disclosure can be suitably used for various applications requiring precision microfabrication by photolithography.
  • etching may be performed using the photosensitive resin layer as a film, or electroforming, which is mainly electroplating, may be performed.
  • the cured film obtained by patterning may be used as a permanent film, for example, as an interlayer insulating film, a wiring protective film, a wiring protective film having an index matching layer, and the like.
  • the photosensitive transfer material according to the present disclosure is used for various wiring formation applications of semiconductor packages, printed circuit boards, sensor substrates, touch panels, electromagnetic shielding materials, conductive films such as film heaters, liquid crystal sealing materials, micromachines or microelectronics fields It can be suitably used for applications such as the formation of structures in
  • the photosensitive resin layer is preferably a colored resin layer containing a pigment.
  • Applications of the colored resin layer include, in addition to those described above, for example, liquid crystal display devices (LCD), and solid-state imaging devices [e.g., CCD (charge-coupled device) and CMOS (complementary metal oxide semiconductor)]. It is suitable for use in forming colored pixels such as filters or a black matrix. Aspects other than the pigment in the colored resin layer are the same as those described above.
  • the photosensitive resin layer may be a colored resin layer containing a pigment.
  • a cover glass with a black frame-shaped light-shielding layer formed on the periphery of the back surface of a transparent glass substrate or the like is attached to the liquid crystal display window.
  • a colored resin layer may be used to form such a light shielding layer.
  • the pigment may be appropriately selected according to the desired hue, and may be selected from black pigments, white pigments, and chromatic pigments other than black and white. Among them, when forming a black pattern, a black pigment is preferably selected as the pigment.
  • black pigment a known black pigment (organic pigment, inorganic pigment, etc.) can be appropriately selected as long as it does not impair the effects of the present disclosure.
  • black pigments include, for example, carbon black, titanium oxide, titanium carbide, iron oxide, titanium oxide and graphite, and carbon black is particularly preferred.
  • carbon black from the viewpoint of surface resistance, carbon black having at least a part of the surface coated with a resin is preferable.
  • the number average particle size of the black pigment is preferably 0.001 ⁇ m to 0.1 ⁇ m, more preferably 0.01 ⁇ m to 0.08 ⁇ m.
  • the particle size refers to the diameter of a circle obtained by obtaining the area of a pigment particle from a photographic image of the pigment particle taken with an electron microscope and considering a circle having the same area as the area of the pigment particle. is an average value obtained by obtaining the above particle size for 100 arbitrary particles and averaging the obtained 100 particle sizes.
  • White pigments described in paragraphs 0015 and 0114 of JP-A-2005-007765 can be used as pigments other than black pigments.
  • titanium oxide, zinc oxide, lithopone, light calcium carbonate, white carbon, aluminum oxide, aluminum hydroxide, or barium sulfate are preferable as inorganic pigments, and titanium oxide or zinc oxide is more preferable.
  • titanium oxide or zinc oxide is more preferable.
  • titanium oxide is more preferable.
  • rutile-type or anatase-type titanium oxide is more preferable, and rutile-type titanium oxide is particularly preferable.
  • the surface of titanium oxide may be subjected to silica treatment, alumina treatment, titania treatment, zirconia treatment, or organic substance treatment, or may be subjected to two or more treatments.
  • the catalytic activity of titanium oxide is suppressed, and the heat resistance, fade resistance, and the like are improved.
  • the surface treatment of the titanium oxide surface is preferably at least one of alumina treatment and zirconia treatment, and particularly preferably both alumina treatment and zirconia treatment.
  • the photosensitive resin layer when the photosensitive resin layer is a colored resin layer, from the viewpoint of transferability, the photosensitive resin layer preferably further contains a chromatic pigment other than the black pigment and the white pigment.
  • a chromatic pigment when a chromatic pigment is included, the particle size of the chromatic pigment is preferably 0.1 ⁇ m or less, more preferably 0.08 ⁇ m or less, from the viewpoint of better dispersibility.
  • chromatic pigments include Victoria Pure Blue BO (Color Index (hereinafter C.I.) 42595), Auramine (C.I. 41000), Fat Black HB (C.I. 26150), and Monolite. ⁇ Yellow GT (C.I. Pigment Yellow 12), Permanent Yellow GR (C.I. Pigment Yellow 17), Permanent Yellow HR (C.I.
  • Pigment Yellow 83 Permanent Carmine FBB (C) Pigment Red 146), Hoster Balm Red ESB (C.I. Pigment Violet 19), Permanent Ruby FBH (C.I. Pigment Red 11), Fastel Pink B Spra (C.I. Pigment Red 81), Monastral Fast Blue (C.I. Pigment Blue 15), Monolite Fast Black B (C.I. Pigment Black 1) and Carbon, C.I. I. Pigment Red 97, C.I. I. Pigment Red 122, C.I. I. Pigment Red 149, C.I. I. Pigment Red 168, C.I. I. Pigment Red 177, C.I. I. Pigment Red 180, C.I. I. Pigment Red 192, C.I. I.
  • C.I. I. Pigment Red 177 is preferred.
  • the content of the pigment is preferably more than 3% by mass and 40% by mass or less, more preferably more than 3% by mass and 35% by mass or less, relative to the total mass of the photosensitive resin layer. , more preferably more than 5% by mass and 35% by mass or less, and particularly preferably 10% by mass or more and 35% by mass or less.
  • the content of pigments other than black pigments is preferably 30% by mass or less, and 1% by mass to 20% by mass is more preferable, and 3% to 15% by mass is even more preferable.
  • the black pigment (preferably carbon black) is added to the photosensitive resin composition in the form of a pigment dispersion. It is preferably introduced into an object.
  • the dispersion liquid may be prepared by adding a mixture obtained by previously mixing a black pigment and a pigment dispersant to an organic solvent (or vehicle) and dispersing the mixture with a dispersing machine.
  • a pigment dispersant may be selected according to the pigment and solvent, and for example, a commercially available dispersant can be used.
  • the vehicle refers to the part of the medium in which the pigment is dispersed when it is made into a pigment dispersion, and is a liquid binder component that holds the black pigment in a dispersed state, and a solvent component that dissolves and dilutes the binder component. (Organic solvent) and.
  • the disperser is not particularly limited, and includes known dispersers such as kneaders, roll mills, attritors, super mills, dissolvers, homomixers, and sand mills. Furthermore, it may be finely pulverized using frictional force by mechanical grinding. Regarding the dispersing machine and the fine pulverization, reference can be made to the description in "Encyclopedia of Pigment” (Kunizo Asakura, 1st edition, Asakura Shoten, 2000, pp. 438, 310).
  • a photosensitive transfer material 10 shown in FIG. 2 has a temporary support 1, a transfer layer 2 including a photosensitive resin layer 3 and a refractive index adjusting layer 5, and a protective film 7 in this order. Further, the photosensitive transfer material 10 shown in FIG. 2 has a form in which the refractive index adjustment layer 5 is arranged, but the refractive index adjustment layer 5 may not be arranged.
  • the temporary support and the protective film used in the photosensitive transfer material of the second embodiment are the same as the temporary support and the protective film in the photosensitive transfer material of the first embodiment, and preferred aspects are also the same.
  • a photosensitive transfer material has a photosensitive resin layer.
  • a pattern can be formed on the transferred body by performing exposure and development after transferring the photosensitive resin layer onto the transferred body. Components that can be contained in the photosensitive resin layer are described in detail below.
  • Alkali-soluble resins include, for example, (meth)acrylic resins, styrene resins, epoxy resins, amide resins, amidoepoxy resins, alkyd resins, phenolic resins, ester resins, urethane resins, and reactions between epoxy resins and (meth)acrylic acid. and an acid-modified epoxy acrylate resin obtained by reacting an epoxy acrylate resin with an acid anhydride.
  • a preferred embodiment of the alkali-soluble resin is a (meth)acrylic resin because of its excellent alkali developability and film formability.
  • the (meth)acrylic resin means a resin having a structural unit derived from a (meth)acrylic compound.
  • the content of structural units derived from the (meth)acrylic compound is preferably 50% by mass or more, more preferably 70% by mass or more, and still more preferably 90% by mass or more, based on all the structural units of the (meth)acrylic resin.
  • the (meth)acrylic resin may be composed only of structural units derived from the (meth)acrylic compound, or may have structural units derived from polymerizable monomers other than the (meth)acrylic compound. . That is, the upper limit of the content of structural units derived from the (meth)acrylic compound is 100% by mass or less with respect to all structural units of the (meth)acrylic resin.
  • (Meth)acrylic compounds include, for example, (meth)acrylic acid, (meth)acrylic acid esters, (meth)acrylamides, and (meth)acrylonitrile.
  • (meth)acrylic acid esters include (meth)acrylic acid alkyl ester, (meth)acrylic acid tetrahydrofurfuryl ester, (meth)acrylic acid dimethylaminoethyl ester, (meth)acrylic acid diethylaminoethyl ester, (meth) ) acrylic acid glycidyl ester, (meth)acrylic acid benzyl ester, 2,2,2-trifluoroethyl (meth)acrylate, and 2,2,3,3-tetrafluoropropyl (meth)acrylate, ( Meth)acrylic acid alkyl esters are preferred.
  • (Meth)acrylamides include, for example, acrylamides such as diacetone acrylamide.
  • Examples of (meth)acrylic acid alkyl esters include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, pentyl (meth)acrylate, and (meth)acrylate.
  • Examples include (meth)acrylic acid alkyl esters having an alkyl group having 1 to 12 carbon atoms such as dodecyl (meth)acrylate.
  • an alkyl (meth)acrylic acid ester having an alkyl group having 1 to 4 carbon atoms is preferable, and methyl (meth)acrylate or ethyl (meth)acrylate is more preferable.
  • the (meth)acrylic resin may have a structural unit other than the structural unit derived from the (meth)acrylic compound.
  • the polymerizable monomer forming the structural unit is not particularly limited as long as it is a compound other than the (meth)acrylic compound copolymerizable with the (meth)acrylic compound.
  • Examples include styrene, vinyl toluene, and ⁇ - Styrene compounds optionally having a substituent at the ⁇ -position or aromatic ring such as methylstyrene, vinyl alcohol esters such as acrylonitrile and vinyl-n-butyl ether, maleic acid, maleic anhydride, monomethyl maleate, maleic acid Maleic acid monoesters such as monoethyl and monoisopropyl maleate, fumaric acid, cinnamic acid, ⁇ -cyanocinnamic acid, itaconic acid and crotonic acid. These polymerizable monomers may be used singly or in combination of two or more.
  • the (meth)acrylic resin preferably has a constitutional unit having an acid group from the viewpoint of improving alkali developability.
  • Acid groups include, for example, carboxy groups, sulfo groups, phosphoric acid groups, and phosphonic acid groups.
  • the (meth)acrylic resin more preferably has a structural unit having a carboxy group, and more preferably has a structural unit derived from the above (meth)acrylic acid.
  • the content of the structural unit having an acid group (preferably a structural unit derived from (meth)acrylic acid) in the (meth)acrylic resin is excellent in developability, relative to the total mass of the (meth)acrylic resin, 10 mass % or more is preferable.
  • the upper limit is not particularly limited, it is preferably 50% by mass or less, more preferably 40% by mass or less, from the viewpoint of excellent alkali resistance.
  • the (meth)acrylic resin more preferably has structural units derived from the (meth)acrylic acid alkyl ester described above.
  • the content of structural units derived from (meth)acrylic acid alkyl ester in the (meth)acrylic resin is preferably 50% by mass to 90% by mass, and 60% by mass to 90% by mass is more preferable, and 65% to 90% by mass is even more preferable.
  • the (meth)acrylic resin a resin having both a structural unit derived from (meth)acrylic acid and a structural unit derived from a (meth)acrylic acid alkyl ester is preferable, and a structural unit derived from (meth)acrylic acid and A resin composed only of structural units derived from a (meth)acrylic acid alkyl ester is more preferable.
  • an acrylic resin having a structural unit derived from methacrylic acid, a structural unit derived from methyl methacrylate, and a structural unit derived from ethyl acrylate is also preferable.
  • the (meth)acrylic resin may have at least one selected from the group consisting of a structural unit derived from methacrylic acid and a structural unit derived from a methacrylic acid alkyl ester, from the viewpoint of better effects in the present disclosure.
  • it has both a structural unit derived from methacrylic acid and a structural unit derived from a methacrylic acid alkyl ester.
  • the total content of the structural units derived from methacrylic acid and the structural units derived from methacrylic acid alkyl esters in the (meth) acrylic resin is 40% by mass or more is preferable, and 60% by mass or more is more preferable.
  • the upper limit is not particularly limited, and may be 100% by mass or less, preferably 80% by mass or less.
  • the (meth)acrylic resin has at least one selected from the group consisting of structural units derived from methacrylic acid and structural units derived from methacrylic acid alkyl esters, and acrylic acid It is also preferable to have at least one selected from the group consisting of structural units derived from and structural units derived from acrylic acid alkyl esters.
  • the total content of the structural units derived from methacrylic acid and the structural units derived from the methacrylic acid alkyl ester is is preferably 60/40 to 80/20 in mass ratio with respect to the total content of
  • the (meth)acrylic resin preferably has an ester group at its terminal from the viewpoint of excellent developability of the photosensitive resin layer after transfer.
  • the terminal portion of the (meth)acrylic resin is composed of a site derived from the polymerization initiator used in the synthesis.
  • a (meth)acrylic resin having an ester group at its terminal can be synthesized by using a polymerization initiator that generates a radical having an ester group.
  • the alkali-soluble resin is preferably an alkali-soluble resin having an acid value of 60 mgKOH/g or more, for example, from the viewpoint of developability.
  • the alkali-soluble resin is, for example, a resin having a carboxy group with an acid value of 60 mgKOH/g or more (so-called carboxy group-containing resin) because it is thermally cross-linked with a cross-linking component by heating and tends to form a strong film. More preferably, it is a (meth)acrylic resin having a carboxy group with an acid value of 60 mgKOH/g or more (so-called carboxy group-containing (meth)acrylic resin).
  • the alkali-soluble resin is a resin having a carboxy group
  • a thermally crosslinkable compound such as a blocked isocyanate compound and thermally crosslinking
  • the three-dimensional crosslinking density can be increased.
  • the carboxy group of the resin having a carboxy group is dehydrated and hydrophobized, the wet heat resistance can be improved.
  • the carboxy group-containing (meth)acrylic resin having an acid value of 60 mgKOH/g or more is not particularly limited as long as it satisfies the acid value conditions described above, and can be appropriately selected from known (meth)acrylic resins.
  • a carboxy group-containing acrylic resin having an acid value of 60 mgKOH/g or more among the polymers described in paragraphs 0033 to 0052 of JP-A-2010-237589, a carboxy group-containing acrylic resin having an acid value of 60 mgKOH/g or more , a carboxy group-containing acrylic resin having an acid value of 60 mgKOH/g or more can be preferably used.
  • the alkali-soluble resin is a styrene-acrylic copolymer.
  • the styrene-acrylic copolymer refers to a resin having a structural unit derived from a styrene compound and a structural unit derived from a (meth)acrylic compound, and a structural unit derived from the styrene compound.
  • the total content of structural units derived from the (meth)acrylic compound is preferably 30% by mass or more, more preferably 50% by mass or more, based on all the structural units of the copolymer.
  • the content of structural units derived from a styrene compound is preferably 1% by mass or more, more preferably 5% by mass or more, more preferably 5% by mass to 80% by mass, based on the total structural units of the copolymer. preferable.
  • the content of the structural unit derived from the (meth)acrylic compound is preferably 5% by mass or more, more preferably 10% by mass or more, based on the total structural units of the copolymer, and is 20% to 95% by mass. % by mass is more preferred.
  • the alkali-soluble resin preferably has an aromatic ring structure, and more preferably has a structural unit having an aromatic ring structure, from the viewpoint of better effects in the present disclosure.
  • monomers forming structural units having an aromatic ring structure include styrene compounds such as styrene, tert-butoxystyrene, methylstyrene, and ⁇ -methylstyrene, and benzyl (meth)acrylate. Among them, styrene compounds are preferred, and styrene is more preferred.
  • the alkali-soluble resin more preferably has a structural unit represented by the following formula (S) (a structural unit derived from styrene) from the viewpoint of more excellent effects in the present disclosure.
  • the content of the structural unit having an aromatic ring structure is 5 mass with respect to all structural units of the alkali-soluble resin, from the viewpoint that the effects in the present disclosure are more excellent. % to 90% by mass, more preferably 10% to 70% by mass, and even more preferably 20% to 60% by mass.
  • the content of the structural unit having an aromatic ring structure in the alkali-soluble resin is preferably 5 mol% to 70 mol% with respect to the total structural units of the alkali-soluble resin, from the viewpoint of more excellent effects in the present disclosure, and 10 mol % to 60 mol % is more preferable, and 20 mol % to 60 mol % is even more preferable.
  • the content of the structural unit represented by the above formula (S) in the alkali-soluble resin is 5 mol% to 70 mol% with respect to the total structural units of the alkali-soluble resin, since the effect in the present disclosure is more excellent. is preferred, 10 mol % to 60 mol % is more preferred, 20 mol % to 60 mol % is even more preferred, and 20 mol % to 50 mol % is particularly preferred.
  • the above-mentioned "structural unit” shall be synonymous with the "monomer unit”.
  • the above-mentioned "monomer unit” may be modified after polymerization by a polymer reaction or the like. The same applies to the following.
  • the alkali-soluble resin preferably has an aliphatic hydrocarbon ring structure from the viewpoint of better effects in the present disclosure.
  • the alkali-soluble resin preferably has structural units having an aliphatic hydrocarbon ring structure.
  • the alkali-soluble resin more preferably has a ring structure in which two or more aliphatic hydrocarbon rings are condensed.
  • rings constituting the aliphatic hydrocarbon ring structure in the constituent unit having the aliphatic hydrocarbon ring structure include tricyclodecane ring, cyclohexane ring, cyclopentane ring, norbornane ring, and isoboron ring.
  • a ring obtained by condensing two or more aliphatic hydrocarbon rings is preferable, and a tetrahydrodicyclopentadiene ring (tricyclo[5.2.1.0 2,6 ]decane ring ) is more preferred.
  • Monomers that form structural units having an aliphatic hydrocarbon ring structure include dicyclopentanyl (meth)acrylate, cyclohexyl (meth)acrylate, and isobornyl (meth)acrylate.
  • the alkali-soluble resin more preferably has a structural unit represented by the following formula (Cy) from the viewpoint of more excellent effects in the present disclosure, and a structural unit represented by the above formula (S) and the following It is more preferable to have a structural unit represented by formula (Cy).
  • RM represents a hydrogen atom or a methyl group
  • R Cy represents a monovalent group having an aliphatic hydrocarbon ring structure
  • RM in formula ( Cy ) is preferably a methyl group.
  • R Cy in the formula (Cy) is preferably a monovalent group having an aliphatic hydrocarbon ring structure having 5 to 20 carbon atoms from the viewpoint of better effects in the present disclosure, and an aliphatic group having 6 to 16 carbon atoms.
  • a monovalent group having an aliphatic hydrocarbon ring structure is more preferred, and a monovalent group having an aliphatic hydrocarbon ring structure having 8 to 14 carbon atoms is even more preferred.
  • the aliphatic hydrocarbon ring structure in R Cy of formula (Cy) may be a monocyclic structure or a polycyclic structure.
  • the aliphatic hydrocarbon ring structure in R Cy of formula (Cy) is a cyclopentane ring structure, a cyclohexane ring structure, a tetrahydrodicyclopentadiene ring structure, a norbornane ring structure, or An isoboron ring structure is preferred, a cyclohexane ring structure or a tetrahydrodicyclopentadiene ring structure is more preferred, and a tetrahydrodicyclopentadiene ring structure is even more preferred.
  • the aliphatic hydrocarbon ring structure in R Cy of formula (Cy) is preferably a ring structure in which two or more aliphatic hydrocarbon rings are condensed, from the viewpoint of more excellent effects in the present disclosure. It is more preferable that the ring is a condensed ring of 1 to 4 aliphatic hydrocarbon rings.
  • the alkali-soluble resin may have one type of structural unit having an aliphatic hydrocarbon ring structure, or may have two or more types.
  • the content of the structural unit having an aliphatic hydrocarbon ring structure is the total structural units of the alkali-soluble resin from the viewpoint that the effect in the present disclosure is more excellent. is preferably 5% by mass to 90% by mass, more preferably 10% by mass to 80% by mass, and even more preferably 20% by mass to 70% by mass.
  • the content of the structural unit having an aliphatic hydrocarbon ring structure in the alkali-soluble resin is 5 mol% to 70 mol% with respect to the total structural units of the alkali-soluble resin, since the effects in the present disclosure are more excellent. It is preferably 10 mol % to 60 mol %, even more preferably 20 mol % to 50 mol %. Furthermore, the content of the structural unit represented by the above formula (Cy) in the alkali-soluble resin is 5 mol% to 70 mol% with respect to the total structural units of the alkali-soluble resin, since the effect in the present disclosure is more excellent. is preferred, 10 mol % to 60 mol % is more preferred, and 20 mol % to 50 mol % is even more preferred.
  • the alkali-soluble resin has a structural unit having an aromatic ring structure and a structural unit having an aliphatic hydrocarbon ring structure
  • the total content of structural units having an aromatic ring structure and a structural unit having an aliphatic hydrocarbon ring structure is From the viewpoint that the effect in the present disclosure is more excellent, 10% by mass to 90% by mass is preferable, 20% by mass to 80% by mass is more preferable, and 40% by mass to 75% by mass is preferable with respect to the total structural units of the alkali-soluble resin. More preferred.
  • the total content of structural units having an aromatic ring structure and structural units having an aliphatic hydrocarbon ring structure in the alkali-soluble resin is relative to all structural units of the alkali-soluble resin, since the effect in the present disclosure is more excellent. , preferably 10 mol % to 80 mol %, more preferably 20 mol % to 70 mol %, even more preferably 40 mol % to 60 mol %. Furthermore, the total content of the structural units represented by the above formula (S) and the structural units represented by the above formula (Cy) in the alkali-soluble resin is the total content of the alkali-soluble resin, since the effect in the present disclosure is more excellent.
  • the molar amount nS of the structural unit represented by the formula (S) and the molar amount nCy of the structural unit represented by the formula (Cy) in the alkali-soluble resin are more excellent in the effects of the present disclosure, It preferably satisfies the relationship represented by the following formula (SCy), more preferably satisfies the following formula (SCy-1), and further preferably satisfies the following formula (SCy-2).
  • the alkali-soluble resin preferably has a constitutional unit having an acid group from the viewpoint of better effects in the present disclosure.
  • the acid group include a carboxy group, a sulfo group, a phosphonic acid group, and a phosphoric acid group, with the carboxy group being preferred.
  • the structural unit having an acid group a structural unit derived from (meth)acrylic acid shown below is preferable, and a structural unit derived from methacrylic acid is more preferable.
  • the alkali-soluble resin may have one type of structural unit having an acid group, or may have two or more types.
  • the content of the structural unit having an acid group is 5% by mass or more with respect to the total structural units of the alkali-soluble resin, since the effects in the present disclosure are more excellent. 50% by mass is preferable, 5% to 40% by mass is more preferable, and 10% to 30% by mass is even more preferable.
  • the content of the structural unit having an acid group in the alkali-soluble resin is preferably 5 mol% to 70 mol%, and 10 mol, based on the total structural units of the alkali-soluble resin, from the viewpoint of more excellent effects in the present disclosure.
  • the content of structural units derived from (meth)acrylic acid in the alkali-soluble resin is preferably 5 mol% to 70 mol% with respect to the total structural units of the alkali-soluble resin, from the viewpoint that the effects of the present disclosure are more excellent. , more preferably 10 mol % to 50 mol %, even more preferably 20 mol % to 40 mol %.
  • the alkali-soluble resin preferably has a reactive group, and more preferably has a structural unit having a reactive group, from the viewpoint of better effects in the present disclosure.
  • the reactive group is preferably a radically polymerizable group, more preferably an ethylenically unsaturated group.
  • the alkali-soluble resin preferably has a structural unit having an ethylenically unsaturated group in its side chain.
  • the term "main chain” refers to the relatively longest bond chain in the molecule of the polymer compound that constitutes the resin
  • side chain refers to an atomic group branched from the main chain. show.
  • the ethylenically unsaturated group is more preferably an allyl group or a (meth)acryloxy group. Examples of structural units having a reactive group include, but are not limited to, those shown below.
  • the alkali-soluble resin may have one type of structural unit having a reactive group, or may have two or more types.
  • the content of the structural unit having a reactive group is 5 mass with respect to all the structural units of the alkali-soluble resin, since the effects in the present disclosure are more excellent.
  • % to 70% by mass more preferably 10% to 50% by mass, and even more preferably 20% to 40% by mass.
  • the content of the structural unit having a reactive group in the alkali-soluble resin is preferably 5 mol% to 70 mol% with respect to the total structural units of the alkali-soluble resin, from the viewpoint that the effects of the present disclosure are more excellent, and 10 mol % to 60 mol % is more preferable, and 20 mol % to 50 mol % is even more preferable.
  • a reactive group into an alkali-soluble resin functional groups such as a hydroxyl group, a carboxyl group, a primary amino group, a secondary amino group, an acetoacetyl group, and a sulfo group may be added to an epoxy compound, a block A method of reacting a compound such as an isocyanate compound, an isocyanate compound, a vinyl sulfone compound, an aldehyde compound, a methylol compound, and a carboxylic acid anhydride can be mentioned.
  • glycidyl (meth) A means of introducing a (meth)acryloxy group into a polymer by reacting an acrylate can be mentioned. By this means, an alkali-soluble resin having (meth)acryloxy groups in side chains can be obtained.
  • the polymerization reaction is preferably carried out at a temperature of 70°C to 100°C, more preferably at a temperature of 80°C to 90°C.
  • an azo initiator is preferable, and for example, V-601 (trade name) or V-65 (trade name) manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd. is more preferable.
  • the polymer reaction is preferably carried out under temperature conditions of 80°C to 110°C. In the polymer reaction, it is preferable to use a catalyst such as an ammonium salt.
  • the resins shown below are preferable because the effects of the present disclosure are more excellent.
  • the content ratio (a to d) of each structural unit shown below, the weight average molecular weight Mw, and the like can be appropriately changed depending on the purpose.
  • the alkali-soluble resin may also contain a polymer having a structural unit having a carboxylic anhydride structure (hereinafter also referred to as "polymer X").
  • the carboxylic anhydride structure may be either a linear carboxylic anhydride structure or a cyclic carboxylic anhydride structure, but is preferably a cyclic carboxylic anhydride structure.
  • the ring of the cyclic carboxylic acid anhydride structure is preferably a 5- to 7-membered ring, more preferably a 5- or 6-membered ring, and still more preferably a 5-membered ring.
  • a structural unit having a carboxylic anhydride structure is a structural unit containing in the main chain a divalent group obtained by removing two hydrogen atoms from a compound represented by the following formula P-1, or a structural unit represented by the following formula P-1 It is preferably a structural unit in which a monovalent group obtained by removing one hydrogen atom from the represented compound is bonded to the main chain directly or via a divalent linking group.
  • R A1a represents a substituent
  • n 1a R A1a may be the same or different
  • Examples of the substituent represented by RA1a include an alkyl group.
  • Z 1a is preferably an alkylene group having 2 to 4 carbon atoms, more preferably an alkylene group having 2 or 3 carbon atoms, and still more preferably an alkylene group having 2 carbon atoms.
  • n1a represents an integer of 0 or more.
  • Z 1a represents an alkylene group having 2 to 4 carbon atoms
  • n 1a is preferably an integer of 0 to 4, more preferably an integer of 0 to 2, even more preferably 0.
  • multiple R A1a may be the same or different.
  • two or more RA1a groups may combine with each other to form a ring, but preferably do not combine with each other to form a ring.
  • the structural unit having a carboxylic anhydride structure is preferably a structural unit derived from an unsaturated carboxylic anhydride, more preferably a structural unit derived from an unsaturated cyclic carboxylic anhydride, and an unsaturated aliphatic cyclic carboxylic acid anhydride.
  • Structural units derived from acid anhydride are more preferred, structural units derived from maleic anhydride or itaconic anhydride are particularly preferred, and structural units derived from maleic anhydride are most preferred.
  • Rx represents a hydrogen atom, a methyl group, a CH2OH group, or a CF3 group
  • Me represents a methyl group
  • the structural unit having a carboxylic anhydride structure in the polymer X may be of one type alone, or may be of two or more types.
  • the total content of structural units having a carboxylic anhydride structure is preferably 0 mol% to 60 mol%, more preferably 5 mol% to 40 mol%, and 10 mol% with respect to all structural units of polymer X. ⁇ 35 mol% is more preferred.
  • the photosensitive resin layer may contain only one type of polymer X, or may contain two or more types.
  • the content of the polymer X is 0.1% by mass to 30% by mass with respect to the total mass of the photosensitive resin layer, because the effect in the present disclosure is more excellent. is preferred, 0.2% by mass to 20% by mass is more preferred, 0.5% by mass to 20% by mass is even more preferred, and 1% by mass to 20% by mass is even more preferred.
  • the weight average molecular weight (Mw) of the alkali-soluble resin is preferably 5,000 or more, more preferably 10,000 or more, still more preferably 10,000 to 50,000, from the viewpoint of better effects in the present disclosure. 000 to 30,000 are particularly preferred.
  • the acid value of the alkali-soluble resin is preferably 10 mgKOH/g to 200 mgKOH/g, more preferably 60 mgKOH/g to 200 mgKOH/g, still more preferably 60 mgKOH/g to 150 mgKOH/g, and particularly preferably 60 mgKOH/g to 110 mgKOH/g. .
  • the acid value of the alkali-soluble resin is a value measured according to the method described in JIS K0070:1992.
  • the photosensitive resin layer may contain only one type of alkali-soluble resin, or may contain two or more types.
  • the content of the alkali-soluble resin is preferably 10% by mass to 90% by mass, more preferably 20% by mass to 80% by mass, based on the total mass of the photosensitive resin layer, from the viewpoint of more excellent effects in the present disclosure. 30% by mass to 70% by mass is more preferable.
  • the photosensitive resin layer contains an ethylenically unsaturated compound.
  • a (meth)acryloxy group is preferred as the ethylenically unsaturated group.
  • the ethylenically unsaturated compound in the present specification is a compound other than the alkali-soluble resin, and preferably has a molecular weight of less than 5,000.
  • preferred aspects of the ethylenically unsaturated compound used in the second embodiment include preferred aspects of the ethylenically unsaturated compound used in the above-described first embodiment.
  • One preferred embodiment of the ethylenically unsaturated compound is a compound represented by the following formula (M) (also simply referred to as "compound M”).
  • Q 2 -R 1 -Q 1 Formula (M) Q 1 and Q 2 each independently represent a (meth)acryloyloxy group, and R 1 represents a divalent linking group having a chain structure.
  • Q 1 and Q 2 in formula (M) are preferably the same group from the viewpoint of ease of synthesis. Moreover, Q 1 and Q 2 in formula (M) are preferably acryloyloxy groups from the viewpoint of reactivity.
  • R 1 in formula (M) is an alkylene group, an alkyleneoxyalkylene group (-L 1 -OL 1 -), or a polyalkyleneoxyalkylene group (-(L 1 -O) p -L 1 -) is preferred, a hydrocarbon group having 2 to 20 carbon atoms or a polyalkyleneoxyalkylene group is more preferred, an alkylene group having 4 to 20 carbon atoms is even more preferred, and 6 to 6 carbon atoms. 18 straight-chain alkylene groups are particularly preferred.
  • the hydrocarbon group may at least partially have a chain structure, and the portion other than the chain structure is not particularly limited. 5 linear alkylene group, arylene group, ether bond, and combinations thereof, preferably an alkylene group or a group in which two or more alkylene groups and one or more arylene groups are combined. , an alkylene group is more preferred, and a linear alkylene group is even more preferred.
  • Each L 1 above independently represents an alkylene group, preferably an ethylene group, a propylene group or a butylene group, more preferably an ethylene group or a 1,2-propylene group.
  • p represents an integer of 2 or more, preferably an integer of 2-10.
  • the number of atoms in the shortest linking chain linking Q 1 and Q 2 in compound M is preferably 3 to 50, more preferably 4 to 40, from the viewpoint of more excellent effects in the present disclosure.
  • 6 to 20 are more preferable, and 8 to 12 are particularly preferable.
  • the number of atoms in the shortest linking chain linking Q1 and Q2 refers to the number of atoms in R1 linking Q1 to the atom in R1 linking Q2 . It is the shortest number of atoms.
  • compound M examples include 1,3-butanediol di(meth)acrylate, tetramethylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,7-heptanediol di(meth)acrylate, 1,8-octanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, 1, 4-cyclohexanediol di(meth)acrylate, tricyclodecanedimethanol di(meth)acrylate, hydrogenated bisphenol A di(meth)acrylate, hydrogenated bisphenol F di(meth)acrylate, polyethylene glycol di(meth)acrylate , polypropylene glycol di(meth)acrylate, poly(ethylene glycol/propylene glycol) di
  • ester monomers can also be used as a mixture.
  • 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, and 1,10-decanediol di(meth)acrylate are preferred because they have superior effects in the present disclosure.
  • neopentyl glycol di(meth)acrylate preferably at least one compound selected from the group consisting of 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth) ) acrylate and 1,10-decanediol di(meth)acrylate, more preferably at least one compound selected from the group consisting of 1,9-nonanediol di(meth)acrylate and 1 , 10-decanediol di(meth)acrylate is more preferable.
  • the ethylenically unsaturated compound more than bifunctional is mentioned.
  • the term "bifunctional or higher ethylenically unsaturated compound” means a compound having two or more ethylenically unsaturated groups in one molecule.
  • a (meth)acryloyl group is preferred as the ethylenically unsaturated group in the ethylenically unsaturated compound.
  • a (meth)acrylate compound is preferable as the ethylenically unsaturated compound.
  • the bifunctional ethylenically unsaturated compound is not particularly limited and can be appropriately selected from known compounds.
  • Examples of bifunctional ethylenically unsaturated compounds other than the compound M include tricyclodecanedimethanol di(meth)acrylate and tricyclodecanedimethanol di(meth)acrylate.
  • bifunctional ethylenically unsaturated compounds include tricyclodecanedimethanol diacrylate (trade name: NK Ester A-DCP, manufactured by Shin-Nakamura Chemical Co., Ltd.), tricyclodecanedimenanol dimethacrylate ( Product name: NK Ester DCP, manufactured by Shin-Nakamura Chemical Co., Ltd.), 1,9-nonanediol diacrylate (product name: NK Ester A-NOD-N, manufactured by Shin-Nakamura Chemical Co., Ltd.), 1,6 -Hexanediol diacrylate (trade name: NK Ester A-HD-N, manufactured by Shin-Nakamura Chemical Co., Ltd.).
  • the tri- or higher functional ethylenically unsaturated compound is not particularly limited and can be appropriately selected from known compounds.
  • Examples of tri- or higher ethylenically unsaturated compounds include dipentaerythritol (tri/tetra/penta/hexa) (meth)acrylate, pentaerythritol (tri/tetra) (meth)acrylate, trimethylolpropane tri(meth)acrylate, Ditrimethylolpropane tetra(meth)acrylate, isocyanuric acid (meth)acrylate, and (meth)acrylate compounds having a glycerin tri(meth)acrylate skeleton can be mentioned.
  • (tri/tetra/penta/hexa) (meth)acrylate is a concept that includes 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.
  • ethylenically unsaturated compounds include caprolactone-modified compounds of (meth)acrylate compounds (KAYARAD (registered trademark) DPCA-20 manufactured by Nippon Kayaku Co., Ltd., A-9300-1CL manufactured by Shin-Nakamura Chemical Co., Ltd., etc.), Alkylene oxide modified compounds of (meth)acrylate compounds (KAYARAD (registered trademark) RP-1040 manufactured by Nippon Kayaku Co., Ltd., ATM-35E, A-9300 manufactured by Shin-Nakamura Chemical Co., Ltd., EBECRYL (manufactured by Daicel Allnex) ( (registered trademark) 135, etc.), and ethoxylated glycerin triacrylate (NK Ester A-GLY-9E, etc. manufactured by Shin-Nakamura Chemical Co., Ltd.).
  • KYARAD registered trademark
  • DPCA-20 Alkylene oxide modified compounds of (meth)acrylate compounds
  • ATM-35E Alkylene oxide modified
  • Ethylenically unsaturated compounds also include urethane (meth)acrylate compounds.
  • Urethane (meth)acrylates include urethane di(meth)acrylates such as propylene oxide-modified urethane di(meth)acrylates and ethylene oxide and propylene oxide-modified urethane di(meth)acrylates.
  • Urethane (meth)acrylates also include trifunctional or higher urethane (meth)acrylates.
  • the lower limit of the number of functional groups is more preferably 6 or more, and still more preferably 8 or more.
  • the upper limit of the number of functional groups is preferably 20 or less.
  • Trifunctional or higher urethane (meth)acrylates include, for example, 8UX-015A (manufactured by Taisei Fine Chemical Co., Ltd.), UA-32P (manufactured by Shin-Nakamura Chemical Co., Ltd.), U-15HA (manufactured by Shin-Nakamura Chemical Co., Ltd. ), UA-1100H (manufactured by Shin-Nakamura Chemical Co., Ltd.), AH-600 (trade name) manufactured by Kyoeisha Chemical Co., Ltd., and UA-306H, UA-306T, UA-306I, UA-510H , and UX-5000 (both manufactured by Nippon Kayaku Co., Ltd.).
  • One preferred embodiment of the ethylenically unsaturated compound is an ethylenically unsaturated compound having an acid group.
  • Acid groups include phosphate groups, sulfo groups, and carboxy groups. Among these, a carboxy group is preferable as the acid group.
  • Examples of the ethylenically unsaturated compound having an acid group include trifunctional to tetrafunctional ethylenically unsaturated compounds having an acid group [pentaerythritol tri- and tetraacrylate (PETA) having a carboxyl group introduced into its skeleton (acid value: 80 mg KOH / g to 120 mg KOH / g)], pentafunctional to hexafunctional ethylenically unsaturated compounds having acid groups (dipentaerythritol penta and hexaacrylate (DPHA) skeletons with carboxy groups introduced [acid value: 25 mg KOH / g ⁇ 70 mgKOH/g)] and the like. If necessary, these trifunctional or higher ethylenically unsaturated compounds having an acid group may be used in combination with a difunctional ethylenically unsaturated compound having an acid group.
  • PETA pentafunctional to hexafunctional ethyl
  • the ethylenically unsaturated compound having an acid group at least one selected from the group consisting of bifunctional or higher ethylenically unsaturated compounds having a carboxy group and carboxylic acid anhydrides thereof is preferable.
  • the ethylenically unsaturated compound having an acid group is at least one selected from the group consisting of a bifunctional or higher ethylenically unsaturated compound having a carboxyl group and its carboxylic acid anhydride, the developability and film strength are improved. increase.
  • the bifunctional or higher ethylenically unsaturated compound having a carboxy group is not particularly limited and can be appropriately selected from known compounds.
  • Examples of bifunctional or higher ethylenically unsaturated compounds having a carboxy group include Aronix (registered trademark) TO-2349 (manufactured by Toagosei Co., Ltd.), Aronix (registered trademark) M-520 (manufactured by Toagosei Co., Ltd.), and Aronix (registered trademark) M-510 (manufactured by Toagosei Co., Ltd.).
  • the ethylenically unsaturated compound having an acid group is preferably a polymerizable compound having an acid group described in paragraphs 0025 to 0030 of JP-A-2004-239942, and the contents described in this publication are incorporated herein.
  • Examples of ethylenically unsaturated compounds include compounds obtained by reacting polyhydric alcohols with ⁇ , ⁇ -unsaturated carboxylic acids, and compounds obtained by reacting glycidyl group-containing compounds with ⁇ , ⁇ -unsaturated carboxylic acids.
  • urethane monomers such as (meth)acrylate compounds having a urethane bond, ⁇ -chloro- ⁇ -hydroxypropyl- ⁇ '-(meth)acryloyloxyethyl-o-phthalate, ⁇ -hydroxyethyl- ⁇ '-(meth)acryloyl Phthalic acid compounds such as oxyethyl-o-phthalate and ⁇ -hydroxypropyl- ⁇ '-(meth)acryloyloxyethyl-o-phthalate, and (meth)acrylic acid alkyl esters are also included. These are used alone or in combination of two or more.
  • Compounds obtained by reacting a polyhydric alcohol with an ⁇ , ⁇ -unsaturated carboxylic acid include, for example, 2,2-bis(4-((meth)acryloxypolyethoxy)phenyl)propane, 2,2-bis Bisphenol A-based (meth)acrylate compounds such as (4-((meth)acryloxypolypropoxy)phenyl)propane and 2,2-bis(4-((meth)acryloxypolyethoxypolypropoxy)phenyl)propane , polyethylene glycol di(meth)acrylate having 2 to 14 ethylene oxide groups, polypropylene glycol di(meth)acrylate having 2 to 14 propylene oxide groups, and 2 to 14 ethylene oxide groups.
  • 2,2-bis(4-((meth)acryloxypolyethoxy)phenyl)propane 2,2-bis Bisphenol A-based (meth)acrylate compounds such as (4-((meth)acryloxypolypropoxy)phenyl)propane and 2,2-bis(
  • an ethylenically unsaturated compound having a tetramethylolmethane structure or a trimethylolpropane structure is preferable, and tetramethylolmethane tri(meth)acrylate, tetramethylolmethanetetra(meth)acrylate, trimethylolpropane tri(meth)acrylate, or di(meth)acrylate.
  • Trimethylolpropane Trimethylolpropane tetraacrylate is more preferred.
  • ethylenically unsaturated compounds examples include caprolactone-modified compounds of ethylenically unsaturated compounds (for example, KAYARAD (registered trademark) DPCA-20 manufactured by Nippon Kayaku Co., Ltd., A-9300-1CL manufactured by Shin-Nakamura Chemical Industry Co., Ltd., etc.) ), alkylene oxide-modified compounds of ethylenically unsaturated compounds (for example, KAYARAD RP-1040 manufactured by Nippon Kayaku Co., Ltd., ATM-35E, A-9300 manufactured by Shin-Nakamura Chemical Co., Ltd., EBECRYL manufactured by Daicel Ornex Co., Ltd. ( (registered trademark) 135, etc.), and ethoxylated glycerin triacrylate (A-GLY-9E, etc., manufactured by Shin-Nakamura Chemical Co., Ltd.).
  • KAYARAD registered trademark
  • DPCA-20 alkylene oxide-modified compounds of e
  • the ethylenically unsaturated compound one containing an ester bond is also preferable from the viewpoint of excellent developability of the photosensitive resin layer after transfer.
  • the ethylenically unsaturated compound containing an ester bond is not particularly limited as long as it contains an ester bond in the molecule, but from the viewpoint of excellent effects in the present disclosure, ethylene unsaturated compounds having a tetramethylolmethane structure or a trimethylolpropane structure Saturated compounds are preferred, and tetramethylolmethane tri(meth)acrylate, tetramethylolmethane tetra(meth)acrylate, trimethylolpropane tri(meth)acrylate, or di(trimethylolpropane)tetraacrylate are more preferred.
  • the ethylenically unsaturated compounds include an ethylenically unsaturated compound having an aliphatic group having 6 to 20 carbon atoms, and an ethylenically unsaturated compound having the above tetramethylolmethane structure or trimethylolpropane structure. It preferably contains a compound and Ethylenically unsaturated compounds having an aliphatic structure with 6 or more carbon atoms include 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, and tricyclodecanedimethanol di(meth)acrylate. (Meth)acrylates are mentioned.
  • the ethylenically unsaturated compound is an ethylenically unsaturated compound having an aliphatic hydrocarbon ring structure (preferably a bifunctional ethylenically unsaturated compound).
  • an ethylenic compound having a ring structure in which two or more aliphatic hydrocarbon rings are condensed preferably a structure selected from the group consisting of a tricyclodecane structure and a tricyclodecene structure
  • An unsaturated compound is preferred, a bifunctional ethylenically unsaturated compound having a ring structure in which two or more aliphatic hydrocarbon rings are condensed is more preferred, and tricyclodecanedimethanol di(meth)acrylate is even more preferred.
  • a cyclopentane structure, a cyclohexane structure, a tricyclodecane structure, a tricyclodecene structure, a norbornane structure, or an isoboron structure is preferable from the viewpoint of more excellent effects in the present disclosure.
  • the molecular weight of the ethylenically unsaturated compound is preferably 200 to 3,000, more preferably 250 to 2,600, still more preferably 280 to 2,200, and particularly preferably 300 to 2,200.
  • the content ratio of ethylenically unsaturated compounds having a molecular weight of 300 or less is relative to the content of all ethylenically unsaturated compounds contained in the photosensitive resin layer. , preferably 30% by mass or less, more preferably 25% by mass or less, and even more preferably 20% by mass or less.
  • the photosensitive resin layer preferably contains a bifunctional or higher ethylenically unsaturated compound, and more preferably contains a trifunctional or higher ethylenically unsaturated compound. More preferably, it contains a functional or tetrafunctional ethylenically unsaturated compound.
  • the photosensitive resin layer comprises a bifunctional ethylenically unsaturated compound having an aliphatic hydrocarbon ring structure and an alkali-soluble polymer having a structural unit having an aliphatic hydrocarbon ring. It preferably contains a resin.
  • the photosensitive resin layer preferably contains a compound represented by formula (M) and an ethylenically unsaturated compound having an acid group.
  • the photosensitive resin layer contains a compound represented by formula (M), an ethylenically unsaturated compound having an acid group, and a thermally crosslinkable compound described later. It preferably contains a compound represented by formula (M), an ethylenically unsaturated compound having an acid group, and a blocked isocyanate compound described later.
  • the photosensitive resin layer comprises a bifunctional ethylenically unsaturated compound (preferably a bifunctional (meth)acrylate compound) and a trifunctional or higher ethylenic unsaturated compound. It preferably contains a saturated compound (preferably a (meth)acrylate compound having a functionality of 3 or more).
  • the photosensitive resin layer contains the compound M and a bifunctional ethylenically unsaturated compound having an aliphatic hydrocarbon ring structure from the viewpoint of rust prevention. is preferred.
  • the photosensitive resin layer is composed of the compound M and an ethylenic unsaturated compound having an acid group, from the viewpoints of substrate adhesion, development residue suppression, and rust prevention.
  • It preferably contains a saturated compound, more preferably contains a compound M, a bifunctional ethylenically unsaturated compound having an aliphatic hydrocarbon ring structure, and an ethylenically unsaturated compound having an acid group, compound M, an aliphatic It is more preferable to contain a bifunctional ethylenically unsaturated compound having a hydrocarbon ring structure, a trifunctional or higher ethylenically unsaturated compound, and an ethylenically unsaturated compound having an acid group, compound M, an aliphatic hydrocarbon ring It is particularly preferable to include a bifunctional ethylenically unsaturated compound having a structure, a tri- or higher functional ethylenically unsaturated compound, an acid group-containing ethylenically unsaturated compound, and a urethane (meth)acrylate compound.
  • the photosensitive resin layer contains 1,9-nonanediol diacrylate and carboxylic acid from the viewpoints of substrate adhesion, development residue suppression, and rust prevention. It preferably contains a polyfunctional ethylenically unsaturated compound having an acid group, including 1,9-nonanediol diacrylate, tricyclodecanedimethanol diacrylate, and a polyfunctional ethylenically unsaturated compound having a carboxylic acid group.
  • 1,9-nonanediol diacrylate preferably 1,9-nonanediol diacrylate, tricyclodecanedimethanol diacrylate, dipentaerythritol hexaacrylate, and an ethylenically unsaturated compound having a carboxylic acid group
  • 1,9- Particularly preferred are nonanediol diacrylate, tricyclodecanedimethanol diacrylate, ethylenically unsaturated compounds having carboxylic acid groups, and urethane acrylate compounds.
  • the photosensitive resin layer may contain a monofunctional ethylenically unsaturated compound as the ethylenically unsaturated compound.
  • the content of the bifunctional or higher ethylenically unsaturated compound in the ethylenically unsaturated compound is 60% by mass to 100% by mass with respect to the total content of all ethylenically unsaturated compounds contained in the photosensitive resin layer. It is preferably 80% by mass to 100% by mass, and even more preferably 90% by mass to 100% by mass.
  • Ethylenically unsaturated compounds may be used singly or in combination of two or more.
  • the content of the ethylenically unsaturated compound in the photosensitive resin layer is preferably 1% by mass to 70% by mass, more preferably 5% by mass to 70% by mass, and 5% by mass with respect to the total mass of the photosensitive resin layer. ⁇ 60% by mass is more preferable, and 5% by mass to 50% by mass is particularly preferable.
  • the photosensitive resin layer contains a photopolymerization initiator.
  • Preferred aspects of the photopolymerization initiator used in the second embodiment include the preferred aspects of the photopolymerization initiator used in the first embodiment described above.
  • a photoinitiator may be used individually by 1 type, and can also use 2 or more types together.
  • the content of the photopolymerization initiator is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and 1.0% by mass with respect to the total mass of the photosensitive resin layer. It is more preferable that it is above.
  • the upper limit thereof is preferably 10% by mass or less, more preferably 5% by mass or less, relative to the total mass of the photosensitive resin layer.
  • the photosensitive resin layer may contain a heterocyclic compound.
  • the heterocyclic ring contained in the heterocyclic compound may be either monocyclic or polycyclic heterocyclic ring.
  • a nitrogen atom, an oxygen atom, and a sulfur atom are mentioned as a heteroatom which a heterocyclic compound has.
  • the heterocyclic compound preferably has at least one atom selected from the group consisting of a nitrogen atom, an oxygen atom and a sulfur atom, more preferably a nitrogen atom.
  • heterocyclic compounds examples include triazole compounds, benzotriazole compounds, tetrazole compounds, thiadiazole compounds, triazine compounds, rhodanine compounds, thiazole compounds, benzothiazole compounds, benzimidazole compounds, benzoxazole compounds, and pyrimidine compounds.
  • the heterocyclic compound is at least one selected from the group consisting of triazole compounds, benzotriazole compounds, tetrazole compounds, thiadiazole compounds, triazine compounds, rhodanine compounds, thiazole compounds, benzimidazole compounds, and benzoxazole compounds.
  • At least one compound selected from the group consisting of triazole compounds, benzotriazole compounds, tetrazole compounds, thiadiazole compounds, thiazole compounds, benzothiazole compounds, benzimidazole compounds, and benzoxazole compounds is more preferred.
  • heterocyclic compound Preferred specific examples of the heterocyclic compound are shown below.
  • triazole compounds and benzotriazole compounds include the following compounds.
  • the following compounds can be exemplified as thiadiazole compounds.
  • triazine compounds include the following compounds.
  • the following compounds can be exemplified as rhodanine compounds.
  • the following compounds can be exemplified as thiazole compounds.
  • the following compounds can be exemplified as benzimidazole compounds.
  • a heterocyclic compound may be used individually by 1 type, and can also use 2 or more types together.
  • the content of the heterocyclic compound is preferably 0.01% by mass to 20.0% by mass, preferably 0.10% by mass, based on the total mass of the photosensitive resin layer. ⁇ 10.0% by mass is more preferable, 0.30% by mass to 8.0% by mass is even more preferable, and 0.50% by mass to 5.0% by mass is particularly preferable.
  • the photosensitive resin layer may contain an aliphatic thiol compound.
  • en-thiol reaction between the aliphatic thiol compound and the ethylenically unsaturated compound suppresses cure shrinkage of the formed film and relieves stress. be done.
  • aliphatic thiol compound a monofunctional aliphatic thiol compound or a polyfunctional aliphatic thiol compound (that is, a bifunctional or higher aliphatic thiol compound) is preferable.
  • polyfunctional aliphatic thiol compounds are more preferable as the aliphatic thiol compound from the viewpoint of adhesion of the formed pattern (particularly, adhesion after exposure).
  • a "polyfunctional aliphatic thiol compound” means an aliphatic compound having two or more thiol groups (also referred to as "mercapto groups”) in the molecule.
  • a low-molecular-weight compound having a molecular weight of 100 or more is preferable as the polyfunctional aliphatic thiol compound.
  • the molecular weight of the polyfunctional aliphatic thiol compound is more preferably 100 to 1,500, still more preferably 150 to 1,000.
  • the number of functional groups of the polyfunctional aliphatic thiol compound for example, from the viewpoint of the adhesion of the pattern to be formed, preferably bifunctional to 10 functional, more preferably bifunctional to octafunctional, further bifunctional to hexafunctional. preferable.
  • polyfunctional aliphatic thiol compounds include trimethylolpropane tris(3-mercaptobutyrate), 1,4-bis(3-mercaptobutyryloxy)butane, pentaerythritol tetrakis(3-mercaptobutyrate), 1,3,5-tris(3-mercaptobutyryloxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, trimethylolethane tris(3-mercaptobutyrate ), tris [(3-mercaptopropionyloxy) ethyl] isocyanurate, trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptopropionate), tetraethylene glycol bis (3-mercaptopropionate pionate), dipentaerythritol hexakis(3-mercaptopropionat
  • polyfunctional aliphatic thiol compounds include trimethylolpropane tris (3-mercaptobutyrate), 1,4-bis (3-mercaptobutyryloxy) butane, and 1,3,5-tris At least one compound selected from the group consisting of (3-mercaptobutyryloxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione is preferred.
  • Examples of monofunctional aliphatic thiol compounds include 1-octanethiol, 1-dodecanethiol, ⁇ -mercaptopropionic acid, methyl-3-mercaptopropionate, 2-ethylhexyl-3-mercaptopropionate, n- Octyl-3-mercaptopropionate, methoxybutyl-3-mercaptopropionate, and stearyl-3-mercaptopropionate.
  • the photosensitive resin layer may contain a single aliphatic thiol compound, or may contain two or more aliphatic thiol compounds.
  • the content of the aliphatic thiol compound is preferably 5% by mass or more, more preferably 5% by mass to 50% by mass, based on the total mass of the photosensitive resin layer. , more preferably 5% to 30% by mass, and particularly preferably 8% to 20% by mass.
  • the photosensitive resin layer preferably contains a thermal crosslinkable compound from the viewpoint of the strength of the resulting cured film and the adhesiveness of the resulting uncured film.
  • a thermal crosslinkable compound used in the photosensitive resin layer of the second embodiment, the thermally crosslinkable compound described above for the photosensitive resin layer of the first embodiment is preferably used.
  • the thermally crosslinkable compounds may be used singly or in combination of two or more.
  • the content of the heat-crosslinkable compound is preferably 1% by mass to 50% by mass, and 5% by mass to 30% by mass, based on the total mass of the photosensitive resin layer. is more preferred.
  • the photosensitive resin layer may contain a surfactant.
  • the surfactant used in the photosensitive resin layer of the second embodiment the surfactant described above for the photosensitive resin layer of the first embodiment is preferably used.
  • Surfactants may be used singly or in combination of two or more.
  • the content of the surfactant is preferably 0.01% by mass to 3.0% by mass, preferably 0.01% by mass, based on the total mass of the photosensitive resin layer. ⁇ 1.0% by mass is more preferable, and 0.05% by mass to 0.80% by mass is even more preferable.
  • the photosensitive resin layer may contain a polymerization inhibitor.
  • a polymerization inhibitor means a compound having a function of delaying or inhibiting a polymerization reaction.
  • the polymerization inhibitor for example, known compounds used as polymerization inhibitors can be used.
  • polymerization inhibitors include phenothiazine, bis(1-dimethylbenzyl)phenothiazine, and phenothiazine compounds such as 3,7-dioctylphenothiazine; bis[3-(3-tert-butyl-4-hydroxy-5-methyl phenyl)propionic acid][ethylenebis(oxyethylene)]2,4-bis[(laurylthio)methyl]-o-cresol, 1,3,5-tris(3,5-di-t-butyl-4-hydroxy benzyl), 1,3,5-tris(4-t-butyl-3-hydroxy-2,6-dimethylbenzyl), 2,4-bis-(n-octylthio)-6-(4-hydroxy-3, 5-di-t-butylanilino)-1,3,5-triazine and hindered phenol compounds such as pentaerythritol tetrakis 3-(3,5-di-tert-but
  • the polymerization inhibitor is preferably at least one selected from the group consisting of a phenothiazine compound, a nitroso compound or a salt thereof, and a hindered phenol compound, since the effects of the present disclosure are more excellent, and phenothiazine, bis[3 -(3-tert-butyl-4-hydroxy-5-methylphenyl)propionic acid][ethylenebis(oxyethylene)]2,4-bis[(laurylthio)methyl]-o-cresol, 1,3,5- More preferred are tris(3,5-di-t-butyl-4-hydroxybenzyl) and N-nitrosophenylhydroxylamine aluminum salt.
  • a polymerization inhibitor may be used individually by 1 type, and can also use 2 or more types together.
  • the content of the polymerization inhibitor is preferably 0.01% by mass to 10.0% by mass, and 0.01 to 5% by mass, based on the total mass of the photosensitive resin layer. 0% by mass is more preferred, and 0.04% to 3.0% by mass is even more preferred.
  • the photosensitive resin layer may contain a hydrogen donating compound.
  • the hydrogen-donating compound has actions such as further improving the sensitivity of the photopolymerization initiator to actinic rays and suppressing inhibition of polymerization of the ethylenically unsaturated compound by oxygen.
  • Hydrogen-donating compounds include, for example, amines and amino acid compounds.
  • amines examples include M.I. R. Sander et al., "Journal of Polymer Society", Vol. JP-A-60-084305, JP-A-62-018537, JP-A-64-033104, and Research Disclosure 33825. More specifically, 4,4′-bis(diethylamino)benzophenone, tris(4-dimethylaminophenyl)methane (alias: leuco crystal violet), triethanolamine, p-dimethylaminobenzoic acid ethyl ester, p-formyl dimethylaniline and p-methylthiodimethylaniline.
  • At least one selected from the group consisting of 4,4′-bis(diethylamino)benzophenone and tris(4-dimethylaminophenyl)methane is preferable as the amines in that the effects of the present disclosure are more excellent.
  • Amino acid compounds include, for example, N-phenylglycine, N-methyl-N-phenylglycine, N-ethyl-N-phenylglycine. Among them, N-phenylglycine is preferable as the amino acid compound because the effects of the present disclosure are more excellent.
  • the hydrogen-donating compound for example, an organometallic compound (such as tributyltin acetate) described in JP-B-48-042965, a hydrogen donor described in JP-B-55-034414, and JP-A-6 Also included are sulfur compounds (such as trithiane) described in JP-A-308727.
  • organometallic compound such as tributyltin acetate
  • hydrogen donor such as JP-B-55-034414
  • JP-A-6 also included are sulfur compounds (such as trithiane) described in JP-A-308727.
  • the hydrogen-donating compounds may be used singly or in combination of two or more.
  • the content of the hydrogen-donating compound is, from the viewpoint of improving the curing rate by the balance between the polymerization growth rate and the chain transfer, relative to the total mass of the photosensitive resin layer. , preferably 0.01% by mass to 10.0% by mass, more preferably 0.01% by mass to 8.0% by mass, and even more preferably 0.03% by mass to 5.0% by mass.
  • the photosensitive resin layer may contain a predetermined amount of impurities.
  • the impurities in the photosensitive resin layer of the second embodiment are the same as the preferred modes of the impurities described above in the photosensitive resin layer of the first embodiment.
  • the photosensitive resin layer may contain residual monomers corresponding to the constituent units of the alkali-soluble resin described above.
  • the residual monomer corresponding to each structural unit of the alkali-soluble resin in the photosensitive resin layer of the second embodiment is It is the same as the preferred embodiment of the monomer.
  • the photosensitive resin layer may contain components (hereinafter also referred to as “other components”) other than the components described above.
  • Other ingredients include, for example, colorants, antioxidants, and particles (eg, metal oxide particles).
  • other additives described in paragraphs 0058 to 0071 of JP-A-2000-310706 are also included as other components.
  • metal oxide particles are preferred.
  • Metals in metal oxide particles also include semimetals such as B, Si, Ge, As, Sb, and Te.
  • the average primary particle size of the particles is, for example, preferably 1 nm to 200 nm, more preferably 3 nm to 80 nm, from the viewpoint of the transparency of the cured film.
  • the average primary particle diameter of particles is calculated by measuring the particle diameters of 200 arbitrary particles using an electron microscope and arithmetically averaging the measurement results. When the shape of the particles is not spherical, the longest side is taken as the particle diameter.
  • the photosensitive resin layer When the photosensitive resin layer contains particles, it may contain only one type of particles having different metal types and different sizes, or may contain two or more types.
  • the photosensitive resin layer does not contain particles, or when the photosensitive resin layer contains particles, the content of the particles is more than 0% by mass and 35% by mass or less with respect to the total mass of the photosensitive resin layer.
  • the content of particles is more preferably 0% by mass to 10% by mass or less with respect to the total mass of the photosensitive resin layer, and does not contain particles, or contains particles More preferably, the amount is more than 0% by mass and 5% by mass or less with respect to the total mass of the photosensitive resin layer, and does not contain particles, or the content of particles is 0% by mass relative to the total mass of the photosensitive resin layer It is more preferably more than 1% by mass or less, and particularly preferably contains no particles.
  • the photosensitive resin layer may contain a coloring agent (pigment, dye, etc.), it is preferred that the photosensitive resin layer does not substantially contain a coloring agent, for example, from the viewpoint of transparency.
  • the content of the coloring agent is preferably less than 1% by mass, more preferably less than 0.1% by mass, relative to the total mass of the photosensitive resin layer.
  • antioxidants examples include 1-phenyl-3-pyrazolidone (alias: phenidone), 1-phenyl-4,4-dimethyl-3-pyrazolidone, and 1-phenyl-4-methyl-4-hydroxymethyl- 3-pyrazolidones such as 3-pyrazolidone; polyhydroxybenzenes such as hydroquinone, catechol, pyrogallol, methylhydroquinone, and chlorohydroquinone; paramethylaminophenol, paraaminophenol, parahydroxyphenylglycine, and paraphenylenediamine be done.
  • the antioxidant is preferably 3-pyrazolidones, more preferably 1-phenyl-3-pyrazolidone.
  • the content of the antioxidant is preferably 0.001% by mass or more, more preferably 0.005% by mass or more, based on the total mass of the photosensitive resin layer. 0.01% by mass or more is more preferable. Although the upper limit is not particularly limited, it is preferably 1% by mass or less.
  • the layer thickness of the photosensitive resin layer is not particularly limited, but is often 30 ⁇ m or less, and is preferably 20 ⁇ m or less, more preferably 15 ⁇ m or less, even more preferably 10 ⁇ m or less, and 5.0 ⁇ m from the viewpoint of more excellent effects in the present disclosure. The following are particularly preferred.
  • the lower limit is preferably 0.60 ⁇ m or more, more preferably 1.5 ⁇ m or more, from the viewpoint that the strength of the film obtained by curing the photosensitive resin layer is excellent.
  • the thickness of the photosensitive resin layer can be calculated, for example, as an average value of arbitrary five points measured by cross-sectional observation with a scanning electron microscope (SEM).
  • the refractive index of the photosensitive resin layer is preferably 1.47 to 1.56, more preferably 1.49 to 1.54.
  • the photosensitive resin layer is preferably achromatic. Specifically, total reflection (incidence angle 8°, light source: D-65 (2° field of view)) has an L * value of 10 to 90 in the CIE1976 (L * , a * , b * ) color space.
  • the a * value is preferably -1.0 to 1.0
  • the b * value is preferably -1.0 to 1.0.
  • the pattern obtained by curing the photosensitive resin layer is preferably achromatic. Specifically, total reflection (incidence angle 8°, light source: D-65 (2° field of view)) is applied to the CIE1976 (L * , a * , b * ) color space, and the L * value of the pattern is 10 to 90.
  • the a * value of the pattern is preferably ⁇ 1.0 to 1.0
  • the b * value of the pattern is preferably ⁇ 1.0 to 1.0.
  • the photosensitive transfer material preferably has a refractive index adjusting layer.
  • a known refractive index adjustment layer can be applied as the refractive index adjustment layer.
  • Materials contained in the refractive index adjustment layer include, for example, alkali-soluble resins, ethylenically unsaturated compounds, metal salts, and particles.
  • the method for controlling the refractive index of the refractive index adjustment layer is not particularly limited, and examples include a method using a resin having a predetermined refractive index alone, a method using a resin and particles, and a composite of a metal salt and a resin. A method using
  • alkali-soluble resins and ethylenically unsaturated compounds examples include the alkali-soluble resins and ethylenically unsaturated compounds described in the "Photosensitive resin layer" section above.
  • Particles include, for example, metal oxide particles and metal particles.
  • the type of metal oxide particles is not particularly limited, and known metal oxide particles can be used.
  • Metals in metal oxide particles also include semimetals such as B, Si, Ge, As, Sb, and Te.
  • the average primary particle size of the particles is, for example, preferably 1 nm to 200 nm, more preferably 3 nm to 80 nm, from the viewpoint of the transparency of the cured film.
  • the average primary particle diameter of particles is calculated by measuring the particle diameters of 200 arbitrary particles using an electron microscope and arithmetically averaging the measurement results. When the shape of the particles is not spherical, the longest side is taken as the particle diameter.
  • metal oxide particles include zirconium oxide particles ( ZrO2 particles), Nb2O5 particles, titanium oxide particles ( TiO2 particles), silicon dioxide particles ( SiO2 particles), and composites thereof. At least one selected from the group consisting of particles is preferred. Among these, at least one selected from the group consisting of zirconium oxide particles and titanium oxide particles is more preferable as the metal oxide particles, for example, from the viewpoint that the refractive index can be easily adjusted.
  • metal oxide particles include calcined zirconium oxide particles (manufactured by CIK Nanotech Co., Ltd., product name: ZRPGM15WT%-F04), calcined zirconium oxide particles (manufactured by CIK Nanotech Co., Ltd., product name: ZRPGM15WT%-F74).
  • calcined zirconium oxide particles manufactured by CIK Nanotech Co., Ltd., product name: ZRPGM15WT%-F75
  • calcined zirconium oxide particles manufactured by CIK Nanotech Co., Ltd., product name: ZRPGM15WT%-F76
  • zirconium oxide particles Nanouse OZ -S30M, manufactured by Nissan Chemical Industries, Ltd.
  • zirconium oxide particles Nanouse OZ-S30K, manufactured by Nissan Chemical Industries, Ltd.
  • the particles may be used singly or in combination of two or more.
  • the content of the particles in the refractive index adjusting layer is preferably 1% by mass to 95% by mass, more preferably 20% by mass to 90% by mass, and 40% by mass to 85% by mass with respect to the total mass of the refractive index adjusting layer. More preferred.
  • the content of the titanium oxide particles is preferably 1% by mass to 95% by mass, more preferably 20% by mass to 90% by mass, relative to the total mass of the refractive index adjusting layer. , 40% by mass to 85% by mass is more preferable.
  • the refractive index of the refractive index adjusting layer is preferably higher than that of the photosensitive resin layer.
  • the refractive index of the refractive index adjusting layer is preferably 1.50 or higher, more preferably 1.55 or higher, even more preferably 1.60 or higher, and particularly preferably 1.65 or higher.
  • the upper limit of the refractive index of the refractive index adjusting layer is preferably 2.10 or less, more preferably 1.85 or less, still more preferably 1.78 or less, and particularly preferably 1.74 or less.
  • the layer thickness of the refractive index adjusting layer is preferably 50 nm to 500 nm, more preferably 55 nm to 110 nm, even more preferably 60 nm to 100 nm.
  • the method for manufacturing the photosensitive transfer material of the second embodiment is not particularly limited, and known methods can be used.
  • a step of forming the layer 3 applying a composition for forming a refractive index adjustment layer on the surface of the photosensitive resin layer 3 to form a coating film, and further drying the coating film to form the refractive index adjustment layer 5. and a method comprising the steps of:
  • the photosensitive transfer material 10 is manufactured by pressing the protective film 7 onto the refractive index adjusting layer 5 of the laminate manufactured by the manufacturing method described above.
  • the method for producing the photosensitive transfer material of the first embodiment includes the step of providing the protective film 7 so as to contact the surface of the refractive index adjustment layer 5 opposite to the side having the temporary support 1, thereby It is preferable to manufacture a photosensitive transfer material 10 comprising a support 1 , a photosensitive resin layer 3 , a refractive index adjusting layer 5 and a protective film 7 .
  • the photosensitive transfer material 10 may be wound up to produce and store a roll-shaped photosensitive transfer material.
  • the photosensitive transfer material in roll form can be provided as it is to the lamination step with a substrate in a roll-to-roll system, which will be described later.
  • the photosensitive resin layer 3 is formed on the surface of the refractive index adjusting layer 5.
  • the photosensitive resin layer 3 is formed on the temporary support 1
  • the refractive index adjustment layer 5 is separately formed on the protective film 7, and the photosensitive resin layer 3 may be formed by adhering the refractive index adjusting layer 5 together.
  • the method for forming the photosensitive resin composition and the photosensitive resin layer in the second embodiment is the same as the method for forming the photosensitive resin composition and the photosensitive resin layer described above in the first embodiment, and is a preferred embodiment. is also the same.
  • the composition for forming the refractive index adjustment layer preferably contains the above-described various components for forming the refractive index adjustment layer and a solvent.
  • the preferred range of the content of each component with respect to the total solid content of the composition is the same as the preferred range of the content of each component with respect to the total mass of the refractive index adjustment layer.
  • the solvent is not particularly limited as long as it can dissolve or disperse the components contained in the refractive index adjusting layer, and is preferably at least one selected from the group consisting of water and water-miscible organic solvents.
  • Water-miscible organic solvents include alcohols having 1 to 3 carbon atoms, acetone, ethylene glycol, and glycerin, with alcohols having 1 to 3 carbon atoms being preferred, and methanol or ethanol being more preferred.
  • a solvent may be used individually by 1 type, and may be used 2 or more types.
  • the content of the solvent is preferably 50 parts by mass to 2,500 parts by mass, more preferably 50 parts by mass to 1,900 parts by mass, and 100 parts by mass to 900 parts by mass with respect to 100 parts by mass of the total solid content of the composition. Part is more preferred.
  • the method for forming the refractive index adjusting layer is not particularly limited as long as it is a method capable of forming a layer containing the above components, and examples thereof include known coating methods (slit coating, spin coating, curtain coating, inkjet coating, etc.). be done.
  • the photosensitive transfer material of the second embodiment can be produced.
  • a method for attaching the protective film to the refractive index adjusting layer is not particularly limited, and includes known methods.
  • the device for bonding the protective film to the refractive index adjusting layer include known laminators such as a vacuum laminator and an autocut laminator.
  • the laminator is equipped with any heatable roller, such as a rubber roller, and can be applied with pressure and heat.
  • a resin pattern manufacturing method is a resin pattern manufacturing method for forming a resin pattern on a substrate using a photosensitive transfer material having a temporary support and a photosensitive resin layer.
  • the outermost layer on the side having the photosensitive resin layer with respect to the temporary support is brought into contact with the substrate and bonded together (hereinafter referred to as "bonding ), a step of pattern-exposing the photosensitive resin layer (hereinafter also referred to as an “exposure step”), and a step of developing the exposed photosensitive resin layer to form a resin pattern (hereinafter referred to as “development Also referred to as "process”.), in this order.
  • At least part of the resin pattern includes a line-and-space pattern, and at least part of the resin pattern includes a line-and-space pattern. More preferably, the line-and-space pattern is included, and the total width of at least one pair of lines and spaces in the line-and-space pattern is 20 ⁇ m or less.
  • a method for manufacturing a laminate according to the present disclosure is a method for manufacturing a laminate having a resin pattern on a substrate using the photosensitive transfer material according to the present disclosure.
  • a method for producing a laminate a method including the protective film peeling step, the bonding step, the exposure step, and the development step in this order is preferable.
  • the method for manufacturing the resin pattern or the method for manufacturing the laminate includes a bonding step.
  • the substrate (the conductive layer when the substrate surface is provided with a conductive layer) is brought into contact with the outermost layer of the photosensitive transfer material on the side having the photosensitive resin layer with respect to the temporary support.
  • the photosensitive transfer material and the substrate are preferably pressure-bonded.
  • the adhesion between the substrate and the outermost layer on the side having the photosensitive resin layer with respect to the temporary support in the photosensitive transfer material is improved, so that the patterned photosensitive after exposure and development It can be suitably used as an etching resist when etching the resin layer conductive layer.
  • the protective film may be removed from the surface of the photosensitive resin layer, and then the photosensitive resin layer may be laminated.
  • a layer other than the protective film for example, a high refractive index layer and / or a low refractive index layer
  • the surface of the photosensitive resin layer on the side not having the temporary support is bonded to the substrate with the layer interposed therebetween.
  • the method for pressure-bonding the substrate and the photosensitive transfer material is not particularly limited, and known transfer methods and lamination methods can be used.
  • the photosensitive transfer material is laminated to the substrate by overlapping the outermost layer of the photosensitive transfer material on the side having the photosensitive resin layer with respect to the temporary support and the substrate, and applying pressure and heat using means such as a roll. It is preferably carried out by applying A known laminator such as a laminator, a vacuum laminator, and an autocut laminator that can further improve productivity can be used for bonding.
  • the lamination temperature is not particularly limited, it is preferably 70° C. to 130° C., for example.
  • the resin pattern manufacturing method and the circuit wiring manufacturing method including the bonding step are performed by a roll-to-roll method.
  • the roll-to-roll method will be described below.
  • the roll-to-roll method uses a substrate that can be wound and unwound as a substrate, and before any step included in the resin pattern manufacturing method or circuit wiring manufacturing method, a substrate or a structure including a substrate A step of unwinding the body (also referred to as an “unwinding step”), and a step of winding up the substrate or a structure containing the substrate after any of the steps (also referred to as a “winding step”), A method in which at least one of the steps (preferably all steps or all steps other than the heating step) is performed while the substrate or a structure including the substrate is being transported.
  • the unwinding method in the unwinding step and the winding method in the winding step are not particularly limited, and known methods may be used in manufacturing methods to which a roll-to-roll system is applied.
  • ⁇ Substrate> As the substrate used in the resin pattern manufacturing method or laminate manufacturing method according to the present disclosure, a known substrate may be used, but a substrate having a conductive layer is preferable, and it is more preferable to have a conductive layer on the surface of the substrate. preferable.
  • the substrate may optionally have any layers other than the conductive layer. Examples of substrates include resin substrates, glass substrates, and semiconductor substrates. Preferred aspects of the substrate are described, for example, in paragraph 0140 of WO2018/155193, the contents of which are incorporated herein.
  • Base materials that constitute the substrate include, for example, glass, silicon, and films.
  • the base material constituting the substrate is preferably transparent.
  • transparent means that the transmittance of light with a wavelength of 400 nm to 700 nm is 80% or more.
  • the refractive index of the substrate constituting the substrate is preferably 1.50 to 1.52.
  • Transparent glass substrates include tempered glass such as Corning's Gorilla Glass. Materials used in JP-A-2010-86684, JP-A-2010-152809, and JP-A-2010-257492 can be used as the transparent glass substrate.
  • film substrate When a film substrate is used as the substrate, it is preferable to use a film substrate with low optical distortion and/or high transparency.
  • film substrates include, for example, polyethylene terephthalate (PET), polyethylene naphthalate, polycarbonate, triacetylcellulose and cycloolefin polymers.
  • a film substrate is preferable as the substrate when manufacturing by the roll-to-roll method. Moreover, when manufacturing the circuit wiring for touchscreens by a roll-to-roll method, it is preferable that a board
  • Examples of the conductive layer that the substrate has include conductive layers that are used for general circuit wiring or touch panel wiring.
  • the conductive layer is preferably at least one layer selected from the group consisting of a metal layer, a conductive metal oxide layer, a graphene layer, a carbon nanotube layer and a conductive polymer layer, from the viewpoint of conductivity and fine line formation.
  • a metal layer is more preferred, and a copper or silver layer is even more preferred.
  • the substrate may have a single conductive layer, or may have two or more layers. When it has two or more conductive layers, it is preferable to have the conductive layers made of different materials.
  • Materials for the conductive layer include metals and conductive metal oxides.
  • Metals include Al, Zn, Cu, Fe, Ni, Cr, Mo, Ag and Au.
  • Conductive metal oxides include ITO (Indium Tin Oxide), IZO (Indium Zinc Oxide) and SiO2 .
  • the term “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.
  • At least one of the plurality of conductive layers preferably contains a conductive metal oxide.
  • the conductive layer an electrode pattern corresponding to a sensor in the visual recognition portion used in a capacitive touch panel or wiring in the peripheral extracting portion is preferable. Preferred embodiments of the conductive layer are described, for example, in paragraph 0141 of WO2018/155193, the contents of which are incorporated herein.
  • a substrate having at least one of a transparent electrode and lead wiring is preferable.
  • the substrate as described above can be suitably used as a touch panel substrate.
  • a transparent electrode can function suitably as an electrode for touch panels.
  • the transparent electrode is preferably composed of a metal oxide film such as ITO (indium tin oxide) and IZO (indium zinc oxide), a metal mesh, and metal thin wires such as silver nanowires.
  • Fine metal wires include fine wires of silver, copper, and the like. Among them, silver conductive materials such as silver mesh and silver nanowire are preferable.
  • a metal is preferable as the material of the routing wiring.
  • metals for the routing wiring include gold, silver, copper, molybdenum, aluminum, titanium, chromium, zinc, manganese, and alloys composed of two or more of these metal elements. Copper, molybdenum, aluminum, or titanium is preferable as the material of the routing wiring, and copper is particularly preferable.
  • the touch panel electrode protective film formed using the photosensitive transfer material according to the present disclosure is for the purpose of protecting the electrodes and the like (that is, at least one of the touch panel electrodes and the touch panel wiring), directly or otherwise. It is preferably provided so as to cover through layers.
  • the method for producing a resin pattern or the method for producing a laminate preferably includes a step of exposing the photosensitive resin layer to pattern exposure (exposure step) after the bonding step.
  • patterned exposure refers to exposure in a form of exposure in a pattern, that is, exposure in which an exposed portion and a non-exposed portion are present.
  • the positional relationship between the exposed area and the unexposed area in pattern exposure is not particularly limited, and is adjusted as appropriate.
  • the detailed arrangement and specific size of the pattern in pattern exposure are not particularly limited.
  • at least part of the pattern is used to improve the display quality of a display device (for example, a touch panel) provided with an input device having circuit wiring manufactured by a circuit wiring manufacturing method, and to reduce the area occupied by lead wiring.
  • the electrode pattern and/or lead-out wiring portion of the touch panel preferably includes fine lines with a width of 20 ⁇ m or less, and more preferably includes fine lines with 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 emits light of a wavelength (for example, 365 nm or 405 nm) that can expose the photosensitive resin layer.
  • a wavelength for example, 365 nm or 405 nm
  • ultra-high pressure mercury lamps, high pressure mercury lamps, metal halide lamps and LEDs are included.
  • the exposure dose is preferably 5 mJ/cm 2 to 200 mJ/cm 2 , more preferably 10 mJ/cm 2 to 100 mJ/cm 2 .
  • Preferred embodiments of the light source, exposure amount and exposure method used for exposure include, for example, paragraphs 0146 to 0147 of WO 2018/155193, the contents of which are incorporated herein.
  • pattern exposure may be performed after peeling the temporary support from the photosensitive resin layer, and before peeling the temporary support, pattern exposure is performed through the temporary support, and then the temporary support is peeled off.
  • the mask may be brought into contact with the photosensitive resin layer for exposure, or may be brought close to the photosensitive resin layer for exposure without contact.
  • the mask may be exposed in contact with the temporary support, or may be exposed in close proximity without contact. In order to prevent contamination of the mask 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 carry out pattern exposure without peeling off the temporary support.
  • the exposure method may be a contact exposure method for contact exposure, a proximity exposure method for non-contact exposure, a projection exposure method using a lens or mirror system, or a direct exposure method using an exposure laser or the like. It can be selected and used.
  • an exposing machine having an appropriate lens numerical aperture (NA) can be used according to the required resolving power and depth of focus.
  • drawing may be performed directly on the photosensitive resin layer, or reduction projection exposure may be performed on the photosensitive resin layer via a lens.
  • the exposure may be performed not only in the air but also in a reduced pressure or a vacuum, or the exposure may be performed by interposing a liquid such as water between the light source and the photosensitive resin layer.
  • the resin pattern manufacturing method or laminate manufacturing method may include a peeling step of peeling off the temporary support between the bonding step and the exposure step, or between the exposure step and the developing step.
  • the peeling method of the temporary support is not particularly limited, and a mechanism similar to the cover film peeling mechanism described in paragraphs 0161 to 0162 of JP-A-2010-072589 can be used.
  • the method for producing a resin pattern preferably includes, after the exposure step, a step of developing the exposed photosensitive resin layer to form a resin pattern (development step).
  • the photosensitive transfer material has a thermoplastic resin layer and a water-soluble resin layer
  • the thermoplastic resin layer and the water-soluble resin layer in the non-exposed area are also removed together with the photosensitive resin layer in the non-exposed area in the development process.
  • the thermoplastic resin layer and the water-soluble resin layer in the exposed portion may also be removed by dissolving or dispersing in the developer.
  • the developer is not particularly limited as long as it can remove the non-image area (non-exposed area) of the photosensitive resin layer. Available.
  • the developer is preferably an alkaline aqueous solution containing a compound having a pKa of 7 to 13 at a concentration of 0.05 mol/L to 5 mol/L (liter).
  • the developer may contain a water-soluble organic solvent and/or a surfactant.
  • Alkaline compounds that can be contained in the alkaline aqueous solution include, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, and choline (2-hydroxyethyltrimethylammonium hydroxide).
  • the developer described in paragraph 0194 of International Publication No. 2015/093271 is also preferably used.
  • a development method that is preferably used includes, for example, the development method described in paragraph 0195 of International Publication No. 2015/093271.
  • the development method is not particularly limited, and may be any of puddle development, shower development, shower and spin development, and dip development.
  • Shower development is a development process in which a non-exposed portion is removed by spraying a developing solution onto the photosensitive resin layer after exposure by showering. After the development step, it is preferable to remove the development residue by spraying a detergent with a shower and rubbing with a brush.
  • the liquid temperature of the developer is not particularly limited, it is preferably 20°C to 40°C.
  • the method for producing the resin pattern or the method for producing the laminate preferably includes a step of peeling off the protective film from the photosensitive transfer material.
  • a method for peeling off the protective film is not limited, and a known method can be applied.
  • the method for producing a resin pattern or the method for producing a laminate includes a step of exposing (post-exposure step) and/or heating (post-baking step) the resin pattern obtained by the developing step. good too.
  • post-exposure step exposing
  • post-baking step heating
  • post-exposure step post-exposure step
  • post-baking is preferably performed after post-exposure.
  • the method for producing a resin pattern or the method for producing a laminate may include arbitrary steps (other steps) other than the steps described above.
  • steps described in the method for manufacturing circuit wiring or the method for manufacturing a touch panel shown below may be mentioned, but are not limited to these steps.
  • the resin pattern manufactured by the resin pattern manufacturing method according to the present disclosure and the laminate manufactured by the laminate manufacturing method according to the present disclosure can be applied to various apparatuses.
  • the device provided with the laminate include an input device and the like, preferably a touch panel, and more preferably a capacitive touch panel.
  • the input device can be applied to display devices such as an organic electroluminescence display device and a liquid crystal display device.
  • the formed resin pattern is preferably used as a protective film for touch panel electrodes or touch panel wiring. That is, the photosensitive transfer material according to the present disclosure is preferably used for forming a touch panel electrode protective film or a touch panel wiring.
  • the method for manufacturing circuit wiring according to the present disclosure is not particularly limited as long as it is a method using the photosensitive transfer material according to the present disclosure.
  • the outermost layer of the photosensitive transfer material according to the present disclosure on the side having a photosensitive resin layer with respect to the temporary support is brought into contact with a substrate having a conductive layer.
  • etching step a step of etching step in this order.
  • the circuit wiring manufacturing method includes a step of etching the substrate in a region where the resin pattern is not arranged (etching step).
  • the conductive layer is etched using the resin pattern formed from the photosensitive resin layer as an etching resist.
  • a known method can be applied, for example, the method described in paragraphs 0209 to 0210 of JP-A-2017-120435, and the method described in paragraphs 0048 to 0054 of JP-A-2010-152155.
  • method a wet etching method in which the substrate is immersed in an etching solution, and a dry etching method such as plasma etching.
  • an acidic or alkaline etchant may be appropriately selected according to the object to be etched.
  • acidic etching solutions include aqueous solutions of acidic components alone selected from hydrochloric acid, sulfuric acid, nitric acid, acetic acid, hydrofluoric acid, oxalic acid and phosphoric acid, and acidic components, ferric chloride, ammonium fluoride and A mixed aqueous solution with a salt selected from potassium permanganate can be mentioned.
  • the acidic component may be a combination of multiple acidic components.
  • Alkaline etching solutions include aqueous solutions of alkali components alone selected from sodium hydroxide, potassium hydroxide, ammonia, organic amines, and salts of organic amines (tetramethylammonium hydroxide, etc.), and alkali components and salts. (potassium permanganate, etc.).
  • the alkaline component may be a component obtained by combining a plurality of alkaline components.
  • a step of removing the remaining resin pattern (removing step).
  • the removal step is not particularly limited and can be performed as necessary, but is preferably performed after the etching step.
  • a method for removing the remaining resin pattern is not particularly limited, but a method of removing by chemical treatment is mentioned, and a method of removing using a removing liquid is preferable.
  • a method for removing the photosensitive resin layer a substrate having a remaining resin pattern is placed in a stirring removal liquid having a liquid temperature of preferably 30° C. to 80° C., more preferably 50° C. to 80° C., for 1 minute or more.
  • a method of immersing for 30 minutes can be mentioned.
  • the remover examples include a remover obtained by dissolving an inorganic alkaline component or an organic alkaline component in water, dimethylsulfoxide, N-methylpyrrolidone, or a mixed solution thereof.
  • inorganic alkaline components include sodium hydroxide and potassium hydroxide.
  • Organic alkaline components include primary amine compounds, secondary amine compounds, tertiary amine compounds and quaternary ammonium salt compounds. Alternatively, it may be removed by a known method such as a spray method, a shower method, or a paddle method using a remover.
  • the circuit wiring manufacturing method may include arbitrary steps (other steps) other than the steps described above. Examples include, but are not limited to, the following steps. Further, the exposure process, the development process, and other processes applicable to the circuit wiring manufacturing method include the processes described in paragraphs 0035 to 0051 of JP-A-2006-23696. Furthermore, other steps include, for example, a step of reducing the visible light reflectance described in paragraph 0172 of WO 2019/022089, and a new step on the insulating film described in paragraph 0172 of WO 2019/022089. Examples include a step of forming a conductive layer, but the present invention is not limited to these steps.
  • the circuit wiring manufacturing method may include a step of performing a process for reducing the visible light reflectance of a part or all of the plurality of conductive layers of the substrate.
  • the treatment for reducing the visible light reflectance includes oxidation treatment.
  • the visible light reflectance of the conductive layer can be reduced by oxidizing the copper to form copper oxide and blackening the conductive layer.
  • the treatment for reducing the visible light reflectance is described in paragraphs 0017 to 0025 of JP-A-2014-150118, and paragraphs 0041, 0042, 0048 and 0058 of JP-A-2013-206315. , the contents of which are incorporated herein.
  • the circuit wiring manufacturing method includes a step of forming an insulating film on the surface of the circuit wiring, and a step of forming a new conductive layer on the surface of the insulating film.
  • a second electrode pattern insulated from the first electrode pattern can be formed.
  • the process of forming the insulating film is not particularly limited, and a known method of forming a permanent film can be used.
  • an insulating film having a desired pattern may be formed by photolithography using an insulating photosensitive material.
  • the step of forming a new conductive layer on the insulating film is not particularly limited.
  • a conductive photosensitive material may be used to form a new conductive layer in a desired pattern by photolithography.
  • the circuit wiring manufacturing method uses a substrate having a plurality of conductive layers on both surfaces of the substrate, and sequentially or simultaneously forms circuits on the conductive layers formed on both surfaces of the substrate.
  • a substrate having a plurality of conductive layers on both surfaces of the substrate and sequentially or simultaneously forms circuits on the conductive layers formed on both surfaces of the substrate.
  • the circuit wiring manufactured by the circuit wiring manufacturing method can be applied to various devices.
  • Examples of devices having circuit wiring manufactured by the above-described manufacturing method include input devices, preferably touch panels, and more preferably capacitive touch panels. Further, the input device can be applied to display devices such as an organic EL display device and a liquid crystal display device.
  • the touch panel manufacturing method according to the present disclosure is not particularly limited as long as it is a method using the photosensitive transfer material according to the present disclosure.
  • the outermost layer on the side having a photosensitive resin layer with respect to the temporary support in the photosensitive transfer material according to the present disclosure is attached in contact with a substrate having a conductive layer. exposing the photosensitive resin layer in a pattern; developing the exposed photosensitive resin layer to form a resin pattern; and etching the substrate in a region where the resin pattern is not arranged. and a step of treating in this order.
  • each step in the method for manufacturing a touch panel and embodiments such as the order of performing each step are described in the above sections "Method for manufacturing resin pattern" and “Method for manufacturing circuit wiring”. and preferred embodiments are also the same.
  • the method for manufacturing a touch panel a known method for manufacturing a touch panel may be referred to, except that the touch panel wiring is formed by the above method. Further, the touch panel manufacturing method may include arbitrary steps (other steps) other than those described above.
  • FIGS. 3 and 4 An example of a mask pattern used for manufacturing a touch panel is shown in FIGS. 3 and 4.
  • FIG. In pattern A shown in FIG. 3 and pattern B shown in FIG. 4, GR is a non-image portion (light-shielding portion), EX is an image portion (exposed portion), and DL is a virtual alignment frame. It is shown
  • the touch panel manufacturing method for example, by exposing the photosensitive resin layer through a mask having a pattern A shown in FIG. . Specifically, it can be produced by the method described in FIG. 1 of International Publication No. 2016/190405.
  • the central portion (pattern portion in which squares are connected) of the exposed portion EX is a portion where a transparent electrode (touch panel electrode) is formed, and the peripheral portion (thin line portion) of the exposed portion EX is This is the portion where the wiring of the peripheral extracting portion is formed.
  • a touch panel having at least a touch panel wiring is manufactured by the touch panel manufacturing method described above.
  • the touch panel preferably has a transparent substrate, electrodes, and an insulating layer or protective layer.
  • a detection method for a touch panel known methods such as a resistive film method, a capacitance method, an ultrasonic method, an electromagnetic induction method, and an optical method can be used. Among them, the capacitance method is preferable.
  • the touch panel type As the touch panel type, the so-called in-cell type (for example, those described in FIGS. 5, 6, 7 and 8 of JP-A-2012-517051), the so-called on-cell type (for example, JP 2013-168125) Those described in FIG. 19, and those described in FIGS. 1 and 5 of JP-A-2012-89102), OGS (One Glass Solution) type, TOL (Touch-on-Lens) type (for example, JP-A 2013-54727), various out-cell types (so-called GG, G1 G2, GFF, GF2, GF1 and G1F, etc.) and other configurations (for example, Japanese Patent Application Laid-Open No. 2013-164871 6). Examples of touch panels include those described in paragraph 0229 of JP-A-2017-120435.
  • a temporary support was produced by the following method.
  • a particle-containing layer-forming composition 1 was obtained by mixing each component according to the formulation shown below. After preparing the particle-containing layer-forming composition 1, it was filtered with a 6 ⁇ m filter (F20, manufactured by Mahle Filter Systems Co., Ltd.), and then a membrane was filtered using a 2 ⁇ 6 radial flow superphobic (manufactured by Polypore Co., Ltd.). Degassed.
  • ⁇ Acrylic polymer AS-563A, manufactured by Daicel Finechem Co., Ltd., solid content 27.5% by mass
  • ⁇ Nonionic surfactant Nel Finechem Co., Ltd., solid content 27.5% by mass
  • Anionic surfactant Rapisol A-90, manufactured by NOF Corporation, diluted with water to a solid content of 1% by mass
  • Carnauba wax dispersion (Cerosol 524, Chukyo Yushi Co., Ltd.
  • Carbodiimide compound (Carbodilite V-02-L2, manufactured by Nisshinbo Co., Ltd., diluted with water to a solid content of 10% by mass) 20.9 parts Matting agent (Snowtex XL, Nissan Chemical Co., Ltd., solid content 40 mass%, average particle diameter 50 nm) 2.8 parts, water 690.2 parts
  • the solidified unstretched film was sequentially biaxially stretched by the following method to form a particle-containing layer with a thickness of 40 nm on a polyethylene terephthalate film with a thickness of 16 ⁇ m.
  • Thermal relaxation temperature 190°C
  • Thermal relaxation rate 4%
  • the temporary support has a polyethylene terephthalate film (base material) and a particle-containing layer in this order.
  • the haze of the temporary support was 0.2%. Haze was measured as total light haze using a haze meter (NDH2000 manufactured by Nippon Denshoku Industries Co., Ltd.).
  • the thickness of the particle-containing layer measured from a cross-sectional TEM photograph of the temporary support was 40 nm.
  • the average particle diameter of the particles contained in the particle-containing layer measured by the method described above using a HT-7700 transmission electron microscope (TEM) manufactured by Hitachi High-Technologies Corporation was 50 nm.
  • BPE-500 2,2-bis (4-(methacryloxypentaethoxy) phenyl) propane, manufactured by Shin-Nakamura Chemical Co., Ltd.
  • M-270 polypropylene glycol diacrylate, manufactured by Toagosei Co., Ltd.
  • A-TMPT Tri Methylolpropane triacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd.
  • SR-454 Ethoxylated (3) trimethylolpropane triacrylate, manufactured by Sartomer A-9300-CL1: ⁇ -caprolactone-modified tris(2-acryloxyethyl) isocyanate Nurate, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.
  • BIMD Photoradical generator (photopolymerization initiator), manufactured by Kurogane Kasei Co., Ltd., 2-(2-chlorophenyl)-4,5-diphenylimidazole dimer SB- PI 701: sensitizer, 4,4'-bis(diethylamino)benzophenone, available from Sanyo Boeki Co., Ltd.
  • CBT-1 rust inhibitor, carboxybenzotriazole, Johoku Chemical Industry Co., Ltd.
  • TDP-G polymerization prohibited agent, phenothiazine, manufactured by Kawaguchi Chemical Industry Co., Ltd.
  • Irganox245 Hindered phenol-based polymerization inhibitor, manufactured by BASF F-552: fluorine-based surfactant, Megafac F552, manufactured by DIC Corporation
  • thermoplastic resin composition Each component shown in Table 2 was mixed to prepare a thermoplastic resin composition.
  • each component of Table 2 is a mass part.
  • the meanings of the abbreviations described in Table 2 are shown below.
  • ⁇ B-1 A compound having the structure shown below (a dye that develops color with an acid)
  • ⁇ C-1 A compound having the structure shown below (photoacid generator, compound described in paragraph 0227 of JP-A-2013-47765, synthesized according to the method described in paragraph 0227.)
  • ⁇ D-3 NK Ester A-DCP (tricyclodecanedimethanol diacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd.)
  • ⁇ D-4 8UX-015A (polyfunctional urethane acrylate compound, Taisei Fine Chemical Co., Ltd.)
  • ⁇ D-5 Aronix TO-2349 (polyfunctional acrylate compound having a carboxy group, manufactured by Toagosei Co., Ltd.)
  • E-1 Megaface F552 (manufactured by DIC Corporation)
  • F-1 Phenothiazine (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.)
  • F-2 CBT-1 (manufactured by Johoku Chemical Industry Co., Ltd.)
  • ⁇ MEK Methyl ethyl ketone
  • ⁇ PGME Propylene glycol monomethyl ether
  • ⁇ PGMEA Propylene glycol monomethyl ether acetate
  • a water-soluble resin composition was prepared by mixing the following components. In addition, the unit of the quantity of each component is a mass part.
  • Ion-exchanged water 38.12 parts Methanol (manufactured by Mitsubishi Gas Chemical Co., Ltd.): 57.17 parts Kuraray Poval 4-88LA (polyvinyl alcohol, manufactured by Kuraray Co., Ltd.): 3.22 parts Polyvinylpyrrolidone K-30 (Japan Catalyst Co., Ltd.): 1.49 parts Megafac F-444 (fluorosurfactant, manufactured by DIC Corporation): 0.0035 parts
  • thermoplastic resin composition was applied onto the base material (polyethylene terephthalate film) of the temporary support using a slit nozzle.
  • the applied thermoplastic resin composition was dried at 100° C. for 120 seconds to form a thermoplastic resin layer having the thickness shown in Table 3.
  • a water-soluble resin composition was applied onto the thermoplastic resin layer using a slit nozzle.
  • the applied water-soluble resin composition was dried at 120° C. for 120 seconds to form a water-soluble resin layer having the thickness shown in Table 3.
  • the photosensitive resin composition shown in Table 3 was applied onto the water-soluble resin layer using a slit nozzle.
  • the coated photosensitive resin composition was dried at 100 ° C. for 120 seconds to form a photosensitive resin layer having a thickness shown in Table 3 (layer structure: coating layer 1 shown in Table 3), and photosensitive A sexual transfer material was obtained.
  • the photosensitive transfer material obtained by the above procedure includes a temporary support, a thermoplastic resin layer, a water-soluble resin layer, and a photosensitive resin layer in this order.
  • Table 3 shows the layer structures (coating layers 1 to 3, 7, 8, and 10) of the thermoplastic resin layer, the water-soluble resin layer, and the photosensitive resin layer.
  • Example 10-13 In the same manner as in Example 1, except that a PET film (manufactured by Toray Industries, Inc., Lumirror 16KS40, thickness: 16 ⁇ m) was used as a temporary support, and that changes were made as appropriate according to the descriptions in Tables 3 and 4. A photosensitive transfer material was obtained.
  • Table 3 shows the layer structures (coating layers 10 to 13) of the thermoplastic resin layer, the water-soluble resin layer and the photosensitive resin layer.
  • Examples 4 to 6 and Comparative Example 1 A photosensitive transfer material was obtained in the same manner as in Example 1, except that the contents were appropriately changed according to the descriptions in Tables 3 and 4.
  • the protective film was peeled off from the obtained photosensitive transfer material, and the peeled photosensitive transfer material was laminated on a substrate (100 ⁇ m PET film coated with a copper layer of 300 nm thick by sputtering) with a sheet laminator.
  • the lamination conditions were a roll temperature of 110° C., a lamination speed of 3 m/min, and a lamination pressure of 0.5 MPa.
  • a PET substrate with a copper layer was produced by forming a copper layer with a thickness of 300 nm on a polyethylene terephthalate (PET) film with a thickness of 100 ⁇ m by sputtering.
  • PET polyethylene terephthalate
  • a vacuum laminator manufactured by MCK Co., Ltd., roll temperature: 110 ° C., linear pressure: 1.0 MPa, linear speed: 3 m / min
  • the photosensitive transfer material and the PET substrate with a copper layer were laminated. pasted together.
  • the obtained laminate includes at least a PET film, a copper layer, a photosensitive resin layer, and a temporary support in this order.
  • the resulting laminate was pressurized and defoamed under conditions of 0.6 MPa and 60° C. for 0.5 hours using an autoclave.
  • a line-and-space pattern mask (the duty ratio is 1:1, and the line width is changed stepwise from 1 ⁇ m to 20 ⁇ m at intervals of 1 ⁇ m) without peeling off the temporary support.
  • the photosensitive resin layer was exposed through. After peeling off the temporary support, development was carried out. Development was performed by shower development for 30 seconds using a 0.95% by mass sodium carbonate aqueous solution at 25°C.
  • the exposure dose (hereinafter referred to as "reference exposure dose") at which the line width of the resin pattern corresponding to the 20 ⁇ m line-and-space pattern of the mask is exactly 20 ⁇ m was determined.
  • a resin pattern was formed by the same method as described above, except that the photosensitive resin layer was exposed with the reference exposure amount. The resin pattern was observed using a scanning electron microscope (SEM). The minimum value of the line width of the resin pattern without peeling of the resin pattern and without residue in the space portion of the resin pattern was adopted as the minimum resolution line width. Table 4 shows the measurement results. The smaller the minimum resolution line width, the better the resolution.
  • the width of the resin pattern having a line width of 10 ⁇ m on the side opposite to the surface in contact with the substrate was observed using a scanning electron microscope (SEM).
  • SEM scanning electron microscope
  • the standard deviation ⁇ of the measured values (hereinafter referred to as “line width fluctuation value”) was measured.
  • the line width variation of the resin pattern was evaluated according to the following criteria.
  • B Line width fluctuation value is 0.3 ⁇ m or more and less than 0.4 ⁇ m.
  • C Line width fluctuation value is 0.4 ⁇ m or more and less than 0.5 ⁇ m.
  • D Line width fluctuation value is 0.5 ⁇ m or more and less than 0.6 ⁇ m.
  • E Line width fluctuation value is 0.6 ⁇ m or more.
  • the cross-sectional shape of the resin pattern skirt (near the base material side) was evaluated according to the following criteria.
  • the photosensitive transfer materials of Examples 1 to 13 give resin patterns with smaller variations in line width than the photosensitive transfer material of Comparative Example 1.
  • the photosensitive transfer materials of Examples 1 to 13 are excellent in resolution, little change in line width of the resin pattern with the lapse of holding time after exposure, and in cross-sectional shape of the obtained resin pattern.
  • Example 14 (second time: PET peeling exposure)) On a 100-micron-thick PET substrate, a second conductive layer of ITO was formed by sputtering to a thickness of 150 nm, and a first conductive layer of copper was formed thereon by a vacuum deposition method to a thickness of 200 nm. Then, a substrate for forming a circuit was obtained.
  • the photosensitive transfer material obtained in Example 1 was laminated on the copper layer (lamination roll temperature 120° C., linear pressure 0.8 MPa, linear velocity 1.0 m/min.). The laminated laminate was subjected to contact pattern exposure using a photomask having a pattern A shown in FIG.
  • the temporary support was peeled off, developed and washed with water to obtain a pattern A.
  • the ITO layer was etched using an ITO etching solution (manufactured by Kanto Chemical Co., Ltd. ITO-02). A substrate on which pattern A was drawn for both copper and ITO was obtained.
  • the remaining photosensitive resin layer (pattern A) was peeled off using a stripping solution (KP-301 manufactured by Kanto Kagaku Co., Ltd.), and the photosensitive transfer material obtained in Example 1 was laminated again on the copper layer ( lamination roll temperature 120° C., linear pressure 0.8 MPa, linear velocity 1.0 m/min.).
  • pattern exposure was performed using a photomask of pattern B shown in FIG. 4, development and washing were performed.
  • the copper layer was etched using Cu-02, and the remaining photosensitive resin layer (pattern B) was peeled off using a peeling solution (KP-301 manufactured by Kanto Kagaku Co., Ltd.) to obtain a circuit wiring board. .
  • the gray portion GR is the light shielding portion
  • the EX is the exposure portion
  • the dotted line portion DL is a virtual alignment frame.
  • the gray portion GR is the light shielding portion
  • the EX is the exposure portion
  • the dotted line portion DL is a virtual alignment frame. It is a thing.

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Abstract

L'invention concerne un matériau de transfert photosensible, et un procédé de fabrication de motif de résine, un procédé de fabrication de câblage de circuit ainsi qu'un procédé de fabrication de panneau tactile qui mettent en œuvre ce matériau de transfert photosensible. Le matériau de transfert photosensible de l'invention possède un support temporaire, et une couche de résine photosensible contenant une résine soluble dans les alcalis, un composé éthyléniquement insaturé et un initiateur de photopolymérisation. Dans le cas où ladite couche de résine photosensible, vis-à-vis d'une quantité exposition à la lumière (Ep) ayant ｍＪ／ｃｍ２ pour unité, présente une largeur de région de réaction de double liaison (W+) après exposition à la lumière selon une quantité d'exposition Ｅｐ＋１０％ d'un motif de lignes et d'espaces de １０μｍ／１０μｍ, et une largeur de région de réaction de double liaison (W-) après exposition à la lumière selon une quantité d'exposition Ｅｐ-１０％ d'un motif de lignes et d'espaces de １０μｍ／１０μｍ, la valeur de la différence de largeur de région de réaction de double liaison (（Ｗ＋）－（Ｗ－）), est inférieure ou égale à １,４５μｍ.
PCT/JP2021/048963 2021-01-29 2021-12-28 Matériau de transfert photosensible, procédé de fabrication de motif de résine, procédé de fabrication de câblage de circuit, et procédé de fabrication de panneau tactile WO2022163301A1 (fr)

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CN202180091894.8A CN116745697A (zh) 2021-01-29 2021-12-28 感光性转印材料、树脂图案的制造方法、电路配线的制造方法及触摸面板的制造方法
JP2022578198A JPWO2022163301A1 (fr) 2021-01-29 2021-12-28

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2013218313A (ja) * 2012-03-15 2013-10-24 Fujifilm Corp 感光性フィルム、静電容量型入力装置の製造方法および静電容量型入力装置、並びに、これを備えた画像表示装置
WO2017033868A1 (fr) * 2015-08-25 2017-03-02 旭化成株式会社 Composition de résine photosensible
JP2019168624A (ja) * 2018-03-26 2019-10-03 ニッコー・マテリアルズ株式会社 感光性樹脂組成物、これを用いたフォトレジストフィルム、及びレジストパターンの形成方法

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2013218313A (ja) * 2012-03-15 2013-10-24 Fujifilm Corp 感光性フィルム、静電容量型入力装置の製造方法および静電容量型入力装置、並びに、これを備えた画像表示装置
WO2017033868A1 (fr) * 2015-08-25 2017-03-02 旭化成株式会社 Composition de résine photosensible
JP2019168624A (ja) * 2018-03-26 2019-10-03 ニッコー・マテリアルズ株式会社 感光性樹脂組成物、これを用いたフォトレジストフィルム、及びレジストパターンの形成方法

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