WO2021220980A1 - Photosensitive transfer material, method for producing resin pattern, method for producing circuit wiring, and method for producing touch panel - Google Patents

Photosensitive transfer material, method for producing resin pattern, method for producing circuit wiring, and method for producing touch panel Download PDF

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Publication number
WO2021220980A1
WO2021220980A1 PCT/JP2021/016522 JP2021016522W WO2021220980A1 WO 2021220980 A1 WO2021220980 A1 WO 2021220980A1 JP 2021016522 W JP2021016522 W JP 2021016522W WO 2021220980 A1 WO2021220980 A1 WO 2021220980A1
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Prior art keywords
resin layer
mass
photosensitive resin
photosensitive
transfer material
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PCT/JP2021/016522
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French (fr)
Japanese (ja)
Inventor
進二 藤本
隆志 有冨
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富士フイルム株式会社
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Priority to CN202180032041.7A priority Critical patent/CN115485621A/en
Priority to JP2022518030A priority patent/JPWO2021220980A1/ja
Publication of WO2021220980A1 publication Critical patent/WO2021220980A1/en

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

Definitions

  • the present disclosure relates to a photosensitive transfer material, a resin pattern manufacturing method, a circuit wiring manufacturing method, and a touch panel manufacturing method.
  • a touch panel such as a capacitance type input device (organic electroluminescence (EL) display device, liquid crystal display device, etc.)
  • the electrode pattern corresponding to the sensor of the visual recognition part, the peripheral wiring part, and the wiring of the take-out wiring part are wired. Etc. is provided inside the touch panel.
  • a layer of a photosensitive resin composition (photosensitive layer) is formed on a substrate using a photosensitive transfer material.
  • a method of providing and exposing the photosensitive layer through a mask having a desired pattern and then developing the photosensitive layer is widely adopted.
  • Japanese Patent Application Laid-Open No. 2008-94803 states that a resin for a binder composed of a linear polymer having a carboxyl group content of 100 to 600 in acid equivalent and a weight average molecular weight of 20,000 to 500,000: 20 to Photopolymerizable resin containing 90% by mass, a photopolymerizable monomer having at least one terminal ethylenically unsaturated group: 5 to 75% by mass, and a photopolymerization initiator containing a specific compound: 0.01 to 30% by mass.
  • a photosensitive resin laminate in which a photosensitive resin layer composed of a composition is provided on a support layer is described.
  • the photosensitive resin layer contains a photopolymerization initiator having a specific structure in order to enhance the dispersion stability of the photopolymerization initiator in a developing solution.
  • a photopolymerization initiator having a specific structure in order to enhance the dispersion stability of the photopolymerization initiator in a developing solution.
  • a photosensitive transfer material in which the generation of scum (aggregate) is suppressed even when the development process is performed for a long time. Further, according to another embodiment of the present invention, a method for manufacturing a resin pattern using the above-mentioned photosensitive transfer material, a method for manufacturing a circuit wiring, and a method for manufacturing a touch panel are provided.
  • the present disclosure includes the following aspects. ⁇ 1> A temporary support and a photosensitive resin layer arranged on the temporary support are provided, and 0.1 m 2 of a photosensitive transfer material is dissolved in 1 liter of a 30 ° C. aqueous solution of 1 mass% sodium carbonate. A photosensitive transfer material having a haze of 60% or less in the resulting solution. ⁇ 2> The photosensitive transfer material according to ⁇ 1>, wherein the thickness of the photosensitive resin layer is 10 ⁇ m or less. ⁇ 3> The photosensitive resin layer contains a polymerizable compound and an alkali-soluble resin, and the ratio of the content of the polymerizable compound to the content of the alkali-soluble resin is 0.85 or less on a mass basis.
  • the photosensitive transfer material according to ⁇ 2> is a photosensitive transfer material according to ⁇ 2>.
  • ⁇ 4> The photosensitive transfer material according to any one of ⁇ 1> to ⁇ 3>, wherein the photosensitive resin layer contains an alkali-soluble resin and the acid value of the alkali-soluble resin is 120 mg / KOH or more.
  • ⁇ 5> The photosensitive transfer material according to any one of ⁇ 1> to ⁇ 4>, wherein the photosensitive resin layer contains an alkali-soluble resin, and the alkali-soluble resin contains a structural unit derived from styrene.
  • ⁇ 6> The photosensitive transfer material according to ⁇ 5>, wherein the content of the structural unit derived from styrene is 40% by mass or more with respect to the total mass of the alkali-soluble resin.
  • ⁇ 7> The photosensitive transfer material according to any one of ⁇ 1> to ⁇ 6>, wherein the photosensitive resin layer contains a polymerizable compound having an acid group.
  • ⁇ 8> The photosensitive transfer material according to any one of ⁇ 1> to ⁇ 7>, further comprising a thermoplastic resin layer between the temporary support and the photosensitive resin layer.
  • ⁇ 9> The step of bonding the surface of the photosensitive resin layer on the side of the photosensitive transfer material not facing the temporary support and the substrate according to any one of ⁇ 1> to ⁇ 8> and the bonding.
  • a method for producing a resin pattern which comprises a step of pattern-exposing the photosensitive resin layer in the photosensitive transfer material after the step, and a step of developing the photosensitive resin layer after the pattern-exposing step to form a resin pattern.
  • a photosensitive transfer material in which the generation of scum (aggregate) is suppressed even when the development process is performed for a long time. Further, according to another embodiment of the present invention, it is possible to provide a method for manufacturing a resin pattern using the above-mentioned photosensitive transfer material, a method for manufacturing a circuit wiring, and a method for manufacturing a touch panel.
  • FIG. 1 is a schematic view showing an example of the configuration of a photosensitive transfer material.
  • the notation that does not describe substitution and non-substitution includes those having no substituent as well as those having a substituent.
  • alkyl group includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
  • (meth) acrylic acid represents both or one of acrylic acid and methacrylic acid
  • (meth) acrylate represents both or one of acrylate and methacrylate.
  • the chemical structural formula in the present specification may be described by a simplified structural formula in which a hydrogen atom is omitted.
  • the amount (content, etc.) of each component means the total amount (total content, etc.) of the plurality of substances, unless otherwise specified, when a plurality of substances contained in each component are present.
  • the numerical range represented by using “-” in the present specification means a range including the numerical values before and after "-" as the lower limit value and the upper limit value.
  • “% by mass” and “% by weight” are synonymous, and “parts by mass” and “parts by weight” are synonymous.
  • the term "process” does not mean only an independent process, and even if it cannot be clearly distinguished from other processes, the term “process” is used as long as the process achieves the intended purpose. included.
  • exposure includes not only exposure using light but also drawing using particle beams such as electron beams and ion beams.
  • the light used for exposure is generally the emission line spectrum of a mercury lamp, far ultraviolet rays typified by an excimer laser, extreme ultraviolet rays (EUV (Extreme ultraviolet lithography) light), and active rays such as X-rays (activity). Energy rays).
  • the weight average molecular weight (Mw) and the number average molecular weight (Mn) are TSKgel GMHxL, TSKgel G4000HxL, and TSKgel unless otherwise specified.
  • a compound in a THF (tetrahydrofuran) solvent was detected by a differential refractometer using a gel permeation chromatography (GPC) analyzer using a G2000HxL (trade name manufactured by Toso Co., Ltd.) column, and standardized. It is a molecular weight converted using polystyrene as a substance.
  • GPC gel permeation chromatography
  • the photosensitive transfer material comprises a temporary support and a photosensitive resin layer arranged on the temporary support, and is exposed to 0.1 m 2 in 1 liter of a 30 ° C. aqueous solution of 1 mass% sodium carbonate.
  • the haze of the solution obtained by dissolving the sex transfer material is 60% or less.
  • scum may be generated and adhere to the development equipment and products.
  • the component that becomes a scum (aggregate) include a polymerizable compound contained in the photosensitive resin layer and a photopolymerization initiator. When these components aggregate in the developer, the haze of the developer increases.
  • the photosensitive transfer material according to the present disclosure is developed because the haze of the solution obtained by dissolving 0.1 m 2 of the photosensitive transfer material in 1 liter of a 30 ° C. aqueous solution of 1 mass% sodium carbonate is 60% or less. Even when the above is performed, the haze of the developing solution is low.
  • the photosensitive transfer material according to the present disclosure it is possible to suppress the generation of scum (aggregate) even when the development process is performed for a long time.
  • the photosensitive transfer material according to the present disclosure includes a temporary support and a photosensitive resin layer arranged on the temporary support.
  • the photosensitive resin layer may be directly arranged on the temporary support without interposing another layer, or may be arranged through another layer. Further, another layer may be arranged on the surface of the photosensitive resin layer opposite to the surface facing the temporary support. Examples of the layer other than the temporary support and the photosensitive resin layer include a thermoplastic resin layer, an intermediate layer, and a cover film.
  • FIG. 1 schematically shows an example of the layer structure of the photosensitive transfer material according to the present disclosure.
  • a temporary support 10 a thermoplastic resin layer 12, an intermediate layer 14, a photosensitive resin layer 16, and a cover film 18 are laminated in this order.
  • the photosensitive transfer material according to the present disclosure has a haze of 60% or less of a solution obtained by dissolving 0.1 m 2 of the photosensitive transfer material in 1 L (liter) of a 30 ° C. aqueous solution of 1 mass% sodium carbonate.
  • the haze measurement method is, for example, the following method.
  • a 1% by mass sodium carbonate aqueous solution is prepared, and the liquid temperature is adjusted to 30 ° C.
  • the haze of the solution obtained by the above method is preferably 30% or less, and more preferably 10% or less, from the viewpoint of further suppressing the generation of scum (aggregates) when the development treatment is performed for a long time. It is preferably 5% or less, more preferably 1% or less, and particularly preferably 1% or less.
  • the photosensitive transfer material according to the present disclosure includes a temporary support.
  • the temporary support is a support that supports a photosensitive resin layer or a laminate containing the photosensitive resin layer and is removable.
  • the temporary support preferably has light transmittance from the viewpoint of enabling exposure of the photosensitive resin layer through the temporary support when pattern-exposing the photosensitive resin layer.
  • “having light transmittance” means that the transmittance of light of the wavelength used for pattern exposure is 50% or more.
  • the temporary support preferably has a light transmittance of 60% or more, preferably 70% or more, at a wavelength (preferably a wavelength of 365 nm) used for pattern exposure. Is more preferable.
  • the transmittance of the layer included in the photosensitive transfer material means that when light is incident in a direction perpendicular to the main surface of the layer (that is, in the thickness direction), the light is emitted through the layer with respect to the intensity of the incident light. It is the ratio of the intensity of the emitted light.
  • the transmittance is measured using the product name "MCPD Series" manufactured by Otsuka Electronics Co., Ltd.
  • the temporary support may be a single layer or a laminated body in which two or more layers are laminated.
  • the base material constituting the temporary support examples include glass, resin film and paper.
  • the base material constituting the temporary support is preferably a resin film from the viewpoint of strength, flexibility and light transmission.
  • the resin film examples include polyethylene terephthalate (PET) film, cellulose triacetate film, polystyrene film and polycarbonate film.
  • PET polyethylene terephthalate
  • the resin film is preferably a PET film, and more preferably a biaxially stretched PET film.
  • the thickness of the temporary support is not particularly limited, and from the viewpoints of strength as a support, flexibility required for bonding to a circuit wiring forming substrate, and light transmission required in the first exposure step. Therefore, it may be appropriately selected according to the material.
  • the thickness of the temporary support is preferably 5 ⁇ m to 100 ⁇ m, and more preferably 10 ⁇ m to 50 ⁇ m from the viewpoint of ease of handling and versatility.
  • the photosensitive transfer material according to the present disclosure includes a photosensitive resin layer.
  • the photosensitive resin layer is preferably a negative photosensitive resin layer in which the solubility of the exposed portion in the developing solution is reduced by exposure and the non-exposed portion is removed by development.
  • the photosensitive resin layer is not limited to the negative photosensitive resin layer, and even if the photosensitive resin layer is a positive photosensitive resin layer in which the solubility of the exposed portion in the developing solution is improved by exposure and the exposed portion is removed by development. good.
  • the photosensitive resin layer can be obtained, for example, by applying a photosensitive resin composition and drying it.
  • the photosensitive resin layer preferably contains the polymer A, the polymerizable compound B, and the photopolymerization initiator.
  • the photosensitive resin layer contains 10% by mass to 90% by mass of the polymer A, 5% by mass to 70% by mass of the polymerizable compound B, and 0.01% by mass of the photopolymerization initiator with respect to the total mass of the photosensitive resin layer. It is preferably contained in an amount of% to 20% by mass.
  • the polymer A is preferably an alkali-soluble resin.
  • the alkali-soluble resin means a polymer that is easily dissolved in an alkaline substance.
  • alkali-soluble means that the solubility of sodium carbonate in 100 g of a 1% by mass aqueous solution at 22 ° C. is 0.1 g or more.
  • the acid value of the polymer A is preferably 120 mgKOH / g or more, and more preferably 150 mgKOH / g or more, from the viewpoint of further suppressing the generation of scum (aggregates) when the development treatment is carried out for a long time. It is preferably 180 mgKOH / g or more, and more preferably 180 mgKOH / g or more.
  • the alkali-soluble resin acts as a dispersant in the developer. When the acid value of the alkali-soluble resin is 120 mgKOH / g or more, it is considered that the effect of dispersing the components insoluble in the developing solution is high and the generation of scum (aggregates) can be suppressed.
  • the upper limit of the acid value of the polymer A is not particularly limited. From the viewpoint of resolution, the acid value of the polymer A is preferably 220 mgKOH / g or less, and more preferably 200 mgKOH / g or less.
  • the acid value is the mass [mg] of potassium hydroxide required to neutralize 1 g of the sample.
  • the unit of acid value 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 the structural unit constituting the polymer A and the content of the structural unit containing an acid group.
  • the weight average molecular weight of the polymer A is preferably 5,000 to 500,000. When the weight average molecular weight is 500,000 or less, the resolution and developability are improved, which is preferable.
  • the weight average molecular weight of the polymer A is more preferably 100,000 or less, further preferably 60,000 or less, and particularly preferably 50,000 or less.
  • the weight average molecular weight is 5,000 or more, the properties of the developed agglomerates and the properties of the unexposed film such as edge fuse properties and cut chip properties in the case of a photosensitive resin laminate can be controlled, which is preferable. ..
  • the weight average molecular weight of the polymer A is more preferably 10,000 or more, further preferably 20,000 or more, and particularly preferably 30,000 or more.
  • the edge fuse property refers to the degree of ease with which the photosensitive resin layer protrudes from the end face of the roll when the photosensitive resin laminate is wound into a roll.
  • the cut chip property refers to the degree of ease with which the chip flies when the unexposed film is cut with a cutter. If this chip adheres to the upper surface of the photosensitive resin laminate or the like, it will be transferred to the mask in a later exposure process or the like, causing a defective product.
  • the dispersity of the polymer A is preferably 1.0 to 6.0, more preferably 1.0 to 5.0, and even more preferably 1.0 to 4.0. It is particularly preferably 0.0 to 3.0.
  • the 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 polymer A preferably contains a structural unit derived from a monomer having an aromatic hydrocarbon group from the viewpoint of suppressing the line width thickening when the focal position is deviated during exposure and the decrease in resolution. ..
  • the aromatic hydrocarbon group include a substituted or unsubstituted phenyl group and a substituted or unsubstituted aralkyl group.
  • the content of the structural unit derived from the monomer having an aromatic hydrocarbon group in the polymer A is preferably 20% by mass or more, preferably 30% by mass or more, based on the total mass of the polymer A. More preferably, it is more preferably 40% by mass or more, particularly preferably 45% by mass or more, and most preferably 50% by mass or more.
  • the upper limit of the content is not particularly limited.
  • the content is preferably 95% by mass or less, and more preferably 85% by mass or less, based on the total mass of the polymer A.
  • the content of the structural unit derived from the monomer having an aromatic hydrocarbon group was determined as a weight average value.
  • the monomer having an aromatic hydrocarbon group examples include a monomer having an aralkyl group, styrene, and a polymerizable styrene derivative (for example, methyl styrene, vinyl toluene, tert-butoxy styrene, acetoxy styrene, 4-vinyl scent). Acids, styrene dimers, and styrene trimers).
  • the monomer having an aromatic hydrocarbon group is preferably a monomer having an aralkyl group or styrene, and more preferably styrene.
  • the content of the structural unit derived from styrene is preferably 40% by mass or more, preferably 40% by mass, based on the total mass of the polymer A. It is more preferably to 80% by mass, further preferably 45% by mass to 70% by mass, and particularly preferably 50% by mass to 55% by mass.
  • aralkyl group examples include a substituted or unsubstituted phenylalkyl group (excluding a benzyl group) and a substituted or unsubstituted benzyl group.
  • the aralkyl group is preferably a substituted or unsubstituted benzyl group.
  • Examples of the monomer having a phenylalkyl group include phenylethyl (meth) acrylate.
  • Examples of the monomer having a benzyl group include (meth) acrylate having a benzyl group and a vinyl monomer having a benzyl group.
  • Examples of the (meth) acrylate having a benzyl group include benzyl (meth) acrylate and chlorobenzyl (meth) acrylate.
  • Examples of the vinyl monomer having a benzyl group include vinylbenzyl chloride and vinylbenzyl alcohol. Among them, the monomer having a benzyl group is preferably benzyl (meth) acrylate.
  • the content of the structural unit derived from benzyl (meth) acrylate is 50% by mass to 95% based on the total mass of the polymer A. It is preferably mass%, more preferably 60% by mass to 90% by mass, further preferably 70% by mass to 90% by mass, and particularly preferably 75% by mass to 90% by mass.
  • the polymer A containing a structural unit derived from a monomer having an aromatic hydrocarbon group includes a structural unit derived from a monomer having an aromatic hydrocarbon group, the first monomer described later, and the first monomer described later, and the following. It is preferable that the polymer contains a structural unit derived from at least one monomer selected from the group consisting of the second monomer.
  • the polymer A containing no structural unit derived from a monomer having an aromatic hydrocarbon group is at least one monomer selected from the group consisting of a first monomer and a second monomer. It is preferable that the polymer contains a structural unit derived from, and contains a structural unit derived from at least one first monomer and a structural unit derived from at least one second monomer. It is more preferable that the polymer is a polymer.
  • the first monomer is a monomer having an anionic group and having at least one polymerizable unsaturated group in the molecule.
  • the first monomer include (meth) acrylic acid, fumaric acid, cinnamic acid, crotonic acid, itaconic acid, 4-vinylbenzoic acid, maleic anhydride, and maleic acid semiester.
  • the first monomer is preferably (meth) acrylic acid.
  • the content of the structural unit derived from the first monomer in the polymer A is preferably 5% by mass to 50% by mass, and 10% by mass to 40% by mass, based on the total mass of the polymer A. Is more preferable, and 15% by mass to 30% by mass is further preferable.
  • (meth) acrylic acid means acrylic acid or methacrylic acid
  • (meth) acryloyl group means an acryloyl group or methacrylic acid group
  • (meth) acrylate means an acryloyl group or methacrylic acid group
  • the second monomer is a monomer that does not have an anionic group and has at least one polymerizable unsaturated group in the molecule.
  • Examples of the second monomer include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, and isobutyl (meth) acrylate.
  • the second monomer is preferably methyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, or n-butyl (meth) acrylate, and methyl (meth) acrylate is particularly preferable.
  • the content of the structural unit derived from the second monomer in the polymer A is preferably 5% by mass to 60% by mass, and 15% by mass to 50% by mass, based on the total mass of the polymer A. Is more preferable, and 20% by mass to 45% by mass is further preferable.
  • the polymer A is at least one type selected from the group consisting of a monomer having an aralkyl group and styrene from the viewpoint of suppressing the line width thickening when the focal position is deviated during exposure and the decrease in resolution. It preferably contains a structural unit derived from the polymer. Specifically, the polymer A is preferably a copolymer containing a structural unit derived from styrene, a structural unit derived from methyl methacrylate, and a structural unit derived from methacrylic acid.
  • the structural unit derived from the monomer having an aromatic hydrocarbon group is 25% by mass to 40% by mass, and the structural unit derived from the first monomer is 20% by mass. It is preferably a polymer containing up to 35% by mass and 30% by mass to 45% by mass of a structural unit derived from the second monomer.
  • the polymer A contains 70% by mass to 90% by mass of a structural unit derived from a monomer having an aromatic hydrocarbon group, and 10 constituent units derived from the first monomer. It is preferably a polymer containing% by mass to 25% by mass.
  • the structural unit derived from the monomer having an aromatic hydrocarbon group is 40% by mass to 60% by mass, and the structural unit derived from the first monomer is 20. It is preferably a polymer containing 10% by mass to 35% by mass and 10% by mass to 25% by mass of a structural unit derived from the second monomer.
  • Polymer A may have a branched structure or an alicyclic structure in the side chain.
  • a branched structure or an alicyclic structure is introduced into the side chain of the polymer A by using a monomer containing a group having a branched structure in the side chain or a monomer containing a group having an alicyclic structure in the side chain. be able to.
  • Examples of the monomer containing a group having a branched structure in the side chain include i-propyl (meth) acrylate, i-butyl (meth) acrylate, s-butyl (meth) acrylate, and t (meth) acrylate.
  • -Butyl, i-amyl (meth) acrylate, t-amyl (meth) acrylate, sec-iso-amyl (meth) acrylate, 2-octyl (meth) acrylate, 3-octyl (meth) acrylate and (Meta) t-octyl acrylate can be mentioned.
  • the monomer containing a group having a branched structure in the side chain is preferably i-propyl (meth) acrylate, i-butyl (meth) acrylate, or t-butyl (meth) acrylate, and (meth) acrylic. More preferably, i-propyl acid acid or t-butyl (meth) acrylate.
  • Examples of the monomer containing a group having an alicyclic structure in the side chain include (meth) acrylate having an alicyclic hydrocarbon group having 5 to 20 carbon atoms.
  • (meth) acrylic acid bicyclo [2.2.1] heptyl-2
  • (Meta) Acrylic Acid-3-Methyl-5-Ethyl-1-adamantyl (Meta) Acrylic Acid-3,5,8-Triethyl-1-adamantyl, (Meta) Acrylic Acid-3,5-Dimethyl-8- Ethyl-1
  • the monomers containing a group having an alicyclic structure in the side chain are cyclohexyl (meth) acrylate, norbornyl (meth) acrylate, isobornyl (meth) acrylate, -1-adamantyl (meth) acrylate, and (meth).
  • -2-adamantyl acrylate fentyl (meth) acrylate, 1-mentyl (meth) acrylate, tricyclodecane (meth) acrylate, cyclohexyl (meth) acrylate, norbornyl (meth) acrylate, ( Isobornyl acrylate, -2-adamantyl (meth) acrylate or tricyclodecane (meth) acrylate are particularly preferred.
  • the photosensitive resin layer may contain the polymer A alone or in combination of two or more.
  • the photosensitive resin layer preferably contains two kinds of the polymer A containing a structural unit derived from a monomer having an aromatic hydrocarbon group.
  • the photosensitive resin layer is a polymer A1 containing a structural unit derived from a monomer having an aromatic hydrocarbon group and a polymer containing no structural unit derived from a monomer having an aromatic hydrocarbon group. It is preferable to include A2.
  • the content of the polymer A1 is preferably 50% by mass or more, more preferably 70% by mass or more, and 80% by mass or more, based on the total mass of the polymer A. Is preferable, and 90% by mass or more is more preferable.
  • a radical polymerization initiator such as benzoyl peroxide or azoisobutyronitrile is added to a solution obtained by diluting one or more of the above monomers with a solvent such as acetone, methyl ethyl ketone or isopropanol. It is preferably carried out by stirring while heating. After completion of the reaction, a solvent may be further added to adjust the concentration to a desired level.
  • a solvent may be further added to adjust the concentration to a desired level.
  • the polymerization method include bulk polymerization, suspension polymerization, and emulsion polymerization, in addition to solution polymerization.
  • the glass transition temperature Tg of the polymer A is preferably 30 ° C to 135 ° C.
  • the Tg of the polymer A is more preferably 130 ° C. or lower, further preferably 120 ° C. or lower, and particularly preferably 110 ° C. or lower.
  • the Tg of the polymer A is more preferably 40 ° C. or higher, further preferably 50 ° C. or higher, particularly preferably 60 ° C. or higher, and most preferably 70 ° C. or higher.
  • the content of the polymer A is preferably in the range of 10% by mass to 90% by mass, more preferably 30% by mass to 70% by mass, and 40% by mass with respect to the total mass of the photosensitive resin layer. It is more preferably% to 60% by mass.
  • the content of the polymer A with respect to the total mass of the photosensitive resin layer is 90% by mass or less, the development time can be controlled, which is preferable.
  • the content of the polymer A with respect to the total mass of the photosensitive resin layer is 10% by mass or more, the edge fuse resistance is improved, which is preferable.
  • the photosensitive resin layer contains a polymerizable compound B having a polymerizable group.
  • the "polymerizable compound” means a compound that polymerizes under the action of a polymerization initiator described later, and is different from the above-mentioned polymer A.
  • the polymerizable group contained in the polymerizable compound B is not particularly limited as long as it is a group involved in the polymerization reaction, and is, for example, an ethylenically unsaturated group such as a vinyl group, an acryloyl group, a methacryloyl group, a styryl group, or a maleimide group;
  • cationically polymerizable groups such as an epoxy group and an oxetane group can be mentioned.
  • the polymerizable group is preferably an ethylenically unsaturated group, more preferably an acryloyl group or a metaacryloyl group.
  • a compound having one or more ethylenically unsaturated groups that is, an ethylenically unsaturated compound
  • the photosensitive resin layer has more excellent photosensitivity, and two in one molecule.
  • a compound having the above ethylenically unsaturated group that is, a polyfunctional ethylenically unsaturated compound
  • the number of ethylenically unsaturated groups contained in one molecule of the ethylenically unsaturated compound is preferably 6 or less, more preferably 3 or less, and 2 or less in terms of excellent resolution and peelability. More preferred.
  • the photosensitive resin layer is a bifunctional ethylenically unsaturated compound having two ethylenically unsaturated groups in one molecule in that the balance between the photosensitivity of the photosensitive resin layer and the resolution and peelability is better. , Or a trifunctional ethylenically unsaturated compound having three ethylenically unsaturated groups, more preferably a bifunctional ethylenically unsaturated compound.
  • the content of the bifunctional ethylenically unsaturated compound is preferably 60% by mass or more, more preferably 70% by mass or more, based on the total mass of the polymerizable compound B from the viewpoint of excellent peelability.
  • the upper limit of the content of the bifunctional ethylenically unsaturated compound is not particularly limited and may be 100% by mass. That is, all the polymerizable compounds B contained in the photosensitive resin layer may be bifunctional ethylenically unsaturated compounds.
  • the ethylenically unsaturated compound is preferably a (meth) acrylate compound.
  • the photosensitive resin layer preferably contains a polymerizable compound B1 having at least one aromatic ring in one molecule and having two ethylenically unsaturated groups.
  • Examples of the aromatic ring contained in the polymerizable compound B1 include aromatic hydrocarbon rings such as a benzene ring, a naphthalene ring and an anthracene ring; aromatics such as a thiophene ring, a furan ring, a pyrrole ring, an imidazole ring, a triazole ring and a pyridine ring. Heterocycles; and fused rings thereof.
  • the aromatic ring contained in the polymerizable compound B1 is preferably an aromatic hydrocarbon ring, more preferably a benzene ring.
  • the aromatic ring may have a substituent.
  • the polymerizable compound B1 preferably has a bisphenol skeleton from the viewpoint of suppressing swelling of the photosensitive resin layer due to the developing solution and improving the resolution.
  • the bisphenol skeleton examples include a bisphenol A skeleton derived from bisphenol A (2,2-bis (4-hydroxyphenyl) propane) and a bisphenol derived from bisphenol F (2,2-bis (4-hydroxyphenyl) methane). Examples thereof include an F skeleton and a bisphenol B skeleton derived from bisphenol B (2,2-bis (4-hydroxyphenyl) butane). Above all, the bisphenol skeleton is preferably a bisphenol A skeleton.
  • Examples of the polymerizable compound B1 having a bisphenol skeleton include a compound having a bisphenol skeleton and two polymerizable groups (preferably (meth) acryloyl groups) bonded to both ends of the bisphenol skeleton.
  • the bisphenol skeleton and the polymerizable group may be directly bonded or may be bonded via one or more alkyleneoxy groups.
  • the alkyleneoxy group bonded to the bisphenol skeleton is preferably an ethyleneoxy group or a propyleneoxy group, and more preferably an ethyleneoxy group.
  • the number of alkyleneoxy groups attached to the bisphenol skeleton is not particularly limited.
  • the number of alkyleneoxy groups added is preferably 4 to 16 per molecule, more preferably 6 to 14.
  • the polymerizable compound B1 having a bisphenol skeleton is described in paragraphs 0072 to 0080 of JP-A-2016-224162, and the contents described in this publication are incorporated in the present specification.
  • the polymerizable compound B1 is preferably a bifunctional ethylenically unsaturated compound having a bisphenol A skeleton, and more preferably 2,2-bis (4-((meth) acryloxypolyalkoxy) phenyl) propane. ..
  • Examples of the 2,2-bis (4-((meth) acryloxipolyalkoxy) phenyl) propane include 2,2-bis (4- (methacryloxydiethoxy) phenyl) propane (FA-324M, Hitachi Chemical Co., Ltd.).
  • Examples of the polymerizable compound B1 include compounds represented by the following general formula (I).
  • R 1 and R 2 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 independently 1 to 39, respectively.
  • n1 + n3 are integers of 2 to 40
  • n2 and n4 are independently integers of 0 to 29, and n2 + n4 are integers of 0 to 30,-(AO)-and.
  • the sequence of repeating units of-(BO)- may be random or block. In the case of a block, either-(AO)-or-(BO)-may be on the bisphenol group side.
  • N1 + n2 + n3 + n4 is preferably 2 to 20, more preferably 2 to 16, and even more preferably 4 to 12. Further, n2 + n4 is preferably 0 to 10, more preferably 0 to 4, further preferably 0 to 2, and particularly preferably 0.
  • the photosensitive resin layer may contain the polymerizable compound B1 alone or in combination of two or more.
  • the content of the polymerizable compound B1 in the photosensitive resin layer is preferably 40% by mass or more, preferably 50% by mass or more, based on the total mass of the polymerizable compound B from the viewpoint of more excellent resolution. It is more preferably 55% by mass or more, and particularly preferably 60% by mass or more.
  • the upper limit of the content of the polymerizable compound B1 is not particularly limited.
  • the content of the polymerizable compound B1 is preferably 99% by mass or less, more preferably 95% by mass or less, still more preferably 90% by mass or less, more preferably 85% by mass or less, based on the total mass of the polymerizable compound B from the viewpoint of peelability. Mass% or less is particularly preferable.
  • the photosensitive resin layer preferably contains a polymerizable compound B2 having an acid group.
  • the polymerizable compound B2 having an acid group disperses components that are insoluble in the developing solution, and can suppress the generation of scum (aggregates).
  • Examples of the acid group include a carboxy group, a phenolic hydroxyl group, a sulfonic acid group and a phosphoric acid group.
  • Examples of the polymerizable compound containing a carboxy group include unsaturated fatty acids such as acrylic acid, methacrylic acid, phthalic acid, fumaric acid, maleic acid, itaconic acid, crotonic acid, and cinnamon acid, and polyfunctional acrylates modified with a carboxy group. Examples include compounds. Examples of the polyfunctional acrylate compound modified with a carboxy group include succinic acid-modified pentaerythritol triacrylate, succinic acid-modified trimethylol propantriacrylate, succinic acid-modified pentaerythritol tetraacrylate, succinic acid-modified dipentaerythritol pentaacrylate, and succinic acid.
  • unsaturated fatty acids such as acrylic acid, methacrylic acid, phthalic acid, fumaric acid, maleic acid, itaconic acid, crotonic acid, and cinnamon acid
  • polyfunctional acrylates modified with a carboxy group examples include compounds. Examples of
  • the polyfunctional acrylate compound modified with a carboxy group may be a commercially available product. Examples of commercially available products include Aronix M-510, Aronix M-520, Aronix TO-2349 and Aronix TO-2359 (all manufactured by Toagosei Co., Ltd.).
  • Examples of the polymerizable compound containing a phenolic hydroxyl group include p-hydroxystyrene, 3,4-dihydroxystyrene, 3,5-dihydroxystyrene, 2,4,6-trihydroxystyrene, (p-hydroxy) benzyl acrylate, and salicylic acid.
  • Examples thereof include modified pentaerythritol triacrylate, salicylic acid-modified trimethylol propantriacrylate, salicylic acid-modified pentaerythritol tetraacrylate, salicylic acid-modified dipentaerythritol pentaacrylate, and salicylic acid-modified dipentaerythritol hexaacrylate.
  • Examples of the polymerizable compound containing a sulfonic acid group include vinyl sulfonic acid, allyl sulfonic acid, styrene sulfonic acid, and butyl sulfonic acid-modified acrylamide.
  • Examples of the polymerizable compound containing a phosphoric acid group include vinyl phosphoric acid, styrene phosphoric acid, and butyl phosphate-modified acrylamide.
  • the polymerizable compound B2 having an acid group is preferably a polymerizable compound having a carboxy group from the viewpoint of further dispersing the components that are insoluble in the developing solution.
  • the photosensitive resin layer may contain the polymerizable compound B2 alone or in combination of two or more.
  • the content of the polymerizable compound B2 in the photosensitive resin layer may be 10% by mass to 40% by mass with respect to the total mass of the polymerizable compound B from the viewpoint of further dispersing the components that are insoluble in the developing solution. It is more preferably 15% by mass to 35% by mass, and even more preferably 20% by mass to 30% by mass.
  • the photosensitive resin layer may contain a polymerizable compound B other than the polymerizable compound B1. Further, the photosensitive resin layer may contain a polymerizable compound B other than the polymerizable compound B2.
  • the polymerizable compound B other than the polymerizable compound B1 and the polymerizable compound B2 is not particularly limited and may be appropriately selected from known compounds.
  • the polymerizable compound B other than the polymerizable compound B1 and the polymerizable compound B2 has a compound having one ethylenically unsaturated group in one molecule (that is, a monofunctional ethylenically unsaturated compound) and an aromatic ring. Examples thereof include bifunctional ethylenically unsaturated compounds and trifunctional or higher functional ethylenically unsaturated compounds.
  • Examples of the monofunctional ethylenically unsaturated compound include ethyl (meth) acrylate, ethylhexyl (meth) acrylate, 2- (meth) acryloyloxyethyl succinate, polyethylene glycol mono (meth) acrylate, and polypropylene glycol mono (meth) acrylate. , And phenoxyethyl (meth) acrylate.
  • bifunctional ethylenically unsaturated compound having no aromatic ring examples include alkylene glycol di (meth) acrylate, polyalkylene glycol di (meth) acrylate, urethane di (meth) acrylate, and trimethylolpropane diacrylate. Be done.
  • alkylene glycol di (meth) acrylate examples include tricyclodecanedimethanol diacrylate (A-DCP, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), tricyclodecanedimethanol dimethacrylate (DCP, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), and the like.
  • 1,9-Nonandiol diacrylate (A-NOD-N, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), 1,6-Hexanediol diacrylate (A-HD-N, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), ethylene glycol dimethacrylate , 1,10-decanediol diacrylate, and neopentyl glycol di (meth) acrylate.
  • polyalkylene glycol di (meth) acrylate examples include polyethylene glycol di (meth) acrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, and polypropylene glycol di (meth) acrylate.
  • Examples of the urethane di (meth) acrylate include propylene oxide-modified urethane di (meth) acrylate, and ethylene oxide and propylene oxide-modified urethane di (meth) acrylate.
  • Examples of commercially available products include 8UX-015A (manufactured by Taisei Fine Chemical Co., Ltd.), UA-32P (manufactured by Shin-Nakamura Chemical Co., Ltd.), and UA-1100H (manufactured by Shin-Nakamura Chemical Co., Ltd.).
  • Examples of the trifunctional or higher functional ethylenically unsaturated compound include dipentaerythritol (tri / tetra / penta / hexa) (meth) acrylate, pentaerythritol (tri / tetra) (meth) acrylate, and trimethylolpropane tri (meth).
  • Examples thereof include acrylates, tri (meth) acrylates of isocyanuric acid, glycerin tri (meth) acrylates, and modified alkylene oxides thereof.
  • (tri / tetra / penta / hexa) (meth) acrylate) is a concept including tri (meth) acrylate, tetra (meth) acrylate, penta (meth) acrylate, and hexa (meth) acrylate.
  • (Tri / tetra) (meth) acrylate” is a concept that includes tri (meth) acrylate and tetra (meth) acrylate.
  • the photosensitive resin layer preferably contains a polymerizable compound B1 and a trifunctional or higher ethylenically unsaturated compound, and more preferably contains a polymerizable compound B1 and two or more trifunctional or higher ethylenically unsaturated compounds. ..
  • the mass ratio of the polymerizable compound B1 to the trifunctional or higher ethylenically unsaturated compound is 1: 1 to 5 :. 1 is preferred, 1.2: 1 to 4: 1 is more preferred, and 1.5: 1 to 3: 1 is even more preferred.
  • alkylene oxide-modified product of the trifunctional or higher functional ethylenically unsaturated compound examples include caprolactone-modified (meth) acrylate compound (KAYARAD (registered trademark) DPCA-20, manufactured by Nippon Kayaku Co., Ltd .; A-9300-1CL, Shin-Nakamura).
  • alkylene oxide-modified (meth) acrylate compound (KAYARAD RP-1040, Nippon Kayaku Co., Ltd .; ATM-35E and A-9300, Shin-Nakamura Chemical Industry Co., Ltd .; EBECRYL (registered trademark) 135, Daicel Ornex), Glycerin triacrylate ethoxylated (A-GLY-9E, manufactured by Shin-Nakamura Chemical Co., Ltd.), Aronix (registered trademark) TO-2349 (manufactured by Toagosei), Aronix M-520 (manufactured by Toagosei) , And Aronix M-510 (manufactured by Toagosei Co., Ltd.).
  • the photosensitive resin layer may contain the polymerizable compound B alone or in combination of two or more.
  • the content of the polymerizable compound B is preferably 10% by mass to 70% by mass, more preferably 20% by mass to 60% by mass, and further preferably 20% by mass to 50% by mass with respect to the total mass of the photosensitive resin layer. preferable.
  • the weight average molecular weight (Mw) of the polymerizable compound B is preferably 200 to 3,000, more preferably 280 to 2,200, and even more preferably 300 to 2,200.
  • the ratio of the content of the polymerizable compound B to the content of the polymer A is preferably 0.85 or less, preferably 0.5 to 0.85, on a mass basis. More preferably, it is more preferably 0.6 to 0.85, and particularly preferably 0.75 to 0.85.
  • the polymerizable compound B that does not dissolve in the developing solution becomes oil droplets, and the alkali-soluble resin acts as a dispersant to prevent the oil droplets from coalescing with each other, resulting in scum (aggregate). Can be suppressed.
  • the photosensitive resin layer may contain components other than the polymer A and the polymerizable compound B.
  • the photosensitive resin layer preferably contains a photopolymerization initiator.
  • the photopolymerization initiator is a compound having an action of initiating the polymerization of a polymerizable compound by active rays such as ultraviolet rays, visible rays, and X-rays.
  • the photopolymerization initiator is not particularly limited, and a known photopolymerization initiator can be used.
  • the photopolymerization initiator examples include a photoradical polymerization initiator and a photocationic polymerization initiator. Above all, the photopolymerization initiator is preferably a photoradical polymerization initiator.
  • Examples of the photoradical polymerization initiator include a photopolymerization initiator having an oxime ester skeleton, a photopolymerization initiator having an ⁇ -aminoalkylphenone skeleton, a photopolymerization initiator having an ⁇ -hydroxyalkylphenone skeleton, and an acylphosphine oxide. Examples thereof include a photopolymerization initiator having a skeleton and a photopolymerization initiator having an N-phenylglycine skeleton.
  • the photosensitive resin layer contains 2,4,5-triarylimidazole dimer and 2,4,5-triarylimidazole dimer as a photoradical polymerization initiator from the viewpoints of photosensitivity, visibility of exposed and non-exposed areas, and resolution. It is preferable to contain at least one selected from the group consisting of the derivatives.
  • the two 2,4,5-triarylimidazole skeletons in the 2,4,5-triarylimidazole dimer and its derivatives may be the same or different.
  • Derivatives of the 2,4,5-triarylimidazole dimer include, for example, 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer, 2- (o-chlorophenyl) -4,5-di. (Methoxyphenyl) imidazole dimer, 2- (o-fluorophenyl) -4,5-diphenylimidazole dimer, 2- (o-methoxyphenyl) -4,5-diphenylimidazole dimer, and 2 -(P-methoxyphenyl) -4,5-diphenylimidazole dimer can be mentioned.
  • the photoradical polymerization initiator may be the polymerization initiator described in paragraphs 0031 to 0042 of JP2011-95716A and paragraphs 0064 to 0081 of JP2015-14783A.
  • photoradical polymerization initiator examples include ethyl dimethylaminobenzoate (DBE, CAS No. 10287-53-3), benzoin methyl ether, anisyl (p, p'-dimethoxybenzyl), and benzophenone.
  • DBE ethyl dimethylaminobenzoate
  • benzoin methyl ether examples include benzoin methyl ether, anisyl (p, p'-dimethoxybenzyl), and benzophenone.
  • Examples of commercially available photoradical polymerization initiators include 2,4-bis (trichloromethyl) -6- [2- (4-methylphenyl) ethenyl] -1,3,5-triazine (trade name: TAZ-). 110, manufactured by Midori Kagaku Co., Ltd.), (trade name: TAZ-111, manufactured by Midori Kagaku Co., Ltd.), 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetraphenyl-1,2 '-Bimidazole (manufactured by Tokyo Kasei Kogyo Co., Ltd.), 1- [4- (Phenylthio) phenyl] -1,2-octanedione-2- (O-benzoyloxime) (trade name: Irgacure (registered trademark) OXE-01 , BASF Japan, Inc.), 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carba
  • a photocationic polymerization initiator is a compound that generates an acid by receiving active light.
  • the photocationic polymerization initiator is not particularly limited, but is preferably a compound that is sensitive to active light having a wavelength of 300 nm or more, preferably a wavelength of 300 nm to 450 nm, and generates an acid. Further, even if the compound is not directly sensitive to the active light having a wavelength of 300 nm or more, if it is a compound that is sensitive to the active light having a wavelength of 300 nm or more and generates an acid when used in combination with a sensitizer, it is combined with the sensitizer. Can be preferably used.
  • photocationic polymerization initiator a photocationic polymerization initiator that generates an acid having a pKa of 4 or less is preferable, a photocationic polymerization initiator that generates an acid having a pKa of 3 or less is more preferable, and an acid having a pKa of 2 or less is generated.
  • Photocationic polymerization initiators are particularly preferred.
  • the lower limit of pKa is not particularly limited, and for example, -10.0 is preferable.
  • photocationic polymerization initiator examples include an ionic photocationic polymerization initiator and a nonionic photocationic polymerization initiator.
  • Examples of the ionic photocationic polymerization initiator include onium salt compounds such as diaryliodonium salt and triarylsulfonium salt, and quaternary ammonium salt.
  • the ionic photocationic polymerization initiator may be the ionic photocationic polymerization initiator described in paragraphs 0114 to 0133 of JP-A-2014-85643.
  • nonionic photocationic polymerization initiator examples include a trichloromethyl-s-triazine compound, a diazomethane compound, an imide sulfonate compound, and an oxime sulfonate compound.
  • the trichloromethyl-s-triazine compound, the diazomethane compound and the imide sulfonate compound may be the compounds described in paragraphs 0083 to 0088 of JP-A-2011-22149.
  • the oxime sulfonate compound may be a compound described in paragraphs 0084 to 0088 of International Publication No. 2018/179640.
  • the photosensitive resin layer may contain one type of photopolymerization initiator alone or two or more types.
  • the content of the photopolymerization initiator is not particularly limited, but is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and 1.0% by mass or more, based on the total mass of the photosensitive resin layer. Is even more preferable.
  • the upper limit of the content of the photopolymerization initiator is not particularly limited.
  • the content of the photopolymerization initiator is preferably 10% by mass or less, more preferably 5% by mass or less, based on the total mass of the photosensitive resin layer.
  • the photosensitive resin layer has a maximum absorption wavelength of 450 nm or more in the wavelength range of 400 nm to 780 nm at the time of color development from the viewpoints of visibility of exposed and unexposed areas, pattern visibility after development, and resolution.
  • the dye N is contained, the detailed mechanism is unknown, but the adhesion to the adjacent layer (for example, the temporary support and the intermediate layer) is improved, and the resolution is more excellent.
  • the term "the maximum absorption wavelength is changed by an acid, a base or a radical” means that the dye in a color-developing state is decolorized by an acid, a base or a radical, and the dye in a decolorized state is an acid. It may mean any aspect of a mode in which a color is developed by a base or a radical, or a mode in which a dye in a color-developing state changes to a color-developing state of another hue.
  • the dye N may be a compound that changes from the decolorized state by exposure to develop a color, or may be a compound that changes from the decolorized state by exposure to decolorize.
  • the dye may change its color development or decolorization state by generating an acid, a base or a radical in the photosensitive resin layer by exposure, and may be a dye in the photosensitive resin layer by the acid, the base or the radical. It may be a dye whose color development or decolorization state changes as the state (for example, pH) changes.
  • the dye N may be a dye that is not exposed and directly receives an acid, a base or a radical as a stimulus to change the state of color development or decolorization.
  • the dye N is preferably a dye whose maximum absorption wavelength is changed by an acid or a radical, and more preferably a dye whose maximum absorption wavelength is changed by a radical. ..
  • the photosensitive resin layer contains both a dye whose maximum absorption wavelength is changed by radicals as dye N and a photoradical polymerization initiator from the viewpoints of visibility and resolution of exposed and non-exposed areas. Is preferable.
  • the dye N is preferably a dye that develops color by an acid, a base, or a radical.
  • a photoradical polymerization initiator As an example of the color development mechanism of dye N, a photoradical polymerization initiator, a photocationic polymerization initiator (photoacid generator) or a photobase generator is added to the photosensitive resin layer, and a photoradical polymerization initiator is added after exposure. Examples thereof include an embodiment in which color is developed by radicals, acids or bases generated from a photocationic polymerization initiator or a photobase generator.
  • the dye N preferably has a maximum absorption wavelength of 550 nm or more in the wavelength range of 400 nm to 780 nm at the time of color development, more preferably 550 to 700 nm. It is more preferably about 650 nm.
  • the dye N may have only one maximum absorption wavelength in the wavelength range of 400 nm to 780 nm at the time of color development, or may have two or more.
  • the maximum absorption wavelength having the highest absorbance among the two or more maximum absorption wavelengths may be 450 nm or more.
  • the transmission spectrum of a solution containing dye N (liquid temperature 25 ° C.) is measured in the range of 400 nm to 780 nm using a spectrophotometer (UV3100, manufactured by Shimadzu Corporation) in an atmospheric atmosphere. However, it is obtained by detecting the wavelength at which the intensity of light is minimized (that is, the maximum absorption wavelength).
  • Examples of the dye that develops or decolorizes by exposure include a leuco compound.
  • Examples of dyes that are decolorized by exposure include leuco compounds, diarylmethane dyes, oxazine dyes, xanthene dyes, iminonaphthoquinone dyes, azomethine dyes and anthraquinone dyes.
  • the dye N is preferably a leuco compound from the viewpoint of visibility of the exposed portion and the non-exposed portion.
  • the leuco compound examples include a leuco compound having a triarylmethane skeleton (triarylmethane dye), a leuco compound having a spiropylan skeleton (spiropylan dye), a leuco compound having a fluorane skeleton (fluorane dye), and a diarylmethane skeleton.
  • Leuco compound (diarylmethane dye), rhodamine lactam skeleton (rhodamine lactam dye), leuco compound having indrill phthalide skeleton (indrill phthalide dye), and leuco auramine skeleton examples thereof include leuco compounds having leuco compounds (leuco auramine dyes).
  • the leuco compound is preferably a triarylmethane dye or a fluorane dye, and a leuco compound having a triphenylmethane skeleton (triphenylmethane dye) or a fluorane dye is more preferable.
  • the leuco compound preferably has a lactone ring, a surujin ring, or a sultone ring from the viewpoint of visibility of the exposed portion and the non-exposed portion.
  • the lactone ring, sultin ring, or sulton ring contained in the leuco compound reacts with a radical generated from the photoradical polymerization initiator or an acid generated from the photocationic polymerization initiator, and changes from a ring-closed state to a ring-opened state to develop color. Or, the color is decolorized by changing from the ring-opened state to the ring-closed state.
  • the leuco compound is preferably a compound having a lactone ring, a sultone ring or a sultone ring and developing a color by opening the ring with a radical or an acid, and more preferably a compound having a lactone ring and developing a color by opening the ring with a radical or an acid. ..
  • Examples of the dye N include the following dyes and leuco compounds.
  • Dyes include Brilliant Green, Ethyl Violet, Methyl Green, Crystal Violet, Basic Fuxin, Methyl Violet 2B, Kinaldine Red, Rose Bengal, Metanyl Yellow, Timor Sulfophthalene, Xylenol Blue, Methyl Orange, Paramethyl Red, Congo Red, benzopurpurin 4B, ⁇ -naphthyl red, Nile blue 2B, Nile blue A, methyl violet, malakite green, parafuxin, Victoria pure blue-naphthalene sulfonate, Victoria pure blue BOH (manufactured by Hodoya Chemical Industry Co., Ltd.), Oil Blue # 603 (manufactured by Orient Chemical Industry Co., Ltd.), Oil Pink # 312 (manufactured by Orient Chemical Industry Co., Ltd.), Oil Red 5B (manufactured by Orient Chemical Industry Co., Ltd.), Oil Scarlet #
  • Leuco compounds include p, p', p "-hexamethyltriaminotriphenylmethane (leucocrystal violet), Pergascript Blue SRB (manufactured by Ciba Geigy), crystal violet lactone, malakite green lactone, benzoyl leucomethylene blue, 2- ( N-phenyl-N-methylamino) -6- (N-p-trill-N-ethyl) aminofluorane, 2-anilino-3-methyl-6- (N-ethyl-p-toluizino) fluorane, 3, 6-Dimethoxyfluorane, 3- (N, N-diethylamino) -5-methyl-7- (N, N-dibenzylamino) fluorane, 3- (N-cyclohexyl-N-methylamino) -6-methyl- 7-anilinofluorane, 3- (N, N-diethylamino) -6-methyl-7
  • the dye N is preferably a dye whose maximum absorption wavelength is changed by radicals from the viewpoints of visibility of exposed and unexposed areas, pattern visibility after development, and resolution, and is a dye that develops color by radicals. Is more preferable.
  • the dye N is preferably leuco crystal violet, crystal violet lactone, brilliant green, or Victoria pure blue-naphthalene sulfonate.
  • the photosensitive resin layer may contain dye N alone or in combination of two or more.
  • the content of the dye N is 0.1% by mass or more with respect to the total mass of the photosensitive resin layer from the viewpoints of visibility of the exposed and non-exposed areas, pattern visibility after development, and resolution. Is more preferable, 0.1% by mass to 10% by mass is more preferable, 0.1% by mass to 5% by mass is further preferable, and 0.1% by mass to 1% by mass is particularly preferable.
  • the content of the dye N means the content of the dye when all of the dye N contained in the photosensitive resin layer is in a colored state.
  • a method for quantifying the content of dye N will be described by taking a dye that develops color by radicals as an example.
  • the absorbance of the solution in which all the dyes are colored is measured by the same method as above except that 3 g of the photosensitive resin layer is dissolved in methyl ethyl ketone instead of the dye. From the absorbance of the obtained solution containing the photosensitive resin layer, the content of the dye contained in the photosensitive resin layer is calculated based on the calibration curve.
  • the photosensitive resin layer preferably contains a surfactant from the viewpoint of thickness uniformity.
  • the surfactant examples include anionic surfactant, cationic surfactant, nonionic surfactant, and amphoteric surfactant. Above all, the surfactant is preferably a nonionic surfactant.
  • nonionic surfactant examples include polyoxyethylene higher alkyl ether, polyoxyethylene higher alkylphenyl ether, polyoxyethylene glycol higher fatty acid diester, silicone-based nonionic surfactant, and fluorine-based nonionic surfactant. Agents can be mentioned.
  • the photosensitive resin layer preferably contains a fluorine-based nonionic surfactant from the viewpoint of improving the resolution. It is considered that this is because the photosensitive resin layer contains the fluorine-based nonionic surfactant, so that the penetration of the etching solution into the photosensitive resin layer is suppressed and the side etching is reduced.
  • fluorine-based nonionic surfactants examples include Megafuck F-551, F-552 and F-554 (all manufactured by DIC Corporation).
  • fluorine-based surfactants include, for example, Megafuck F-171, F-172, F-173, F-176, F-177, F-141, F-142, F-143, F. -144, F-437, F-475, F-477, F-479, F-482, 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, MFS-578, MFS-579, MFS-586, MFS-587, R-41, R -141-LM, R-01, R-40, R-40-LM, RS-43, TF-1956, RS-90, R-94, RS-72-K, DS-21 (above, DIC Co., Ltd.) , Florard FC430, FC431, FC171 (all manufactured by Sumitomo 3M Co., Ltd.), Surfron S-3
  • a fluorine-based surfactant an acrylic compound having a molecular structure having a functional group containing a fluorine atom, and when heat is applied, a portion of the functional group containing a fluorine atom is cut and the fluorine atom volatilizes.
  • fluorine-based surfactants include the Megafuck DS series manufactured by DIC Corporation (The Chemical Daily (February 22, 2016), Nikkei Sangyo Shimbun (February 23, 2016)), for example, Megafuck. DS-21 can be mentioned.
  • the fluorine-based surfactant it is also preferable to use a polymer of a fluorine atom-containing vinyl ether compound having a fluorinated alkyl group or a fluorinated alkylene ether group and a hydrophilic vinyl ether compound.
  • a block polymer can also be used as the fluorine-based surfactant.
  • the fluorine-based surfactant has a structural unit derived from a (meth) acrylate compound having a fluorine atom and 2 or more (preferably 5 or more) alkyleneoxy groups (preferably ethyleneoxy groups and propyleneoxy groups).
  • a fluorine-containing polymer compound containing a structural unit derived from a (meth) acrylate compound can also be preferably used.
  • fluorine-based surfactant a fluorine-containing polymer having an ethylenically unsaturated bond-containing group in the side chain can also be used.
  • Megafvck RS-101, RS-102, RS-718K, RS-72-K (all manufactured by DIC Corporation) and the like can be mentioned.
  • fluorine-based surfactant from the viewpoint of improving environmental suitability, compounds having a linear perfluoroalkyl group having 7 or more carbon atoms, such as perfluorooctanoic acid (PFOA) and perfluorooctanesulfonic acid (PFOS), are used. It is preferably a surfactant derived from an alternative material.
  • PFOA perfluorooctanoic acid
  • PFOS perfluorooctanesulfonic acid
  • Nonionic surfactants include glycerol, trimethylolpropane, trimethylolethane and their ethoxylates and propoxylates (eg, glycerol propoxylate, glycerol ethoxylate, etc.), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, etc.
  • Polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester, Pluronic L10, L31, L61, L62, 10R5, 17R2, 25R2 (or more) , BASF), Tetronic 304, 701, 704, 901, 904, 150R1 (above, BASF), Solsparse 20000 (above, Nippon Lubrizol Co., Ltd.), NCW-101, NCW-1001, NCW -1002 (above, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), Pionin D-6112, D-6112-W, D-6315 (above, manufactured by Takemoto Yushi Co., Ltd.), Orphine E1010, Surfinol 104, 400, 440 (above, manufactured by Nissin Chemical Industry Co., Ltd.) and the like can
  • silicone-based surfactant examples include a linear polymer composed of a siloxane bond and a modified siloxane polymer in which an organic group is introduced into a side chain or a terminal.
  • silicone-based surfactants include DOWNSIL 8032 ADDITIVE, Torre Silicone DC3PA, Torre Silicone SH7PA, Torre Silicone DC11PA, Torre Silicone SH21PA, Torre Silicone SH28PA, Torre Silicone SH29PA, Torre Silicone SH30PA, Torre Silicone SH8400 (above, Toray).
  • the surfactants are the surfactant described in paragraphs 0120 to 0125 of International Publication No. 2018/179640, the surfactant described in paragraph 0017 of Japanese Patent No. 45027884, and the paragraph of JP-A-2009-237362. It may be the surfactant described in 0060 to 0071.
  • the photosensitive resin layer may contain one type of surfactant alone or two or more types.
  • the content of the surfactant is preferably 0.001% by mass to 10% by mass, more preferably 0.01% by mass to 3% by mass, based on the total mass of the photosensitive resin layer.
  • the photosensitive resin layer may contain a known additive in addition to the above components, if necessary.
  • the additive examples include a radical polymerization inhibitor, a sensitizer, a plasticizer, a heterocyclic compound, benzotriazoles, carboxybenzotriazoles, a resin other than polymer A, and a solvent.
  • the photosensitive resin layer may contain each additive alone or in combination of two or more.
  • the photosensitive resin layer may contain a radical polymerization inhibitor.
  • radical polymerization inhibitor examples include the thermal polymerization inhibitor described in paragraph 0018 of Japanese Patent No. 4502784.
  • examples of the radical polymerization inhibitor include phenothiazine, phenoxazine, 4-methoxyphenol, naphthylamine, cuprous chloride, N-nitrosophenylhydroxyamine aluminum salt, and diphenylnitrosamine.
  • the radical polymerization inhibitor is preferably phenothiazine, phenoxazine, 4-methoxyphenol or N-nitrosophenylhydroxyamine aluminum salt.
  • benzotriazoles include 1,2,3-benzotriazole, 1-chloro-1,2,3-benzotriazole, bis (N-2-ethylhexyl) aminomethylene-1,2,3-benzotriazole, and the like. Examples thereof include bis (N-2-ethylhexyl) aminomethylene-1,2,3-tolyltriazole and bis (N-2-hydroxyethyl) aminomethylene-1,2,3-benzotriazole.
  • carboxybenzotriazoles examples include 4-carboxy-1,2,3-benzotriazole, 5-carboxy-1,2,3-benzotriazole, and N- (N, N-di-2-ethylhexyl) aminomethylene.
  • Examples thereof include di-n-butylaminomethyl) -5-carboxybenzotriazole and 1- (2-di-n-butylaminomethyl) -6-carboxybenzotriazole.
  • Examples of commercially available products of carboxybenzotriazoles include CBT-1 (manufactured by Johoku Chemical Industry Co., Ltd.).
  • the total content of the radical polymerization inhibitor, benzotriazols, and carboxybenzotriazols is preferably 0.01% by mass to 3% by mass with respect to the total mass of the photosensitive resin layer. It is more preferably 0.05% by mass to 1% by mass.
  • the content is 0.01% by mass or more, the storage stability of the photosensitive resin composition is excellent.
  • the content is 3% by mass or less, the sensitivity can be maintained and the decolorization of the dye can be suppressed.
  • the photosensitive resin layer may contain a sensitizer.
  • the sensitizer is not particularly limited, and known sensitizers, dyes and pigments can be used.
  • the sensitizer include dialkylaminobenzophenone compounds, pyrazoline compounds, anthracene compounds, coumarin compounds, xanthone compounds, thioxanthone compounds, acridone compounds, oxazole compounds, benzoxazole compounds, thiazole compounds, benzothiazole compounds, and triazole compounds (for example, 1,2,4-triazole), stillben compounds, triazine compounds, thiophene compounds, naphthalimide compounds, triarylamine compounds, and aminoaclydin compounds.
  • the photosensitive resin layer may contain one kind of sensitizer alone or two or more kinds.
  • the content of the sensitizer can be appropriately selected depending on the purpose.
  • the content of the sensitizer is 0.01% by mass to 5% by mass with respect to the total mass of the photosensitive resin layer from the viewpoint of improving the sensitivity to the light source and improving the curing rate by balancing the polymerization rate and the chain transfer. It is preferably by mass%, more preferably 0.05% by mass to 1% by mass.
  • the photosensitive resin layer may contain at least one selected from the group consisting of a plasticizer and a heterocyclic compound.
  • plasticizer and the heterocyclic compound examples include the compounds described in paragraphs 097 to 0103 and 0111 to 0118 of International Publication No. 2018/179640.
  • the photosensitive resin layer may contain a resin other than the polymer A.
  • Resins other than polymer A include acrylic resins, styrene-acrylic copolymers (however, the content of constituent units derived from styrene is 40% by mass or less), polyurethane, polyvinyl alcohol, polyvinyl formal, polyamide, and the like. Examples thereof include polyester, epoxy resin, polyacetal, polyhydroxystyrene, polyimide, polybenzoxazole, polysiloxane, polyethyleneimine, polyallylamine, and polyalkylene glycol.
  • the photosensitive resin layer may contain a solvent.
  • the solvent may remain in the photosensitive resin layer.
  • the photosensitive resin layer includes metal oxide particles, antioxidants, rust inhibitors, chain transfer agents, dispersants, acid growth agents, development accelerators, conductive fibers, thermal radical polymerization initiators, and thermal acid generators. , UV absorbers, thickeners, cross-linking agents, organic or inorganic precipitation inhibitors and other known additives may be further contained.
  • Additives that may be contained in the photosensitive resin layer are described in paragraphs 0165 to 0184 of Japanese Patent Application Laid-Open No. 2014-85643, and the contents of this publication are incorporated in the present specification.
  • the thickness of the photosensitive resin layer is preferably 10 ⁇ m or less, more preferably 5 ⁇ m or less, further preferably 3 ⁇ m or less, and particularly preferably 2 ⁇ m or less.
  • the thickness of the photosensitive resin layer is, for example, 0.5 ⁇ m.
  • each layer provided in the photosensitive transfer material is based on the observation image obtained by observing the cross section in the direction perpendicular to the main surface of the photosensitive transfer material with a scanning electron microscope (SEM).
  • SEM scanning electron microscope
  • the light transmittance of the photosensitive resin layer at a wavelength of 365 nm is preferably 10% or more, preferably 30% or more, and more preferably 50% or more.
  • the upper limit of the light transmittance of the photosensitive resin layer at a wavelength of 365 nm is not particularly limited, but is preferably 99.9%.
  • 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 photosensitive resin composition containing the polymer A, the polymerizable compound B and a solvent is prepared, and the photosensitive resin composition is applied to the surface of a temporary support or the like.
  • Examples thereof include a method of forming by drying a coating film of a photosensitive resin composition.
  • Examples of the photosensitive resin composition used for forming the photosensitive resin layer include a composition containing a polymer A, a polymerizable compound B, the above-mentioned 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.
  • solvent contained in the photosensitive resin composition is not particularly limited as long as the polymer A, the polymerizable compound B and the above optional components can be dissolved or dispersed, and known solvents can be used.
  • alkylene glycol ether for example, alkylene glycol ether, alkylene glycol ether acetate, alcohol (for example, methanol and ethanol), ketone (for example, acetone and methyl ethyl ketone), aromatic hydrocarbon (for example, toluene), aprotonic polar solvent (for example).
  • alcohol for example, methanol and ethanol
  • ketone for example, acetone and methyl ethyl ketone
  • aromatic hydrocarbon for example, toluene
  • aprotonic polar solvent for example.
  • N, N-dimethylformamide cyclic ethers (eg, tetrahydrofuran), esters, amides, lactones, and mixed solvents containing two or more of these.
  • the photosensitive resin composition is selected from at least the group consisting of alkylene glycol ether and alkylene glycol ether acetate. It is preferable to contain one kind.
  • the solvent is more preferably a mixed solvent containing at least one selected from the group consisting of alkylene glycol ether and alkylene glycol ether acetate solvent and at least one selected from the group consisting of ketone and cyclic ether.
  • a mixed solvent containing at least one selected from the group consisting of alkylene glycol ether and alkylene glycol ether acetate, a ketone, and cyclic ether is more preferable.
  • alkylene glycol ether examples include ethylene glycol monoalkyl ether, ethylene glycol dialkyl ether, propylene glycol monoalkyl ether, propylene glycol dialkyl ether, diethylene glycol dialkyl ether, dipropylene glycol monoalkyl ether and dipropylene glycol dialkyl ether.
  • alkylene glycol ether acetate examples include ethylene glycol monoalkyl ether acetate, propylene glycol monoalkyl ether acetate, diethylene glycol monoalkyl ether acetate and dipropylene glycol monoalkyl ether acetate.
  • the solvent may be the solvent described in paragraphs 0092 to 0094 of International Publication No. 2018/179640 and the solvent described in paragraph 0014 of JP-A-2018-177789, and the contents thereof are incorporated in the present specification. Is done.
  • the photosensitive resin composition may contain one type of solvent alone, or may contain two or more types of solvent.
  • the content of the solvent in the photosensitive resin composition is preferably 50 parts by mass to 1,900 parts by mass, more preferably 100 parts by mass to 900 parts by mass, based on 100 parts by mass of the total solid content in the photosensitive resin composition. ..
  • the method for preparing the photosensitive resin composition is not particularly limited.
  • a photosensitive resin composition is prepared by preparing a solution in which each component is dissolved in the above solvent in advance and mixing the obtained solution in a predetermined ratio. There is a method of preparing.
  • the photosensitive resin composition is preferably filtered using a filter having a pore size of 0.2 ⁇ m to 30 ⁇ m before forming the photosensitive resin layer.
  • the method of applying the photosensitive resin composition is not particularly limited, and it may be applied by a known method.
  • Examples of the coating method include slit coating, spin coating, curtain coating and inkjet coating.
  • the photosensitive resin layer may be formed by applying the photosensitive resin composition on a cover film described later and drying it.
  • the photosensitive resin layer may contain a predetermined amount of impurities.
  • impurities include sodium, potassium, magnesium, calcium, iron, manganese, copper, aluminum, titanium, chromium, cobalt, nickel, zinc, tin, halogen and ions thereof.
  • halide ions, sodium ions, and potassium ions are likely to be mixed as impurities, so the content is preferably as follows.
  • the content of impurities in the photosensitive resin layer is preferably 80 ppm or less, more preferably 10 ppm or less, still more preferably 2 ppm or less on a mass basis.
  • the content of impurities in the photosensitive resin layer can be 1 ppb or more or 0.1 ppm or more on a mass basis.
  • 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 specific compounds of benzene, formaldehyde, trichlorethylene, 1,3-butadiene, carbon tetrachloride, chloroform, N, N-dimethylformamide, N, N-dimethylacetamide, and hexane in the photosensitive resin layer is low. Is preferable.
  • the content of the specific compound in the photosensitive resin layer is preferably 100 ppm or less, more preferably 20 ppm or less, still more preferably 4 ppm or less on a mass basis.
  • the lower limit of the content is preferably 10 ppb, more preferably 100 ppb on a mass basis.
  • the content of the specific compound can be suppressed in the same manner as the above impurities.
  • the content of the specific compound can be quantified by a known measurement method.
  • the water content in the photosensitive resin layer is preferably 0.01% by mass to 1.0% by mass, more preferably 0.05% by mass to 0.5% by mass, from the viewpoint of improving reliability and laminateability. ..
  • the photosensitive transfer material according to the present disclosure preferably includes a thermoplastic resin layer between the temporary support and the photosensitive resin layer.
  • thermoplastic resin layer When the thermoplastic resin layer is arranged between the temporary support and the photosensitive resin layer, the followability to the substrate in the bonding process with the substrate is improved, and air bubbles between the substrate and the photosensitive transfer material are improved. Is suppressed, and the adhesion to the adjacent layer (for example, temporary support) is improved.
  • thermoplastic resin layer contains an alkali-soluble resin as the thermoplastic resin.
  • alkali-soluble means that the solubility of sodium carbonate in 100 g of a 1% by mass aqueous solution at 22 ° C. is 0.1 g or more.
  • alkali-soluble resin examples include acrylic resin, polystyrene, styrene-acrylic copolymer, polyurethane, polyvinyl alcohol, polyvinyl formal, polyamide, polyester, epoxy resin, polyacetal, polyhydroxystyrene, polyimide, polybenzoxazole, and polysiloxane.
  • alkali-soluble resin examples include acrylic resin, polystyrene, styrene-acrylic copolymer, polyurethane, polyvinyl alcohol, polyvinyl formal, polyamide, polyester, epoxy resin, polyacetal, polyhydroxystyrene, polyimide, polybenzoxazole, and polysiloxane.
  • examples thereof include polyethyleneimine, polyallylamine and polyalkylene glycol.
  • an acrylic resin is preferable from the viewpoint of developability and adhesion to an adjacent layer.
  • the acrylic resin was selected from the group consisting of a structural unit derived from (meth) acrylic acid, a structural unit derived from (meth) acrylic acid ester, and a structural unit derived from (meth) acrylic acid amide. It means a resin having at least one structural unit.
  • the total content of the structural unit derived from (meth) acrylic acid, the structural unit derived from (meth) acrylic acid ester, and the structural unit derived from (meth) acrylic acid amide is that of the acrylic resin. It is preferably 50% by mass or more with respect to the total mass.
  • the total content of the structural unit derived from (meth) acrylic acid and the structural unit derived from (meth) acrylic acid ester is preferably 30% by mass to 100% by mass with respect to the total mass of the acrylic resin. , 50% by mass to 100% by mass, more preferably.
  • the alkali-soluble resin is preferably a polymer having an acid group.
  • the acid group include a carboxy group, a sulfo group, a phosphoric acid group and a phosphonic acid group, and a carboxy group is preferable.
  • the upper limit of the acid value of the alkali-soluble resin is not particularly limited.
  • the acid value of the alkali-soluble resin 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.
  • Examples of the carboxy group-containing acrylic resin having an acid value of 60 mgKOH / g or more include an alkali-soluble resin which is a carboxy group-containing acrylic resin having an acid value of 60 mgKOH / g or more among the polymers described in paragraph 0025 of JP2011-95716A. , 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 JP2010-237589A, and paragraphs 0053 to 0068 of JP2016-224162A.
  • the binder polymers a carboxy group-containing acrylic resin having an acid value of 60 mgKOH / g or more can be mentioned. Twice
  • the content of the structural unit having a carboxy group in the carboxy group-containing acrylic resin is preferably 5% by mass to 50% by mass, more preferably 10% by mass to 40% by mass, and 12% by mass with respect to the total mass of the acrylic resin. % To 30% by mass is more preferable.
  • an acrylic resin having a structural unit derived from (meth) acrylic acid is particularly preferable from the viewpoint of developability and adhesion to an adjacent layer.
  • the alkali-soluble resin may have a reactive group.
  • the reactive group may be any addition-polymerizable group, and an ethylenically unsaturated group; a polycondensable group such as a hydroxy group or a carboxy group; a polyadditive reactive group such as an epoxy group or a (block) isocyanate group may be used. Can be mentioned.
  • the weight average molecular weight (Mw) of the alkali-soluble resin is preferably 1,000 or more, more preferably 10,000 to 100,000, and even more preferably 20,000 to 50,000.
  • the thermoplastic resin layer may contain one kind of alkali-soluble resin alone or two or more kinds.
  • the content of the alkali-soluble resin is preferably 10% by mass to 99% by mass, preferably 20% by mass to 90% by mass, based on the total mass of the thermoplastic resin layer from the viewpoint of developability and adhesion to the adjacent layer. Is more preferable, 40% by mass to 80% by mass is further preferable, and 50% by mass to 70% by mass is particularly preferable.
  • the thermoplastic resin layer contains a dye (also simply referred to as "dye B") having a maximum absorption wavelength of 450 nm or more in the wavelength range of 400 nm to 780 nm at the time of color development and whose maximum absorption wavelength is changed by an acid, a base, or a radical. It is preferable to do so.
  • the preferred embodiment of the dye B is the same as the preferred embodiment of the dye N except for the points described later.
  • the dye B is preferably a dye whose maximum absorption wavelength is changed by an acid or radical, and more preferably a dye whose maximum absorption wavelength is changed by an acid, from the viewpoint of visibility and resolution of exposed and unexposed areas. ..
  • the thermoplastic layer contains both a dye whose maximum absorption wavelength changes depending on the acid as the dye B and a compound that generates an acid by light, which will be described later. It is preferable to contain it.
  • thermoplastic resin layer may contain dye B alone or in combination of two or more.
  • the content of the dye B is preferably 0.2% by mass or more, preferably 0.2% by mass to 6% by mass, based on the total mass of the thermoplastic resin layer from the viewpoint of visibility of the exposed part and the non-exposed part. More preferably, 0.2% by mass to 5% by mass is further preferable, and 0.25% by mass to 3.0% by mass is particularly preferable.
  • the content of the dye B means the content of the dye when all of the dye B contained in the thermoplastic resin layer is in a colored state.
  • a method for quantifying the content of dye B will be described by taking a dye that develops color by radicals as an example.
  • the absorbance of the solution in which all the dyes are colored is measured by the same method as above except that 0.1 g of the thermoplastic resin layer is dissolved in methyl ethyl ketone instead of the dye. From the absorbance of the obtained solution containing the thermoplastic resin layer, the amount of the dye contained in the thermoplastic resin layer is calculated based on the calibration curve.
  • thermoplastic resin layer may contain a compound that generates an acid, a base, or a radical by light (also simply referred to as “Compound C”).
  • the compound C a compound that generates an acid, a base, or a radical by receiving active rays such as ultraviolet rays and visible rays is preferable.
  • Compound C may be a known photoacid generator, photobase generator, and photoradical polymerization initiator (photoradical generator). Above all, compound C is preferably a photoacid generator.
  • thermoplastic resin layer preferably contains a photoacid generator from the viewpoint of resolution.
  • the photoacid generator include a photocationic polymerization initiator that may be contained in the above-mentioned photosensitive resin layer, and the same preferred embodiments are used except for the points described below.
  • the photoacid generator is preferably at least one compound selected from the group consisting of an onium salt compound and an oxime sulfonate compound, and has sensitivity, resolution and adhesion. From the viewpoint of the above, it is more preferable that the compound is an oxime sulfonate compound. Further, as the photoacid generator, a photoacid generator having the following structure is also preferable.
  • thermoplastic resin layer may contain a photoradical polymerization initiator.
  • photoradical polymerization initiator include a photoradical polymerization initiator that may be contained in the photosensitive resin layer described above, and the preferred embodiment is also the same.
  • thermoplastic resin layer may contain a photobase generator.
  • the photobase generator is not particularly limited as long as it is a known photobase generator, and for example, 2-nitrobenzylcyclohexylcarbamate, triphenylmethanol, O-carbamoyl hydroxylamide, O-carbamoyloxime, [[(2,2).
  • the thermoplastic resin layer may contain one type of compound C alone, or may contain two or more types of compound C.
  • the content of compound C is preferably 0.1% by mass to 10% by mass, preferably 0.5% by mass, based on the total mass of the thermoplastic resin layer from the viewpoint of visibility and resolution of the exposed and unexposed areas. More preferably, it is by mass% to 5% by mass.
  • thermoplastic resin layer preferably contains a plasticizer from the viewpoints of resolution, adhesion to adjacent layers, and developability.
  • the plasticizer preferably has a smaller molecular weight (weight average molecular weight (Mw) in the case of an oligomer or polymer) than the alkali-soluble resin.
  • the molecular weight of the plasticizer is preferably 200 to 2,000.
  • the plasticizer is not particularly limited as long as it is a compound that develops plasticity by being compatible with an alkali-soluble resin.
  • the plasticizer preferably has an alkyleneoxy group in the molecule from the viewpoint of imparting plasticity, and a polyalkylene glycol compound is more preferable.
  • the alkyleneoxy group contained in the plasticizer more preferably has a polyethyleneoxy structure or a polypropyleneoxy structure.
  • the plasticizer preferably contains a (meth) acrylate compound from the viewpoint of resolution and storage stability.
  • the alkali-soluble resin is an acrylic resin and the plasticizer contains a (meth) acrylate compound.
  • Examples of the (meth) acrylate compound used as a plasticizer include the (meth) acrylate compound described as the polymerizable compound B contained in the photosensitive resin layer described above.
  • thermoplastic resin layer and the photosensitive resin layer when the thermoplastic resin layer and the photosensitive resin layer are directly contacted and laminated, it is preferable that the thermoplastic resin layer and the photosensitive resin layer contain the same (meth) acrylate compound.
  • the thermoplastic resin layer and the photosensitive resin layer each contain the same (meth) acrylate compound, the diffusion of components between the layers is suppressed and the storage stability is improved.
  • thermoplastic resin layer contains a (meth) acrylate compound as a plasticizer
  • the (meth) acrylate compound does not polymerize even in the exposed portion after exposure from the viewpoint of adhesion to the adjacent layer.
  • the (meth) acrylate compound used as a plasticizer is polyfunctional (meth) having two or more (meth) acryloyl groups in one molecule from the viewpoint of resolution, adhesion to adjacent layers, and developability. It is preferably a meta) acrylate compound.
  • the (meth) acrylate compound used as a plasticizer is preferably a (meth) acrylate compound having an acid group or a urethane (meth) acrylate compound.
  • the thermoplastic resin layer may contain one type of plasticizer alone, or may contain two or more types of plasticizer.
  • the content of the plastic agent is preferably 1% by mass to 70% by mass, preferably 10% by mass or more, based on the total mass of the thermoplastic resin layer from the viewpoint of resolution, adhesion to the adjacent layer, and developability. 60% by mass is more preferable, and 20% by mass to 50% by mass is particularly preferable.
  • the thermoplastic resin layer preferably contains a surfactant from the viewpoint of thickness uniformity.
  • the surfactant include surfactants that may be contained in the above-mentioned photosensitive resin layer, and the preferred embodiment is the same.
  • the thermoplastic resin layer may contain one type of surfactant alone or two or more types.
  • the content of the surfactant is preferably 0.001% by mass to 10% by mass, more preferably 0.01% by mass to 3% by mass, based on the total mass of the thermoplastic resin layer.
  • the thermoplastic resin layer may contain a sensitizer.
  • the sensitizer is not particularly limited, and examples thereof include a sensitizer that may be contained in the above-mentioned photosensitive resin layer.
  • the thermoplastic resin layer may contain one type of sensitizer alone or two or more types.
  • the content of the sensitizer can be appropriately selected depending on the purpose, but from the viewpoint of improving the sensitivity to the light source and the visibility of the exposed and non-exposed areas, 0.01 mass with respect to the total mass of the thermoplastic resin layer.
  • the range of% to 5% by mass is preferable, and the range of 0.05% by mass to 1% by mass is more preferable.
  • thermoplastic resin layer may contain known additives, if necessary. Further, the thermoplastic resin layer is described in paragraphs 0189 to 0193 of JP-A-2014-85643, and the contents described in this publication are incorporated in the present specification.
  • the thickness of the thermoplastic resin layer is not particularly limited, but is preferably 1 ⁇ m or more, more preferably 2 ⁇ m or more, from the viewpoint of adhesion to adjacent layers.
  • the upper limit of the thickness of the thermoplastic resin layer is not particularly limited.
  • the thickness of the thermoplastic resin layer is preferably 20 ⁇ m or less, more preferably 10 ⁇ m or less, still more preferably 5 ⁇ m or less, from the viewpoint of developability and resolvability.
  • thermoplastic resin layer is not particularly limited as long as it is a method capable of forming a layer containing the above components.
  • thermoplastic resin layer for example, a thermoplastic resin composition containing the above components and a solvent is prepared, and the thermoplastic resin composition is applied to the surface of a temporary support or the like to form the thermoplastic resin composition.
  • a method for forming the thermoplastic resin layer for example, a thermoplastic resin composition containing the above components and a solvent is prepared, and the thermoplastic resin composition is applied to the surface of a temporary support or the like to form the thermoplastic resin composition.
  • examples thereof include a method of forming by drying a coating film of an object.
  • thermoplastic resin composition preferably contains a solvent in order to adjust the viscosity of the thermoplastic resin composition and facilitate the formation of the thermoplastic resin layer.
  • the solvent contained in the thermoplastic resin composition is not particularly limited as long as the above-mentioned components contained in the thermoplastic resin layer can be dissolved or dispersed.
  • thermoplastic resin composition examples include a solvent that may be contained in the above-mentioned photosensitive resin composition, and the preferred embodiment is also the same.
  • the solvent contained in the thermoplastic resin composition may be one kind alone or two or more kinds.
  • the content of the solvent in the thermoplastic resin composition is preferably 50 parts by mass to 1,900 parts by mass, more preferably 100 parts by mass to 900 parts by mass, based on 100 parts by mass of the total solid content in the thermoplastic resin composition. ..
  • thermoplastic resin composition and the formation of the thermoplastic resin layer may be carried out according to the method for preparing the photosensitive resin composition and the method for forming the photosensitive resin layer described above.
  • thermoplastic resin composition For example, a solution in which each component contained in the thermoplastic resin layer is dissolved in the above solvent is prepared in advance, and the obtained solution is mixed at a predetermined ratio to prepare a thermoplastic resin composition, which is then obtained.
  • the obtained thermoplastic resin composition is applied to the surface of the temporary support, and the coating film of the thermoplastic resin composition is dried to form the thermoplastic resin layer.
  • thermoplastic resin layer may be formed on the surface of the intermediate layer.
  • the photosensitive transfer material preferably has an intermediate layer between the thermoplastic resin layer and the photosensitive resin layer.
  • the intermediate layer By arranging the intermediate layer, it is possible to suppress the mixing of the components when the plurality of layers are applied and when the layers are stored after application.
  • the intermediate layer is preferably a water-soluble layer from the viewpoint of developability and suppressing mixing of components during application of the plurality of layers and storage after application.
  • water-soluble means that the solubility in 100 g of water having a liquid temperature of 22 ° C. and a pH of 7.0 is 0.1 g or more.
  • the intermediate layer examples include an oxygen blocking layer having an oxygen blocking function, which is described as a "separation layer" in Japanese Patent Application Laid-Open No. 5-72724.
  • an oxygen blocking layer having an oxygen blocking function
  • 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 blocking layer used as the intermediate layer may be appropriately selected from the known layers described in the above publications and the like.
  • the intermediate layer is preferably 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.).
  • the intermediate layer preferably contains a resin.
  • the resin contained in the intermediate layer include polyvinyl alcohol-based resin, polyvinylpyrrolidone-based resin, cellulose-based resin, acrylamide-based resin, polyethylene oxide-based resin, gelatin, vinyl ether-based resin, polyamide, and copolymers thereof. And other resins.
  • the resin contained in the intermediate layer a water-soluble resin is preferable. Further, the resin contained in the intermediate layer includes the polymer A contained in the photosensitive resin layer and the thermoplastic resin (alkali) contained in the thermoplastic resin layer from the viewpoint of suppressing the mixing of the components between the plurality of layers. It is preferable that the resin is different from any of the soluble resins).
  • the intermediate layer preferably contains polyvinyl alcohol from the viewpoint of oxygen blocking property and suppressing mixing of components during application of the plurality of layers and storage after application, and contains both polyvinyl alcohol and polyvinylpyrrolidone. It is more preferable to contain it.
  • the intermediate layer may contain the above resin alone or in combination of two or more.
  • the content of the resin in the intermediate layer is not particularly limited, but is based on the total mass of the intermediate layer from the viewpoint of oxygen blocking property and suppressing the mixing of components during application of the plurality of layers and storage after application. , 50% by mass to 100% by mass, more preferably 70% by mass to 100% by mass, further preferably 80 to 100% by mass, and particularly preferably 90% by mass to 100% by mass.
  • the intermediate layer may contain an additive such as a surfactant, if necessary.
  • the thickness of the intermediate layer is not particularly limited, but is preferably 0.1 ⁇ m to 5 ⁇ m, and more preferably 0.5 ⁇ m to 3 ⁇ m.
  • the oxygen blocking property is not lowered, and the mixing of the components at the time of applying the plurality of layers and at the time of storage after application can be suppressed. Further, when the thickness of the intermediate layer is within the above range, an increase in the intermediate layer removal time during development can be suppressed.
  • the method for forming the intermediate layer is not particularly limited, and for example, an intermediate layer composition containing the above resin and any additive is prepared and applied to the surface of the thermoplastic resin layer or the photosensitive resin layer to form the intermediate layer composition.
  • examples thereof include a method of forming an intermediate layer by drying a coating film of an object.
  • the intermediate layer composition preferably contains a solvent in order to adjust the viscosity of the intermediate layer composition and facilitate the formation of the intermediate layer.
  • the solvent contained in the intermediate layer composition is not particularly limited as long as the above resin can be dissolved or dispersed, and at least one selected from the group consisting of water and a water-miscible organic solvent is preferable, and water or water or water is preferable.
  • a mixed solvent of water and a water-miscible organic solvent is more preferable.
  • water-miscible organic solvent examples include alcohols having 1 to 3 carbon atoms, acetone, ethylene glycol and glycerin, and alcohols having 1 to 3 carbon atoms are preferable, and methanol or ethanol is more preferable.
  • the photosensitive transfer material preferably includes a cover film that is in contact with a surface of the photosensitive resin layer that does not face the temporary support.
  • a cover film that is in contact with a surface of the photosensitive resin layer that does not face the temporary support.
  • first surface the surface of the photosensitive resin layer facing the temporary support
  • second surface the surface opposite to the first surface
  • the material constituting the cover film examples include a resin film and paper. Above all, the material constituting the cover film is preferably a resin film from the viewpoint of strength and flexibility.
  • the resin film examples include polyethylene film, polypropylene film, polyethylene terephthalate film, cellulose triacetate film, polystyrene film, and polycarbonate film. Above all, the resin film is preferably a polyethylene film, a polypropylene film, or a polyethylene terephthalate film.
  • the thickness of the cover film is not particularly limited, but is preferably 5 ⁇ m to 100 ⁇ m, and more preferably 10 ⁇ m to 50 ⁇ m.
  • the arithmetic mean roughness Ra value of the surface of the cover film in contact with the photosensitive resin layer is preferably 0.3 ⁇ m or less from the viewpoint of excellent resolution. 1 ⁇ m or less is more preferable, and 0.05 ⁇ m or less is further preferable. It is considered that when the Ra value on the surface of the cover film is within the above range, the uniformity of the layer thickness of the photosensitive resin layer and the formed resin pattern is improved.
  • the lower limit of the Ra value on the surface of the cover film is not particularly limited.
  • the Ra value on the surface of the cover film is preferably 0.001 ⁇ m or more.
  • the Ra value on the surface of the cover film is measured by the following method. Using a three-dimensional optical profiler (New View7300, manufactured by Zygo), the surface of the cover film is measured under the following conditions to obtain a surface profile of the optical film. As the measurement / analysis software, Microscope Application of MetroPro ver 8.3.2 is used. Next, the Surface Map screen is displayed with the above analysis software, and histogram data is obtained in the Surface Map screen. From the obtained histogram data, the arithmetic mean roughness is calculated to obtain the Ra value of the surface of the cover film. When the cover film is attached to the photosensitive transfer material, the cover film may be peeled from the photosensitive transfer material and the Ra value of the surface on the peeled side may be measured.
  • the photosensitive transfer material may include a layer other than the above-mentioned layer (hereinafter, also referred to as “other layer”).
  • Other layers include, for example, a contrast enhancement layer.
  • the contrast enhancement layer is described in paragraph 0134 of WO 2018/179640. Further, other layers are described in paragraphs 0194 to 0196 of Japanese Patent Application Laid-Open No. 2014-85643. The contents of these publications are incorporated herein by reference.
  • the method for producing the photosensitive transfer material according to the present disclosure is not particularly limited, and a known production method, for example, a known method for forming each layer can be used.
  • the method for producing the 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 the one having the configuration shown in FIG.
  • FIG. 1 is a schematic view showing an example of the configuration of the photosensitive transfer material according to the present disclosure.
  • the photosensitive transfer material 100 shown in FIG. 1 has a structure in which a temporary support 10, a thermoplastic resin layer 12, an intermediate layer 14, a photosensitive resin layer 16, and a cover film 18 are laminated in this order.
  • thermoplastic resin layer is applied by applying the thermoplastic resin composition to the surface of the temporary support 10 and then drying the coating film of the thermoplastic resin composition.
  • a step of forming the intermediate layer 12 a step of applying the intermediate layer composition to the surface of the thermoplastic resin layer 12, and then drying the coating film of the intermediate layer composition to form the intermediate layer 14, and a step of forming the intermediate layer 14 on the surface of the intermediate layer 14.
  • the step of drying the coating film of the photosensitive resin composition to form the photosensitive resin layer 16 and the step of pressing the cover film 18 against the photosensitive resin layer 16 are included. The method can be mentioned.
  • the photosensitive resin composition is applied to the surface of the temporary support.
  • a photosensitive resin composition in the case of laminating a thermoplastic resin layer, a thermoplastic resin composition
  • the temporary support is applied. Is virtually divided into two regions at the center in the thickness direction, and is applied to the surface on the region side where the number of foreign substances is small.
  • the region on the photosensitive resin layer side from the center in the thickness direction is set as the first region and the region on the side opposite to the photosensitive resin layer from the center in the thickness direction is set as the second region.
  • the photosensitive resin composition in the case of laminating the thermoplastic resin layer, the thermoplastic resin composition
  • the photosensitive resin composition on the surface that is not in contact with the casting drum during the manufacturing of the temporary support. Is preferably applied.
  • thermoplastic resin composition containing at least one selected from the group consisting of an alkylene glycol ether solvent and an alkylene glycol ether acetate solvent, and a water- and water-mixable organic solvent.
  • a photosensitive resin containing at least one selected from the group consisting of an intermediate layer composition containing at least one of the above, polymer A, polymerizable compound B, and an alkylene glycol ether solvent and an alkylene glycol ether acetate solvent. It is preferable to use with the composition.
  • thermoplastic resin layer 12 and the intermediate layer 14 during the application of the intermediate layer composition to the surface of the thermoplastic resin layer 12 and / or the storage period of the laminate having the coating film of the intermediate layer composition. It is possible to suppress mixing with the components contained in. Further, the components and the photosensitive resin contained in the intermediate layer 14 during the application of the photosensitive resin composition to the surface of the intermediate layer 14 and / or the storage period of the laminate having the coating film of the photosensitive resin composition. Mixing with the components contained in the layer 16 can be suppressed.
  • the method for producing a photosensitive transfer material includes a step of providing a cover film 18 so as to be in contact with the second surface of the photosensitive resin layer 16, thereby including a temporary support 10, a thermoplastic resin layer 12, and an intermediate. It is preferable to manufacture the photosensitive transfer material 100 including the layer 14, the photosensitive resin layer 16 and the cover film 18.
  • the photosensitive transfer material 100 in the form of a roll may be produced and stored by winding the photosensitive transfer material 100.
  • the photosensitive transfer material in the form of a roll can be provided as it is in the process of bonding with a substrate in a roll-to-roll method described later.
  • the method for producing the resin pattern is not particularly limited as long as it is the method for producing the resin pattern using the above-mentioned photosensitive transfer material.
  • the method for producing the resin pattern includes a step of bonding the surface (that is, the second surface) of the photosensitive resin layer on the photosensitive transfer material on the side not facing the temporary support and the substrate (hereinafter, “bonding step”). (Also also referred to as), a step of pattern-exposing the photosensitive resin layer (hereinafter, also referred to as “exposure step”), and a step of developing the photosensitive resin layer after the pattern exposure step to form a resin pattern (hereinafter, “exposed step”). It is preferable that the method includes "development step") in this order.
  • the circuit wiring manufacturing method is not particularly limited as long as it is a circuit wiring manufacturing method using the above-mentioned photosensitive transfer material.
  • the circuit wiring manufacturing method includes the bonding step, the exposure step, the developing step, and the step of etching the substrate in the region where the resin pattern is not arranged (hereinafter, also referred to as “etching step”). The method is preferred.
  • the method for producing the resin pattern preferably includes a bonding step.
  • the bonding step it is preferable that the substrate (or the conductive layer when the conductive layer is provided on the surface of the substrate) is brought into contact with the second surface of the photosensitive resin layer, and the photosensitive transfer material and the substrate are pressure-bonded. ..
  • the patterned photosensitive resin layer after exposure and development is suitably used as an etching resist for etching. be able to.
  • the cover film may be removed from the surface of the photosensitive resin layer and then bonded.
  • the method of crimping the substrate and the photosensitive transfer material is not particularly limited, and a known transfer method and laminating method can be used.
  • the photosensitive transfer material is bonded to the substrate by stacking the substrate on the second surface side of the photosensitive resin layer and applying pressure and heating by means such as a roll.
  • a known laminator such as a laminator, a vacuum laminator, and an auto-cut laminator capable of further increasing productivity can be used.
  • the resin pattern manufacturing method including the bonding step and the circuit wiring manufacturing method are preferably performed by a roll-to-roll method.
  • the roll-to-roll method is a structure in which a substrate that can be wound and unwound is used as the substrate, and the substrate or the substrate is included before any of the steps included in the resin pattern manufacturing method or the circuit wiring manufacturing method. It includes a step of unwinding a body (also referred to as a “unwinding step”) and a step of winding a substrate or a structure including the substrate (also referred to as a “winding step”) after any of the steps.
  • a method in which at least one of the steps is performed while transporting the substrate or the structure including the substrate.
  • the unwinding method in the unwinding process and the winding method in the winding process are not particularly limited, and a known method may be used in the manufacturing method to which the roll-to-roll method is applied.
  • a known substrate can be used as the substrate used for forming the resin pattern using the photosensitive transfer material according to the present disclosure.
  • the substrate is preferably a substrate having a conductive layer, and more preferably a substrate having a conductive layer on the surface of the base material.
  • the substrate may have an arbitrary layer other than the conductive layer, if necessary.
  • the base material constituting the substrate examples include glass, silicon, and a resin film.
  • the substrate is preferably transparent.
  • transparent means that the transmittance of light having a wavelength of 400 nm to 700 nm is 80% or more.
  • the refractive index of the base material is preferably 1.50 to 1.52.
  • the transparent glass base material examples include tempered glass represented by Corning's gorilla glass. Further, as the transparent glass substrate, the materials described in JP-A-2010-86684, JP-A-2010-152809 and JP-A-2010-257492 can be used.
  • the base material is preferably a resin film having low optical distortion and / or high transparency.
  • resin films include polyethylene terephthalate (PET) films, polyethylene naphthalate films, polycarbonate films, triacetyl cellulose films and cycloolefin polymer films.
  • the base material is preferably a resin film. Further, when the circuit wiring for the touch panel is manufactured by the roll-to-roll method, the base material is preferably a resin sheet.
  • Examples of the conductive layer contained in the substrate include a conductive layer used for general circuit wiring or touch panel wiring.
  • the conductive layer may be at least one layer selected from the group consisting of a metal layer, a conductive metal oxide layer, a graphene layer, a carbon nanotube layer, and a conductive polymer layer from the viewpoint of conductivity and fine wire forming property. It is preferably a metal layer, more preferably a copper layer or a silver layer.
  • the substrate may have one conductive layer alone, or may have two or more conductive layers. When the substrate has two or more conductive layers, it is preferable that the substrate has two or more different conductive layers.
  • Examples of the material of the conductive layer include metals and conductive metal oxides.
  • Examples of the metal include Al, Zn, Cu, Fe, Ni, Cr, Mo, Ag and Au.
  • the conductive metal oxide examples include ITO (Indium Tin Oxide), IZO (Indium Zinc Oxide) and SiO 2 .
  • conductivity means that the volume resistivity is less than 1 ⁇ 10 6 ⁇ cm.
  • the volume resistivity of the conductive metal oxide is preferably less than 1 ⁇ 10 4 ⁇ cm.
  • At least one of the plurality of conductive layers contains a conductive metal oxide.
  • the conductive layer is preferably an electrode pattern corresponding to the sensor of the visual recognition part used in the capacitive touch panel or the wiring of the peripheral extraction part.
  • the method for producing the resin pattern preferably includes a step (exposure step) of pattern-exposing the photosensitive resin layer after the bonding step.
  • At least a part of the pattern preferably the electrode pattern of the touch panel and / or the portion of the take-out wiring
  • the pattern preferably includes a thin wire having a width of 20 ⁇ m or less, and more preferably contains a thin wire having a width of 10 ⁇ m or less. It is possible to improve the display quality of a display device (for example, a touch panel) including an input device having a circuit wiring manufactured by a method of manufacturing a circuit wiring, and to reduce the area occupied by the take-out wiring.
  • the light source used for exposure is not particularly limited as long as it is a light source that irradiates the photosensitive resin layer with light having a wavelength that allows exposure (for example, 365 nm or 405 nm), and can be appropriately selected and used.
  • the light source include an ultra-high pressure mercury lamp, a high pressure mercury lamp, a metal halide lamp, and an LED (Light Emitting Diode).
  • the exposure amount is preferably 5 mJ / cm 2 to 200 mJ / cm 2 , and more preferably 10 mJ / cm 2 to 100 mJ / cm 2 .
  • the temporary support may be peeled off from the photosensitive resin layer and then pattern-exposed, or the temporary support may be peeled off after pattern-exposure through the temporary support.
  • the mask and the photosensitive resin layer may be brought into contact with each other for exposure, or the mask and the photosensitive resin layer may be exposed without being brought into contact with each other. ..
  • the temporary support is exposed without being peeled off, the mask and the temporary support may be brought into contact with each other for exposure, or the mask and the temporary support may be exposed without being brought into contact with each other.
  • the exposure method is a contact exposure method in the case of contact exposure, a proximity exposure method in the case of a non-contact exposure method, a lens-based or mirror-based projection exposure method, or a direct exposure method using an exposure laser or the like. Can be appropriately selected and used.
  • an exposure machine having an appropriate numerical aperture (NA) of the lens can be used depending on the required resolution and depth of focus.
  • the photosensitive resin layer may be directly exposed, or the photosensitive resin layer may be subjected to reduced projection exposure via a lens. Further, the exposure may be performed not only in the atmosphere but also under reduced pressure or vacuum. Further, a liquid such as water may be interposed between the light source and the photosensitive resin layer for exposure.
  • the method for producing a resin pattern preferably includes, after the above-mentioned exposure step, a step (development step) of developing the exposed photosensitive resin layer to form a resin pattern.
  • thermoplastic resin layer and the intermediate layer in the non-exposed portion are also removed together with the photosensitive resin layer in the non-exposed portion in the developing process. Further, in the developing step, the thermoplastic resin layer and the intermediate layer of the exposed portion may also be removed in a form of being dissolved or dispersed in the developing solution.
  • the exposed photosensitive resin layer can be developed using a developing solution.
  • the developing solution is not particularly limited as long as the non-image portion (non-exposed portion) of the photosensitive resin layer can be removed, and for example, a known developing solution such as the developing solution described in JP-A-5-72724 is used. can.
  • 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 (liter) to 5 mol / L.
  • the developer may contain at least one selected from the group consisting of water-soluble organic solvents and surfactants.
  • the developer described in paragraph 0194 of International Publication No. 2015/093271 is also preferable.
  • the development method is not particularly limited, and may be any of paddle development, shower development, shower and spin development, and dip development.
  • shower development is a development process for removing a non-exposed portion by spraying a developing solution on the photosensitive resin layer after exposure by a shower.
  • the cleaning agent After the developing step, it is preferable to spray the cleaning agent with a shower and rub with a brush to remove the developing residue.
  • the temperature of the developing solution is not particularly limited, but is preferably 20 ° C to 40 ° C.
  • the resin pattern is not arranged in the laminated body in which the resin patterns manufactured by the manufacturing method including the bonding step, the exposure step, and the developing step are laminated in this order. It is preferable to include a step (etching step) of etching the substrate in the region.
  • the resin pattern formed from the photosensitive resin layer is used as an etching resist to etch the substrate.
  • etching treatment As a method of etching treatment, a known method can be applied, and for example, the method described in paragraphs 0209 to 0210 of JP2017-120435A and the method described in paragraphs 0048 to 0054 of JP2010-152155A. Examples thereof include a wet etching method in which the material is immersed in an etching solution, and a dry etching method such as plasma etching.
  • an acidic or alkaline etching solution may be appropriately selected according to the etching target.
  • the acidic etching solution examples include an aqueous solution of an acidic component alone selected from hydrochloric acid, sulfuric acid, nitric acid, acetic acid, hydrofluoric acid, oxalic acid and phosphoric acid, and the acidic component, ferric chloride, ammonium fluoride and Examples thereof include a mixed aqueous solution with a salt selected from potassium permanganate.
  • the acidic component may be a component in which a plurality of acidic components are combined.
  • an alkaline component and a salt for example, a mixed aqueous solution with (for example, potassium permanganate) can be mentioned.
  • the alkaline component may be a component in which a plurality of alkaline components are combined.
  • the removal step is not particularly limited and can be performed as needed, but it is preferably performed after the etching step.
  • the method for removing the remaining resin pattern is not particularly limited, but a method for removing it by chemical treatment can be mentioned.
  • a method for removing the remaining resin pattern a method of removing with a removing liquid is preferable.
  • a substrate having a residual resin pattern is placed in a removing liquid during stirring at a liquid temperature of preferably 30 ° C. to 80 ° C., more preferably 50 ° C. to 80 ° C. for 1 minute to.
  • a method of immersing for 30 minutes can be mentioned.
  • Examples of the removing liquid include a removing liquid in which an inorganic alkaline component or an organic alkaline component is dissolved in water, dimethyl sulfoxide, N-methylpyrrolidone, or a mixed solution thereof.
  • Examples of the inorganic alkaline component include sodium hydroxide and potassium hydroxide.
  • Examples of the organic alkali component include a primary amine compound, a secondary amine compound, a tertiary amine compound and a quaternary ammonium salt compound.
  • the removing liquid may be used to remove the remaining resin pattern by a known method such as a spray method, a shower method and a paddle method.
  • the circuit wiring manufacturing method may include an arbitrary step (other steps) other than the above-mentioned steps.
  • steps can be mentioned, but the steps are not limited to these steps.
  • examples of the exposure step, the developing step, and other steps applicable to the method for manufacturing the circuit wiring include the steps described in paragraphs 0035 to 0051 of JP-A-2006-23696.
  • the method for producing the resin pattern preferably includes a step of peeling the cover film from the photosensitive transfer material.
  • the method for peeling the cover film is not particularly limited, and a known method can be applied.
  • the method for manufacturing a circuit wiring may include a step of reducing the visible light reflectance of a part or all of the conductive layer provided on the substrate.
  • Oxidation treatment can be mentioned as a treatment for reducing the visible light reflectance.
  • the visible light reflectance of the conductive layer can be reduced by oxidizing copper to copper oxide and blackening the conductive layer.
  • the method for manufacturing the circuit wiring preferably includes a step of forming an insulating film on the surface of the circuit wiring and a step of forming a new conductive layer on the surface of the insulating film.
  • the step of forming the insulating film is not particularly limited, and examples thereof include a known method of forming a permanent film. Further, an insulating film having a desired pattern may be formed by photolithography using a photosensitive material having an insulating property.
  • the step of forming a new conductive layer on the insulating film is not particularly limited, and for example, a new conductive layer having a desired pattern may be formed by photolithography using a photosensitive material having conductivity.
  • a substrate having a plurality of conductive layers on both surfaces of the base material it is also preferable to use a substrate having a plurality of conductive layers on both surfaces of the base material, and to form a circuit sequentially or simultaneously on the conductive layers formed on both surfaces of the base material.
  • a touch panel circuit wiring having a first conductive pattern formed on one surface of the base material and a second conductive pattern formed on the other surface can be formed. It is also preferable to form the touch panel circuit wiring having such a configuration from both sides of the base material by roll-to-roll.
  • the circuit wiring manufactured by the method of manufacturing the circuit wiring can be applied to various devices.
  • Examples of the device provided with the circuit wiring manufactured by the above manufacturing method include an input device, a touch panel is preferable, and a capacitance type touch panel is more preferable.
  • the input device can be applied to a display device such as an organic EL display device and a liquid crystal display device.
  • the method for manufacturing the touch panel is not particularly limited as long as it is the method for manufacturing the touch panel using the above-mentioned photosensitive transfer material.
  • the touch panel manufacturing method includes the bonding step, the exposure step, the developing step, and the step of etching the substrate in the region where the resin pattern is not arranged (hereinafter, also referred to as “etching step”). Is preferable.
  • each step in the touch panel manufacturing method and the embodiment such as the order in which each step is performed are as described in the above-mentioned "Circuit wiring manufacturing method", and the preferred embodiments are also the same.
  • the method for manufacturing the touch panel a known method for manufacturing the touch panel may be referred to except that the wiring for the touch panel is formed by the above method.
  • the touch panel manufacturing method may include an arbitrary step (other steps) other than the above steps.
  • a touch panel having at least wiring for the touch panel is manufactured by the above-mentioned manufacturing method of the touch panel.
  • the touch panel preferably has a transparent substrate, electrodes, and an insulating layer or a protective layer.
  • Examples of the detection method on the touch panel include known methods such as a resistive film method, a capacitance method, an ultrasonic method, an electromagnetic induction method, and an optical method. Above all, the detection method on the touch panel is preferably the capacitance method.
  • St Styrene (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.)
  • MAA Methacrylic acid (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.)
  • MMA Methyl methacrylate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.)
  • V-601 2,2'-azobis (isobutyric acid) dimethyl (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., polymerization initiator)
  • PGMEA Propylene Glycol Monomethyl Ether Acetate
  • PGMEA 116.5 parts was placed in a three-necked flask, and the temperature was raised to 90 ° C. in a nitrogen atmosphere.
  • St 52.0 parts
  • the acid value of the polymer A was 189 mgKOH / g, the weight average molecular weight was 60,000, and the glass transition temperature was 131 ° C.
  • Polymers A-1, A-2, A-4 and A-5 Polymers A-1, A-2, and the same method as in the synthesis of polymer A-3, except that the type and amount of the monomers used in the synthesis of the polymer were changed as shown in Table 1 below.
  • A-4 and A-5 were synthesized to obtain a composition containing 30.0% by mass of the polymer.
  • BnMA means benzyl methacrylate (manufactured by Mitsubishi Gas Chemical Company, Inc.).
  • Table 1 shows the weight average molecular weight (Mw), acid value and glass transition temperature (Tg) of the obtained polymer.
  • -Polymerizable compound B -Polymerizable compound B-1: NK ester BPE-500 (2,2-bis (4- (methacryloxypentaethoxy) phenyl) propane, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.) -Polymerizable compound B-2: NK ester BPE-200 (2,2-bis (4- (methacryloxydiethoxy) phenyl) propane, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.) -Polymerizable compound B-3: NK ester A-TMPT (trimethylolpropane triacrylate, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.) -Polymerizable compound B-4: Aronix TO-2349 (Compound having the following structure, manufactured by Toagosei Co., Ltd.)
  • Dye N-1 LCV (Leuko Crystal Violet, manufactured by Tokyo Chemical Industry Co., Ltd., color is developed by radicals
  • Dye N-2 Brilliant Green (manufactured by Tokyo Chemical Industry Co., Ltd.)
  • ⁇ Antioxidant ⁇ -Irganox245 ethylene bis (oxyethylene) bis- (3- (5-tert-butyl-4-hydroxy-m-tolyl) propionate), manufactured by BASF
  • Example 1 A PET film having a thickness of 30 ⁇ m was prepared as a temporary support. A photosensitive resin composition was applied to the surface of the temporary support using a slit-shaped nozzle so that the coating width was 1.0 m and the layer thickness after drying was 5 ⁇ m. The coating film of the photosensitive resin composition was dried at 80 ° C. for 40 seconds to form a photosensitive resin layer, and a photosensitive transfer material was obtained.
  • Examples 2 to 13, Comparative Example 1, Comparative Example 2 Same as in Example 1 except that the thickness of the photosensitive resin layer and the types and amounts of the polymer A and the polymerizable compound B contained in the photosensitive resin layer were changed to the values shown in Tables 2 and 3. A photosensitive transfer material was obtained by the above method.
  • the "styrene content" of "polymer A” indicates the content of the structural unit derived from styrene with respect to the total mass of the polymer A contained in the photosensitive resin layer.
  • the “content” of the “polymer A” indicates the content of the polymer A with respect to the total mass of the photosensitive resin layer.
  • the polymerizable compound B the content (mass%) of each polymerizable compound with respect to the total mass of the photosensitive resin layer is described.
  • M / B ratio indicates the ratio of the content of the polymerizable compound B to the content of the polymer A.
  • ⁇ Preparation of intermediate layer composition The following components were mixed to prepare an intermediate layer composition.
  • -Ion exchanged water 38.12 parts-Methanol (manufactured by Mitsubishi Gas Chemical Company): 57.17 parts-Clarepovar PVA-205 (polyvinyl alcohol, manufactured by Kuraray Co., Ltd.): 3.22 parts-Polyvinylpyrrolidone K-30 (Manufactured by Nippon Catalyst Co., Ltd.): 1.49 parts, Megafuck F-444 (Fluorine-based nonionic surfactant, manufactured by DIC Co., Ltd.): 0.0 015 copies
  • thermoplastic resin composition ⁇ Preparation of thermoplastic resin composition> The following components were mixed to prepare a thermoplastic resin composition. ⁇ Copolymer of benzyl methacrylate, methacrylic acid and acrylic acid (solid content concentration 30.0%, Mw30000, acid value 153 mgKOH / g): 42.85 parts ⁇ NK ester A-DCP (tricyclodecanedimethanol diacrylate, Shin-Nakamura Chemical Co., Ltd.): 4.63 parts, 8UX-015A (polyfunctional urethane acrylate compound, manufactured by Taisei Fine Chemical Co., Ltd.): 2.31 parts, Aronix TO-2349 (manufactured by Toa Synthetic Co., Ltd.): 0.77 parts, A compound having the structure shown below (a photoacid generator, a compound synthesized according to the method described in paragraph 0227 of JP2013-47765A): 0.32 parts.
  • a PET film having a thickness of 30 ⁇ m was prepared as a temporary support.
  • a thermoplastic resin composition was applied to the surface of the temporary support using a slit-shaped nozzle so that the coating width was 1.0 m and the layer thickness after drying was 3.0 ⁇ m.
  • the formed coating film of the thermoplastic resin composition was dried at 80 ° C. for 40 seconds to form a thermoplastic resin layer.
  • An intermediate layer composition was applied to the surface of the formed thermoplastic resin layer using a slit-shaped nozzle so that the coating width was 1.0 m and the layer thickness after drying was 1.2 ⁇ m.
  • the coating film of the intermediate layer composition was dried at 80 ° C. for 40 seconds to form an intermediate layer.
  • a photosensitive resin composition was applied to the surface of the formed intermediate layer using a slit-shaped nozzle so that the coating width was 1.0 m and the layer thickness after drying was 2 ⁇ m.
  • the coating film of the photosensitive resin composition was dried at 80 ° C. for 40 seconds to form a photosensitive resin layer, and a photosensitive transfer material was obtained.
  • the haze was measured using the photosensitive transfer materials obtained in Examples and Comparative Examples, and the resolution, cushioning property and scum generation were evaluated.
  • the measurement method and evaluation method are as follows. The evaluation results are shown in Tables 2 and 3.
  • a PET substrate with a copper layer was produced by forming a copper layer having a thickness of 200 nm on a polyethylene terephthalate (PET) film having a thickness of 100 ⁇ m by a sputtering method. After unwinding the photosensitive transfer material in the form of a roll, the photosensitive transfer material and the PET substrate with a copper layer were bonded together so that the photosensitive resin layer and the copper layer were in contact with each other to obtain a laminate.
  • the bonding step was performed under the conditions of a roll temperature of 120 ° C., a linear pressure of 1.0 MPa, and a linear velocity of 0.5 m / min.
  • the photosensitive resin layer was exposed by irradiating an ultra-high pressure mercury lamp (exposure main wavelength: 365 nm) from the temporary support side of the obtained laminate via a photomask.
  • the ratio of the widths of the transmission region and the light-shielding region is 1: 1 and the line width (and space width) changes stepwise from 1 ⁇ m to 20 ⁇ m every 1 ⁇ m. It had a line and space pattern.
  • the photosensitive resin layer has a line width of a line-and-space pattern and a line width of a resin pattern formed by exposure by irradiation light passing through a region where the space width is 20 ⁇ m. The amount of exposure to light was adjusted.
  • the laminate After peeling the temporary support from the exposed laminate, the laminate was shower-developed for 30 seconds using a 1.0 mass% sodium carbonate aqueous solution at a liquid temperature of 25 ° C.
  • the unexposed photosensitive resin layer was removed from the laminate to prepare a resin pattern having the above-mentioned stepwise changing line-and-space pattern on the surface of the copper layer.
  • the intermediate layer and the thermoplastic resin layer were also removed by this developing step.
  • the pattern shape and the presence or absence of residue of the photosensitive resin layer in the space portion are observed for each line width using a scanning electron microscope (product name "S-4800", manufactured by Hitachi High-Technology Co., Ltd.). bottom.
  • the minimum line width of the resin pattern in which the cured photosensitive resin layer was not peeled off at the line portion and there was no residue of the photosensitive resin layer was determined as the resolution.
  • the evaluation criteria are as follows. A level of 3 or higher is a level at which there is no problem in practical use. 5: The resolution is 4 ⁇ m or less. 4: The resolution is 5 ⁇ m or 6 ⁇ m. 3: The resolution is 7 ⁇ m or 8 ⁇ m. 2: The resolution is 9 ⁇ m or 10 ⁇ m. 1: The resolution is 11 ⁇ m or more.
  • a PET substrate with a copper layer was produced by forming a copper layer having a thickness of 200 nm on a polyethylene terephthalate (PET) film having a thickness of 100 ⁇ m by a sputtering method.
  • a PET substrate with a copper layer was etched to prepare a substrate having a step having a line-and-space copper pattern having a height of 200 nm and a width of 1000 ⁇ m.
  • the photosensitive transfer material and the substrate were bonded together so that the photosensitive resin layer and the copper layer were in contact with each other to obtain a laminate.
  • the bonding step was performed under atmospheric pressure under the conditions of a linear pressure of 1.0 MPa and a linear velocity of 4 m / min while changing the roll temperature every 5 ° C.
  • the lowest temperature at which air bubbles can be bonded to the step without air bubbles (hereinafter referred to as "air bubble-free laminating temperature”) was used as an index of cushioning property. It can be said that the lower the temperature at which they can be bonded without air bubbles being mixed, the better the cushioning property.
  • the evaluation criteria are as follows. A level of 3 or higher is a level at which there is no problem in practical use. 5: The temperature at which bubbles can be laminated is 70 ° C. or lower.
  • Bubble-free laminating temperature is 75 ° C or higher and 85 ° C or lower.
  • the temperature at which bubbles can be laminated is 90 ° C. or higher and 100 ° C. or lower.
  • Bubble-free laminating temperature is 105 ° C or higher and 115 ° C or lower.
  • the temperature at which bubbles can be laminated is 120 ° C. or higher.
  • the rest of the solution was allowed to stand in a room at 25 ° C. for 24 hours. After 24 hours, the state of occurrence of agglomerates (scums) in the tank containing the rest of the solution was visually observed.
  • the evaluation criteria are as follows. A level of 3 or higher is a level at which there is no problem in practical use. 6: The mass of the filtration residue was less than 1 mg, and no scum (aggregate) was observed in the tank. 5: The mass of the filtration residue was 1 mg or more and less than 2 mg, and no scum (aggregate) was observed in the tank. 4: The mass of the filtration residue was 1 mg or more and less than 2 mg, but scum (aggregates) was observed in the tank.
  • the mass of the filtration residue is 2 mg or more and less than 5 mg.
  • the mass of the filtration residue is 5 mg or more and less than 10 mg.
  • the mass of the filtration residue was 10 mg or more, or a large amount of solid scum (aggregate) was observed in the tank.
  • the haze of the solution obtained by dissolving 0.1 m 2 of the photosensitive transfer material in 1 liter of a 30 ° C. aqueous solution of 1 mass% sodium carbonate has a haze. Since it was 60% or less, it was found that the generation of scum (aggregate) was small.
  • Example 3 since the acid value of the alkali-soluble resin contained in the photosensitive resin layer is 120 mg / KOH or more, less scum (aggregates) is generated and the resolution is excellent as compared with Example 1.
  • Example 3 the ratio of the content of the polymerizable compound to the content of the alkali-soluble resin contained in the photosensitive resin layer is 0.85 or less on a mass basis, and therefore, as compared with Example 13, scum (aggregation) (aggregation). There are few things).
  • Example 8 since the alkali-soluble resin contained in the photosensitive resin layer contains a structural unit derived from styrene, less scum (aggregates) is generated as compared with Example 7.
  • Example 10 since the thickness of the photosensitive resin layer is 10 ⁇ m or less, less scum (aggregates) is generated as compared with Example 9.
  • Example 11 contains a polymerizable compound having an acid group, less scum (aggregates) is generated as compared with Example 8.
  • the photosensitive transfer material according to the present disclosure can be suitably used for various applications requiring precision microfabrication by photolithography.
  • the photosensitive resin layer may be used as a coating for etching, or electroforming may be performed mainly by electroplating.
  • the cured film obtained by patterning may be used as a permanent film.
  • the cured film may be used as, for example, an interlayer insulating film, a wiring protective film, or a wiring protective film having an index matching layer.
  • the photosensitive transfer material according to the present disclosure includes materials for forming various wirings such as semiconductor packages, printed circuit boards, sensor substrates, touch panels, electromagnetic wave shielding materials, conductive films such as film heaters, and liquid crystal seals. It can be suitably used as a material for forming a structure in the field of materials, micromachines, and microelectronics.

Abstract

A photosensitive transfer material according to the present invention and applications therefor, the photosensitive transfer material comprising a temporary support and a photosensitive resin layer disposed on the temporary support, wherein a solution obtained by dissolving 0.1 m2 of the photosensitive transfer material in 1 liter of a 30°C 1 mass% aqueous solution of sodium carbonate has a haze of 60% or less.

Description

感光性転写材料、樹脂パターンの製造方法、回路配線の製造方法及びタッチパネルの製造方法Photosensitive transfer material, resin pattern manufacturing method, circuit wiring manufacturing method, and touch panel manufacturing method
　本開示は、感光性転写材料、樹脂パターンの製造方法、回路配線の製造方法及びタッチパネルの製造方法に関する。 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.
　静電容量型入力装置等のタッチパネルを備えた表示装置（有機エレクトロルミネッセンス（ＥＬ）表示装置、液晶表示装置等）では、視認部のセンサーに相当する電極パターン、周辺配線部分及び取り出し配線部分の配線等の導電層パターンがタッチパネル内部に設けられている。 In display devices equipped with a touch panel such as a capacitance type input device (organic electroluminescence (EL) display device, liquid crystal display device, etc.), the electrode pattern corresponding to the sensor of the visual recognition part, the peripheral wiring part, and the wiring of the take-out wiring part are wired. Etc. is provided inside the touch panel.
　一般的にパターン化した層の形成には、必要とするパターン形状を得るための工程数が少ないことから、感光性転写材料を用いて基板上に感光性樹脂組成物の層（感光層）を設け、感光層に対して所望のパターンを有するマスクを介して露光した後、現像する方法が広く採用されている。 Generally, in forming a patterned layer, the number of steps for obtaining a required pattern shape is small, so a layer of a photosensitive resin composition (photosensitive layer) is formed on a substrate using a photosensitive transfer material. A method of providing and exposing the photosensitive layer through a mask having a desired pattern and then developing the photosensitive layer is widely adopted.
　例えば、特開２００８－９４８０３号公報には、カルボキシル基含有量が酸当量で１００～６００であり、かつ、重量平均分子量が２万～５０万の線状重合体からなるバインダー用樹脂：２０～９０質量％、少なくとも一つの末端エチレン性不飽和基を有する光重合性モノマー：５～７５質量％、特定の化合物を含有する光重合開始剤：０．０１～３０質量％を含有する感光性樹脂組成物からなる感光性樹脂層を支持層上に設けた感光性樹脂積層体が記載されている。 For example, Japanese Patent Application Laid-Open No. 2008-94803 states that a resin for a binder composed of a linear polymer having a carboxyl group content of 100 to 600 in acid equivalent and a weight average molecular weight of 20,000 to 500,000: 20 to Photopolymerizable resin containing 90% by mass, a photopolymerizable monomer having at least one terminal ethylenically unsaturated group: 5 to 75% by mass, and a photopolymerization initiator containing a specific compound: 0.01 to 30% by mass. A photosensitive resin laminate in which a photosensitive resin layer composed of a composition is provided on a support layer is described.
　特開２００８－９４８０３号公報では、現像液中での光重合開始剤の分散安定性を高めるために、特定の構造を有する光重合開始剤を感光性樹脂層に含有させていると考えられる。しかしながら、現像液中には、光重合開始剤以外にも、分散安定性に劣る成分が存在し、そのような成分はスカム（凝集物）を発生させる原因となり得る。 In JP-A-2008-94803, it is considered that the photosensitive resin layer contains a photopolymerization initiator having a specific structure in order to enhance the dispersion stability of the photopolymerization initiator in a developing solution. However, in addition to the photopolymerization initiator, there are components in the developer that are inferior in dispersion stability, and such components can cause scum (aggregates) to be generated.
　本発明の一の実施形態によれば、現像処理を長時間行った場合においてもスカム（凝集物）の発生が抑制される感光性転写材料が提供される。また、本発明の他の実施形態によれば、上記感光性転写材料を用いた樹脂パターンの製造方法、回路配線の製造方法及びタッチパネルの製造方法が提供される。 According to one embodiment of the present invention, there is provided a photosensitive transfer material in which the generation of scum (aggregate) is suppressed even when the development process is performed for a long time. Further, according to another embodiment of the present invention, a method for manufacturing a resin pattern using the above-mentioned photosensitive transfer material, a method for manufacturing a circuit wiring, and a method for manufacturing a touch panel are provided.
　本開示は、以下の態様を含む。
＜１＞仮支持体と、仮支持体上に配置された感光性樹脂層と、を備え、１質量％炭酸ナトリウムの３０℃水溶液１リットルに０．１ｍ２の感光性転写材料を溶解させて得られる溶液のヘイズが６０％以下である、感光性転写材料。
＜２＞感光性樹脂層の厚さが１０μｍ以下である、＜１＞に記載の感光性転写材料。
＜３＞感光性樹脂層は、重合性化合物とアルカリ可溶性樹脂とを含み、アルカリ可溶性樹脂の含有量に対する重合性化合物の含有量の比率が、質量基準で０．８５以下である、＜１＞又は＜２＞に記載の感光性転写材料。
＜４＞感光性樹脂層は、アルカリ可溶性樹脂を含み、アルカリ可溶性樹脂の酸価は１２０ｍｇ／ＫＯＨ以上である、＜１＞～＜３＞のいずれか１つに記載の感光性転写材料。
＜５＞感光性樹脂層は、アルカリ可溶性樹脂を含み、アルカリ可溶性樹脂は、スチレンに由来する構成単位を含む、＜１＞～＜４＞のいずれか１つに記載の感光性転写材料。
＜６＞スチレンに由来する構成単位の含有量が、アルカリ可溶性樹脂の全質量に対して４０質量％以上である、＜５＞に記載の感光性転写材料。
＜７＞感光性樹脂層は、酸基を有する重合性化合物を含む、＜１＞～＜６＞のいずれか１つに記載の感光性転写材料。
＜８＞仮支持体と感光性樹脂層との間に、熱可塑性樹脂層をさらに備える、＜１＞～＜７＞のいずれか１つに記載の感光性転写材料。
＜９＞＜１＞～＜８＞のいずれか１つに記載の感光性転写材料における感光性樹脂層の仮支持体と対向していない側の面と基板とを貼り合わせる工程と、貼り合わせる工程後の感光性転写材料における感光性樹脂層をパターン露光する工程と、パターン露光する工程後の感光性樹脂層を現像して樹脂パターンを形成する工程と、を含む、樹脂パターンの製造方法。
＜１０＞＜１＞～＜８＞のいずれか１つに記載の感光性転写材料における感光性樹脂層の仮支持体と対向していない側の面と基板とを貼り合わせる工程と、貼り合わせる工程後の感光性転写材料における感光性樹脂層をパターン露光する工程と、パターン露光する工程後の感光性樹脂層を現像して樹脂パターンを形成する工程と、樹脂パターンが配置されていない領域における基板をエッチング処理する工程と、を含む、回路配線の製造方法。
＜１１＞＜１＞～＜８＞のいずれか１つに記載の感光性転写材料における感光性樹脂層の仮支持体と対向していない側の面と基板とを貼り合わせる工程と、貼り合わせる工程後の感光性転写材料における感光性樹脂層をパターン露光する工程と、パターン露光する工程後の感光性樹脂層を現像して樹脂パターンを形成する工程と、樹脂パターンが配置されていない領域における基板をエッチング処理する工程と、を含む、タッチパネルの製造方法。 The present disclosure includes the following aspects.
<1> A temporary support and a photosensitive resin layer arranged on the temporary support are provided, and 0.1 m 2 of a photosensitive transfer material is dissolved in 1 liter of a 30 ° C. aqueous solution of 1 mass% sodium carbonate. A photosensitive transfer material having a haze of 60% or less in the resulting solution.
<2> The photosensitive transfer material according to <1>, wherein the thickness of the photosensitive resin layer is 10 μm or less.
<3> The photosensitive resin layer contains a polymerizable compound and an alkali-soluble resin, and the ratio of the content of the polymerizable compound to the content of the alkali-soluble resin is 0.85 or less on a mass basis. <1> Alternatively, the photosensitive transfer material according to <2>.
<4> The photosensitive transfer material according to any one of <1> to <3>, wherein the photosensitive resin layer contains an alkali-soluble resin and the acid value of the alkali-soluble resin is 120 mg / KOH or more.
<5> The photosensitive transfer material according to any one of <1> to <4>, wherein the photosensitive resin layer contains an alkali-soluble resin, and the alkali-soluble resin contains a structural unit derived from styrene.
<6> The photosensitive transfer material according to <5>, wherein the content of the structural unit derived from styrene is 40% by mass or more with respect to the total mass of the alkali-soluble resin.
<7> The photosensitive transfer material according to any one of <1> to <6>, wherein the photosensitive resin layer contains a polymerizable compound having an acid group.
<8> The photosensitive transfer material according to any one of <1> to <7>, further comprising a thermoplastic resin layer between the temporary support and the photosensitive resin layer.
<9> The step of bonding the surface of the photosensitive resin layer on the side of the photosensitive transfer material not facing the temporary support and the substrate according to any one of <1> to <8> and the bonding. A method for producing a resin pattern, which comprises a step of pattern-exposing the photosensitive resin layer in the photosensitive transfer material after the step, and a step of developing the photosensitive resin layer after the pattern-exposing step to form a resin pattern.
<10> The step of bonding the surface of the photosensitive resin layer on the side of the photosensitive transfer material not facing the temporary support and the substrate according to any one of <1> to <8> and the bonding. A step of pattern-exposing the photosensitive resin layer in the photosensitive transfer material after the step, a step of developing the photosensitive resin layer after the pattern-exposing step to form a resin pattern, and a region where the resin pattern is not arranged. A method of manufacturing a circuit wiring, including a step of etching a substrate.
<11> The step of bonding the substrate to the surface of the photosensitive resin layer not facing the temporary support in the photosensitive transfer material according to any one of <1> to <8>. A step of pattern-exposing the photosensitive resin layer in the photosensitive transfer material after the step, a step of developing the photosensitive resin layer after the pattern-exposing step to form a resin pattern, and a region where the resin pattern is not arranged. A method for manufacturing a touch panel, which includes a step of etching a substrate.
　本発明の一の実施形態によれば、現像処理を長時間行った場合においてもスカム（凝集物）の発生が抑制される感光性転写材料を提供することができる。また、本発明の他の実施形態によれば、上記感光性転写材料を用いた樹脂パターンの製造方法、回路配線の製造方法及びタッチパネルの製造方法を提供することができる。 According to one embodiment of the present invention, it is possible to provide a photosensitive transfer material in which the generation of scum (aggregate) is suppressed even when the development process is performed for a long time. Further, according to another embodiment of the present invention, it is possible to provide a method for manufacturing a resin pattern using the above-mentioned photosensitive transfer material, a method for manufacturing a circuit wiring, and a method for manufacturing a touch panel.
図１は、感光性転写材料の構成の一例を示す概略図である。FIG. 1 is a schematic view showing an example of the configuration of a photosensitive transfer material.
　以下、本開示の内容について説明する。なお、添付の図面を参照しながら説明するが、符号は省略する場合がある。 The contents of this disclosure will be described below. Although the description will be given with reference to the attached drawings, the reference numerals may be omitted.
　本明細書における基（原子団）の表記において、置換及び無置換を記していない表記は、置換基を有さないものと共に置換基を有するものをも包含する。例えば「アルキル基」との表記は、置換基を有さないアルキル基（無置換アルキル基）のみならず、置換基を有するアルキル基（置換アルキル基）をも包含する。
　本明細書において、「（メタ）アクリル酸」はアクリル酸及びメタクリル酸の双方又はいずれか一方を表し、「（メタ）アクリレート」はアクリレート及びメタクリレートの双方又はいずれか一方を表す。
　また、本明細書における化学構造式は、水素原子を省略した簡略構造式で記載する場合もある。 In the notation of a group (atomic group) in the present specification, the notation that does not describe substitution and non-substitution includes those having no substituent as well as those having a substituent. For example, the notation "alkyl group" includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
In the present specification, "(meth) acrylic acid" represents both or one of acrylic acid and methacrylic acid, and "(meth) acrylate" represents both or one of acrylate and methacrylate.
Further, the chemical structural formula in the present specification may be described by a simplified structural formula in which a hydrogen atom is omitted.
　本明細書において、各成分の量（含有量等）は、各成分に含まれる物質が複数存在する場合、特に断らない限り、それら複数の物質の合計量（合計含有量等）を意味する。
　本明細書において「～」を用いて表される数値範囲は、「～」の前後に記載される数値を下限値及び上限値として含む範囲を意味する。
　本明細書において、「質量％」と「重量％」とは同義であり、「質量部」と「重量部」とは同義である。 In the present specification, the amount (content, etc.) of each component means the total amount (total content, etc.) of the plurality of substances, unless otherwise specified, when a plurality of substances contained in each component are present.
The numerical range represented by using "-" in the present specification means a range including the numerical values before and after "-" as the lower limit value and the upper limit value.
In the present specification, "% by mass" and "% by weight" are synonymous, and "parts by mass" and "parts by weight" are synonymous.
　本明細書において「工程」との語は、独立した工程のみを意味せず、他の工程と明確に区別できない場合であっても所期の目的が達成される工程であれば、本用語に含まれる。
　本明細書において「露光」とは、特に断らない限り、光を用いた露光のみならず、電子線及びイオンビーム等の粒子線を用いた描画も含む。また、露光に用いられる光としては、一般的に、水銀灯の輝線スペクトル、エキシマレーザに代表される遠紫外線、極紫外線
（ＥＵＶ（Extreme ultraviolet lithography）光）、及び、Ｘ線等の活性光線（活性エネルギー線）が挙げられる。 In the present specification, the term "process" does not mean only an independent process, and even if it cannot be clearly distinguished from other processes, the term "process" is used as long as the process achieves the intended purpose. included.
Unless otherwise specified, the term "exposure" as used herein includes not only exposure using light but also drawing using particle beams such as electron beams and ion beams. The light used for exposure is generally the emission line spectrum of a mercury lamp, far ultraviolet rays typified by an excimer laser, extreme ultraviolet rays (EUV (Extreme ultraviolet lithography) light), and active rays such as X-rays (activity). Energy rays).
　本明細書において、重量平均分子量（Ｍｗ）及び数平均分子量（Ｍｎ）は、特に断りのない限り、ＴＳＫｇｅｌ　ＧＭＨｘＬ、ＴＳＫｇｅｌ　Ｇ４０００ＨｘＬ、ＴＳＫｇｅｌ
　Ｇ２０００ＨｘＬ（何れも東ソー（株）製の商品名）のカラムを使用したゲルパーミエーションクロマトグラフィ（ＧＰＣ：Gel Permeation Chromatography）分析装置により、ＴＨＦ（テトラヒドロフラン）溶剤中の化合物を示差屈折計により検出し、標準物質としてポリスチレンを用いて換算した分子量である。
　本明細書において、２以上の好ましい態様の組み合わせは、より好ましい態様である。 In the present specification, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are TSKgel GMHxL, TSKgel G4000HxL, and TSKgel unless otherwise specified.
A compound in a THF (tetrahydrofuran) solvent was detected by a differential refractometer using a gel permeation chromatography (GPC) analyzer using a G2000HxL (trade name manufactured by Toso Co., Ltd.) column, and standardized. It is a molecular weight converted using polystyrene as a substance.
In the present specification, a combination of two or more preferred embodiments is a more preferred embodiment.
［感光性転写材料］
　本開示に係る感光性転写材料は、仮支持体と、仮支持体上に配置された感光性樹脂層と、を備え、１質量％炭酸ナトリウムの３０℃水溶液１リットルに０．１ｍ２の感光性転写材料を溶解させて得られる溶液のヘイズが６０％以下である。 [Photosensitive transfer material]
The photosensitive transfer material according to the present disclosure comprises a temporary support and a photosensitive resin layer arranged on the temporary support, and is exposed to 0.1 m 2 in 1 liter of a 30 ° C. aqueous solution of 1 mass% sodium carbonate. The haze of the solution obtained by dissolving the sex transfer material is 60% or less.
　長時間現像処理を行っていると、スカム（凝集物）が発生し、現像設備及び製品に付着する場合がある。スカム（凝集物）となる成分としては、感光性樹脂層に含まれる重合性化合物、及び光重合開始剤が挙げられる。これらの成分が、現像液中で凝集すると、現像液のヘイズが上昇する。 If the development process is performed for a long time, scum (aggregate) may be generated and adhere to the development equipment and products. Examples of the component that becomes a scum (aggregate) include a polymerizable compound contained in the photosensitive resin layer and a photopolymerization initiator. When these components aggregate in the developer, the haze of the developer increases.
　本開示に係る感光性転写材料は、１質量％炭酸ナトリウムの３０℃水溶液１リットルに０．１ｍ２の感光性転写材料を溶解させて得られる溶液のヘイズが６０％以下であるため、現像処理を行った場合にも、現像液のヘイズは低い。本開示に係る感光性転写材料を用いることにより、現像処理を長時間行った場合においてもスカム（凝集物）の発生を抑制することができる。 The photosensitive transfer material according to the present disclosure is developed because the haze of the solution obtained by dissolving 0.1 m 2 of the photosensitive transfer material in 1 liter of a 30 ° C. aqueous solution of 1 mass% sodium carbonate is 60% or less. Even when the above is performed, the haze of the developing solution is low. By using the photosensitive transfer material according to the present disclosure, it is possible to suppress the generation of scum (aggregate) even when the development process is performed for a long time.
　以下、本開示に係る感光性転写材料について、詳細に説明する。 Hereinafter, the photosensitive transfer material according to the present disclosure will be described in detail.
　本開示に係る感光性転写材料は、仮支持体と、仮支持体上に配置された感光性樹脂層とを備える。仮支持体上には、感光性樹脂層が他の層を介さずに直接配置されていてもよいし、他の層を介して配置されていてもよい。また、感光性樹脂層の仮支持体と対向する面とは反対側の面に他の層が配置されていてもよい。仮支持体及び感光性樹脂層以外の他の層としては、例えば、熱可塑性樹脂層、中間層及びカバーフィルムが挙げられる。 The photosensitive transfer material according to the present disclosure includes a temporary support and a photosensitive resin layer arranged on the temporary support. The photosensitive resin layer may be directly arranged on the temporary support without interposing another layer, or may be arranged through another layer. Further, another layer may be arranged on the surface of the photosensitive resin layer opposite to the surface facing the temporary support. Examples of the layer other than the temporary support and the photosensitive resin layer include a thermoplastic resin layer, an intermediate layer, and a cover film.
　図１は、本開示に係る感光性転写材料の層構成の一例を概略的に示している。図１に示す感光性転写材料１００は、仮支持体１０と、熱可塑性樹脂層１２と、中間層１４と、感光性樹脂層１６と、カバーフィルム１８とがこの順に積層されている。 FIG. 1 schematically shows an example of the layer structure of the photosensitive transfer material according to the present disclosure. In the photosensitive transfer material 100 shown in FIG. 1, a temporary support 10, a thermoplastic resin layer 12, an intermediate layer 14, a photosensitive resin layer 16, and a cover film 18 are laminated in this order.
　本開示に係る感光性転写材料は、１質量％炭酸ナトリウムの３０℃水溶液１Ｌ（リットル）に０．１ｍ２の感光性転写材料を溶解させて得られる溶液のヘイズが６０％以下である。ヘイズの測定方法は、例えば、以下の方法で行われる。 The photosensitive transfer material according to the present disclosure has a haze of 60% or less of a solution obtained by dissolving 0.1 m 2 of the photosensitive transfer material in 1 L (liter) of a 30 ° C. aqueous solution of 1 mass% sodium carbonate. The haze measurement method is, for example, the following method.
　まず、１質量％の炭酸ナトリウム水溶液を準備し、液温を３０℃に調整する。炭酸ナトリウム水溶液２００ｍＬに０．０２ｍ２の感光性転写材料を入れる。気泡を混入しないように注意しながら、３０℃で４時間撹拌する。撹拌後、不溶の仮支持体を取り出し、感光性転写材料が溶解した溶液のヘイズを測定する。ヘイズは、ヘイズメーター（製品名「ＮＤＨ４０００」、日本電色工業社製）を用い、液体測定用ユニット及び光路長２０ｍｍの液体測定専用セルを用いて測定される。なお、感光性転写材料に、カバーフィルムが含まれている場合には、剥離してから１質量％の炭酸ナトリウム水溶液に感光性転写材料を入れる。 First, a 1% by mass sodium carbonate aqueous solution is prepared, and the liquid temperature is adjusted to 30 ° C. Add 0.02 m 2 of photosensitive transfer material to 200 mL of an aqueous sodium carbonate solution. Stir at 30 ° C. for 4 hours, being careful not to mix air bubbles. After stirring, the insoluble temporary support is taken out, and the haze of the solution in which the photosensitive transfer material is dissolved is measured. The haze is measured using a haze meter (product name "NDH4000", manufactured by Nippon Denshoku Kogyo Co., Ltd.), a liquid measuring unit, and a liquid measuring cell having an optical path length of 20 mm. If the photosensitive transfer material contains a cover film, the photosensitive transfer material is put into a 1% by mass aqueous sodium carbonate solution after being peeled off.
　上記方法で得られる溶液のヘイズは、現像処理を長時間行った場合にスカム（凝集物）の発生をより抑制する観点から、３０％以下であることが好ましく、１０％以下であることがより好ましく、５％以下であることがさらに好ましく、１％以下であることが特に好ましい。 The haze of the solution obtained by the above method is preferably 30% or less, and more preferably 10% or less, from the viewpoint of further suppressing the generation of scum (aggregates) when the development treatment is performed for a long time. It is preferably 5% or less, more preferably 1% or less, and particularly preferably 1% or less.
＜仮支持体＞
　本開示に係る感光性転写材料は、仮支持体を備える。
　仮支持体は、感光性樹脂層、又は感光性樹脂層を含む積層体を支持し、かつ、剥離可能な支持体である。 <Temporary support>
The photosensitive transfer material according to the present disclosure includes a temporary support.
The temporary support is a support that supports a photosensitive resin layer or a laminate containing the photosensitive resin layer and is removable.
　仮支持体は、感光性樹脂層をパターン露光する際に、仮支持体を介した感光性樹脂層の露光を可能にする観点から、光透過性を有することが好ましい。なお、本明細書において「光透過性を有する」とは、パターン露光に使用する波長の光の透過率が５０％以上であることを意味する。 The temporary support preferably has light transmittance from the viewpoint of enabling exposure of the photosensitive resin layer through the temporary support when pattern-exposing the photosensitive resin layer. In addition, in this specification, "having light transmittance" means that the transmittance of light of the wavelength used for pattern exposure is 50% or more.
　仮支持体は、感光性樹脂層の露光感度向上の観点から、パターン露光に使用する波長（好ましくは波長３６５ｎｍ）の光の透過率が６０％以上であることが好ましく、７０％以上であることがより好ましい。 From the viewpoint of improving the exposure sensitivity of the photosensitive resin layer, the temporary support preferably has a light transmittance of 60% or more, preferably 70% or more, at a wavelength (preferably a wavelength of 365 nm) used for pattern exposure. Is more preferable.
　なお、感光性転写材料が備える層の透過率とは、層の主面に垂直な方向（すなわち、厚さ方向）に光を入射させたときの、入射光の強度に対する層を通過して出射した出射光の強度の比率である。透過率は、大塚電子社製の製品名「ＭＣＰＤ　Ｓｅｒｉｅｓ」を用いて測定される。 The transmittance of the layer included in the photosensitive transfer material means that when light is incident in a direction perpendicular to the main surface of the layer (that is, in the thickness direction), the light is emitted through the layer with respect to the intensity of the incident light. It is the ratio of the intensity of the emitted light. The transmittance is measured using the product name "MCPD Series" manufactured by Otsuka Electronics Co., Ltd.
　仮支持体は１層であってもよく、２層以上が積層された積層体であってもよい。 The temporary support may be a single layer or a laminated body in which two or more layers are laminated.
　仮支持体を構成する基材としては、例えば、ガラス、樹脂フィルム及び紙が挙げられる。仮支持体を構成する基材は、強度、可撓性及び光透過性の観点から、樹脂フィルムであることが好ましい。 Examples of the base material constituting the temporary support include glass, resin film and paper. The base material constituting the temporary support is preferably a resin film from the viewpoint of strength, flexibility and light transmission.
　樹脂フィルムとしては、ポリエチレンテレフタレート（ＰＥＴ：ｐｏｌｙｅｔｈｙｌｅｎｅ　ｔｅｒｅｐｈｔｈａｌａｔｅ）フィルム、トリ酢酸セルロースフィルム、ポリスチレンフィルム及びポリカーボネートフィルムが挙げられる。中でも、樹脂フィルムは、ＰＥＴフィルムであることが好ましく、２軸延伸ＰＥＴフィルムであることがより好ましい。 Examples of the resin film include polyethylene terephthalate (PET) film, cellulose triacetate film, polystyrene film and polycarbonate film. Among them, the resin film is preferably a PET film, and more preferably a biaxially stretched PET film.
　仮支持体の厚さは、特に制限されず、支持体としての強度、回路配線形成用基板との貼り合わせに求められる可撓性、及び、最初の露光工程で要求される光透過性の観点から、材質に応じて適宜選択すればよい。 The thickness of the temporary support is not particularly limited, and from the viewpoints of strength as a support, flexibility required for bonding to a circuit wiring forming substrate, and light transmission required in the first exposure step. Therefore, it may be appropriately selected according to the material.
　仮支持体の厚さは、５μｍ～１００μｍが好ましく、取扱い易さ及び汎用性の点から、１０μｍ～５０μｍがより好ましい。 The thickness of the temporary support is preferably 5 μm to 100 μm, and more preferably 10 μm to 50 μm from the viewpoint of ease of handling and versatility.
〔感光性樹脂層〕
　本開示に係る感光性転写材料は、感光性樹脂層を備える。感光性樹脂層は、露光により露光部の現像液に対する溶解性が低下し、非露光部が現像により除去されるネガ型感光性樹脂層であることが好ましい。しかし、感光性樹脂層はネガ型感光性樹脂層に制限されず、露光により露光部の現像液に対する溶解性が向上し、露光部が現像により除去されるポジ型感光性樹脂層であってもよい。 [Photosensitive resin layer]
The photosensitive transfer material according to the present disclosure includes a photosensitive resin layer. The photosensitive resin layer is preferably a negative photosensitive resin layer in which the solubility of the exposed portion in the developing solution is reduced by exposure and the non-exposed portion is removed by development. However, the photosensitive resin layer is not limited to the negative photosensitive resin layer, and even if the photosensitive resin layer is a positive photosensitive resin layer in which the solubility of the exposed portion in the developing solution is improved by exposure and the exposed portion is removed by development. good.
　感光性樹脂層は、例えば、感光性樹脂組成物を塗布し、乾燥させることにより得られる。 The photosensitive resin layer can be obtained, for example, by applying a photosensitive resin composition and drying it.
　感光性樹脂層は、重合体Ａ、重合性化合物Ｂ、及び光重合開始剤を含むことが好ましい。感光性樹脂層は、感光性樹脂層の全質量に対して、重合体Ａを１０質量％～９０質量％、重合性化合物Ｂを５質量％～７０質量％、光重合開始剤を０．０１質量％～２０質量％含むことが好ましい。以下、各成分を順に説明する。 The photosensitive resin layer preferably contains the polymer A, the polymerizable compound B, and the photopolymerization initiator. The photosensitive resin layer contains 10% by mass to 90% by mass of the polymer A, 5% by mass to 70% by mass of the polymerizable compound B, and 0.01% by mass of the photopolymerization initiator with respect to the total mass of the photosensitive resin layer. It is preferably contained in an amount of% to 20% by mass. Hereinafter, each component will be described in order.
＜成分＞
（重合体Ａ）
　重合体Ａは、アルカリ可溶性樹脂であることが好ましい。アルカリ可溶性樹脂は、アルカリ物質に溶け易い高分子を意味する。なお、本明細書において、「アルカリ可溶性」とは、２２℃において炭酸ナトリウムの１質量％水溶液１００ｇへの溶解度が０．１ｇ以上であることを意味する。 <Ingredients>
(Polymer A)
The polymer A is preferably an alkali-soluble resin. The alkali-soluble resin means a polymer that is easily dissolved in an alkaline substance. In the present specification, "alkali-soluble" means that the solubility of sodium carbonate in 100 g of a 1% by mass aqueous solution at 22 ° C. is 0.1 g or more.
　重合体Ａの酸価は、現像処理を長時間行った場合にスカム（凝集物）の発生をより抑制する観点から、１２０ｍｇＫＯＨ／ｇ以上であることが好ましく、１５０ｍｇＫＯＨ／ｇ以上であることがより好ましく、１８０ｍｇＫＯＨ／ｇ以上であることがさらに好ましい。アルカリ可溶性樹脂は現像液中で分散剤として作用する。アルカリ可溶性樹脂の酸価が１２０ｍｇＫＯＨ／ｇ以上であると、現像液に溶解しない成分を分散させる効果が高く、スカム（凝集物）の発生を抑制することができると考えられる。 The acid value of the polymer A is preferably 120 mgKOH / g or more, and more preferably 150 mgKOH / g or more, from the viewpoint of further suppressing the generation of scum (aggregates) when the development treatment is carried out for a long time. It is preferably 180 mgKOH / g or more, and more preferably 180 mgKOH / g or more. The alkali-soluble resin acts as a dispersant in the developer. When the acid value of the alkali-soluble resin is 120 mgKOH / g or more, it is considered that the effect of dispersing the components insoluble in the developing solution is high and the generation of scum (aggregates) can be suppressed.
　重合体Ａの酸価の上限値は特に制限されない。重合体Ａの酸価は、解像度の観点から、２２０ｍｇＫＯＨ／ｇ以下であることが好ましく、２００ｍｇＫＯＨ／ｇ以下であることがより好ましい。 The upper limit of the acid value of the polymer A is not particularly limited. From the viewpoint of resolution, the acid value of the polymer A is preferably 220 mgKOH / g or less, and more preferably 200 mgKOH / g or less.
　なお、酸価は、試料１ｇを中和するのに必要な水酸化カリウムの質量［ｍｇ］である。 The acid value is the mass [mg] of potassium hydroxide required to neutralize 1 g of the sample.
　本明細書においては、酸価の単位をｍｇＫＯＨ／ｇと記載する。酸価は、例えば、化合物中における酸基の平均含有量から算出できる。 In this specification, the unit of acid value is described as mgKOH / g. The acid value can be calculated, for example, from the average content of acid groups in the compound.
　重合体Ａの酸価は、重合体Ａを構成する構成単位の種類及び酸基を含有する構成単位の含有量により調整すればよい。 The acid value of the polymer A may be adjusted according to the type of the structural unit constituting the polymer A and the content of the structural unit containing an acid group.
　重合体Ａの重量平均分子量は、５，０００～５００，０００であることが好ましい。重量平均分子量が５００，０００以下であると、解像性及び現像性が向上するため好ましい。重合体Ａの重量平均分子量は、１００，０００以下であることがより好ましく、６０，０００以下であることがさらに好ましく、５０，０００以下であることが特に好ましい。一方で、重量平均分子量が５，０００以上であると、現像凝集物の性状、並びに感光性樹脂積層体とした場合のエッジフューズ性、カットチップ性等の未露光膜の性状を制御できるため好ましい。重合体Ａの重量平均分子量は、１０，０００以上であることがより好ましく、２０，０００以上であることがさらに好ましく、３０，０００以上であることが特に好ましい。エッジフューズ性とは、感光性樹脂積層体としてロール状に巻き取った場合に、ロールの端面からの、感光性樹脂層のはみ出し易さの程度をいう。カットチップ性とは、未露光膜をカッターで切断した場合に、チップの飛び易さの程度をいう。このチップが感光性樹脂積層体の上面等に付着すると、後の露光工程等でマスクに転写して、不良品の原因となる。 The weight average molecular weight of the polymer A is preferably 5,000 to 500,000. When the weight average molecular weight is 500,000 or less, the resolution and developability are improved, which is preferable. The weight average molecular weight of the polymer A is more preferably 100,000 or less, further preferably 60,000 or less, and particularly preferably 50,000 or less. On the other hand, when the weight average molecular weight is 5,000 or more, the properties of the developed agglomerates and the properties of the unexposed film such as edge fuse properties and cut chip properties in the case of a photosensitive resin laminate can be controlled, which is preferable. .. The weight average molecular weight of the polymer A is more preferably 10,000 or more, further preferably 20,000 or more, and particularly preferably 30,000 or more. The edge fuse property refers to the degree of ease with which the photosensitive resin layer protrudes from the end face of the roll when the photosensitive resin laminate is wound into a roll. The cut chip property refers to the degree of ease with which the chip flies when the unexposed film is cut with a cutter. If this chip adheres to the upper surface of the photosensitive resin laminate or the like, it will be transferred to the mask in a later exposure process or the like, causing a defective product.
　重合体Ａの分散度は、１．０～６．０であることが好ましく、１．０～５．０であることがより好ましく、１．０～４．０であることがさらに好ましく、１．０～３．０であることが特に好ましい。本開示で、分子量は、ゲルパーミエーションクロマトグラフィーを用いて測定される値である。また分散度は、数平均分子量に対する重量平均分子量の比（重量平均分子量／数平均分子量）である。  The dispersity of the polymer A is preferably 1.0 to 6.0, more preferably 1.0 to 5.0, and even more preferably 1.0 to 4.0. It is particularly preferably 0.0 to 3.0. In the present disclosure, the 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).
　重合体Ａは、露光時の焦点位置がずれたときの線幅太り、及び、解像度の低下を抑制する観点から、芳香族炭化水素基を有する単量体に由来する構成単位を含むことが好ましい。芳香族炭化水素基としては、例えば、置換又は非置換のフェニル基、及び、置換又は非置換のアラルキル基が挙げられる。重合体Ａにおける芳香族炭化水素基を有する単量体に由来する構成単位の含有量は、重合体Ａの全質量に対して、２０質量％以上であることが好ましく、３０質量％以上であることがより好ましく、４０質量％以上であることがさらに好ましく、４５質量％以上であることが特に好ましく、５０質量％以上であることが最も好ましい。上記含有量の上限値は特に限定されない。上記含有量は、重合体Ａの全質量を基準として、９５質量％以下であることが好ましく、８５質量％以下であることがより好ましい。なお、重合体Ａを複数種類含有する場合には、芳香族炭化水素基を有する単量体に由来する構成単位の含有量は、重量平均値として求めた。  The polymer A preferably contains a structural unit derived from a monomer having an aromatic hydrocarbon group from the viewpoint of suppressing the line width thickening when the focal position is deviated during exposure and the decrease in resolution. .. Examples of the aromatic hydrocarbon group include a substituted or unsubstituted phenyl group and a substituted or unsubstituted aralkyl group. The content of the structural unit derived from the monomer having an aromatic hydrocarbon group in the polymer A is preferably 20% by mass or more, preferably 30% by mass or more, based on the total mass of the polymer A. More preferably, it is more preferably 40% by mass or more, particularly preferably 45% by mass or more, and most preferably 50% by mass or more. The upper limit of the content is not particularly limited. The content is preferably 95% by mass or less, and more preferably 85% by mass or less, based on the total mass of the polymer A. When a plurality of types of the polymer A were contained, the content of the structural unit derived from the monomer having an aromatic hydrocarbon group was determined as a weight average value.
　芳香族炭化水素基を有する単量体としては、例えば、アラルキル基を有するモノマー、スチレン、及び重合可能なスチレン誘導体（例えば、メチルスチレン、ビニルトルエン、ｔｅｒｔ－ブトキシスチレン、アセトキシスチレン、４－ビニル安息香酸、スチレンダイマー、及びスチレントリマー）が挙げられる。中でも、芳香族炭化水素基を有する単量体は、アラルキル基を有するモノマー、又はスチレンであることが好ましく、スチレンであることがより好ましい。 Examples of the monomer having an aromatic hydrocarbon group include a monomer having an aralkyl group, styrene, and a polymerizable styrene derivative (for example, methyl styrene, vinyl toluene, tert-butoxy styrene, acetoxy styrene, 4-vinyl scent). Acids, styrene dimers, and styrene trimers). Among them, the monomer having an aromatic hydrocarbon group is preferably a monomer having an aralkyl group or styrene, and more preferably styrene.
　芳香族炭化水素基を有する単量体がスチレンである場合、スチレンに由来する構成単位の含有量は、重合体Ａの全質量を基準として、４０質量％以上であることが好ましく、４０質量％～８０質量％であることがより好ましく、４５質量％～７０質量％であることがさらに好ましく、５０質量％～５５質量％であることが特に好ましい。 When the monomer having an aromatic hydrocarbon group is styrene, the content of the structural unit derived from styrene is preferably 40% by mass or more, preferably 40% by mass, based on the total mass of the polymer A. It is more preferably to 80% by mass, further preferably 45% by mass to 70% by mass, and particularly preferably 50% by mass to 55% by mass.
　アラルキル基としては、置換又は非置換のフェニルアルキル基（ベンジル基を除く）、及び置換又は非置換のベンジル基が挙げられる。アラルキル基は、置換又は非置換のベンジル基であることが好ましい。  Examples of the aralkyl group include a substituted or unsubstituted phenylalkyl group (excluding a benzyl group) and a substituted or unsubstituted benzyl group. The aralkyl group is preferably a substituted or unsubstituted benzyl group.
　フェニルアルキル基を有する単量体としては、フェニルエチル（メタ）アクリレートが挙げられる。  Examples of the monomer having a phenylalkyl group include phenylethyl (meth) acrylate.
　ベンジル基を有する単量体としては、ベンジル基を有する（メタ）アクリレート及びベンジル基を有するビニルモノマーが挙げられる。ベンジル基を有する（メタ）アクリレートとしては、例えば、ベンジル（メタ）アクリレート及びクロロベンジル（メタ）アクリレートが挙げられる。ベンジル基を有するビニルモノマーとしては、例えば、ビニルベンジルクロリド及びビニルベンジルアルコールが挙げられる。中でも、ベンジル基を有する単量体はベンジル（メタ）アクリレートであることが好ましい。芳香族炭化水素基を有する単量体がベンジル（メタ）アクリレートである場合、ベンジル（メタ）アクリレートに由来する構成単位の含有量は、重合体Ａの全質量を基準として、５０質量％～９５質量％であることが好ましく、６０質量％～９０質量％であることがより好ましく、７０質量％～９０質量％であることがさらに好ましく、７５質量％～９０質量％であることが特に好ましい。  Examples of the monomer having a benzyl group include (meth) acrylate having a benzyl group and a vinyl monomer having a benzyl group. Examples of the (meth) acrylate having a benzyl group include benzyl (meth) acrylate and chlorobenzyl (meth) acrylate. Examples of the vinyl monomer having a benzyl group include vinylbenzyl chloride and vinylbenzyl alcohol. Among them, the monomer having a benzyl group is preferably benzyl (meth) acrylate. When the monomer having an aromatic hydrocarbon group is benzyl (meth) acrylate, the content of the structural unit derived from benzyl (meth) acrylate is 50% by mass to 95% based on the total mass of the polymer A. It is preferably mass%, more preferably 60% by mass to 90% by mass, further preferably 70% by mass to 90% by mass, and particularly preferably 75% by mass to 90% by mass.
　芳香族炭化水素基を有する単量体に由来する構成単位を含有する重合体Ａは、芳香族炭化水素基を有する単量体に由来する構成単位と、後述する第一の単量体及び後述する第二の単量体からなる群より選択される少なくとも１種の単量体に由来する構成単位とを含有する重合体であることが好ましい。  The polymer A containing a structural unit derived from a monomer having an aromatic hydrocarbon group includes a structural unit derived from a monomer having an aromatic hydrocarbon group, the first monomer described later, and the first monomer described later, and the following. It is preferable that the polymer contains a structural unit derived from at least one monomer selected from the group consisting of the second monomer.
　芳香族炭化水素基を有する単量体に由来する構成単位を含有しない重合体Ａは、第一の単量体及び第二の単量体からなる群より選択される少なくとも１種の単量体に由来する構成単位を含有する重合体であることが好ましく、少なくとも１種の第一の単量体に由来する構成単位と少なくとも１種の第二の単量体に由来する構成単位とを含有する重合体であることがより好ましい。  The polymer A containing no structural unit derived from a monomer having an aromatic hydrocarbon group is at least one monomer selected from the group consisting of a first monomer and a second monomer. It is preferable that the polymer contains a structural unit derived from, and contains a structural unit derived from at least one first monomer and a structural unit derived from at least one second monomer. It is more preferable that the polymer is a polymer.
　第一の単量体は、アニオン性基を有し、かつ、分子中に少なくとも１つの重合性不飽和基を有する単量体である。第一の単量体としては、例えば、（メタ）アクリル酸、フマル酸、ケイ皮酸、クロトン酸、イタコン酸、４－ビニル安息香酸、マレイン酸無水物、及びマレイン酸半エステルが挙げられる。中でも、第一の単量体は、（メタ）アクリル酸であることが好ましい。 The first monomer is a monomer having an anionic group and having at least one polymerizable unsaturated group in the molecule. Examples of the first monomer include (meth) acrylic acid, fumaric acid, cinnamic acid, crotonic acid, itaconic acid, 4-vinylbenzoic acid, maleic anhydride, and maleic acid semiester. Among them, the first monomer is preferably (meth) acrylic acid.
　重合体Ａにおける第一の単量体に由来する構成単位の含有量は、重合体Ａの全質量に対して、５質量％～５０質量％であることが好ましく、１０質量％～４０質量％であることがより好ましく、１５質量％～３０質量％であることがさらに好ましい。  The content of the structural unit derived from the first monomer in the polymer A is preferably 5% by mass to 50% by mass, and 10% by mass to 40% by mass, based on the total mass of the polymer A. Is more preferable, and 15% by mass to 30% by mass is further preferable.
　なお、本明細書において「（メタ）アクリル酸」とは、アクリル酸又はメタクリル酸を意味し、「（メタ）アクリロイル基」とは、アクリロイル基又はメタクリロイル基を意味し、かつ「（メタ）アクリレート」とは、「アクリレート」又は「メタクリレート」を意味する。  In the present specification, "(meth) acrylic acid" means acrylic acid or methacrylic acid, and "(meth) acryloyl group" means an acryloyl group or methacrylic acid group, and "(meth) acrylate". "" Means "acrylate" or "methacrylate".
　第二の単量体は、アニオン性基を有さず、かつ、分子中に少なくとも１個の重合性不飽和基を有する単量体である。第二の単量体としては、例えば、メチル（メタ）アクリレート、エチル（メタ）アクリレート、ｎ－プロピル（メタ）アクリレート、イソプロピル（メタ）アクリレート、ｎ－ブチル（メタ）アクリレート、イソブチル（メタ）アクリレート、ｔｅｒｔ－ブチル（メタ）アクリレート、２－ヒドロキシエチル（メタ）アクリレート、２－ヒドロキシプロピル（メタ）アクリレート、シクロヘキシル（メタ）アクリレート、２－エチルヘキシル（メタ）アクリレート等の（メタ）アクリレート；酢酸ビニル等のビニルエステル；及び（メタ）アクリロニトリルが挙げられる。中でも、第二の単量体は、メチル（メタ）アクリレート、２－エチルヘキシル（メタ）アクリレート、又はｎ－ブチル（メタ）アクリレートであることが好ましく、メチル（メタ）アクリレートが特に好ましい。 The second monomer is a monomer that does not have an anionic group and has at least one polymerizable unsaturated group in the molecule. Examples of the second monomer include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, and isobutyl (meth) acrylate. , Tart-butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate and other (meth) acrylates; vinyl acetate and the like. Vinyl esters; and (meth) acrylonitriles. Among them, the second monomer is preferably methyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, or n-butyl (meth) acrylate, and methyl (meth) acrylate is particularly preferable.
　重合体Ａにおける第二の単量体に由来する構成単位の含有量は、重合体Ａの全質量に対して、５質量％～６０質量％であることが好ましく、１５質量％～５０質量％であることがより好ましく、２０質量％～４５質量％であることがさらに好ましい。 The content of the structural unit derived from the second monomer in the polymer A is preferably 5% by mass to 60% by mass, and 15% by mass to 50% by mass, based on the total mass of the polymer A. Is more preferable, and 20% by mass to 45% by mass is further preferable.
　重合体Ａは、露光時の焦点位置がずれたときの線幅太り、及び、解像度の低下を抑制する観点からアラルキル基を有する単量体及びスチレンからなる群より選択される少なくとも１種の単量体に由来する構成単位を含有することが好ましい。具体的には、重合体Ａは、スチレンに由来する構成単位、メチルメタクリレートに由来する構成単位及びメタクリル酸に由来する構成単位を含む共重合体であることが好ましい。 The polymer A is at least one type selected from the group consisting of a monomer having an aralkyl group and styrene from the viewpoint of suppressing the line width thickening when the focal position is deviated during exposure and the decrease in resolution. It preferably contains a structural unit derived from the polymer. Specifically, the polymer A is preferably a copolymer containing a structural unit derived from styrene, a structural unit derived from methyl methacrylate, and a structural unit derived from methacrylic acid.
　第１の態様として、重合体Ａは、芳香族炭化水素基を有する単量体に由来する構成単位を２５質量％～４０質量％、第一の単量体に由来する構成単位を２０質量％～３５質量％、第二の単量体に由来する構成単位を３０質量％～４５質量％含む重合体であることが好ましい。また、第２の態様として、重合体Ａは、芳香族炭化水素基を有する単量体に由来する構成単位を７０質量％～９０質量％、第一の単量体に由来する構成単位を１０質量％～２５質量％含む重合体であることが好ましい。また、第３の態様として、重合体Ａは、芳香族炭化水素基を有する単量体に由来する構成単位を４０質量％～６０質量％、第一の単量体に由来する構成単位を２０質量％～３５質量％、第二の単量体に由来する構成単位を１０質量％～２５質量％含む重合体であることが好ましい。 In the first aspect, in the polymer A, the structural unit derived from the monomer having an aromatic hydrocarbon group is 25% by mass to 40% by mass, and the structural unit derived from the first monomer is 20% by mass. It is preferably a polymer containing up to 35% by mass and 30% by mass to 45% by mass of a structural unit derived from the second monomer. Further, as a second aspect, the polymer A contains 70% by mass to 90% by mass of a structural unit derived from a monomer having an aromatic hydrocarbon group, and 10 constituent units derived from the first monomer. It is preferably a polymer containing% by mass to 25% by mass. Further, as a third aspect, in the polymer A, the structural unit derived from the monomer having an aromatic hydrocarbon group is 40% by mass to 60% by mass, and the structural unit derived from the first monomer is 20. It is preferably a polymer containing 10% by mass to 35% by mass and 10% by mass to 25% by mass of a structural unit derived from the second monomer.
　重合体Ａは、側鎖に分岐構造又は脂環構造を有してもよい。側鎖に分岐構造を有する基を含有するモノマー、又は、側鎖に脂環構造を有する基を含有するモノマーを使用することによって、重合体Ａの側鎖に分岐構造又は脂環構造を導入することができる。 Polymer A may have a branched structure or an alicyclic structure in the side chain. A branched structure or an alicyclic structure is introduced into the side chain of the polymer A by using a monomer containing a group having a branched structure in the side chain or a monomer containing a group having an alicyclic structure in the side chain. be able to.
　側鎖に分岐構造を有する基を含有するモノマーとしては、例えば、（メタ）アクリル酸ｉ－プロピル、（メタ）アクリル酸ｉ－ブチル、（メタ）アクリル酸ｓ－ブチル、（メタ）アクリル酸ｔ－ブチル、（メタ）アクリル酸ｉ－アミル、（メタ）アクリル酸ｔ－アミル、（メタ）アクリル酸ｓｅｃ－ｉｓｏ－アミル、（メタ）アクリル酸２－オクチル、（メタ）アクリル酸３－オクチル及び（メタ）アクリル酸ｔ－オクチルが挙げられる。中でも、側鎖に分岐構造を有する基を含有するモノマーは、（メタ）アクリル酸ｉ－プロピル、（メタ）アクリル酸ｉ－ブチル、又は（メタ）アクリル酸ｔ－ブチルが好ましく、（メタ）アクリル酸ｉ－プロピル又は（メタ）アクリル酸ｔ－ブチルがより好ましい。 Examples of the monomer containing a group having a branched structure in the side chain include i-propyl (meth) acrylate, i-butyl (meth) acrylate, s-butyl (meth) acrylate, and t (meth) acrylate. -Butyl, i-amyl (meth) acrylate, t-amyl (meth) acrylate, sec-iso-amyl (meth) acrylate, 2-octyl (meth) acrylate, 3-octyl (meth) acrylate and (Meta) t-octyl acrylate can be mentioned. Among them, the monomer containing a group having a branched structure in the side chain is preferably i-propyl (meth) acrylate, i-butyl (meth) acrylate, or t-butyl (meth) acrylate, and (meth) acrylic. More preferably, i-propyl acid acid or t-butyl (meth) acrylate.
　側鎖に脂環構造を有する基を含有するモノマーとしては、例えば、炭素原子数５個～２０個の脂環式炭化水素基を有する（メタ）アクリレートが挙げられる。具体的には、側鎖に脂環構造を有する基を含有するモノマーとして、（メタ）アクリル酸（ビシクロ［２．２．１］ヘプチル－２）、（メタ）アクリル酸－１－アダマンチル、（メタ）アクリル酸－２－アダマンチル、（メタ）アクリル酸－３－メチル－１－アダマンチル、（メタ）アクリル酸－３，５－ジメチル－１－アダマンチル、（メタ）アクリル酸－３－エチルアダマンチル、（メタ）アクリル酸－３－メチル－５－エチル－１－アダマンチル、（メタ）アクリル酸－３，５，８－トリエチル－１－アダマンチル、（メタ）アクリル酸－３，５－ジメチル－８－エチル－１－アダマンチル、（メタ）アクリル酸２－メチル－２－アダマンチル、（メタ）アクリル酸２－エチル－２－アダマンチル、（メタ）アクリル酸３－ヒドロキシ－１－アダマンチル、（メタ）アクリル酸オクタヒドロ－４，７－メンタノインデン－５－イル、（メタ）アクリル酸オクタヒドロ－４，７－メンタノインデン－１－イルメチル、（メタ）アクリル酸－１－メンチル、（メタ）アクリル酸トリシクロデカン、（メタ）アクリル酸－３－ヒドロキシ－２，６，６－トリメチル－ビシクロ［３．１．１］ヘプチル、（メタ）アクリル酸－３，７，７－トリメチル－４－ヒドロキシ－ビシクロ［４．１．０］ヘプチル、（メタ）アクリル酸ノルボルニル、（メタ）アクリル酸イソボルニル、（メタ）アクリル酸フェンチル、（メタ）アクリル酸－２，２，５－トリメチルシクロヘキシル及び（メタ）アクリル酸シクロヘキシルが挙げられる。中でも、側鎖に脂環構造を有する基を含有するモノマーは、（メタ）アクリル酸シクロヘキシル、（メタ）アクリル酸ノルボルニル、（メタ）アクリル酸イソボルニル、（メタ）アクリル酸－１－アダマンチル、（メタ）アクリル酸－２－アダマンチル、（メタ）アクリル酸フェンチル、（メタ）アクリル酸１－メンチル、（メタ）アクリル酸トリシクロデカンが好ましく、（メタ）アクリル酸シクロヘキシル、（メタ）アクリル酸ノルボルニル、（メタ）アクリル酸イソボルニル、（メタ）アクリル酸－２－アダマンチル又は（メタ）アクリル酸トリシクロデカンが特に好ましい。 Examples of the monomer containing a group having an alicyclic structure in the side chain include (meth) acrylate having an alicyclic hydrocarbon group having 5 to 20 carbon atoms. Specifically, as a monomer containing a group having an alicyclic structure in the side chain, (meth) acrylic acid (bicyclo [2.2.1] heptyl-2), (meth) acrylic acid-1-adamantyl, ( -2-adamantyl (meth) acrylate, -3-methyl-1-adamantyl (meth) acrylate, -3,5-dimethyl-1-adamantyl (meth) acrylate, -3-ethyladamantyl (meth) acrylate, (Meta) Acrylic Acid-3-Methyl-5-Ethyl-1-adamantyl, (Meta) Acrylic Acid-3,5,8-Triethyl-1-adamantyl, (Meta) Acrylic Acid-3,5-Dimethyl-8- Ethyl-1-adamantyl, 2-methyl-2-adamantyl (meth) acrylate, 2-ethyl-2-adamantyl (meth) acrylate, 3-hydroxy-1-adamantyl (meth) acrylate, (meth) acrylic acid Octahydro-4,7-mentanoinden-5-yl, (meth) acrylate Octahydro-4,7-mentanoinden-1-ylmethyl, (meth) acrylate-1-mentyl, (meth) acrylate tricyclo Decane, (meth) acrylic acid-3-hydroxy-2,6,6-trimethyl-bicyclo [3.1.1] heptyl, (meth) acrylic acid-3,7,7-trimethyl-4-hydroxy-bicyclo [ 4.1.0] Heptyl, norbornyl (meth) acrylate, isobornyl (meth) acrylate, fentyl (meth) acrylate, -2,2,5-trimethylcyclohexyl (meth) acrylate and cyclohexyl (meth) acrylate Can be mentioned. Among them, the monomers containing a group having an alicyclic structure in the side chain are cyclohexyl (meth) acrylate, norbornyl (meth) acrylate, isobornyl (meth) acrylate, -1-adamantyl (meth) acrylate, and (meth). ) -2-adamantyl acrylate, fentyl (meth) acrylate, 1-mentyl (meth) acrylate, tricyclodecane (meth) acrylate, cyclohexyl (meth) acrylate, norbornyl (meth) acrylate, ( Isobornyl acrylate, -2-adamantyl (meth) acrylate or tricyclodecane (meth) acrylate are particularly preferred.
　感光性樹脂層は、重合体Ａを、１種単独で含有してもよいし、２種以上含有してもよい。重合体Ａを２種以上含む場合には、感光性樹脂層は、芳香族炭化水素基を有する単量体に由来する構成単位を含む重合体Ａを２種含むことが好ましい。また、感光性樹脂層は、芳香族炭化水素基を有する単量体に由来する構成単位を含む重合体Ａ１と、芳香族炭化水素基を有する単量体に由来する構成単位を含まない重合体Ａ２と、を含むことが好ましい。後者の場合、重合体Ａ１の含有量は、重合体Ａの全質量を基準として、５０質量％以上であることが好ましく、７０質量％以上であることがより好ましく、８０質量％以上であることが好ましく、９０質量％以上であることがより好ましい。  The photosensitive resin layer may contain the polymer A alone or in combination of two or more. When two or more kinds of the polymer A are contained, the photosensitive resin layer preferably contains two kinds of the polymer A containing a structural unit derived from a monomer having an aromatic hydrocarbon group. Further, the photosensitive resin layer is a polymer A1 containing a structural unit derived from a monomer having an aromatic hydrocarbon group and a polymer containing no structural unit derived from a monomer having an aromatic hydrocarbon group. It is preferable to include A2. In the latter case, the content of the polymer A1 is preferably 50% by mass or more, more preferably 70% by mass or more, and 80% by mass or more, based on the total mass of the polymer A. Is preferable, and 90% by mass or more is more preferable.
　重合体Ａの合成は、上記の一又は複数の単量体を、アセトン、メチルエチルケトン、イソプロパノール等の溶剤で希釈した溶液に、過酸化ベンゾイル、アゾイソブチロニトリル等のラジカル重合開始剤を適量添加し、加熱しながら攪拌することにより行われることが好ましい。反応終了後、さらに溶剤を加えて、所望の濃度に調整してもよい。重合方法としては、溶液重合以外に、塊状重合、懸濁重合、及び乳化重合が挙げられる。  For the synthesis of polymer A, an appropriate amount of a radical polymerization initiator such as benzoyl peroxide or azoisobutyronitrile is added to a solution obtained by diluting one or more of the above monomers with a solvent such as acetone, methyl ethyl ketone or isopropanol. It is preferably carried out by stirring while heating. After completion of the reaction, a solvent may be further added to adjust the concentration to a desired level. Examples of the polymerization method include bulk polymerization, suspension polymerization, and emulsion polymerization, in addition to solution polymerization.
　重合体Ａのガラス転移温度Ｔｇは、３０℃～１３５℃であることが好ましい。感光性樹脂層に、１３５℃以下のＴｇを有する重合体Ａを含有させることによって、露光時の焦点位置がずれたときの線幅太り、及び、解像度の低下を抑制することができる。重合体ＡのＴｇは、１３０℃以下であることがより好ましく、１２０℃以下であることがさらに好ましく、１１０℃以下であることが特に好ましい。また、感光性樹脂層に、３０℃以上のＴｇを有する重合体Ａを含有させることは、耐エッジフューズ性を向上させる観点から好ましい。重合体ＡのＴｇは、４０℃以上であることがより好ましく、５０℃以上であることがさらに好ましく、６０℃以上であることが特に好ましく、７０℃以上であることが最も好ましい。 The glass transition temperature Tg of the polymer A is preferably 30 ° C to 135 ° C. By incorporating the polymer A having a Tg of 135 ° C. or lower in the photosensitive resin layer, it is possible to suppress the line width thickening and the decrease in resolution when the focal position is deviated during exposure. The Tg of the polymer A is more preferably 130 ° C. or lower, further preferably 120 ° C. or lower, and particularly preferably 110 ° C. or lower. Further, it is preferable to include the polymer A having a Tg of 30 ° C. or higher in the photosensitive resin layer from the viewpoint of improving the edge fuse resistance. The Tg of the polymer A is more preferably 40 ° C. or higher, further preferably 50 ° C. or higher, particularly preferably 60 ° C. or higher, and most preferably 70 ° C. or higher.
　重合体Ａの含有量は、感光性樹脂層の全質量に対して、１０質量％～９０質量％の範囲であることが好ましく、３０質量％～７０質量％であることがより好ましく、４０質量％～６０質量％であることがさらに好ましい。感光性樹脂層の全質量に対する重合体Ａの含有量が９０質量％以下であると、現像時間を制御することができるため好ましい。一方、感光性樹脂層の全質量に対する重合体Ａの含有量が１０質量％以上であると、耐エッジフューズ性が向上するため好ましい。 The content of the polymer A is preferably in the range of 10% by mass to 90% by mass, more preferably 30% by mass to 70% by mass, and 40% by mass with respect to the total mass of the photosensitive resin layer. It is more preferably% to 60% by mass. When the content of the polymer A with respect to the total mass of the photosensitive resin layer is 90% by mass or less, the development time can be controlled, which is preferable. On the other hand, when the content of the polymer A with respect to the total mass of the photosensitive resin layer is 10% by mass or more, the edge fuse resistance is improved, which is preferable.
（重合性化合物Ｂ）
　感光性樹脂層は、重合性基を有する重合性化合物Ｂを含有する。
　本明細書において「重合性化合物」とは、後述する重合開始剤の作用を受けて重合する化合物であって、上述した重合体Ａとは異なる化合物を意味する。 (Polymerizable compound B)
The photosensitive resin layer contains a polymerizable compound B having a polymerizable group.
In the present specification, the "polymerizable compound" means a compound that polymerizes under the action of a polymerization initiator described later, and is different from the above-mentioned polymer A.
　重合性化合物Ｂが有する重合性基としては、重合反応に関与する基であれば特に制限されず、例えば、ビニル基、アクリロイル基、メタクリロイル基、スチリル基、マレイミド基等のエチレン性不飽和基；及び、エポキシ基、オキセタン基等のカチオン重合性基が挙げられる。 The polymerizable group contained in the polymerizable compound B is not particularly limited as long as it is a group involved in the polymerization reaction, and is, for example, an ethylenically unsaturated group such as a vinyl group, an acryloyl group, a methacryloyl group, a styryl group, or a maleimide group; In addition, cationically polymerizable groups such as an epoxy group and an oxetane group can be mentioned.
　重合性基は、エチレン性不飽和基であることが好ましく、アクリロイル基又はメタアクリロイル基であることがより好ましい。 The polymerizable group is preferably an ethylenically unsaturated group, more preferably an acryloyl group or a metaacryloyl group.
　重合性化合物Ｂとしては、感光性樹脂層の感光性がより優れる点で、１つ以上のエチレン性不飽和基を有する化合物（すなわち、エチレン性不飽和化合物）が好ましく、一分子中に２つ以上のエチレン性不飽和基を有する化合物（すなわち、多官能エチレン性不飽和化合物）がより好ましい。 As the polymerizable compound B, a compound having one or more ethylenically unsaturated groups (that is, an ethylenically unsaturated compound) is preferable in that the photosensitive resin layer has more excellent photosensitivity, and two in one molecule. A compound having the above ethylenically unsaturated group (that is, a polyfunctional ethylenically unsaturated compound) is more preferable.
　また、解像性及び剥離性により優れる点で、エチレン性不飽和化合物が一分子中に有するエチレン性不飽和基の数は、６つ以下が好ましく、３つ以下がより好ましく、２つ以下がさらに好ましい。 Further, the number of ethylenically unsaturated groups contained in one molecule of the ethylenically unsaturated compound is preferably 6 or less, more preferably 3 or less, and 2 or less in terms of excellent resolution and peelability. More preferred.
　感光性樹脂層は、感光性樹脂層の感光性と、解像性及び剥離性とのバランスがより優れる点で、一分子中に２つのエチレン性不飽和基を有する２官能エチレン性不飽和化合物、又は３つのエチレン性不飽和基を有する３官能エチレン性不飽和化合物を含有することが好ましく、２官能エチレン性不飽和化合物を含有することがより好ましい。 The photosensitive resin layer is a bifunctional ethylenically unsaturated compound having two ethylenically unsaturated groups in one molecule in that the balance between the photosensitivity of the photosensitive resin layer and the resolution and peelability is better. , Or a trifunctional ethylenically unsaturated compound having three ethylenically unsaturated groups, more preferably a bifunctional ethylenically unsaturated compound.
　２官能エチレン性不飽和化合物の含有量は、剥離性に優れる点から、重合性化合物Ｂの全質量に対して６０質量％以上が好ましく、７０質量％以上がより好ましい。２官能エチレン性不飽和化合物の含有量の上限値は特に制限されず、１００質量％であってもよい。すなわち、感光性樹脂層に含まれる重合性化合物Ｂが全て２官能エチレン性不飽和化合物であってもよい。 The content of the bifunctional ethylenically unsaturated compound is preferably 60% by mass or more, more preferably 70% by mass or more, based on the total mass of the polymerizable compound B from the viewpoint of excellent peelability. The upper limit of the content of the bifunctional ethylenically unsaturated compound is not particularly limited and may be 100% by mass. That is, all the polymerizable compounds B contained in the photosensitive resin layer may be bifunctional ethylenically unsaturated compounds.
　また、エチレン性不飽和化合物は、（メタ）アクリレート化合物が好ましい。 The ethylenically unsaturated compound is preferably a (meth) acrylate compound.
－重合性化合物Ｂ１－
　感光性樹脂層は、一分子中に少なくとも１つの芳香環を有し、かつ、２つのエチレン性不飽和基を有する重合性化合物Ｂ１を含有することが好ましい。 -Polymerizable compound B1-
The photosensitive resin layer preferably contains a polymerizable compound B1 having at least one aromatic ring in one molecule and having two ethylenically unsaturated groups.
　重合性化合物Ｂ１が有する芳香環としては、例えば、ベンゼン環、ナフタレン環及びアントラセン環等の芳香族炭化水素環；チオフェン環、フラン環、ピロール環、イミダゾール環、トリアゾール環、ピリジン環等の芳香族複素環；及びこれらの縮合環が挙げられる。重合性化合物Ｂ１が有する芳香環は、芳香族炭化水素環であることが好ましく、ベンゼン環であることがより好ましい。なお、上記芳香環は、置換基を有していてもよい。 Examples of the aromatic ring contained in the polymerizable compound B1 include aromatic hydrocarbon rings such as a benzene ring, a naphthalene ring and an anthracene ring; aromatics such as a thiophene ring, a furan ring, a pyrrole ring, an imidazole ring, a triazole ring and a pyridine ring. Heterocycles; and fused rings thereof. The aromatic ring contained in the polymerizable compound B1 is preferably an aromatic hydrocarbon ring, more preferably a benzene ring. The aromatic ring may have a substituent.
　重合性化合物Ｂ１は、現像液による感光性樹脂層の膨潤を抑制して、解像性を向上させる観点から、ビスフェノール骨格を有することが好ましい。 The polymerizable compound B1 preferably has a bisphenol skeleton from the viewpoint of suppressing swelling of the photosensitive resin layer due to the developing solution and improving the resolution.
　ビスフェノール骨格としては、例えば、ビスフェノールＡ（２，２－ビス（４－ヒドロキシフェニル）プロパン）に由来するビスフェノールＡ骨格、ビスフェノールＦ（２，２－ビス（４－ヒドロキシフェニル）メタン）に由来するビスフェノールＦ骨格、及び、ビスフェノールＢ（２，２－ビス（４－ヒドロキシフェニル）ブタン）に由来するビスフェノールＢ骨格が挙げられる。中でも、ビスフェノール骨格は、ビスフェノールＡ骨格であることが好ましい。 Examples of the bisphenol skeleton include a bisphenol A skeleton derived from bisphenol A (2,2-bis (4-hydroxyphenyl) propane) and a bisphenol derived from bisphenol F (2,2-bis (4-hydroxyphenyl) methane). Examples thereof include an F skeleton and a bisphenol B skeleton derived from bisphenol B (2,2-bis (4-hydroxyphenyl) butane). Above all, the bisphenol skeleton is preferably a bisphenol A skeleton.
　ビスフェノール骨格を有する重合性化合物Ｂ１としては、例えば、ビスフェノール骨格と、ビスフェノール骨格の両端に結合した２つの重合性基（好ましくは（メタ）アクリロイル基）とを有する化合物が挙げられる。 Examples of the polymerizable compound B1 having a bisphenol skeleton include a compound having a bisphenol skeleton and two polymerizable groups (preferably (meth) acryloyl groups) bonded to both ends of the bisphenol skeleton.
　ビスフェノール骨格と重合性基とは、直接結合してもよく、１つ以上のアルキレンオキシ基を介して結合してもよい。ビスフェノール骨格と結合するアルキレンオキシ基は、エチレンオキシ基又はプロピレンオキシ基であることが好ましく、エチレンオキシ基であることがより好ましい。ビスフェノール骨格と結合するアルキレンオキシ基の付加数は特に制限されない。アルキレンオキシ基の付加数は１分子あたり４個～１６個が好ましく、６個～１４個がより好ましい。 The bisphenol skeleton and the polymerizable group may be directly bonded or may be bonded via one or more alkyleneoxy groups. The alkyleneoxy group bonded to the bisphenol skeleton is preferably an ethyleneoxy group or a propyleneoxy group, and more preferably an ethyleneoxy group. The number of alkyleneoxy groups attached to the bisphenol skeleton is not particularly limited. The number of alkyleneoxy groups added is preferably 4 to 16 per molecule, more preferably 6 to 14.
　ビスフェノール骨格を有する重合性化合物Ｂ１については、特開２０１６－２２４１６２号公報の段落００７２～００８０に記載されており、この公報に記載の内容は本明細書に組み込まれる。 The polymerizable compound B1 having a bisphenol skeleton is described in paragraphs 0072 to 0080 of JP-A-2016-224162, and the contents described in this publication are incorporated in the present specification.
　重合性化合物Ｂ１は、ビスフェノールＡ骨格を有する２官能エチレン性不飽和化合物であることが好ましく、２，２－ビス（４－（（メタ）アクリロキシポリアルコキシ）フェニル）プロパンであることがより好ましい。 The polymerizable compound B1 is preferably a bifunctional ethylenically unsaturated compound having a bisphenol A skeleton, and more preferably 2,2-bis (4-((meth) acryloxypolyalkoxy) phenyl) propane. ..
　２，２－ビス（４－（（メタ）アクリロキシポリアルコキシ）フェニル）プロパンとしては、例えば、２，２－ビス（４－（メタクリロキシジエトキシ）フェニル）プロパン（ＦＡ－３２４Ｍ、日立化成社製）、２，２－ビス（４－（メタクリロキシエトキシプロポキシ）フェニル）プロパン、２，２－ビス（４－（メタクリロキシペンタエトキシ）フェニル）プロパン（ＢＰＥ－５００、新中村化学工業社製）、２，２－ビス（４－（メタクリロキシドデカエトキシテトラプロポキシ）フェニル）プロパン（ＦＡ－３２００ＭＹ、日立化成社製）、２，２－ビス（４－（メタクリロキシペンタデカエトキシ）フェニル）プロパン（ＢＰＥ－１３００、新中村化学工業社製）、２，２－ビス（４－（メタクリロキシジエトキシ）フェニル）プロパン（ＢＰＥ－２００、新中村化学工業社製）、及び、エトキシ化（１０）ビスフェノールＡジアクリレート（ＮＫエステルＡ－ＢＰＥ－１０、新中村化学工業社製）が挙げられる。 Examples of the 2,2-bis (4-((meth) acryloxipolyalkoxy) phenyl) propane 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- (methacryloxypentethoxy) phenyl) propane (BPE-500, manufactured by Shin-Nakamura Chemical Co., Ltd.) , 2,2-Bis (4- (methacryloxydodecaethoxytetrapropoxy) phenyl) propane (FA-3200MY, manufactured by Hitachi Chemical Co., Ltd.), 2,2-bis (4- (methacryloxypentadecaethoxy) phenyl) propane ( BPE-1300, manufactured by Shin-Nakamura Chemical Co., Ltd.), 2,2-bis (4- (methacryloxydiethoxy) phenyl) propane (BPE-200, manufactured by Shin-Nakamura Chemical Co., Ltd.), and ethoxylated (10) bisphenol A diacrylate (NK ester A-BPE-10, manufactured by Shin-Nakamura Chemical Co., Ltd.) can be mentioned.
　重合性化合物Ｂ１としては、下記一般式（Ｉ）で表される化合物が挙げられる。 
Figure JPOXMLDOC01-appb-C000001
　式中、Ｒ１及びＲ２は、それぞれ独立に、水素原子又はメチル基を表し、ＡはＣ２Ｈ４であり、ＢはＣ３Ｈ６であり、ｎ１及びｎ３はそれぞれ独立に１～３９の整数であり、かつｎ１＋ｎ３は２～４０の整数であり、ｎ２及びｎ４はそれぞれ独立に０～２９の整数であり、かつｎ２＋ｎ４は０～３０の整数であり、－（Ａ－Ｏ）－及び－（Ｂ－Ｏ）－の繰り返し単位の配列は、ランダムであってもブロックであってもよい。ブロックの場合、－（Ａ－Ｏ）－と－（Ｂ－Ｏ）－のいずれがビスフェノール基側であってもよい。 Examples of the polymerizable compound B1 include compounds represented by the following general formula (I).
Figure JPOXMLDOC01-appb-C000001
In the formula, R 1 and R 2 independently represent a hydrogen atom or a methyl group, A is C 2 H 4 , B is C 3 H 6 , and n 1 and n 3 are independently 1 to 39, respectively. , And n1 + n3 are integers of 2 to 40, n2 and n4 are independently integers of 0 to 29, and n2 + n4 are integers of 0 to 30,-(AO)-and. The sequence of repeating units of-(BO)-may be random or block. In the case of a block, either-(AO)-or-(BO)-may be on the bisphenol group side.
　ｎ１＋ｎ２＋ｎ３＋ｎ４は、２～２０であることが好ましく、２～１６であることがより好ましく、４～１２であることがさらに好ましい。また、ｎ２＋ｎ４は、０～１０であることが好ましく、０～４であることがより好ましく、０～２であることがさらに好ましく、０であることが特に好ましい。 N1 + n2 + n3 + n4 is preferably 2 to 20, more preferably 2 to 16, and even more preferably 4 to 12. Further, n2 + n4 is preferably 0 to 10, more preferably 0 to 4, further preferably 0 to 2, and particularly preferably 0.
　感光性樹脂層は、重合性化合物Ｂ１を、１種単独で含有してもよいし、２種以上含有してもよい。 The photosensitive resin layer may contain the polymerizable compound B1 alone or in combination of two or more.
　感光性樹脂層中、重合性化合物Ｂ１の含有量は、解像性がより優れる点から、重合性化合物Ｂの全質量に対して、４０質量％以上であることが好ましく、５０質量％以上であることがより好ましく、５５質量％以上であることがさらに好ましく、６０質量％以上であることが特に好ましい。重合性化合物Ｂ１の含有量の上限値は特に制限されない。重合性化合物Ｂ１の含有量は、剥離性の点から、重合性化合物Ｂの全質量に対して、９９質量％以下が好ましく、９５質量％以下がより好ましく、９０質量％以下がさらに好ましく、８５質量％以下が特に好ましい。 The content of the polymerizable compound B1 in the photosensitive resin layer is preferably 40% by mass or more, preferably 50% by mass or more, based on the total mass of the polymerizable compound B from the viewpoint of more excellent resolution. It is more preferably 55% by mass or more, and particularly preferably 60% by mass or more. The upper limit of the content of the polymerizable compound B1 is not particularly limited. The content of the polymerizable compound B1 is preferably 99% by mass or less, more preferably 95% by mass or less, still more preferably 90% by mass or less, more preferably 85% by mass or less, based on the total mass of the polymerizable compound B from the viewpoint of peelability. Mass% or less is particularly preferable.
－重合性化合物Ｂ２－
　感光性樹脂層は、酸基を有する重合性化合物Ｂ２を含有することが好ましい。酸基を有する重合性化合物Ｂ２によって、現像液に溶解しない成分が分散され、スカム（凝集物）の発生を抑制することができる。 -Polymerizable compound B2-
The photosensitive resin layer preferably contains a polymerizable compound B2 having an acid group. The polymerizable compound B2 having an acid group disperses components that are insoluble in the developing solution, and can suppress the generation of scum (aggregates).
　酸基としては、例えば、カルボキシ基、フェノール性水酸基、スルホン酸基及びリン酸基が挙げられる。 Examples of the acid group include a carboxy group, a phenolic hydroxyl group, a sulfonic acid group and a phosphoric acid group.
　カルボキシ基を含有する重合性化合物としては、アクリル酸、メタクリル酸、フタル酸、フマル酸、マレイン酸、イタコン酸、クロトン酸、シナモン酸等の不飽和脂肪酸、及び、カルボキシ基で変性した多官能アクリレート化合物が挙げられる。カルボキシ基で変性した多官能アクリレート化合物としては、例えば、コハク酸変性ペンタエリスリトールトリアクリレート、コハク酸変性トリメチロールプロパントリアクリレート、コハク酸変性ペンタエリスリトールテトラアクリレート、コハク酸変性ジペンタエリスリトールペンタアクリレート、コハク酸変性ジペンタエリスリトールヘキサアクリレート、アジピン酸変性ペンタエリスリトールトリアクリレート、アジピン酸変性トリメチロールプロパントリアクリレート、アジピン酸変性ペンタエリスリトールテトラアクリレート、アジピン酸変性ジペンタエリスリトールペンタアクリレート、及びアジピン酸変性ジペンタエリスリトールテトラアクリレートが挙げられる。カルボキシ基で変性した多官能アクリレート化合物は、市販品であってもよい。市販品としては、アロニックスＭ－５１０、アロニックスＭ－５２０、アロニックスＴＯ－２３４９及びアロニックスＴＯ－２３５９（以上、東亞合成社製）が挙げられる。 Examples of the polymerizable compound containing a carboxy group include unsaturated fatty acids such as acrylic acid, methacrylic acid, phthalic acid, fumaric acid, maleic acid, itaconic acid, crotonic acid, and cinnamon acid, and polyfunctional acrylates modified with a carboxy group. Examples include compounds. Examples of the polyfunctional acrylate compound modified with a carboxy group include succinic acid-modified pentaerythritol triacrylate, succinic acid-modified trimethylol propantriacrylate, succinic acid-modified pentaerythritol tetraacrylate, succinic acid-modified dipentaerythritol pentaacrylate, and succinic acid. Modified Dipentaerythritol Hexaacrylate, Adipic Acid Modified Pentaerythritol Triacrylate, Adipic Acid Modified Trimethylol Propanetriacrylate, Adipic Acid Modified Pentaerythritol Tetraacrylate, Adipic Acid Modified Dipentaerythritol Pentaacrylate, and Adipic Acid Modified Dipentaerythritol Tetraacrylate Can be mentioned. The polyfunctional acrylate compound modified with a carboxy group may be a commercially available product. Examples of commercially available products include Aronix M-510, Aronix M-520, Aronix TO-2349 and Aronix TO-2359 (all manufactured by Toagosei Co., Ltd.).
　フェノール性水酸基を含有する重合性化合物としては、ｐ－ヒドロキシスチレン、３，４－ジヒドロキシスチレン、３，５－ジヒドロキシスチレン、２，４，６－トリヒドロキシスチレン、（ｐ－ヒドロキシ）ベンジルアクリレート、サリチル酸変性ペンタエリスリトールトリアクリレート、サリチル酸変性トリメチロールプロパントリアクリレート、サリチル酸変性ペンタエリスリトールテトラアクリレート、サリチル酸変性ジペンタエリスリトールペンタアクリレート、及びサリチル酸変性ジペンタエリスリトールヘキサアクリレートが挙げられる。 Examples of the polymerizable compound containing a phenolic hydroxyl group include p-hydroxystyrene, 3,4-dihydroxystyrene, 3,5-dihydroxystyrene, 2,4,6-trihydroxystyrene, (p-hydroxy) benzyl acrylate, and salicylic acid. Examples thereof include modified pentaerythritol triacrylate, salicylic acid-modified trimethylol propantriacrylate, salicylic acid-modified pentaerythritol tetraacrylate, salicylic acid-modified dipentaerythritol pentaacrylate, and salicylic acid-modified dipentaerythritol hexaacrylate.
　スルホン酸基を含有する重合性化合物としては、ビニルスルホン酸、アリルスルホン酸、スチレンスルホン酸、及びブチルスルホン酸変性アクリルアミドが挙げられる。 Examples of the polymerizable compound containing a sulfonic acid group include vinyl sulfonic acid, allyl sulfonic acid, styrene sulfonic acid, and butyl sulfonic acid-modified acrylamide.
　リン酸基を含有する重合性化合物としては、ビニルリン酸、スチレンリン酸、及びブチルリン酸変性アクリルアミドが挙げられる。 Examples of the polymerizable compound containing a phosphoric acid group include vinyl phosphoric acid, styrene phosphoric acid, and butyl phosphate-modified acrylamide.
　中でも、酸基を有する重合性化合物Ｂ２は、現像液に溶解しない成分をより分散させる観点から、カルボキシ基を有する重合性化合物であることが好ましい。 Among them, the polymerizable compound B2 having an acid group is preferably a polymerizable compound having a carboxy group from the viewpoint of further dispersing the components that are insoluble in the developing solution.
　感光性樹脂層は、重合性化合物Ｂ２を、１種単独で含有してもよいし、２種以上含有してもよい。 The photosensitive resin layer may contain the polymerizable compound B2 alone or in combination of two or more.
　感光性樹脂層中、重合性化合物Ｂ２の含有量は、現像液に溶解しない成分をより分散させる観点から、重合性化合物Ｂの全質量に対して、１０質量％～４０質量％であることが好ましく、１５質量％～３５質量％であることがより好ましく、２０質量％～３０質量％であることがさらに好ましい。 The content of the polymerizable compound B2 in the photosensitive resin layer may be 10% by mass to 40% by mass with respect to the total mass of the polymerizable compound B from the viewpoint of further dispersing the components that are insoluble in the developing solution. It is more preferably 15% by mass to 35% by mass, and even more preferably 20% by mass to 30% by mass.
　感光性樹脂層は、重合性化合物Ｂ１以外の重合性化合物Ｂを含有してもよい。また、感光性樹脂層は、重合性化合物Ｂ２以外の重合性化合物Ｂを含有してもよい。
　重合性化合物Ｂ１及び重合性化合物Ｂ２以外の重合性化合物Ｂは、特に制限されず、公知の化合物の中から適宜選択できる。例えば、重合性化合物Ｂ１及び重合性化合物Ｂ２以外の重合性化合物Ｂとしては、一分子中に１つのエチレン性不飽和基を有する化合物（すなわち、単官能エチレン性不飽和化合物）、芳香環を有さない２官能エチレン性不飽和化合物、及び、３官能以上のエチレン性不飽和化合物が挙げられる。 The photosensitive resin layer may contain a polymerizable compound B other than the polymerizable compound B1. Further, the photosensitive resin layer may contain a polymerizable compound B other than the polymerizable compound B2.
The polymerizable compound B other than the polymerizable compound B1 and the polymerizable compound B2 is not particularly limited and may be appropriately selected from known compounds. For example, the polymerizable compound B other than the polymerizable compound B1 and the polymerizable compound B2 has a compound having one ethylenically unsaturated group in one molecule (that is, a monofunctional ethylenically unsaturated compound) and an aromatic ring. Examples thereof include bifunctional ethylenically unsaturated compounds and trifunctional or higher functional ethylenically unsaturated compounds.
　単官能エチレン性不飽和化合物としては、例えば、エチル（メタ）アクリレート、エチルヘキシル（メタ）アクリレート、２－（メタ）アクリロイルオキシエチルサクシネート、ポリエチレングリコールモノ（メタ）アクリレート、ポリプロピレングリコールモノ（メタ）アクリレート、及び、フェノキシエチル（メタ）アクリレートが挙げられる。 Examples of the monofunctional ethylenically unsaturated compound include ethyl (meth) acrylate, ethylhexyl (meth) acrylate, 2- (meth) acryloyloxyethyl succinate, polyethylene glycol mono (meth) acrylate, and polypropylene glycol mono (meth) acrylate. , And phenoxyethyl (meth) acrylate.
　芳香環を有さない２官能エチレン性不飽和化合物としては、例えば、アルキレングリコールジ（メタ）アクリレート、ポリアルキレングリコールジ（メタ）アクリレート、ウレタンジ（メタ）アクリレート、及び、トリメチロールプロパンジアクリレートが挙げられる。 Examples of the bifunctional ethylenically unsaturated compound having no aromatic ring include alkylene glycol di (meth) acrylate, polyalkylene glycol di (meth) acrylate, urethane di (meth) acrylate, and trimethylolpropane diacrylate. Be done.
　アルキレングリコールジ（メタ）アクリレートとしては、例えば、トリシクロデカンジメタノールジアクリレート（Ａ－ＤＣＰ、新中村化学工業社製）、トリシクロデカンジメタノールジメタクリレート（ＤＣＰ、新中村化学工業社製）、１，９－ノナンジオールジアクリレート（Ａ－ＮＯＤ－Ｎ、新中村化学工業社製）、１，６－ヘキサンジオールジアクリレート（Ａ－ＨＤ－Ｎ、新中村化学工業社製）、エチレングリコールジメタクリレート、１，１０－デカンジオールジアクリレート、及び、ネオペンチルグリコールジ（メタ）アクリレートが挙げられる。 Examples of the alkylene glycol di (meth) acrylate include tricyclodecanedimethanol diacrylate (A-DCP, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), tricyclodecanedimethanol dimethacrylate (DCP, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), and the like. 1,9-Nonandiol diacrylate (A-NOD-N, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), 1,6-Hexanediol diacrylate (A-HD-N, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), ethylene glycol dimethacrylate , 1,10-decanediol diacrylate, and neopentyl glycol di (meth) acrylate.
　ポリアルキレングリコールジ（メタ）アクリレートとしては、例えば、ポリエチレングリコールジ（メタ）アクリレート、ジプロピレングリコールジアクリレート、トリプロピレングリコールジアクリレート、及び、ポリプロピレングリコールジ（メタ）アクリレートが挙げられる。 Examples of the polyalkylene glycol di (meth) acrylate include polyethylene glycol di (meth) acrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, and polypropylene glycol di (meth) acrylate.
　ウレタンジ（メタ）アクリレートとしては、例えば、プロピレンオキサイド変性ウレタンジ（メタ）アクリレート、並びに、エチレンオキサイド及びプロピレンオキサイド変性ウレタンジ（メタ）アクリレートが挙げられる。市販品としては、例えば、８ＵＸ－０１５Ａ（大成ファインケミカル社製）、ＵＡ－３２Ｐ（新中村化学工業社製）、及び、ＵＡ－１１００Ｈ（新中村化学工業社製）が挙げられる。 Examples of the urethane di (meth) acrylate include propylene oxide-modified urethane di (meth) acrylate, and ethylene oxide and propylene oxide-modified urethane di (meth) acrylate. Examples of commercially available products include 8UX-015A (manufactured by Taisei Fine Chemical Co., Ltd.), UA-32P (manufactured by Shin-Nakamura Chemical Co., Ltd.), and UA-1100H (manufactured by Shin-Nakamura Chemical Co., Ltd.).
　３官能以上のエチレン性不飽和化合物としては、例えば、ジペンタエリスリトール（トリ／テトラ／ペンタ／ヘキサ）（メタ）アクリレート、ペンタエリスリトール（トリ／テトラ）（メタ）アクリレート、トリメチロールプロパントリ（メタ）アクリレート、ジトリメチロールプロパンテトラ（メタ）アクリレート、トリメチロールエタントリ（メタ）
アクリレート、イソシアヌル酸トリ（メタ）アクリレート、グリセリントリ（メタ）アクリレート、並びに、これらのアルキレンオキサイド変性物が挙げられる。 Examples of the trifunctional or higher functional ethylenically unsaturated compound include dipentaerythritol (tri / tetra / penta / hexa) (meth) acrylate, pentaerythritol (tri / tetra) (meth) acrylate, and trimethylolpropane tri (meth). Acrylate, ditrimethylolpropane tetra (meth) acrylate, trimethylolethanetri (meth)
Examples thereof include acrylates, tri (meth) acrylates of isocyanuric acid, glycerin tri (meth) acrylates, and modified alkylene oxides thereof.
　ここで、「（トリ／テトラ／ペンタ／ヘキサ）（メタ）アクリレート」は、トリ（メタ）アクリレート、テトラ（メタ）アクリレート、ペンタ（メタ）アクリレート、及びヘキサ（メタ）アクリレートを包含する概念であり、「（トリ／テトラ）（メタ）アクリレート」は、トリ（メタ）アクリレート及びテトラ（メタ）アクリレートを包含する概念である。 Here, "(tri / tetra / penta / hexa) (meth) acrylate" is a concept including tri (meth) acrylate, tetra (meth) acrylate, penta (meth) acrylate, and hexa (meth) acrylate. , "(Tri / tetra) (meth) acrylate" is a concept that includes tri (meth) acrylate and tetra (meth) acrylate.
　感光性樹脂層は、重合性化合物Ｂ１及び３官能以上のエチレン性不飽和化合物を含むことが好ましく、重合性化合物Ｂ１及び２種以上の３官能以上のエチレン性不飽和化合物を含むことがより好ましい。この場合、重合性化合物Ｂ１と３官能以上のエチレン性不飽和化合物との質量比（重合性化合物Ｂ１の全質量：３官能以上のエチレン性不飽和化合物の全質量）は１：１～５：１が好ましく、１.２：１～４：１がより好ましく、１.５：１～３：１がさらに好ましい。 The photosensitive resin layer preferably contains a polymerizable compound B1 and a trifunctional or higher ethylenically unsaturated compound, and more preferably contains a polymerizable compound B1 and two or more trifunctional or higher ethylenically unsaturated compounds. .. In this case, the mass ratio of the polymerizable compound B1 to the trifunctional or higher ethylenically unsaturated compound (total mass of the polymerizable compound B1: total mass of the trifunctional or higher ethylenically unsaturated compound) is 1: 1 to 5 :. 1 is preferred, 1.2: 1 to 4: 1 is more preferred, and 1.5: 1 to 3: 1 is even more preferred.
　３官能以上のエチレン性不飽和化合物のアルキレンオキサイド変性物としては、例えば、カプロラクトン変性（メタ）アクリレート化合物（ＫＡＹＡＲＡＤ（登録商標）ＤＰＣＡ－２０、日本化薬社製；Ａ－９３００－１ＣＬ、新中村化学工業社製）、アルキレンオキサイド変性（メタ）アクリレート化合物（ＫＡＹＡＲＡＤ　ＲＰ－１０４０、日本化薬社製；ＡＴＭ－３５Ｅ及びＡ－９３００、新中村化学工業社製；ＥＢＥＣＲＹＬ（登録商標）１３５、ダイセル・オルネクス社製）、エトキシ化グリセリントリアクリレート（Ａ－ＧＬＹ－９Ｅ、新中村化学工業社製）、アロニックス（登録商標）ＴＯ－２３４９（東亞合成社製）、アロニックスＭ－５２０（東亞合成社製）、及び、アロニックスＭ－５１０（東亞合成社製）が挙げられる。 Examples of the alkylene oxide-modified product of the trifunctional or higher functional ethylenically unsaturated compound include caprolactone-modified (meth) acrylate compound (KAYARAD (registered trademark) DPCA-20, manufactured by Nippon Kayaku Co., Ltd .; A-9300-1CL, Shin-Nakamura). Chemical Industry Co., Ltd.), alkylene oxide-modified (meth) acrylate compound (KAYARAD RP-1040, Nippon Kayaku Co., Ltd .; ATM-35E and A-9300, Shin-Nakamura Chemical Industry Co., Ltd .; EBECRYL (registered trademark) 135, Daicel Ornex), Glycerin triacrylate ethoxylated (A-GLY-9E, manufactured by Shin-Nakamura Chemical Co., Ltd.), Aronix (registered trademark) TO-2349 (manufactured by Toagosei), Aronix M-520 (manufactured by Toagosei) , And Aronix M-510 (manufactured by Toagosei Co., Ltd.).
　　感光性樹脂層は、重合性化合物Ｂを、１種単独で含有してもよいし、２種以上含有してもよい。 The photosensitive resin layer may contain the polymerizable compound B alone or in combination of two or more.
　重合性化合物Ｂの含有量は、感光性樹脂層の全質量に対して、１０質量％～７０質量％が好ましく、２０質量％～６０質量％がより好ましく、２０質量％～５０質量％がさらに好ましい。 The content of the polymerizable compound B is preferably 10% by mass to 70% by mass, more preferably 20% by mass to 60% by mass, and further preferably 20% by mass to 50% by mass with respect to the total mass of the photosensitive resin layer. preferable.
　重合性化合物Ｂの重量平均分子量（Ｍｗ）は、２００～３，０００が好ましく、２８０～２，２００がより好ましく、３００～２，２００がさらに好ましい。 The weight average molecular weight (Mw) of the polymerizable compound B is preferably 200 to 3,000, more preferably 280 to 2,200, and even more preferably 300 to 2,200.
　重合体Ａ（好ましくは、アルカリ可溶性樹脂）の含有量に対する重合性化合物Ｂの含有量の比率は、質量基準で０．８５以下であることが好ましく、０．５～０．８５であることがより好ましく、０．６～０．８５であることがさらに好ましく、０．７５～０．８５であることが特に好ましい。上記比率であると、現像液に溶解しない重合性化合物Ｂが油滴となり、アルカリ可溶性樹脂が分散剤として作用して油滴同士が合一するのを抑制することができ、スカム（凝集物）の発生を抑制することができる。 The ratio of the content of the polymerizable compound B to the content of the polymer A (preferably an alkali-soluble resin) is preferably 0.85 or less, preferably 0.5 to 0.85, on a mass basis. More preferably, it is more preferably 0.6 to 0.85, and particularly preferably 0.75 to 0.85. At the above ratio, the polymerizable compound B that does not dissolve in the developing solution becomes oil droplets, and the alkali-soluble resin acts as a dispersant to prevent the oil droplets from coalescing with each other, resulting in scum (aggregate). Can be suppressed.
（任意成分）
　感光性樹脂層は、重合体Ａ及び重合性化合物Ｂ以外の成分を含有してもよい。 (Arbitrary ingredient)
The photosensitive resin layer may contain components other than the polymer A and the polymerizable compound B.
－光重合開始剤－
　感光性樹脂層は、光重合開始剤を含有することが好ましい。 -Photopolymerization initiator-
The photosensitive resin layer preferably contains a photopolymerization initiator.
　光重合開始剤は、紫外線、可視光線、Ｘ線等の活性光線によって、重合性化合物の重合を開始させる作用を有する化合物である。光重合開始剤としては、特に制限されず、公知の光重合開始剤を用いることができる。 The photopolymerization initiator is a compound having an action of initiating the polymerization of a polymerizable compound by active rays such as ultraviolet rays, visible rays, and X-rays. The photopolymerization initiator is not particularly limited, and a known photopolymerization initiator can be used.
　光重合開始剤としては、例えば、光ラジカル重合開始剤及び光カチオン重合開始剤が挙げられる。中でも、光重合開始剤は、光ラジカル重合開始剤であることが好ましい。 Examples of the photopolymerization initiator include a photoradical polymerization initiator and a photocationic polymerization initiator. Above all, the photopolymerization initiator is preferably a photoradical polymerization initiator.
　光ラジカル重合開始剤としては、例えば、オキシムエステル骨格を有する光重合開始剤、α－アミノアルキルフェノン骨格を有する光重合開始剤、α－ヒドロキシアルキルフェノン骨格を有する光重合開始剤、アシルフォスフィンオキサイド骨格を有する光重合開始剤、及び、Ｎ－フェニルグリシン骨格を有する光重合開始剤が挙げられる。 Examples of the photoradical polymerization initiator include a photopolymerization initiator having an oxime ester skeleton, a photopolymerization initiator having an α-aminoalkylphenone skeleton, a photopolymerization initiator having an α-hydroxyalkylphenone skeleton, and an acylphosphine oxide. Examples thereof include a photopolymerization initiator having a skeleton and a photopolymerization initiator having an N-phenylglycine skeleton.
　また、感光性樹脂層は、感光性、露光部及び非露光部の視認性、並びに、解像性の観点から、光ラジカル重合開始剤として、２，４，５－トリアリールイミダゾール二量体及びその誘導体からなる群より選択される少なくとも１種を含むことが好ましい。なお、２，４，５－トリアリールイミダゾール二量体及びその誘導体における２つの２，４，５－トリアリールイミダゾール骨格は、同一であっても異なっていてもよい。 Further, the photosensitive resin layer contains 2,4,5-triarylimidazole dimer and 2,4,5-triarylimidazole dimer as a photoradical polymerization initiator from the viewpoints of photosensitivity, visibility of exposed and non-exposed areas, and resolution. It is preferable to contain at least one selected from the group consisting of the derivatives. The two 2,4,5-triarylimidazole skeletons in the 2,4,5-triarylimidazole dimer and its derivatives may be the same or different.
　２，４，５－トリアリールイミダゾール二量体の誘導体としては、例えば、２－（ｏ－クロロフェニル）－４，５－ジフェニルイミダゾール二量体、２－（ｏ－クロロフェニル）－４，５－ジ（メトキシフェニル）イミダゾール二量体、２－（ｏ－フルオロフェニル）－４，５－ジフェニルイミダゾール二量体、２－（ｏ－メトキシフェニル）－４，５－ジフェニルイミダゾール二量体、及び、２－（ｐ－メトキシフェニル）－４，５－ジフェニルイミダゾール二量体が挙げられる。 Derivatives of the 2,4,5-triarylimidazole dimer include, for example, 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer, 2- (o-chlorophenyl) -4,5-di. (Methoxyphenyl) imidazole dimer, 2- (o-fluorophenyl) -4,5-diphenylimidazole dimer, 2- (o-methoxyphenyl) -4,5-diphenylimidazole dimer, and 2 -(P-methoxyphenyl) -4,5-diphenylimidazole dimer can be mentioned.
　光ラジカル重合開始剤は、特開２０１１－９５７１６号公報の段落００３１～００４２、及び、特開２０１５－１４７８３号公報の段落００６４～００８１に記載の重合開始剤であってもよい。 The photoradical polymerization initiator may be the polymerization initiator described in paragraphs 0031 to 0042 of JP2011-95716A and paragraphs 0064 to 0081 of JP2015-14783A.
　光ラジカル重合開始剤としては、例えば、ジメチルアミノ安息香酸エチル（ＤＢＥ、ＣＡＳ　Ｎｏ．１０２８７－５３－３）、ベンゾインメチルエーテル、アニシル（ｐ，ｐ’－ジメトキシベンジル）、及びベンゾフェノンが挙げられる。 Examples of the photoradical polymerization initiator include ethyl dimethylaminobenzoate (DBE, CAS No. 10287-53-3), benzoin methyl ether, anisyl (p, p'-dimethoxybenzyl), and benzophenone.
　光ラジカル重合開始剤の市販品としては、例えば、２，４－ビス（トリクロロメチル）－６－［２－（４－メチルフェニル）エテニル］－１，３，５－トリアジン（商品名：ＴＡＺ－１１０、みどり化学社製）、（商品名：ＴＡＺ－１１１、みどり化学社製）、２，２’－ビス（２－クロロフェニル）－４，４’，５，５’－テトラフェニル－１，２’－ビイミダゾール（東京化成工業社製）、１－［４－（フェニルチオ）フェニル］－１，２－オクタンジオン－２－（Ｏ－ベンゾイルオキシム）（商品名：Ｉｒｇａｃｕｒｅ（登録商標）ＯＸＥ－０１、ＢＡＳＦジャパン社製）、１－［９－エチル－６－（２－メチルベンゾイル）－９Ｈ－カルバゾール－３－イル］エタノン－１－（Ｏ－アセチルオキシム）（商品名：Ｉｒｇａｃｕｒｅ　ＯＸＥ－０２、ＢＡＳＦジャパン社製）、Ｉｒｇａｃｕｒｅ　ＯＸＥ－０３（ＢＡＳＦジャパン社製）、Ｉｒｇａｃｕｒｅ　ＯＸＥ－０４（ＢＡＳＦジャパン社製）、２－（ジメチルアミノ）－２－［（４－メチルフェニル）メチル］－１－［４－（４－モルフォリニル）フェニル］－１－ブタノン（商品名：Ｏｍｎｉｒａｄ　３７９ＥＧ、ＩＧＭ　Ｒｅｓｉｎｓ　Ｂ．Ｖ．社製）、２－メチル－１－（４－メチルチオフェニル）－２－モルフォリノプロパン－１－オン（商品名：Ｏｍｎｉｒａｄ　９０７、ＩＧＭ　Ｒｅｓｉｎｓ　Ｂ．Ｖ．製）、２－ヒドロキシ－１－｛４－［４－（２－ヒドロキシ－２－メチルプロピオニル）ベンジル］フェニル｝－２－メチルプロパン－１－オン（商品名：Ｏｍｎｉｒａｄ　１２７、ＩＧＭ　Ｒｅｓｉｎｓ　Ｂ．Ｖ．製）、２－ベンジル－２－ジメチルアミノ－１－（４－モルフォリノフェニル）ブタノン－１（商品名：Ｏｍｎｉｒａｄ　３６９、ＩＧＭ　Ｒｅｓｉｎｓ　Ｂ．Ｖ．社製）、２－ヒドロキシ－２－メチル－１－フェニルプロパン－１－オン（商品名：Ｏｍｎｉｒａｄ　１１７３、ＩＧＭ　Ｒｅｓｉｎｓ　Ｂ．Ｖ．製）、１－ヒドロキシシクロヘキシルフェニルケトン（商品名：Ｏｍｎｉｒａｄ　１８４、ＩＧＭ　Ｒｅｓｉｎｓ　Ｂ．Ｖ．社製）、２，２－ジメトキシ－１，２－ジフェニルエタン－１－オン（商品名：Ｏｍｎｉｒａｄ　６５１、ＩＧＭ　Ｒｅｓｉｎｓ　Ｂ．Ｖ．社製）、２，４，６－トリメチルベンゾイル－ジフェニルフォスフィンオキサイド（商品名：Ｏｍｎｉｒａｄ　ＴＰＯ　Ｈ、ＩＧＭ　Ｒｅｓｉｎｓ　Ｂ．Ｖ．製）、ビス（２，４，６－トリメチルベンゾイル）フェニルフォスフィンオキサイド（商品名：Ｏｍｎｉｒａｄ　８１９、ＩＧＭ　Ｒｅｓｉｎｓ　Ｂ．Ｖ．製）、オキシムエステル系の光重合開始剤（商品名：Ｌｕｎａｒ　６、ＤＫＳＨジャパン（株）製）、２，２’－ビス（２－クロロフェニル）－４，４’，５，５’－テトラフェニルビスイミダゾール（２－（２－クロロフェニル）－４，５－ジフェニルイミダゾール二量体）（商品名：Ｂ－ＣＩＭ、Ｈａｍｐｆｏｒｄ社製）、及び、２－（ｏ－クロロフェニル）－４，５－ジフェニルイミダゾール二量体（商品名：ＢＣＴＢ、東京化成工業社製）が挙げられる。 Examples of commercially available photoradical polymerization initiators include 2,4-bis (trichloromethyl) -6- [2- (4-methylphenyl) ethenyl] -1,3,5-triazine (trade name: TAZ-). 110, manufactured by Midori Kagaku Co., Ltd.), (trade name: TAZ-111, manufactured by Midori Kagaku Co., Ltd.), 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetraphenyl-1,2 '-Bimidazole (manufactured by Tokyo Kasei Kogyo Co., Ltd.), 1- [4- (Phenylthio) phenyl] -1,2-octanedione-2- (O-benzoyloxime) (trade name: Irgacure (registered trademark) OXE-01 , BASF Japan, Inc.), 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-3-yl] etanone-1- (O-acetyloxime) (trade name: Irgacure OXE-02, BASF Japan), Irgacure OXE-03 (BASF Japan), Irgacure OXE-04 (BASF Japan), 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1-[ 4- (4-morpholinyl) phenyl] -1-butanone (trade name: Omnirad 379EG, manufactured by IGM Resins VV), 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane-1 -On (trade name: Omnirad 907, manufactured by IGM Resins BV), 2-hydroxy-1- {4- [4- (2-hydroxy-2-methylpropionyl) benzyl] phenyl} -2-methylpropane- 1-ON (trade name: Omnirad 127, manufactured by IGM Resins BV), 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone-1 (trade name: Omnirad 369, IGM Resins B) .V.), 2-Hydroxy-2-methyl-1-phenylpropan-1-one (trade name: Omnirad 1173, IGM Resins B.V.), 1-hydroxycyclohexylphenylketone (trade name: Omnirad) 184, IGM Resins B.V.), 2,2-dimethoxy-1,2-diphenylethane-1-one (trade name: Omnirad 651, IGM Resins B.V.), 2,4,6 -Trimethylbenzoyl-diphenylphosphine oxide (trade name: Omnirad TPO H, IGM Resins) B. V. , Bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide (trade name: Omnirad 819, IGM Resins BV), oxime ester-based photopolymerization initiator (trade name: Lunar 6, DKSH) Made by Japan Co., Ltd., 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetraphenylbisimidazole (2- (2-chlorophenyl) -4,5-diphenylimidazole dihydrate Body) (trade name: B-CIM, manufactured by Hampford) and 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer (trade name: BCTB, manufactured by Tokyo Kasei Kogyo Co., Ltd.).
　光カチオン重合開始剤（光酸発生剤）は、活性光線を受けて酸を発生する化合物である。光カチオン重合開始剤は、特に制限されないが、波長３００ｎｍ以上、好ましくは波長３００ｎｍ～４５０ｎｍの活性光線に感応し、酸を発生する化合物であることが好ましい。また、波長３００ｎｍ以上の活性光線に直接感応しない化合物であっても、増感剤と併用することによって波長３００ｎｍ以上の活性光線に感応し、酸を発生する化合物であれば、増感剤と組み合わせて好ましく用いることができる。 A photocationic polymerization initiator (photoacid generator) is a compound that generates an acid by receiving active light. The photocationic polymerization initiator is not particularly limited, but is preferably a compound that is sensitive to active light having a wavelength of 300 nm or more, preferably a wavelength of 300 nm to 450 nm, and generates an acid. Further, even if the compound is not directly sensitive to the active light having a wavelength of 300 nm or more, if it is a compound that is sensitive to the active light having a wavelength of 300 nm or more and generates an acid when used in combination with a sensitizer, it is combined with the sensitizer. Can be preferably used.
　光カチオン重合開始剤は、ｐＫａが４以下の酸を発生する光カチオン重合開始剤が好ましく、ｐＫａが３以下の酸を発生する光カチオン重合開始剤がより好ましく、ｐＫａが２以下の酸を発生する光カチオン重合開始剤が特に好ましい。ｐＫａの下限値は特に制限されず、例えば、－１０．０が好ましい。 As the photocationic polymerization initiator, a photocationic polymerization initiator that generates an acid having a pKa of 4 or less is preferable, a photocationic polymerization initiator that generates an acid having a pKa of 3 or less is more preferable, and an acid having a pKa of 2 or less is generated. Photocationic polymerization initiators are particularly preferred. The lower limit of pKa is not particularly limited, and for example, -10.0 is preferable.
　光カチオン重合開始剤としては、イオン性光カチオン重合開始剤及び非イオン性光カチオン重合開始剤が挙げられる。 Examples of the photocationic polymerization initiator include an ionic photocationic polymerization initiator and a nonionic photocationic polymerization initiator.
　イオン性光カチオン重合開始剤として、例えば、ジアリールヨードニウム塩、トリアリールスルホニウム塩等のオニウム塩化合物、及び、第４級アンモニウム塩が挙げられる。 Examples of the ionic photocationic polymerization initiator include onium salt compounds such as diaryliodonium salt and triarylsulfonium salt, and quaternary ammonium salt.
　イオン性光カチオン重合開始剤は、特開２０１４－８５６４３号公報の段落０１１４～０１３３に記載のイオン性光カチオン重合開始剤であってもよい。 The ionic photocationic polymerization initiator may be the ionic photocationic polymerization initiator described in paragraphs 0114 to 0133 of JP-A-2014-85643.
　非イオン性光カチオン重合開始剤としては、例えば、トリクロロメチル－ｓ－トリアジン化合物、ジアゾメタン化合物、イミドスルホネート化合物、及び、オキシムスルホネート化合物が挙げられる。トリクロロメチル－ｓ－トリアジン化合物、ジアゾメタン化合物及びイミドスルホネート化合物は、特開２０１１－２２１４９４号公報の段落００８３～００８８に記載の化合物であってもよい。また、オキシムスルホネート化合物は、国際公開第２０１８／１７９６４０号の段落００８４～００８８に記載の化合物であってもよい。 Examples of the nonionic photocationic polymerization initiator include a trichloromethyl-s-triazine compound, a diazomethane compound, an imide sulfonate compound, and an oxime sulfonate compound. The trichloromethyl-s-triazine compound, the diazomethane compound and the imide sulfonate compound may be the compounds described in paragraphs 0083 to 0088 of JP-A-2011-22149. Further, the oxime sulfonate compound may be a compound described in paragraphs 0084 to 0088 of International Publication No. 2018/179640.
　感光性樹脂層は、光重合開始剤を、１種単独で含有してもよいし、２種以上を含有してもよい。 The photosensitive resin layer may contain one type of photopolymerization initiator alone or two or more types.
　光重合開始剤の含有量は、特に制限されないが、感光性樹脂層の全質量に対して、０．１質量％以上が好ましく、０．５質量％以上がより好ましく、１．０質量％以上がさらに好ましい。光重合開始剤の含有量の上限値は特に制限されない。光重合開始剤の含有量は、感光性樹脂層の全質量に対して、１０質量％以下が好ましく、５質量％以下がより好ましい。 The content of the photopolymerization initiator is not particularly limited, but is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and 1.0% by mass or more, based on the total mass of the photosensitive resin layer. Is even more preferable. The upper limit of the content of the photopolymerization initiator is not particularly limited. The content of the photopolymerization initiator is preferably 10% by mass or less, more preferably 5% by mass or less, based on the total mass of the photosensitive resin layer.
－色素－
　感光性樹脂層は、露光部及び非露光部の視認性、現像後のパターン視認性、並びに、解像性の観点から、発色時の波長範囲４００ｎｍ～７８０ｎｍにおける最大吸収波長が４５０ｎｍ以上であり、かつ、酸、塩基、又はラジカルにより最大吸収波長が変化する色素（以下、単に「色素Ｎ」ともいう。）を含有することが好ましい。色素Ｎを含有すると、詳細なメカニズムは不明であるが、隣接する層（例えば仮支持体及び中間層）との密着性が向上し、解像性により優れる。 -Dye-
The photosensitive resin layer has a maximum absorption wavelength of 450 nm or more in the wavelength range of 400 nm to 780 nm at the time of color development from the viewpoints of visibility of exposed and unexposed areas, pattern visibility after development, and resolution. Moreover, it is preferable to contain a dye whose maximum absorption wavelength changes depending on an acid, a base, or a radical (hereinafter, also simply referred to as "dye N"). When the dye N is contained, the detailed mechanism is unknown, but the adhesion to the adjacent layer (for example, the temporary support and the intermediate layer) is improved, and the resolution is more excellent.
　本明細書において、色素が「酸、塩基又はラジカルにより極大吸収波長が変化する」とは、発色状態にある色素が酸、塩基又はラジカルにより消色する態様、消色状態にある色素が酸、塩基又はラジカルにより発色する態様、及び、発色状態にある色素が他の色相の発色状態に変化する態様のいずれの態様を意味してもよい。 In the present specification, the term "the maximum absorption wavelength is changed by an acid, a base or a radical" means that the dye in a color-developing state is decolorized by an acid, a base or a radical, and the dye in a decolorized state is an acid. It may mean any aspect of a mode in which a color is developed by a base or a radical, or a mode in which a dye in a color-developing state changes to a color-developing state of another hue.
　具体的には、色素Ｎは、露光により消色状態から変化して発色する化合物であってもよく、露光により発色状態から変化して消色する化合物であってもよい。この場合、露光により酸、塩基又はラジカルが感光性樹脂層内で発生することにより、発色又は消色の状態が変化する色素であってもよく、酸、塩基又はラジカルにより感光性樹脂層内の状態（例えばｐＨ）が変化することで発色又は消色の状態が変化する色素であってもよい。また、色素Ｎは、露光を受けず、酸、塩基又はラジカルを刺激として直接受けて発色又は消色の状態が変化する色素でもよい。 Specifically, the dye N may be a compound that changes from the decolorized state by exposure to develop a color, or may be a compound that changes from the decolorized state by exposure to decolorize. In this case, the dye may change its color development or decolorization state by generating an acid, a base or a radical in the photosensitive resin layer by exposure, and may be a dye in the photosensitive resin layer by the acid, the base or the radical. It may be a dye whose color development or decolorization state changes as the state (for example, pH) changes. Further, the dye N may be a dye that is not exposed and directly receives an acid, a base or a radical as a stimulus to change the state of color development or decolorization.
　中でも、露光部及び非露光部の視認性、並びに解像性の観点から、色素Ｎは、酸又はラジカルにより最大吸収波長が変化する色素が好ましく、ラジカルにより最大吸収波長が変化する色素がより好ましい。 Among them, from the viewpoint of visibility and resolution of the exposed and non-exposed areas, the dye N is preferably a dye whose maximum absorption wavelength is changed by an acid or a radical, and more preferably a dye whose maximum absorption wavelength is changed by a radical. ..
　感光性樹脂層は、露光部及び非露光部の視認性、並びに解像性の観点から、色素Ｎとしてラジカルにより最大吸収波長が変化する色素、及び、光ラジカル重合開始剤の両者を含有することが好ましい。 The photosensitive resin layer contains both a dye whose maximum absorption wavelength is changed by radicals as dye N and a photoradical polymerization initiator from the viewpoints of visibility and resolution of exposed and non-exposed areas. Is preferable.
　また、露光部及び非露光部の視認性の観点から、色素Ｎは、酸、塩基、又はラジカルにより発色する色素であることが好ましい。 Further, from the viewpoint of visibility of the exposed portion and the non-exposed portion, the dye N is preferably a dye that develops color by an acid, a base, or a radical.
　色素Ｎの発色機構の例としては、感光性樹脂層に光ラジカル重合開始剤、光カチオン重合開始剤（光酸発生剤）又は光塩基発生剤を添加して、露光後に光ラジカル重合開始剤、光カチオン重合開始剤又は光塩基発生剤から発生するラジカル、酸又は塩基によって発色する態様が挙げられる。 As an example of the color development mechanism of dye N, a photoradical polymerization initiator, a photocationic polymerization initiator (photoacid generator) or a photobase generator is added to the photosensitive resin layer, and a photoradical polymerization initiator is added after exposure. Examples thereof include an embodiment in which color is developed by radicals, acids or bases generated from a photocationic polymerization initiator or a photobase generator.
　色素Ｎは、露光部及び非露光部の視認性の観点から、発色時の波長範囲４００ｎｍ～７８０ｎｍにおける極大吸収波長が、５５０ｎｍ以上であることが好ましく、５５０～７００ｎｍであることがより好ましく、５５０ｎｍ～６５０ｎｍであることがさらに好ましい。 From the viewpoint of visibility of the exposed and non-exposed areas, the dye N preferably has a maximum absorption wavelength of 550 nm or more in the wavelength range of 400 nm to 780 nm at the time of color development, more preferably 550 to 700 nm. It is more preferably about 650 nm.
　また、色素Ｎは、発色時の波長範囲４００ｎｍ～７８０ｎｍにおける極大吸収波長を１つのみ有していてもよく、２つ以上有していてもよい。色素Ｎが発色時の波長範囲４００～７８０ｎｍにおける極大吸収波長を２つ以上有する場合は、２つ以上の極大吸収波長のうち吸光度が最も高い極大吸収波長が４５０ｎｍ以上であればよい。 Further, the dye N may have only one maximum absorption wavelength in the wavelength range of 400 nm to 780 nm at the time of color development, or may have two or more. When the dye N has two or more maximum absorption wavelengths in the wavelength range of 400 to 780 nm at the time of color development, the maximum absorption wavelength having the highest absorbance among the two or more maximum absorption wavelengths may be 450 nm or more.
　色素Ｎの極大吸収波長は、大気雰囲気下で、分光光度計（ＵＶ３１００、島津製作所製）を用いて、４００ｎｍ～７８０ｎｍの範囲で色素Ｎを含有する溶液（液温２５℃）の透過スペクトルを測定し、光の強度が極小となる波長（すなわち、極大吸収波長）を検出することにより得られる。 For the maximum absorption wavelength of dye N, the transmission spectrum of a solution containing dye N (liquid temperature 25 ° C.) is measured in the range of 400 nm to 780 nm using a spectrophotometer (UV3100, manufactured by Shimadzu Corporation) in an atmospheric atmosphere. However, it is obtained by detecting the wavelength at which the intensity of light is minimized (that is, the maximum absorption wavelength).
　露光により発色又は消色する色素としては、例えば、ロイコ化合物が挙げられる。露光により消色する色素としては、例えば、ロイコ化合物、ジアリールメタン系色素、オキザジン系色素、キサンテン系色素、イミノナフトキノン系色素、アゾメチン系色素及びアントラキノン系色素が挙げられる。中でも、色素Ｎは、露光部及び非露光部の視認性の観点から、ロイコ化合物であることが好ましい。 Examples of the dye that develops or decolorizes by exposure include a leuco compound. Examples of dyes that are decolorized by exposure include leuco compounds, diarylmethane dyes, oxazine dyes, xanthene dyes, iminonaphthoquinone dyes, azomethine dyes and anthraquinone dyes. Above all, the dye N is preferably a leuco compound from the viewpoint of visibility of the exposed portion and the non-exposed portion.
　ロイコ化合物としては、例えば、トリアリールメタン骨格を有するロイコ化合物（トリアリールメタン系色素）、スピロピラン骨格を有するロイコ化合物（スピロピラン系色素）、フルオラン骨格を有するロイコ化合物（フルオラン系色素）、ジアリールメタン骨格を有するロイコ化合物（ジアリールメタン系色素）、ローダミンラクタム骨格を有するロイコ化合物（ローダミンラクタム系色素）、インドリルフタリド骨格を有するロイコ化合物（インドリルフタリド系色素）、及び、ロイコオーラミン骨格を有するロイコ化合物（ロイコオーラミン系色素）が挙げられる。 Examples of the leuco compound include a leuco compound having a triarylmethane skeleton (triarylmethane dye), a leuco compound having a spiropylan skeleton (spiropylan dye), a leuco compound having a fluorane skeleton (fluorane dye), and a diarylmethane skeleton. Leuco compound (diarylmethane dye), rhodamine lactam skeleton (rhodamine lactam dye), leuco compound having indrill phthalide skeleton (indrill phthalide dye), and leuco auramine skeleton Examples thereof include leuco compounds having leuco compounds (leuco auramine dyes).
　中でも、ロイコ化合物は、トリアリールメタン系色素又はフルオラン系色素であることが好ましく、トリフェニルメタン骨格を有するロイコ化合物（トリフェニルメタン系色素）又はフルオラン系色素がより好ましい。 Among them, the leuco compound is preferably a triarylmethane dye or a fluorane dye, and a leuco compound having a triphenylmethane skeleton (triphenylmethane dye) or a fluorane dye is more preferable.
　ロイコ化合物は、露光部及び非露光部の視認性の観点から、ラクトン環、スルチン環又はスルトン環を有することが好ましい。ロイコ化合物が有するラクトン環、スルチン環又はスルトン環は、光ラジカル重合開始剤から発生するラジカル又は光カチオン重合開始剤から発生する酸と反応することにより、閉環状態から開環状態へ変化して発色するか、又は、開環状態から閉環状態へ変化して消色する。ロイコ化合物は、ラクトン環、スルチン環又はスルトン環を有し、ラジカル又は酸により開環して発色する化合物が好ましく、ラクトン環を有し、ラジカル又は酸により開環して発色する化合物がより好ましい。 The leuco compound preferably has a lactone ring, a surujin ring, or a sultone ring from the viewpoint of visibility of the exposed portion and the non-exposed portion. The lactone ring, sultin ring, or sulton ring contained in the leuco compound reacts with a radical generated from the photoradical polymerization initiator or an acid generated from the photocationic polymerization initiator, and changes from a ring-closed state to a ring-opened state to develop color. Or, the color is decolorized by changing from the ring-opened state to the ring-closed state. The leuco compound is preferably a compound having a lactone ring, a sultone ring or a sultone ring and developing a color by opening the ring with a radical or an acid, and more preferably a compound having a lactone ring and developing a color by opening the ring with a radical or an acid. ..
　色素Ｎとしては、例えば、以下の染料及びロイコ化合物が挙げられる。
　染料としては、ブリリアントグリーン、エチルバイオレット、メチルグリーン、クリスタルバイオレット、ベイシックフクシン、メチルバイオレット２Ｂ、キナルジンレッド、ローズベンガル、メタニルイエロー、チモールスルホフタレイン、キシレノールブルー、メチルオレンジ、パラメチルレッド、コンゴーレッド、ベンゾプルプリン４Ｂ、α－ナフチルレッド、ナイルブルー２Ｂ、ナイルブルーＡ、メチルバイオレット、マラカイトグリーン、パラフクシン、ビクトリアピュアブルー－ナフタレンスルホン酸塩、ビクトリアピュアブルーＢＯＨ（保土谷化学工業社製）、オイルブルー＃６０３（オリヱント化学工業社製）、オイルピンク＃３１２（オリヱント化学工業社製）、オイルレッド５Ｂ（オリヱント化学工業社製）、オイルスカーレット＃３０８（オリヱント化学工業社製）、オイルレッドＯＧ（オリヱント化学工業社製）、オイルレッドＲＲ（オリヱント化学工業社製）、オイルグリーン＃５０２（オリヱント化学工業社製）、スピロンレッドＢＥＨスペシャル（保土谷化学工業社製）、ｍ－クレゾールパープル、クレゾールレッド、ローダミンＢ、ローダミン６Ｇ、スルホローダミンＢ、オーラミン、４－ｐ－ジエチルアミノフェニルイミノナフトキノン、２－カルボキシアニリノ－４－ｐ－ジエチルアミノフェニルイミノナフトキノン、２－カルボキシステアリルアミノ－４－ｐ－Ｎ，Ｎ－ビス（ヒドロキシエチル）アミノ－フェニルイミノナフトキノン、１－フェニル－３－メチル－４－ｐ－ジエチルアミノフェニルイミノ－５－ピラゾロン、及び、１－β－ナフチル－４－ｐ－ジエチルアミノフェニルイミノ－５－ピラゾロンが挙げられる。 Examples of the dye N include the following dyes and leuco compounds.
Dyes include Brilliant Green, Ethyl Violet, Methyl Green, Crystal Violet, Basic Fuxin, Methyl Violet 2B, Kinaldine Red, Rose Bengal, Metanyl Yellow, Timor Sulfophthalene, Xylenol Blue, Methyl Orange, Paramethyl Red, Congo Red, benzopurpurin 4B, α-naphthyl red, Nile blue 2B, Nile blue A, methyl violet, malakite green, parafuxin, Victoria pure blue-naphthalene sulfonate, Victoria pure blue BOH (manufactured by Hodoya Chemical Industry Co., Ltd.), Oil Blue # 603 (manufactured by Orient Chemical Industry Co., Ltd.), Oil Pink # 312 (manufactured by Orient Chemical Industry Co., Ltd.), Oil Red 5B (manufactured by Orient Chemical Industry Co., Ltd.), Oil Scarlet # 308 (manufactured by Orient Chemical Industry Co., Ltd.), Oil Red OG (Manufactured by Orient Chemical Industry Co., Ltd.), Oil Red RR (manufactured by Orient Chemical Industry Co., Ltd.), Oil Green # 502 (manufactured by Orient Chemical Industry Co., Ltd.), Spiron Red BEH Special (manufactured by Hodoya Chemical Industry Co., Ltd.), m-cresol purple, Cresol Red , Rhodamine B, Rhodamine 6G, SulfoRhodamine B, Auramine, 4-p-diethylaminophenyliminonaphthoquinone, 2-carboxyanilino-4-p-diethylaminophenyliminonaphthoquinone, 2-carboxystearylamino-4-p-N, N -Bis (hydroxyethyl) amino-phenyliminonaphthoquinone, 1-phenyl-3-methyl-4-p-diethylaminophenylimino-5-pyrazolone, and 1-β-naphthyl-4-p-diethylaminophenylimino-5- Pyrazolone can be mentioned.
　ロイコ化合物としては、ｐ，ｐ’，ｐ”－ヘキサメチルトリアミノトリフェニルメタン（ロイコクリスタルバイオレット）、Ｐｅｒｇａｓｃｒｉｐｔ　Ｂｌｕｅ　ＳＲＢ（チバガイギー社製）、クリスタルバイオレットラクトン、マラカイトグリーンラクトン、ベンゾイルロイコメチレンブルー、２－（Ｎ－フェニル－Ｎ－メチルアミノ）－６－（Ｎ－ｐ－トリル－Ｎ－エチル）アミノフルオラン、２－アニリノ－３－メチル－６－（Ｎ－エチル－ｐ－トルイジノ）フルオラン、３，６－ジメトキシフルオラン、３－（Ｎ，Ｎ－ジエチルアミノ）－５－メチル－７－（Ｎ，Ｎ－ジベンジルアミノ）フルオラン、３－（Ｎ－シクロヘキシル－Ｎ－メチルアミノ）－６－メチル－７－アニリノフルオラン、３－（Ｎ，Ｎ－ジエチルアミノ）－６－メチル－７－アニリノフルオラン、３－（Ｎ，Ｎ－ジエチルアミノ）－６－メチル－７－キシリジノフルオラン、３－（Ｎ，Ｎ－ジエチルアミノ）－６－メチル－７－クロロフルオラン、３－（Ｎ，Ｎ－ジエチルアミノ）－６－メトキシ－７－アミノフルオラン、３－（Ｎ，Ｎ－ジエチルアミノ）－７－（４－クロロアニリノ）フルオラン、３－（Ｎ，Ｎ－ジエチルアミノ）－７－クロロフルオラン、３－（Ｎ，Ｎ－ジエチルアミノ）－７－ベンジルアミノフルオラン、３－（Ｎ，Ｎ－ジエチルアミノ）－７，８－ベンゾフロオラン、３－（Ｎ，Ｎ－ジブチルアミノ）－６－メチル－７－アニリノフルオラン、３－（Ｎ，Ｎ－ジブチルアミノ）－６－メチル－７－キシリジノフルオラン、３－ピペリジノ－６－メチル－７－アニリノフルオラン、３－ピロリジノ－６－メチル－７－アニリノフルオラン、３，３－ビス（１－エチル－２－メチルインドール－３－イル）フタリド、３，３－ビス（１－ｎ－ブチル－２－メチルインドール－３－イル）フタリド、３，３－ビス（ｐ－ジメチルアミノフェニル）－６－ジメチルアミノフタリド、３－（４－ジエチルアミノ－２－エトキシフェニル）－３－（１－エチル－２－メチルインドール－３－イル）－４－フタリド、３－（４－ジエチルアミノフェニル）－３－（１－エチル－２－メチルインドール－３－イル）フタリド、及び、３’，６’－ビス（ジフェニルアミノ）スピロイソベンゾフラン－１（３Ｈ），９’－［９Ｈ］キサンテン－３－オンが挙げられる。 Leuco compounds include p, p', p "-hexamethyltriaminotriphenylmethane (leucocrystal violet), Pergascript Blue SRB (manufactured by Ciba Geigy), crystal violet lactone, malakite green lactone, benzoyl leucomethylene blue, 2- ( N-phenyl-N-methylamino) -6- (N-p-trill-N-ethyl) aminofluorane, 2-anilino-3-methyl-6- (N-ethyl-p-toluizino) fluorane, 3, 6-Dimethoxyfluorane, 3- (N, N-diethylamino) -5-methyl-7- (N, N-dibenzylamino) fluorane, 3- (N-cyclohexyl-N-methylamino) -6-methyl- 7-anilinofluorane, 3- (N, N-diethylamino) -6-methyl-7-anilinofluorane, 3- (N, N-diethylamino) -6-methyl-7-xylidinofluorane, 3 -(N, N-diethylamino) -6-methyl-7-chlorofluorine, 3- (N, N-diethylamino) -6-methoxy-7-aminofluorane, 3- (N, N-diethylamino) -7 -(4-Chloroanilino) fluorane, 3- (N, N-diethylamino) -7-chlorofluorane, 3- (N, N-diethylamino) -7-benzylaminofluorane, 3- (N, N-diethylamino) -7,8-benzofluorolane, 3- (N, N-dibutylamino) -6-methyl-7-anilinofluoran, 3- (N, N-dibutylamino) -6-methyl-7-xylidino Fluolan, 3-piperidino-6-methyl-7-anilinofluoran, 3-pyrrolidino-6-methyl-7-anilinofluoran, 3,3-bis (1-ethyl-2-methylindole-3-3) Il) phthalide, 3,3-bis (1-n-butyl-2-methylindol-3-yl) phthalide, 3,3-bis (p-dimethylaminophenyl) -6-dimethylaminophthalide, 3-( 4-Diethylamino-2-ethoxyphenyl) -3- (1-ethyl-2-methylindole-3-yl) -4-phthalide, 3- (4-diethylaminophenyl) -3- (1-ethyl-2-methyl) Indol-3-yl) phthalide and 3', 6'-bis (diphenylamino) spiroisobenzofuran-1 (3H), 9'-[9H] xanthen-3-one can be mentioned.
　色素Ｎは、露光部及び非露光部の視認性、現像後のパターン視認性、並びに、解像性の観点から、ラジカルにより最大吸収波長が変化する色素であることが好ましく、ラジカルにより発色する色素であることがより好ましい。 The dye N is preferably a dye whose maximum absorption wavelength is changed by radicals from the viewpoints of visibility of exposed and unexposed areas, pattern visibility after development, and resolution, and is a dye that develops color by radicals. Is more preferable.
　色素Ｎは、ロイコクリスタルバイオレット、クリスタルバイオレットラクトン、ブリリアントグリーン、又は、ビクトリアピュアブルー－ナフタレンスルホン酸塩であることが好ましい。 The dye N is preferably leuco crystal violet, crystal violet lactone, brilliant green, or Victoria pure blue-naphthalene sulfonate.
　感光性樹脂層は、色素Ｎを、１種単独で含有してもよいし、２種以上含有してもよい。 The photosensitive resin layer may contain dye N alone or in combination of two or more.
　色素Ｎの含有量は、露光部及び非露光部の視認性、現像後のパターン視認性、並びに、解像性の観点から、感光性樹脂層の全質量に対して、０．１質量％以上が好ましく、０．１質量％～１０質量％がより好ましく、０．１質量％～５質量％がさらに好ましく、０．１質量％～１質量％が特に好ましい。 The content of the dye N is 0.1% by mass or more with respect to the total mass of the photosensitive resin layer from the viewpoints of visibility of the exposed and non-exposed areas, pattern visibility after development, and resolution. Is more preferable, 0.1% by mass to 10% by mass is more preferable, 0.1% by mass to 5% by mass is further preferable, and 0.1% by mass to 1% by mass is particularly preferable.
　色素Ｎの含有量は、感光性樹脂層に含まれる色素Ｎの全てを発色状態にした場合の色素の含有量を意味する。以下に、ラジカルにより発色する色素を例として、色素Ｎの含有量の定量方法について説明する。 The content of the dye N means the content of the dye when all of the dye N contained in the photosensitive resin layer is in a colored state. Hereinafter, a method for quantifying the content of dye N will be described by taking a dye that develops color by radicals as an example.
　メチルエチルケトン１００ｍＬに、色素０．００１ｇ及び０．０１ｇ溶解させた溶液を調製する。得られた各溶液に、光ラジカル重合開始剤（Ｉｒｇａｃｕｒｅ　ＯＸＥ０１、ＢＡＳＦジャパン社製）を加え、３６５ｎｍの光を照射することによりラジカルを発生させ、全ての色素を発色状態にする。その後、大気雰囲気下で、分光光度計（ＵＶ３１００、島津製作所製）を用いて、液温が２５℃である各溶液の吸光度を測定し、検量線を作成する。 Prepare a solution in which 0.001 g and 0.01 g of dye are dissolved in 100 mL of methyl ethyl ketone. A photoradical polymerization initiator (Irgacure OXE01, manufactured by BASF Japan Ltd.) is added to each of the obtained solutions, and radicals are generated by irradiating with light of 365 nm to bring all the dyes into a colored state. Then, in an air atmosphere, the absorbance of each solution having a liquid temperature of 25 ° C. is measured using a spectrophotometer (UV3100, manufactured by Shimadzu Corporation) to prepare a calibration curve.
　次に、色素に代えて感光性樹脂層３ｇをメチルエチルケトンに溶解させること以外は上記と同様の方法で、色素を全て発色させた溶液の吸光度を測定する。得られた感光性樹脂層を含有する溶液の吸光度から、検量線に基づいて感光性樹脂層に含まれる色素の含有量を算出する。 Next, the absorbance of the solution in which all the dyes are colored is measured by the same method as above except that 3 g of the photosensitive resin layer is dissolved in methyl ethyl ketone instead of the dye. From the absorbance of the obtained solution containing the photosensitive resin layer, the content of the dye contained in the photosensitive resin layer is calculated based on the calibration curve.
－界面活性剤－
　感光性樹脂層は、厚さ均一性の観点から、界面活性剤を含有することが好ましい。 -Surfactant-
The photosensitive resin layer preferably contains a surfactant from the viewpoint of thickness uniformity.
　界面活性剤としては、例えば、アニオン性界面活性剤、カチオン性界面活性剤、ノニオン性界面活性剤、及び、両性界面活性剤が挙げられる。中でも、界面活性剤は、ノニオン性界面活性剤であることが好ましい。 Examples of the surfactant include anionic surfactant, cationic surfactant, nonionic surfactant, and amphoteric surfactant. Above all, the surfactant is preferably a nonionic surfactant.
　ノニオン性界面活性剤としては、例えば、ポリオキシエチレン高級アルキルエーテル、ポリオキシエチレン高級アルキルフェニルエーテル、ポリオキシエチレングリコールの高級脂肪酸ジエステル、シリコーン系ノニオン性界面活性剤、及び、フッ素系ノニオン性界面活性剤が挙げられる。 Examples of the nonionic surfactant include polyoxyethylene higher alkyl ether, polyoxyethylene higher alkylphenyl ether, polyoxyethylene glycol higher fatty acid diester, silicone-based nonionic surfactant, and fluorine-based nonionic surfactant. Agents can be mentioned.
　感光性樹脂層は、解像性を向上させる観点から、フッ素系ノニオン性界面活性剤を含有することが好ましい。感光性樹脂層がフッ素系ノニオン性界面活性剤を含有することにより、エッチング液の感光性樹脂層への浸透が抑制され、サイドエッチングが低減するためであると考えられる。 The photosensitive resin layer preferably contains a fluorine-based nonionic surfactant from the viewpoint of improving the resolution. It is considered that this is because the photosensitive resin layer contains the fluorine-based nonionic surfactant, so that the penetration of the etching solution into the photosensitive resin layer is suppressed and the side etching is reduced.
　フッ素系ノニオン性界面活性剤の市販品としては、例えば、メガファックＦ－５５１、Ｆ－５５２及びＦ－５５４（いずれもＤＩＣ社製）が挙げられる。 Examples of commercially available fluorine-based nonionic surfactants include Megafuck F-551, F-552 and F-554 (all manufactured by DIC Corporation).
　また、フッ素系界面活性剤の市販品としては、例えば、メガファック　Ｆ－１７１、Ｆ－１７２、Ｆ－１７３、Ｆ－１７６、Ｆ－１７７、Ｆ－１４１、Ｆ－１４２、Ｆ－１４３、Ｆ－１４４、Ｆ－４３７、Ｆ－４７５、Ｆ－４７７、Ｆ－４７９、Ｆ－４８２、Ｆ－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、ＭＦＳ－５７８、ＭＦＳ－５７９、ＭＦＳ－５８６、ＭＦＳ－５８７、Ｒ－４１、Ｒ－４１－ＬＭ、Ｒ－０１、Ｒ－４０、Ｒ－４０－ＬＭ、ＲＳ－４３、ＴＦ－１９５６、ＲＳ－９０、Ｒ－９４、ＲＳ－７２－Ｋ、ＤＳ－２１（以上、ＤＩＣ株式会社製）、フロラード　ＦＣ４３０、ＦＣ４３１、ＦＣ１７１（以上、住友スリーエム（株）製）、サーフロンＳ－３８２、ＳＣ－１０１、ＳＣ－１０３、ＳＣ－１０４、ＳＣ－１０５、ＳＣ－１０６８、ＳＣ－３８１、ＳＣ－３８３、Ｓ－３９３、ＫＨ－４０（以上、ＡＧＣ（株）製）、ＰｏｌｙＦｏｘ　ＰＦ６３６、ＰＦ６５６、ＰＦ６３２０、ＰＦ６５２０、ＰＦ７００２（以上、ＯＭＮＯＶＡ社製）、フタージェント　７１０ＦＬ、７１０ＦＭ、６１０ＦＭ、６０１ＡＤ、６０１ＡＤＨ２、６０２Ａ、２１５Ｍ、２４５Ｆ、２５１、２１２Ｍ、２５０、２０９Ｆ、２２２Ｆ、２０８Ｇ、７１０ＬＡ、７１０ＦＳ、７３０ＬＭ、６５０ＡＣ、６８１、６８３（以上、（株）ＮＥＯＳ製）等
が挙げられる。 Commercially available products of fluorine-based surfactants include, for example, Megafuck F-171, F-172, F-173, F-176, F-177, F-141, F-142, F-143, F. -144, F-437, F-475, F-477, F-479, F-482, 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, MFS-578, MFS-579, MFS-586, MFS-587, R-41, R -141-LM, R-01, R-40, R-40-LM, RS-43, TF-1956, RS-90, R-94, RS-72-K, DS-21 (above, DIC Co., Ltd.) , Florard FC430, FC431, FC171 (all manufactured by Sumitomo 3M Co., Ltd.), Surfron S-382, SC-101, SC-103, SC-104, SC-105, SC-1068, SC-381, SC -383, S-393, KH-40 (above, manufactured by AGC Co., Ltd.), PolyFox PF636, PF656, PF6320, PF6520, PF7002 (above, manufactured by OMNOVA), Surfactant 710FL, 710FM, 610FM, 601AD, 601ADH2, 602A, 215M, 245F, 251, 212M, 250, 209F, 222F, 208G, 710LA, 710FS, 730LM, 650AC, 681, 683 (all manufactured by NEOS Co., Ltd.) and the like can be mentioned.
　また、フッ素系界面活性剤としては、フッ素原子を含有する官能基を持つ分子構造を有し、熱を加えるとフッ素原子を含有する官能基の部分が切断されてフッ素原子が揮発するアクリル系化合物も好適に使用できる。このようなフッ素系界面活性剤としては、ＤＩＣ（株）製のメガファック　ＤＳシリーズ（化学工業日報（２０１６年２月２２日）、日経
産業新聞（２０１６年２月２３日））、例えばメガファック　ＤＳ－２１が挙げられる。
　また、フッ素系界面活性剤としては、フッ素化アルキル基またはフッ素化アルキレンエーテル基を有するフッ素原子含有ビニルエーテル化合物と、親水性のビニルエーテル化合物との重合体を用いることも好ましい。
　また、フッ素系界面活性剤としては、ブロックポリマーも使用できる。
　また、フッ素系界面活性剤としては、フッ素原子を有する（メタ）アクリレート化合物に由来する構成単位と、アルキレンオキシ基（好ましくはエチレンオキシ基、プロピレンオキシ基）を２以上（好ましくは５以上）有する（メタ）アクリレート化合物に由来する構成単位と、を含む含フッ素高分子化合物も好ましく使用できる。
　また、フッ素系界面活性剤としては、エチレン性不飽和結合含有基を側鎖に有する含フッ素重合体も使用できる。メガファック　ＲＳ－１０１、ＲＳ－１０２、ＲＳ－７１８Ｋ、ＲＳ－７２－Ｋ（以上、ＤＩＣ株式会社製）等が挙げられる。 Further, as a fluorine-based surfactant, an acrylic compound having a molecular structure having a functional group containing a fluorine atom, and when heat is applied, a portion of the functional group containing a fluorine atom is cut and the fluorine atom volatilizes. Can also be preferably used. Examples of such fluorine-based surfactants include the Megafuck DS series manufactured by DIC Corporation (The Chemical Daily (February 22, 2016), Nikkei Sangyo Shimbun (February 23, 2016)), for example, Megafuck. DS-21 can be mentioned.
Further, as the fluorine-based surfactant, it is also preferable to use a polymer of a fluorine atom-containing vinyl ether compound having a fluorinated alkyl group or a fluorinated alkylene ether group and a hydrophilic vinyl ether compound.
A block polymer can also be used as the fluorine-based surfactant.
The fluorine-based surfactant has a structural unit derived from a (meth) acrylate compound having a fluorine atom and 2 or more (preferably 5 or more) alkyleneoxy groups (preferably ethyleneoxy groups and propyleneoxy groups). A fluorine-containing polymer compound containing a structural unit derived from a (meth) acrylate compound can also be preferably used.
Further, as the fluorine-based surfactant, a fluorine-containing polymer having an ethylenically unsaturated bond-containing group in the side chain can also be used. Megafvck RS-101, RS-102, RS-718K, RS-72-K (all manufactured by DIC Corporation) and the like can be mentioned.
　フッ素系界面活性剤としては、環境適性向上の観点から、パーフルオロオクタン酸（ＰＦＯＡ）及びパーフルオロオクタンスルホン酸（ＰＦＯＳ）等の炭素数が７以上の直鎖状パーフルオロアルキル基を有する化合物の代替材料に由来する界面活性剤であることが好ましい。 As the fluorine-based surfactant, from the viewpoint of improving environmental suitability, compounds having a linear perfluoroalkyl group having 7 or more carbon atoms, such as perfluorooctanoic acid (PFOA) and perfluorooctanesulfonic acid (PFOS), are used. It is preferably a surfactant derived from an alternative material.
　ノニオン系界面活性剤としては、グリセロール、トリメチロールプロパン、トリメチロールエタン並びにそれらのエトキシレート及びプロポキシレート（例えば、グリセロールプロポキシレート、グリセロールエトキシレート等）、ポリオキシエチレンラウリルエーテル、ポリオキシエチレンステアリルエーテル、ポリオキシエチレンオレイルエーテル、ポリオキシエチレンオクチルフェニルエーテル、ポリオキシエチレンノニルフェニルエーテル、ポリエチレングリコールジラウレート、ポリエチレングリコールジステアレート、ソルビタン脂肪酸エステル、プルロニック　Ｌ１０、Ｌ３１、Ｌ６１、Ｌ６２、１０Ｒ５、１７Ｒ２、２５Ｒ２（以上、ＢＡＳＦ社製）、テトロニック　３０４、７０１、７０４、９０１、９０４、１５０Ｒ１（以上、ＢＡＳＦ社製）、ソルスパース　２００００（以上、日本ルーブリゾール（株）製）、ＮＣＷ－１０１、ＮＣＷ－１００１、ＮＣＷ－１００２（以上、富士フイルム和光純薬（株）製）、パイオニン　Ｄ－６１１２、Ｄ－６１１２－Ｗ、Ｄ－６３１５（以上、竹本油脂（株）製）、オルフィンＥ１０１０、サーフィノール１０４、４００、４４０（以上、日信化学工業（株）製）等が挙げられる。 Nonionic surfactants include glycerol, trimethylolpropane, trimethylolethane and their ethoxylates and propoxylates (eg, glycerol propoxylate, glycerol ethoxylate, etc.), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, etc. Polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester, Pluronic L10, L31, L61, L62, 10R5, 17R2, 25R2 (or more) , BASF), Tetronic 304, 701, 704, 901, 904, 150R1 (above, BASF), Solsparse 20000 (above, Nippon Lubrizol Co., Ltd.), NCW-101, NCW-1001, NCW -1002 (above, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), Pionin D-6112, D-6112-W, D-6315 (above, manufactured by Takemoto Yushi Co., Ltd.), Orphine E1010, Surfinol 104, 400, 440 (above, manufactured by Nissin Chemical Industry Co., Ltd.) and the like can be mentioned.
　シリコーン系界面活性剤としては、シロキサン結合からなる直鎖状ポリマー、及び、側
鎖や末端に有機基を導入した変性シロキサンポリマーが挙げられる。
　シリコーン系界面活性剤の具体例としては、ＤＯＷＳＩＬ　８０３２　ＡＤＤＩＴＩＶＥ、トーレシリコーンＤＣ３ＰＡ、トーレシリコーンＳＨ７ＰＡ、トーレシリコーンＤＣ１１ＰＡ、トーレシリコーンＳＨ２１ＰＡ、トーレシリコーンＳＨ２８ＰＡ、トーレシリコーンＳＨ２９ＰＡ、トーレシリコーンＳＨ３０ＰＡ、トーレシリコーンＳＨ８４００（以上、東レ・ダウコーニング（株）製）並びに、Ｘ－２２－４９５２、Ｘ－２２－４２７２、Ｘ－２２－６２６６、ＫＦ－３５１Ａ、Ｋ３５４Ｌ、ＫＦ－３５５Ａ、ＫＦ－９４５、ＫＦ－６４０、ＫＦ－６４２、ＫＦ－６４３、Ｘ－２２－６１９１、Ｘ－２２－４５１５、ＫＦ－６００４、ＫＰ－３４１、ＫＦ－６００１、ＫＦ－６００２（以上、信越シリコーン株式会社製）、Ｆ－４４４０、ＴＳＦ－４３００、ＴＳＦ－４４４５、ＴＳＦ－４４６０、ＴＳＦ－４４５２（以上、モメンティブ・パフォーマンス・マテリアルズ社製）、ＢＹＫ３０７、ＢＹＫ３２３、ＢＹＫ３３０（以上、ビックケミー社製）等が挙げられる。 Examples of the silicone-based surfactant include a linear polymer composed of a siloxane bond and a modified siloxane polymer in which an organic group is introduced into a side chain or a terminal.
Specific examples of silicone-based surfactants include DOWNSIL 8032 ADDITIVE, Torre Silicone DC3PA, Torre Silicone SH7PA, Torre Silicone DC11PA, Torre Silicone SH21PA, Torre Silicone SH28PA, Torre Silicone SH29PA, Torre Silicone SH30PA, Torre Silicone SH8400 (above, Toray). (Made by Dow Corning Co., Ltd.), X-22-4952, X-22-2272, X-22-6266, KF-351A, K354L, KF-355A, KF-945, KF-640, KF-642, KF-643, X-22-6191, X-22-4515, KF-6004, KP-341, KF-6001, KF-6002 (all manufactured by Shin-Etsu Silicone Co., Ltd.), F-4440, TSF-4300, TSF -4445, TSF-4460, TSF-4452 (above, manufactured by Momentive Performance Materials), BYK307, BYK323, BYK330 (above, manufactured by Big Chemie) and the like.
　界面活性剤は、国際公開第２０１８／１７９６４０号の段落０１２０～０１２５に記載の界面活性剤、特許第４５０２７８４号公報の段落００１７に記載の界面活性剤、及び、特開２００９－２３７３６２号公報の段落００６０～００７１に記載の界面活性剤であってもよい。 The surfactants are the surfactant described in paragraphs 0120 to 0125 of International Publication No. 2018/179640, the surfactant described in paragraph 0017 of Japanese Patent No. 45027884, and the paragraph of JP-A-2009-237362. It may be the surfactant described in 0060 to 0071.
　感光性樹脂層は、界面活性剤を、１種単独で含有してもよいし、２種以上含有してもよい。 The photosensitive resin layer may contain one type of surfactant alone or two or more types.
　界面活性剤の含有量は、感光性樹脂層の全質量に対して、０．００１質量％～１０質量％が好ましく、０．０１質量％～３質量％がより好ましい。 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.
－添加剤－
　感光性樹脂層は、上記成分以外に、必要に応じて公知の添加剤を含有してもよい。 -Additive-
The photosensitive resin layer may contain a known additive in addition to the above components, if necessary.
　添加剤としては、例えば、ラジカル重合禁止剤、増感剤、可塑剤、ヘテロ環状化合物、ベンゾトリアゾール類、カルボキシベンゾトリアゾール類、重合体Ａ以外の樹脂、及び、溶剤が挙げられる。感光性樹脂層は、各添加剤を１種単独で含有してもよいし、２種以上を含有してもよい。 Examples of the additive include a radical polymerization inhibitor, a sensitizer, a plasticizer, a heterocyclic compound, benzotriazoles, carboxybenzotriazoles, a resin other than polymer A, and a solvent. The photosensitive resin layer may contain each additive alone or in combination of two or more.
　感光性樹脂層は、ラジカル重合禁止剤を含有してもよい。 The photosensitive resin layer may contain a radical polymerization inhibitor.
　ラジカル重合禁止剤としては、例えば、特許第４５０２７８４号公報の段落００１８に記載の熱重合防止剤が挙げられる。また、ラジカル重合禁止剤としては、フェノチアジン、フェノキサジン、４－メトキシフェノール、ナフチルアミン、塩化第一銅、Ｎ－ニトロソフェニルヒドロキシアミンアルミニウム塩、及び、ジフェニルニトロソアミンが挙げられる。中でも、ラジカル重合禁止剤は、フェノチアジン、フェノキサジン、４－メトキシフェノール又はＮ－ニトロソフェニルヒドロキシアミンアルミニウム塩であることが好ましい。 Examples of the radical polymerization inhibitor include the thermal polymerization inhibitor described in paragraph 0018 of Japanese Patent No. 4502784. Examples of the radical polymerization inhibitor include phenothiazine, phenoxazine, 4-methoxyphenol, naphthylamine, cuprous chloride, N-nitrosophenylhydroxyamine aluminum salt, and diphenylnitrosamine. Among them, the radical polymerization inhibitor is preferably phenothiazine, phenoxazine, 4-methoxyphenol or N-nitrosophenylhydroxyamine aluminum salt.
　ベンゾトリアゾール類としては、例えば、１，２，３－ベンゾトリアゾール、１－クロロ－１，２，３－ベンゾトリアゾール、ビス（Ｎ－２－エチルヘキシル）アミノメチレン－１，２，３－ベンゾトリアゾール、ビス（Ｎ－２－エチルヘキシル）アミノメチレン－１，２，３－トリルトリアゾール、及び、ビス（Ｎ－２－ヒドロキシエチル）アミノメチレン－１，２，３－ベンゾトリアゾールが挙げられる。  Examples of benzotriazoles include 1,2,3-benzotriazole, 1-chloro-1,2,3-benzotriazole, bis (N-2-ethylhexyl) aminomethylene-1,2,3-benzotriazole, and the like. Examples thereof include bis (N-2-ethylhexyl) aminomethylene-1,2,3-tolyltriazole and bis (N-2-hydroxyethyl) aminomethylene-1,2,3-benzotriazole.
　カルボキシベンゾトリアゾール類としては、例えば、４－カルボキシ－１，２，３－ベンゾトリアゾール、５－カルボキシ－１，２，３－ベンゾトリアゾール、Ｎ－（Ｎ，Ｎ－ジ－２－エチルヘキシル）アミノメチレンカルボキシベンゾトリアゾール、Ｎ－（Ｎ，Ｎ－ジ－２－ヒドロキシエチル）アミノメチレンカルボキシベンゾトリアゾール、及び、Ｎ－（Ｎ，Ｎ－ジ－２－エチルヘキシル）アミノエチレンカルボキシベンゾトリアゾール、１－（２－ジ－ｎ－ブチルアミノメチル）－５－カルボキシベンゾトリアゾール及び１－（２－ジ－ｎ－ブチルアミノメチル）－６－カルボキシベンゾトリアゾールが挙げられる。カルボキシベンゾトリアゾール類の市販品としては、例えば、ＣＢＴ－１（城北化学工業社製）が挙げられる。 Examples of carboxybenzotriazoles include 4-carboxy-1,2,3-benzotriazole, 5-carboxy-1,2,3-benzotriazole, and N- (N, N-di-2-ethylhexyl) aminomethylene. Carboxybenzotriazole, N- (N, N-di-2-hydroxyethyl) aminomethylenecarboxybenzotriazole, and N- (N, N-di-2-ethylhexyl) aminoethylenecarboxybenzotriazole, 1- (2-) Examples thereof include di-n-butylaminomethyl) -5-carboxybenzotriazole and 1- (2-di-n-butylaminomethyl) -6-carboxybenzotriazole. Examples of commercially available products of carboxybenzotriazoles include CBT-1 (manufactured by Johoku Chemical Industry Co., Ltd.).
　ラジカル重合禁止剤、ベンゾトリアゾ－ル類、及びカルボキシベンゾトリアゾ－ル類の合計含有量は、感光性樹脂層の全質量に対して、０．０１質量％～３質量％であることが好ましく、０．０５質量％～１質量％であることがより好ましい。上記含有量が０．０１質量％以上であると、感光性樹脂組成物の保存安定性が優れる。一方、上記含有量が３質量％以下であると、感度を維持し、染料の脱色を抑制することができる。  The total content of the radical polymerization inhibitor, benzotriazols, and carboxybenzotriazols is preferably 0.01% by mass to 3% by mass with respect to the total mass of the photosensitive resin layer. It is more preferably 0.05% by mass to 1% by mass. When the content is 0.01% by mass or more, the storage stability of the photosensitive resin composition is excellent. On the other hand, when the content is 3% by mass or less, the sensitivity can be maintained and the decolorization of the dye can be suppressed.
　感光性樹脂層は、増感剤を含有してもよい。 The photosensitive resin layer may contain a sensitizer.
　増感剤としては、特に制限されず、公知の増感剤、染料及び顔料を用いることができる。増感剤としては、例えば、ジアルキルアミノベンゾフェノン化合物、ピラゾリン化合物、アントラセン化合物、クマリン化合物、キサントン化合物、チオキサントン化合物、アクリドン化合物、オキサゾール化合物、ベンゾオキサゾール化合物、チアゾール化合物、ベンゾチアゾール化合物、トリアゾール化合物（例えば、１，２，４－トリアゾール）、スチルベン化合物、トリアジン化合物、チオフェン化合物、ナフタルイミド化合物、トリアリールアミン化合物、及び、アミノアクリジン化合物が挙げられる。 The sensitizer is not particularly limited, and known sensitizers, dyes and pigments can be used. Examples of the sensitizer include dialkylaminobenzophenone compounds, pyrazoline compounds, anthracene compounds, coumarin compounds, xanthone compounds, thioxanthone compounds, acridone compounds, oxazole compounds, benzoxazole compounds, thiazole compounds, benzothiazole compounds, and triazole compounds (for example, 1,2,4-triazole), stillben compounds, triazine compounds, thiophene compounds, naphthalimide compounds, triarylamine compounds, and aminoaclydin compounds.
　感光性樹脂層は、増感剤を１種単独で含有してもよいし、２種以上を含有してもよい。 The photosensitive resin layer may contain one kind of sensitizer alone or two or more kinds.
　感光性樹脂層が増感剤を含有する場合、増感剤の含有量は、目的により適宜選択できる。増感剤の含有量は、光源に対する感度の向上、及び、重合速度と連鎖移動のバランスによる硬化速度の向上の観点から、感光性樹脂層の全質量に対して、０．０１質量％～５質量％であることが好ましく、０．０５質量％～１質量％であることがより好ましい。 When the photosensitive resin layer contains a sensitizer, the content of the sensitizer can be appropriately selected depending on the purpose. The content of the sensitizer is 0.01% by mass to 5% by mass with respect to the total mass of the photosensitive resin layer from the viewpoint of improving the sensitivity to the light source and improving the curing rate by balancing the polymerization rate and the chain transfer. It is preferably by mass%, more preferably 0.05% by mass to 1% by mass.
　感光性樹脂層は、可塑剤及びヘテロ環状化合物からなる群より選択される少なくとも１種を含有してもよい。 The photosensitive resin layer may contain at least one selected from the group consisting of a plasticizer and a heterocyclic compound.
　可塑剤及びヘテロ環状化合物としては、国際公開第２０１８／１７９６４０号の段落００９７～０１０３及び０１１１～０１１８に記載の化合物が挙げられる。 Examples of the plasticizer and the heterocyclic compound include the compounds described in paragraphs 097 to 0103 and 0111 to 0118 of International Publication No. 2018/179640.
　感光性樹脂層は、重合体Ａ以外の樹脂を含有してもよい。 The photosensitive resin layer may contain a resin other than the polymer A.
　重合体Ａ以外の樹脂としては、アクリル樹脂、スチレン－アクリル共重合体（ただし、スチレンに由来する構成単位の含有量が４０質量％以下であるもの）、ポリウレタン、ポリビニルアルコール、ポリビニルホルマール、ポリアミド、ポリエステル、エポキシ樹脂、ポリアセタール、ポリヒドロキシスチレン、ポリイミド、ポリベンゾオキサゾール、ポリシロキサン、ポリエチレンイミン、ポリアリルアミン、及び、ポリアルキレングリコールが挙げられる。 Resins other than polymer A include acrylic resins, styrene-acrylic copolymers (however, the content of constituent units derived from styrene is 40% by mass or less), polyurethane, polyvinyl alcohol, polyvinyl formal, polyamide, and the like. Examples thereof include polyester, epoxy resin, polyacetal, polyhydroxystyrene, polyimide, polybenzoxazole, polysiloxane, polyethyleneimine, polyallylamine, and polyalkylene glycol.
　感光性樹脂層は、溶剤を含有してもよい。溶剤を含む感光性樹脂組成物を乾燥させて感光性樹脂層を形成した場合、感光性樹脂層に溶剤が残留することがある。 The photosensitive resin layer may contain a solvent. When the photosensitive resin composition containing a solvent is dried to form a photosensitive resin layer, the solvent may remain in the photosensitive resin layer.
　また、感光性樹脂層は、金属酸化物粒子、酸化防止剤、防錆剤、連鎖移動剤、分散剤、酸増殖剤、現像促進剤、導電性繊維、熱ラジカル重合開始剤、熱酸発生剤、紫外線吸収剤、増粘剤、架橋剤、有機又は無機の沈殿防止剤等の公知の添加剤をさらに含有してもよい。 The photosensitive resin layer includes metal oxide particles, antioxidants, rust inhibitors, chain transfer agents, dispersants, acid growth agents, development accelerators, conductive fibers, thermal radical polymerization initiators, and thermal acid generators. , UV absorbers, thickeners, cross-linking agents, organic or inorganic precipitation inhibitors and other known additives may be further contained.
　感光性樹脂層が含有してもよい添加剤については特開２０１４－８５６４３号公報の段落０１６５～０１８４に記載されており、この公報の内容は本明細書に組み込まれる。 Additives that may be contained in the photosensitive resin layer are described in paragraphs 0165 to 0184 of Japanese Patent Application Laid-Open No. 2014-85643, and the contents of this publication are incorporated in the present specification.
＜物性等＞
　感光性樹脂層の厚さは、１０μｍ以下であることが好ましく、５μｍ以下であることがより好ましく、３μｍ以下であることがさらに好ましく、２μｍ以下であることが特に好ましい。感光性樹脂層の厚さを薄くすると、感光性樹脂層に含まれる、現像液に溶解しない成分の量を減らすことができるため、スカム（凝集物）の発生を抑制することができる。感光性樹脂層の厚さの下限値は、例えば、０．５μｍである。 <Physical characteristics, etc.>
The thickness of the photosensitive resin layer is preferably 10 μm or less, more preferably 5 μm or less, further preferably 3 μm or less, and particularly preferably 2 μm or less. By reducing the thickness of the photosensitive resin layer, the amount of components contained in the photosensitive resin layer that are insoluble in the developing solution can be reduced, so that the generation of scum (aggregates) can be suppressed. The lower limit of the thickness of the photosensitive resin layer is, for example, 0.5 μm.
　感光性転写材料が備える各層の厚さは、感光性転写材料の主面に対し垂直な方向の断面を走査型電子顕微鏡（ＳＥＭ：Scanning Electron Microscope）により観察し、得られた観察画像に基づいて各層の厚さを１０点以上計測し、その平均値として算出される。 The thickness of each layer provided in the photosensitive transfer material is based on the observation image obtained by observing the cross section in the direction perpendicular to the main surface of the photosensitive transfer material with a scanning electron microscope (SEM). The thickness of each layer is measured at 10 points or more and calculated as the average value.
　密着性により優れる点から、感光性樹脂層の波長３６５ｎｍの光透過率は、１０％以上が好ましく、３０％以上が好ましく、５０％以上がより好ましい。感光性樹脂層の波長３６５ｎｍの光透過率の上限値は特に制限されないが、９９．９％が好ましい。 From the viewpoint of excellent adhesion, the light transmittance of the photosensitive resin layer at a wavelength of 365 nm is preferably 10% or more, preferably 30% or more, and more preferably 50% or more. The upper limit of the light transmittance of the photosensitive resin layer at a wavelength of 365 nm is not particularly limited, but is preferably 99.9%.
＜形成方法＞
　感光性樹脂層の形成方法は、上記の成分を含有する層を形成可能な方法であれば特に制限されない。 <Formation method>
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.
　感光性樹脂層の形成方法としては、例えば、重合体Ａ、重合性化合物Ｂ及び溶剤を含有する感光性樹脂組成物を調製し、仮支持体等の表面に感光性樹脂組成物を塗布し、感光性樹脂組成物の塗膜を乾燥させることにより形成する方法が挙げられる。 As a method for forming the photosensitive resin layer, for example, a photosensitive resin composition containing the polymer A, the polymerizable compound B and a solvent is prepared, and the photosensitive resin composition is applied to the surface of a temporary support or the like. Examples thereof include a method of forming by drying a coating film of a photosensitive resin composition.
　感光性樹脂層の形成に使用される感光性樹脂組成物としては、例えば、重合体Ａ、重合性化合物Ｂ、上記の任意成分及び溶剤を含有する組成物が挙げられる。 Examples of the photosensitive resin composition used for forming the photosensitive resin layer include a composition containing a polymer A, a polymerizable compound B, the above-mentioned optional components and a solvent.
　感光性樹脂組成物は、感光性樹脂組成物の粘度を調節し、感光性樹脂層の形成を容易にするため、溶剤を含有することが好ましい。 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.
（溶剤）
　感光性樹脂組成物に含有される溶剤としては、重合体Ａ、重合性化合物Ｂ及び上記の任意成分を溶解又は分散可能であれば特に制限されず、公知の溶剤を使用できる。 (solvent)
The solvent contained in the photosensitive resin composition is not particularly limited as long as the polymer A, the polymerizable compound B and the above optional components can be dissolved or dispersed, and known solvents can be used.
　溶剤としては、例えば、アルキレングリコールエーテル、アルキレングリコールエーテルアセテート、アルコール（例えば、メタノール及びエタノール）、ケトン（例えば、アセトン及びメチルエチルケトン）、芳香族炭化水素（例えば、トルエン）、非プロトン性極性溶剤（例えば、Ｎ，Ｎ－ジメチルホルムアミド）、環状エーテル（例えば、テトラヒドロフラン）、エステル、アミド、ラクトン、及びこれらの２種以上を含む混合溶剤が挙げられる。 As the solvent, for example, alkylene glycol ether, alkylene glycol ether acetate, alcohol (for example, methanol and ethanol), ketone (for example, acetone and methyl ethyl ketone), aromatic hydrocarbon (for example, toluene), aprotonic polar solvent (for example). , N, N-dimethylformamide), cyclic ethers (eg, tetrahydrofuran), esters, amides, lactones, and mixed solvents containing two or more of these.
　仮支持体、熱可塑性樹脂層、中間層及び感光性樹脂層を備える感光性転写材料を作製する場合、感光性樹脂組成物は、アルキレングリコールエーテル及びアルキレングリコールエーテルアセテートからなる群より選択される少なくとも１種を含有することが好ましい。中でも、溶剤は、アルキレングリコールエーテル及びアルキレングリコールエーテルアセテート溶剤からなる群より選択される少なくとも１種と、ケトン及び環状エーテルからなる群より選択される少なくとも１種とを含む混合溶剤であることがより好ましく、アルキレングリコールエーテル及びアルキレングリコールエーテルアセテートからなる群より選択される少なくとも１種、ケトン、並びに環状エーテルを少なくとも含む混合溶剤がさらに好ましい。 When producing a photosensitive transfer material comprising a temporary support, a thermoplastic resin layer, an intermediate layer and a photosensitive resin layer, the photosensitive resin composition is selected from at least the group consisting of alkylene glycol ether and alkylene glycol ether acetate. It is preferable to contain one kind. Among them, the solvent is more preferably a mixed solvent containing at least one selected from the group consisting of alkylene glycol ether and alkylene glycol ether acetate solvent and at least one selected from the group consisting of ketone and cyclic ether. Preferably, a mixed solvent containing at least one selected from the group consisting of alkylene glycol ether and alkylene glycol ether acetate, a ketone, and cyclic ether is more preferable.
　アルキレングリコールエーテルとしては、例えば、エチレングリコールモノアルキルエーテル、エチレングリコールジアルキルエーテル、プロピレングリコールモノアルキルエーテル、プロピレングリコールジアルキルエーテル、ジエチレングリコールジアルキルエーテル、ジプロピレングリコールモノアルキルエーテル及びジプロピレングリコールジアルキルエーテルが挙げられる。 Examples of the alkylene glycol ether include ethylene glycol monoalkyl ether, ethylene glycol dialkyl ether, propylene glycol monoalkyl ether, propylene glycol dialkyl ether, diethylene glycol dialkyl ether, dipropylene glycol monoalkyl ether and dipropylene glycol dialkyl ether.
　アルキレングリコールエーテルアセテートとしては、例えば、エチレングリコールモノアルキルエーテルアセテート、プロピレングリコールモノアルキルエーテルアセテート、ジエチレングリコールモノアルキルエーテルアセテート及びジプロピレングリコールモノアルキルエーテルアセテートが挙げられる。 Examples of the alkylene glycol ether acetate include ethylene glycol monoalkyl ether acetate, propylene glycol monoalkyl ether acetate, diethylene glycol monoalkyl ether acetate and dipropylene glycol monoalkyl ether acetate.
　溶剤は、国際公開第２０１８／１７９６４０号の段落００９２～００９４に記載の溶剤、及び、特開２０１８－１７７８８９公報の段落００１４に記載の溶剤であってもよく、これらの内容は本明細書に組み込まれる。 The solvent may be the solvent described in paragraphs 0092 to 0094 of International Publication No. 2018/179640 and the solvent described in paragraph 0014 of JP-A-2018-177789, and the contents thereof are incorporated in the present specification. Is done.
　感光性樹脂組成物は、溶剤を１種単独で含有してもよく、２種以上を含有してもよい。
　感光性樹脂組成物における溶剤の含有量は、感光性樹脂組成物中の全固形分１００質量部に対し、５０質量部～１，９００質量部が好ましく、１００質量部～９００質量部がより好ましい。  The photosensitive resin composition may contain one type of solvent alone, or may contain two or more types of solvent.
The content of the solvent in the photosensitive resin composition is preferably 50 parts by mass to 1,900 parts by mass, more preferably 100 parts by mass to 900 parts by mass, based on 100 parts by mass of the total solid content in the photosensitive resin composition. ..
　感光性樹脂組成物の調製方法は特に制限されず、例えば、各成分を上記溶剤に溶解させた溶液を予め調製し、得られた溶液を所定の割合で混合することにより、感光性樹脂組成物を調製する方法が挙げられる。 The method for preparing the photosensitive resin composition is not particularly limited. For example, a photosensitive resin composition is prepared by preparing a solution in which each component is dissolved in the above solvent in advance and mixing the obtained solution in a predetermined ratio. There is a method of preparing.
　感光性樹脂組成物は、感光性樹脂層を形成する前に、孔径０．２μｍ～３０μｍのフィルターを用いてろ過することが好ましい。 The photosensitive resin composition is preferably filtered using a filter having a pore size of 0.2 μm to 30 μm before forming the photosensitive resin layer.
　感光性樹脂組成物の塗布方法は特に制限されず、公知の方法で塗布すればよい。塗布方法としては、例えば、スリット塗布、スピン塗布、カーテン塗布及びインクジェット塗布が挙げられる。 The method of applying the photosensitive resin composition is not particularly limited, and it may be applied by a known method. Examples of the coating method include slit coating, spin coating, curtain coating and inkjet coating.
　また、感光性樹脂層は、感光性樹脂組成物を後述するカバーフィルム上に塗布し、乾燥させることにより形成してもよい。 Further, the photosensitive resin layer may be formed by applying the photosensitive resin composition on a cover film described later and drying it.
＜不純物等＞
　感光性樹脂層は、所定量の不純物を含んでいてもよい。不純物としては、ナトリウム、カリウム、マグネシウム、カルシウム、鉄、マンガン、銅、アルミニウム、チタン、クロム、コバルト、ニッケル、亜鉛、スズ、ハロゲン及びこれらのイオンが挙げられる。中でも、ハロゲン化物イオン、ナトリウムイオン、及び、カリウムイオンは不純物として混入し易いため、下記の含有量にすることが好ましい。 <Impurities, etc.>
The photosensitive resin layer may contain a predetermined amount of impurities. Examples of impurities include sodium, potassium, magnesium, calcium, iron, manganese, copper, aluminum, titanium, chromium, cobalt, nickel, zinc, tin, halogen and ions thereof. Of these, halide ions, sodium ions, and potassium ions are likely to be mixed as impurities, so the content is preferably as follows.
　感光性樹脂層における不純物の含有量は、質量基準で、８０ｐｐｍ以下が好ましく、１０ｐｐｍ以下がより好ましく、２ｐｐｍ以下がさらに好ましい。感光性樹脂層における不純物の含有量は、質量基準で、１ｐｐｂ以上又は０．１ｐｐｍ以上とすることができる。 The content of impurities in the photosensitive resin layer is preferably 80 ppm or less, more preferably 10 ppm or less, still more preferably 2 ppm or less on a mass basis. The content of impurities in the photosensitive resin layer can be 1 ppb or more or 0.1 ppm or more on a mass basis.
　不純物を上記範囲にする方法としては、感光性樹脂層の原料として不純物の含有量が少ないものを選択すること、感光性樹脂層の形成時に不純物の混入を防ぐこと、及び、感光性樹脂層の形成時に洗浄して不純物を除去することが挙げられる。このような方法により、不純物の含有量を上記範囲内とすることができる。 As a method of setting impurities in the above range, selecting a material having a low impurity content as a raw material of the photosensitive resin layer, preventing impurities from being mixed during the formation of the photosensitive resin layer, and making the photosensitive resin layer Examples include cleaning at the time of formation to remove impurities. By such a method, the content of impurities can be kept within the above range.
　不純物は、例えば、ＩＣＰ（Inductively Coupled Plasma）発光分光分析法、原子吸光分光法、イオンクロマトグラフィー法等の公知の方法で定量できる。 Impurities can be quantified by known methods such as ICP (Inductively Coupled Plasma) emission spectroscopy, atomic absorption spectroscopy, and ion chromatography.
　感光性樹脂層における、ベンゼン、ホルムアルデヒド、トリクロロエチレン、１，３－ブタジエン、四塩化炭素、クロロホルム、Ｎ，Ｎ－ジメチルホルムアミド、Ｎ，Ｎ－ジメチルアセトアミド、及び、ヘキサンの特定化合物の含有量は、少ないことが好ましい。感光性樹脂層中における特定化合物の含有量は、質量基準で、１００ｐｐｍ以下が好ましく、２０ｐｐｍ以下がより好ましく、４ｐｐｍ以下が更に好ましい。含有量の下限値は、質量基準で、１０ｐｐｂが好ましく、１００ｐｐｂがより好ましい。特定化合物の含有量は、上記不純物と同様の方法で抑制できる。また、特定化合物の含有量は、公知の測定法により定量できる。 The content of specific compounds of benzene, formaldehyde, trichlorethylene, 1,3-butadiene, carbon tetrachloride, chloroform, N, N-dimethylformamide, N, N-dimethylacetamide, and hexane in the photosensitive resin layer is low. Is preferable. The content of the specific compound in the photosensitive resin layer is preferably 100 ppm or less, more preferably 20 ppm or less, still more preferably 4 ppm or less on a mass basis. The lower limit of the content is preferably 10 ppb, more preferably 100 ppb on a mass basis. The content of the specific compound can be suppressed in the same manner as the above impurities. In addition, the content of the specific compound can be quantified by a known measurement method.
　感光性樹脂層における水の含有量は、信頼性及びラミネート性を向上させる点から、０．０１質量％～１．０質量％が好ましく、０．０５質量％～０．５質量％がより好ましい。 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 laminateability. ..
〔熱可塑性樹脂層〕
　本開示に係る感光性転写材料は、仮支持体と感光性樹脂層との間に、熱可塑性樹脂層を備えることが好ましい。仮支持体と感光性樹脂層との間に熱可塑性樹脂層が配置されると、基板との貼り合わせ工程における基板への追従性が向上して、基板と感光性転写材料との間の気泡の混入が抑制され、隣接する層（例えば、仮支持体）との密着性が向上する。 [Thermoplastic resin layer]
The photosensitive transfer material according to the present disclosure preferably includes a thermoplastic resin layer between the temporary support and the photosensitive resin layer. When the thermoplastic resin layer is arranged between the temporary support and the photosensitive resin layer, the followability to the substrate in the bonding process with the substrate is improved, and air bubbles between the substrate and the photosensitive transfer material are improved. Is suppressed, and the adhesion to the adjacent layer (for example, temporary support) is improved.
＜成分＞
（アルカリ可溶性樹脂）
　熱可塑性樹脂層は、熱可塑性樹脂として、アルカリ可溶性樹脂を含有する。 <Ingredients>
(Alkali-soluble resin)
The thermoplastic resin layer contains an alkali-soluble resin as the thermoplastic resin.
　なお、本明細書において、「アルカリ可溶性」とは、２２℃において炭酸ナトリウムの１質量％水溶液１００ｇへの溶解度が０．１ｇ以上であることを意味する。 In the present specification, "alkali-soluble" means that the solubility of sodium carbonate in 100 g of a 1% by mass aqueous solution at 22 ° C. is 0.1 g or more.
　アルカリ可溶性樹脂としては、例えば、アクリル樹脂、ポリスチレン、スチレン－アクリル共重合体、ポリウレタン、ポリビニルアルコール、ポリビニルホルマール、ポリアミド、ポリエステル、エポキシ樹脂、ポリアセタール、ポリヒドロキシスチレン、ポリイミド、ポリベンゾオキサゾール、ポリシロキサン、ポリエチレンイミン、ポリアリルアミン及びポリアルキレングリコールが挙げられる。 Examples of the alkali-soluble resin include acrylic resin, polystyrene, styrene-acrylic copolymer, polyurethane, polyvinyl alcohol, polyvinyl formal, polyamide, polyester, epoxy resin, polyacetal, polyhydroxystyrene, polyimide, polybenzoxazole, and polysiloxane. Examples thereof include polyethyleneimine, polyallylamine and polyalkylene glycol.
　アルカリ可溶性樹脂としては、現像性及び隣接する層との密着性の観点から、アクリル樹脂が好ましい。 As the alkali-soluble resin, an acrylic resin is preferable from the viewpoint of developability and adhesion to an adjacent layer.
　ここで、アクリル樹脂は、（メタ）アクリル酸に由来する構成単位、（メタ）アクリル酸エステルに由来する構成単位、及び、（メタ）アクリル酸アミドに由来する構成単位よりなる群から選ばれた少なくとも１種の構成単位を有する樹脂を意味する。 Here, the acrylic resin was selected from the group consisting of a structural unit derived from (meth) acrylic acid, a structural unit derived from (meth) acrylic acid ester, and a structural unit derived from (meth) acrylic acid amide. It means a resin having at least one structural unit.
　アクリル樹脂としては、（メタ）アクリル酸に由来する構成単位、（メタ）アクリル酸エステルに由来する構成単位、及び、（メタ）アクリル酸アミドに由来する構成単位の合計含有量が、アクリル樹脂の全質量に対して５０質量％以上であることが好ましい。 As the acrylic resin, the total content of the structural unit derived from (meth) acrylic acid, the structural unit derived from (meth) acrylic acid ester, and the structural unit derived from (meth) acrylic acid amide is that of the acrylic resin. It is preferably 50% by mass or more with respect to the total mass.
　中でも、（メタ）アクリル酸に由来する構成単位及び（メタ）アクリル酸エステルに由来する構成単位の合計含有量が、アクリル樹脂の全質量に対して３０質量％～１００質量％であることが好ましく、５０質量％～１００質量％であることがより好ましい。 Above all, the total content of the structural unit derived from (meth) acrylic acid and the structural unit derived from (meth) acrylic acid ester is preferably 30% by mass to 100% by mass with respect to the total mass of the acrylic resin. , 50% by mass to 100% by mass, more preferably.
　また、アルカリ可溶性樹脂は、酸基を有する重合体であることが好ましい。酸基としては、カルボキシ基、スルホ基、リン酸基及びホスホン酸基が挙げられ、カルボキシ基が好ましい。 Further, the alkali-soluble resin is preferably a polymer having an acid group. Examples of the acid group include a carboxy group, a sulfo group, a phosphoric acid group and a phosphonic acid group, and a carboxy group is preferable.
　アルカリ可溶性樹脂の酸価の上限値は、特に制限されない。アルカリ可溶性樹脂の酸価は、２００ｍｇＫＯＨ／ｇ以下が好ましく、１５０ｍｇＫＯＨ／ｇ以下がより好ましい。 The upper limit of the acid value of the alkali-soluble resin is not particularly limited. The acid value of the alkali-soluble resin is preferably 200 mgKOH / g or less, more preferably 150 mgKOH / g or less.
　酸価６０ｍｇＫＯＨ／ｇ以上のカルボキシ基含有アクリル樹脂としては、特に制限されず、公知の樹脂から適宜選択して用いることができる。 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.
　酸価６０ｍｇＫＯＨ／ｇ以上のカルボキシ基含有アクリル樹脂としては、例えば、特開２０１１－９５７１６号公報の段落００２５に記載のポリマーのうち酸価６０ｍｇＫＯＨ／ｇ以上のカルボキシ基含有アクリル樹脂であるアルカリ可溶性樹脂、特開２０１０－２３７５８９号公報の段落００３３～００５２に記載のポリマーのうちの酸価６０ｍｇＫＯＨ／ｇ以上のカルボキシ基含有アクリル樹脂、及び、特開２０１６－２２４１６２号公報の段落００５３～００６８に記載のバインダーポリマーのうちの酸価６０ｍｇＫＯＨ／ｇ以上のカルボキシ基含有アクリル樹脂が挙げられる。　 Examples of the carboxy group-containing acrylic resin having an acid value of 60 mgKOH / g or more include an alkali-soluble resin which is a carboxy group-containing acrylic resin having an acid value of 60 mgKOH / g or more among the polymers described in paragraph 0025 of JP2011-95716A. , 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 JP2010-237589A, and paragraphs 0053 to 0068 of JP2016-224162A. Among the binder polymers, a carboxy group-containing acrylic resin having an acid value of 60 mgKOH / g or more can be mentioned. Twice
　上記カルボキシ基含有アクリル樹脂におけるカルボキシ基を有する構成単位の含有量は、アクリル樹脂の全質量に対して、５質量％～５０質量％が好ましく、１０質量％～４０質量％がより好ましく、１２質量％～３０質量％がさらに好ましい。 The content of the structural unit having a carboxy group in the carboxy group-containing acrylic resin is preferably 5% by mass to 50% by mass, more preferably 10% by mass to 40% by mass, and 12% by mass with respect to the total mass of the acrylic resin. % To 30% by mass is more preferable.
　アルカリ可溶性樹脂は、現像性及び隣接する層との密着性の観点から、（メタ）アクリル酸に由来する構成単位を有するアクリル樹脂が特に好ましい。 As the alkali-soluble resin, 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.
　アルカリ可溶性樹脂は、反応性基を有していてもよい。反応性基としては、付加重合可能な基であればよく、エチレン性不飽和基；ヒドロキシ基、カルボキシ基等の重縮合性基；エポキシ基、（ブロック）イソシアネート基等の重付加反応性基が挙げられる。 The alkali-soluble resin may have a reactive group. The reactive group may be any addition-polymerizable group, and an ethylenically unsaturated group; a polycondensable group such as a hydroxy group or a carboxy group; a polyadditive reactive group such as an epoxy group or a (block) isocyanate group may be used. Can be mentioned.
　アルカリ可溶性樹脂の重量平均分子量（Ｍｗ）は、１，０００以上が好ましく、１万～１０万がより好ましく、２万～５万がさらに好ましい。 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.
　熱可塑性樹脂層は、アルカリ可溶性樹脂を１種単独で含有してもよく、２種以上を含有してもよい。
　アルカリ可溶性樹脂の含有量は、現像性及び隣接する層との密着性の観点から、熱可塑性樹脂層の全質量に対して、１０質量％～９９質量％が好ましく、２０質量％～９０質量％がより好ましく、４０質量％～８０質量％がさらに好ましく、５０質量％～７０質量％が特に好ましい。 The thermoplastic resin layer may contain one kind of alkali-soluble resin alone or two or more kinds.
The content of the alkali-soluble resin is preferably 10% by mass to 99% by mass, preferably 20% by mass to 90% by mass, based on the total mass of the thermoplastic resin layer from the viewpoint of developability and adhesion to the adjacent layer. Is more preferable, 40% by mass to 80% by mass is further preferable, and 50% by mass to 70% by mass is particularly preferable.
（色素）
　熱可塑性樹脂層は、発色時の波長範囲４００ｎｍ～７８０ｎｍにおける最大吸収波長が４５０ｎｍ以上であり、酸、塩基、又はラジカルにより最大吸収波長が変化する色素（単に「色素Ｂ」ともいう。）を含有することが好ましい。色素Ｂの好ましい態様は、後述する点以外は、色素Ｎの好ましい態様と同様である。 (Dye)
The thermoplastic resin layer contains a dye (also simply referred to as "dye B") having a maximum absorption wavelength of 450 nm or more in the wavelength range of 400 nm to 780 nm at the time of color development and whose maximum absorption wavelength is changed by an acid, a base, or a radical. It is preferable to do so. The preferred embodiment of the dye B is the same as the preferred embodiment of the dye N except for the points described later.
　色素Ｂは、露光部及び非露光部の視認性並びに解像性の観点から、酸又はラジカルにより最大吸収波長が変化する色素が好ましく、酸により最大吸収波長が変化する色素であることがより好ましい。 The dye B is preferably a dye whose maximum absorption wavelength is changed by an acid or radical, and more preferably a dye whose maximum absorption wavelength is changed by an acid, from the viewpoint of visibility and resolution of exposed and unexposed areas. ..
　熱可塑性層は、露光部及び非露光部の視認性並びに解像性の観点から、色素Ｂとしての酸により最大吸収波長が変化する色素、及び、後述する光により酸を発生する化合物の両者を含有することが好ましい。 From the viewpoint of visibility and resolution of the exposed and unexposed areas, the thermoplastic layer contains both a dye whose maximum absorption wavelength changes depending on the acid as the dye B and a compound that generates an acid by light, which will be described later. It is preferable to contain it.
　熱可塑性樹脂層は、色素Ｂを、１種単独で含有してもよいし、２種以上含有してもよい。 The thermoplastic resin layer may contain dye B alone or in combination of two or more.
　色素Ｂの含有量は、露光部及び非露光部の視認性の観点から、熱可塑性樹脂層の全質量に対して、０．２質量％以上が好ましく、０．２質量％～６質量％がより好ましく、０．２質量％～５質量％がさらに好ましく、０．２５質量％～３．０質量％が特に好ましい。 The content of the dye B is preferably 0.2% by mass or more, preferably 0.2% by mass to 6% by mass, based on the total mass of the thermoplastic resin layer from the viewpoint of visibility of the exposed part and the non-exposed part. More preferably, 0.2% by mass to 5% by mass is further preferable, and 0.25% by mass to 3.0% by mass is particularly preferable.
　ここで、色素Ｂの含有量は、熱可塑性樹脂層に含まれる色素Ｂの全てを発色状態にした場合の色素の含有量を意味する。以下に、ラジカルにより発色する色素を例に、色素Ｂの含有量の定量方法を説明する。 Here, 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. Hereinafter, a method for quantifying the content of dye B will be described by taking a dye that develops color by radicals as an example.
　メチルエチルケトン１００ｍＬに、色素０．００１ｇ及び０．０１ｇを溶解させた溶液を調製する。得られた各溶液に、光ラジカル重合開始剤（Ｉｒｇａｃｕｒｅ　ＯＸＥ０１、ＢＡＳＦジャパン社製）を加え、３６５ｎｍの光を照射することによりラジカルを発生させ、全ての色素を発色状態にする。その後、大気雰囲気下で、分光光度計（ＵＶ３１００、島津製作所製）を用いて、液温が２５℃である各溶液の吸光度を測定し、検量線を作成する。 Prepare a solution in which 0.001 g and 0.01 g of dye are dissolved in 100 mL of methyl ethyl ketone. A photoradical polymerization initiator (Irgacure OXE01, manufactured by BASF Japan Ltd.) is added to each of the obtained solutions, and radicals are generated by irradiating with light of 365 nm to bring all the dyes into a colored state. Then, in an air atmosphere, the absorbance of each solution having a liquid temperature of 25 ° C. is measured using a spectrophotometer (UV3100, manufactured by Shimadzu Corporation) to prepare a calibration curve.
　次に、色素に代えて熱可塑性樹脂層０．１ｇをメチルエチルケトンに溶解させること以外は上記と同様の方法で、色素を全て発色させた溶液の吸光度を測定する。得られた熱可塑性樹脂層を含有する溶液の吸光度から、検量線に基づいて熱可塑性樹脂層に含まれる色素の量を算出する。 Next, the absorbance of the solution in which all the dyes are colored is measured by the same method as above except that 0.1 g of the thermoplastic resin layer is dissolved in methyl ethyl ketone instead of the dye. From the absorbance of the obtained solution containing the thermoplastic resin layer, the amount of the dye contained in the thermoplastic resin layer is calculated based on the calibration curve.
（光により酸、塩基又はラジカルを発生する化合物）
　熱可塑性樹脂層は、光により酸、塩基又はラジカルを発生する化合物（単に「化合物Ｃ」ともいう。）を含有してもよい。 (Compounds that generate acids, bases or radicals with light)
The thermoplastic resin layer may contain a compound that generates an acid, a base, or a radical by light (also simply referred to as “Compound C”).
　化合物Ｃとしては、紫外線及び可視光線等の活性光線を受けて、酸、塩基、又はラジカルを発生する化合物が好ましい。 As the compound C, a compound that generates an acid, a base, or a radical by receiving active rays such as ultraviolet rays and visible rays is preferable.
　化合物Ｃは、公知の、光酸発生剤、光塩基発生剤、及び、光ラジカル重合開始剤（光ラジカル発生剤）であってもよい。中でも、化合物Ｃは光酸発生剤であることが好ましい。 Compound C may be a known photoacid generator, photobase generator, and photoradical polymerization initiator (photoradical generator). Above all, compound C is preferably a photoacid generator.
－光酸発生剤－
　熱可塑性樹脂層は、解像性の観点から、光酸発生剤を含有することが好ましい。
　光酸発生剤としては、上述した感光性樹脂層が含有してもよい光カチオン重合開始剤が挙げられ、後述する点以外は好ましい態様も同じである。 -Photoacid generator-
The thermoplastic resin layer preferably contains a photoacid generator from the viewpoint of resolution.
Examples of the photoacid generator include a photocationic polymerization initiator that may be contained in the above-mentioned photosensitive resin layer, and the same preferred embodiments are used except for the points described below.
　光酸発生剤は、感度及び解像性の観点から、オニウム塩化合物、及び、オキシムスルホネート化合物からなる群より選ばれた少なくとも１種の化合物であることが好ましく、感度、解像性及び密着性の観点から、オキシムスルホネート化合物であることがより好ましい。
　また、光酸発生剤は、以下の構造を有する光酸発生剤も好ましい。 From the viewpoint of sensitivity and resolution, the photoacid generator is preferably at least one compound selected from the group consisting of an onium salt compound and an oxime sulfonate compound, and has sensitivity, resolution and adhesion. From the viewpoint of the above, it is more preferable that the compound is an oxime sulfonate compound.
Further, as the photoacid generator, a photoacid generator having the following structure is also preferable.
Figure JPOXMLDOC01-appb-C000002
Figure JPOXMLDOC01-appb-C000002
－光ラジカル重合開始剤－
　熱可塑性樹脂層は、光ラジカル重合開始剤を含有してもよい。
　光ラジカル重合開始剤としては、上述した感光性樹脂層が含有してもよい光ラジカル重合開始剤が挙げられ、好ましい態様も同じである。 -Photoradical polymerization initiator-
The thermoplastic resin layer may contain a photoradical polymerization initiator.
Examples of the photoradical polymerization initiator include a photoradical polymerization initiator that may be contained in the photosensitive resin layer described above, and the preferred embodiment is also the same.
－光塩基発生剤－
　熱可塑性樹脂層は、光塩基発生剤を含有してもよい。
　光塩基発生剤としては、公知の光塩基発生剤であれば特に制限されず、例えば、２－ニトロベンジルシクロヘキシルカルバメート、トリフェニルメタノール、Ｏ－カルバモイルヒドロキシルアミド、Ｏ－カルバモイルオキシム、［［（２，６－ジニトロベンジル）オキシ］カルボニル］シクロヘキシルアミン、ビス［［（２－ニトロベンジル）オキシ］カルボニル］ヘキサン１，６－ジアミン、４－（メチルチオベンゾイル）－１－メチル－１－モルホリノエタン、（４－モルホリノベンゾイル）－１－ベンジル－１－ジメチルアミノプロパン、Ｎ－（２－ニトロベンジルオキシカルボニル）ピロリジン、ヘキサアンミンコバルト（ＩＩＩ）トリス（トリフェニルメチルボレート）、２－ベンジル－２－ジメチルアミノ－１－（４－モルホリノフェニル）－ブタノン、２，６－ジメチル－３，５－ジアセチル－４－（２－ニトロフェニル）－１，４－ジヒドロピリジン、及び、２，６－ジメチル－３，５－ジアセチル－４－（２，４－ジニトロフェニル）－１，４－ジヒドロピリジンが挙げられる。 -Photobase generator-
The thermoplastic resin layer may contain a photobase generator.
The photobase generator is not particularly limited as long as it is a known photobase generator, and for example, 2-nitrobenzylcyclohexylcarbamate, triphenylmethanol, O-carbamoyl hydroxylamide, O-carbamoyloxime, [[(2,2). 6-Dinitrobenzyl) oxy] carbonyl] cyclohexylamine, bis [[(2-nitrobenzyl) oxy] carbonyl] hexane 1,6-diamine, 4- (methylthiobenzoyl) -1-methyl-1-morpholinoetan, (4) -Morholinobenzoyl) -1-benzyl-1-dimethylaminopropane, N- (2-nitrobenzyloxycarbonyl) pyrrolidine, hexaammine cobalt (III) tris (triphenylmethylborate), 2-benzyl-2-dimethylamino- 1- (4-morpholinophenyl) -butanone, 2,6-dimethyl-3,5-diacetyl-4- (2-nitrophenyl) -1,4-dihydropyridine, and 2,6-dimethyl-3,5- Examples thereof include diacetyl-4- (2,4-dinitrophenyl) -1,4-dihydropyridine.
　熱可塑性樹脂層は、化合物Ｃを、１種単独で含有してもよいし、２種以上を含有してもよい。 The thermoplastic resin layer may contain one type of compound C alone, or may contain two or more types of compound C.
　化合物Ｃの含有量は、露光部及び非露光部の視認性並びに解像性の観点から、熱可塑性樹脂層の全質量に対して、０．１質量％～１０質量％が好ましく、０．５質量％～５質量％がより好ましい。 The content of compound C is preferably 0.1% by mass to 10% by mass, preferably 0.5% by mass, based on the total mass of the thermoplastic resin layer from the viewpoint of visibility and resolution of the exposed and unexposed areas. More preferably, it is by mass% to 5% by mass.
（可塑剤）
　熱可塑性樹脂層は、解像性、隣接する層との密着性及び現像性の観点から、可塑剤を含有することが好ましい。 (Plasticizer)
The thermoplastic resin layer preferably contains a plasticizer from the viewpoints of resolution, adhesion to adjacent layers, and developability.
　可塑剤は、アルカリ可溶性樹脂よりも分子量（オリゴマー又はポリマーである場合は重量平均分子量（Ｍｗ））が小さいことが好ましい。可塑剤の分子量（重量平均分子量（Ｍｗ））は、２００～２，０００が好ましい。 The plasticizer preferably has a smaller molecular weight (weight average molecular weight (Mw) in the case of an oligomer or polymer) than the alkali-soluble resin. The molecular weight of the plasticizer (weight average molecular weight (Mw)) is preferably 200 to 2,000.
　可塑剤は、アルカリ可溶性樹脂と相溶して可塑性を発現する化合物であれば特に制限されない。可塑剤は、可塑性付与の観点から、分子中にアルキレンオキシ基を有することが好ましく、ポリアルキレングリコール化合物がより好ましい。可塑剤に含まれるアルキレンオキシ基は、ポリエチレンオキシ構造又はポリプロピレンオキシ構造を有することがより好ましい。 The plasticizer is not particularly limited as long as it is a compound that develops plasticity by being compatible with an alkali-soluble resin. The plasticizer preferably has an alkyleneoxy group in the molecule from the viewpoint of imparting plasticity, and a polyalkylene glycol compound is more preferable. The alkyleneoxy group contained in the plasticizer more preferably has a polyethyleneoxy structure or a polypropyleneoxy structure.
　また、可塑剤は、解像性及び保存安定性の観点から、（メタ）アクリレート化合物を含有することが好ましい。相溶性、解像性及び隣接する層との密着性の観点から、アルカリ可溶性樹脂がアクリル樹脂であり、かつ、可塑剤が（メタ）アクリレート化合物を含有することがより好ましい。 Further, the plasticizer preferably contains a (meth) acrylate compound from the viewpoint of resolution and storage stability. From the viewpoint of compatibility, resolution and adhesion to the adjacent layer, it is more preferable that the alkali-soluble resin is an acrylic resin and the plasticizer contains a (meth) acrylate compound.
　可塑剤として用いられる（メタ）アクリレート化合物としては、上述した感光性樹脂層に含有される重合性化合物Ｂとして記載した（メタ）アクリレート化合物が挙げられる。 Examples of the (meth) acrylate compound used as a plasticizer include the (meth) acrylate compound described as the polymerizable compound B contained in the photosensitive resin layer described above.
　感光性転写材料において、熱可塑性樹脂層と感光性樹脂層とが直接接触して積層される場合、熱可塑性樹脂層及び感光性樹脂層が同じ（メタ）アクリレート化合物を含有することが好ましい。熱可塑性樹脂層及び感光性樹脂層がそれぞれ、同じ（メタ）アクリレート化合物を含有すると、層間の成分拡散が抑制され、保存安定性が向上する。 In the photosensitive transfer material, when the thermoplastic resin layer and the photosensitive resin layer are directly contacted and laminated, it is preferable that the thermoplastic resin layer and the photosensitive resin layer contain the same (meth) acrylate compound. When the thermoplastic resin layer and the photosensitive resin layer each contain the same (meth) acrylate compound, the diffusion of components between the layers is suppressed and the storage stability is improved.
　熱可塑性樹脂層が可塑剤として（メタ）アクリレート化合物を含有する場合、隣接する層との密着性の観点から、露光後の露光部においても（メタ）アクリレート化合物が重合しないことが好ましい。 When the thermoplastic resin layer contains a (meth) acrylate compound as a plasticizer, it is preferable that the (meth) acrylate compound does not polymerize even in the exposed portion after exposure from the viewpoint of adhesion to the adjacent layer.
　また、可塑剤として用いられる（メタ）アクリレート化合物は、解像性、隣接する層との密着性及び現像性の観点から、一分子中に２つ以上の（メタ）アクリロイル基を有する多官能（メタ）アクリレート化合物であることが好ましい。 In addition, the (meth) acrylate compound used as a plasticizer is polyfunctional (meth) having two or more (meth) acryloyl groups in one molecule from the viewpoint of resolution, adhesion to adjacent layers, and developability. It is preferably a meta) acrylate compound.
　さらに、可塑剤として用いられる（メタ）アクリレート化合物は、酸基を有する（メタ）アクリレート化合物、又は、ウレタン（メタ）アクリレート化合物であることも好ましい。 Further, the (meth) acrylate compound used as a plasticizer is preferably a (meth) acrylate compound having an acid group or a urethane (meth) acrylate compound.
　熱可塑性樹脂層は、可塑剤を１種単独で含有してもよいし、２種以上を含有してもよい。 The thermoplastic resin layer may contain one type of plasticizer alone, or may contain two or more types of plasticizer.
　可塑剤の含有量は、解像性、隣接する層との密着性及び現像性の観点から、熱可塑性樹脂層の全質量に対して、１質量％～７０質量％が好ましく、１０質量％～６０質量％がより好ましく、２０質量％～５０質量％が特に好ましい。 The content of the plastic agent is preferably 1% by mass to 70% by mass, preferably 10% by mass or more, based on the total mass of the thermoplastic resin layer from the viewpoint of resolution, adhesion to the adjacent layer, and developability. 60% by mass is more preferable, and 20% by mass to 50% by mass is particularly preferable.
（界面活性剤）
　熱可塑性樹脂層は、厚さ均一性の観点から、界面活性剤を含有することが好ましい。界面活性剤としては、上述した感光性樹脂層が含有してもよい界面活性剤が挙げられ、好ましい態様も同じである。 (Surfactant)
The thermoplastic resin layer preferably contains a surfactant from the viewpoint of thickness uniformity. Examples of the surfactant include surfactants that may be contained in the above-mentioned photosensitive resin layer, and the preferred embodiment is the same.
　熱可塑性樹脂層は、界面活性剤を１種単独で含有してもよいし、２種以上を含有してもよい。 The thermoplastic resin layer may contain one type of surfactant alone or two or more types.
　界面活性剤の含有量は、熱可塑性樹脂層の全質量に対し、０．００１質量％～１０質量％が好ましく、０．０１質量％～３質量％がより好ましい。 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.
（増感剤）
　熱可塑性樹脂層は、増感剤を含有してもよい。増感剤としては、特に制限されず、上述した感光性樹脂層が含有してもよい増感剤が挙げられる。 (Sensitizer)
The thermoplastic resin layer may contain a sensitizer. The sensitizer is not particularly limited, and examples thereof include a sensitizer that may be contained in the above-mentioned photosensitive resin layer.
　熱可塑性樹脂層は、増感剤を、１種単独で含有してもよいし、２種以上を含有してもよい。 The thermoplastic resin layer may contain one type of sensitizer alone or two or more types.
　増感剤の含有量は、目的により適宜選択できるが、光源に対する感度の向上、及び、露光部及び非露光部の視認性の観点から、熱可塑性樹脂層の全質量に対し、０．０１質量％～５質量％の範囲が好ましく、０．０５質量％～１質量％の範囲がより好ましい。 The content of the sensitizer can be appropriately selected depending on the purpose, but from the viewpoint of improving the sensitivity to the light source and the visibility of the exposed and non-exposed areas, 0.01 mass with respect to the total mass of the thermoplastic resin layer. The range of% to 5% by mass is preferable, and the range of 0.05% by mass to 1% by mass is more preferable.
（添加剤等）
　熱可塑性樹脂層は、上記成分以外に、必要に応じて公知の添加剤を含有してもよい。また、熱可塑性樹脂層については、特開２０１４－８５６４３号公報の段落０１８９～０１９３に記載されており、この公報に記載の内容は本明細書に組み込まれる。 (Additives, etc.)
In addition to the above components, the thermoplastic resin layer may contain known additives, if necessary. 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 in the present specification.
＜物性等＞
　熱可塑性樹脂層の厚さは、特に制限されないが、隣接する層との密着性の観点から、１μｍ以上が好ましく、２μｍ以上がより好ましい。熱可塑性樹脂層の厚さの上限値は特に制限されない。熱可塑性樹脂層の厚さは、現像性及び解像性の観点から、２０μｍ以下が好ましく、１０μｍ以下がより好ましく、５μｍ以下がさらに好ましい。 <Physical characteristics, etc.>
The thickness of the thermoplastic resin layer is not particularly limited, but is preferably 1 μm or more, more preferably 2 μm or more, from the viewpoint of adhesion to adjacent layers. The upper limit of the thickness of the thermoplastic resin layer is not particularly limited. The thickness of the thermoplastic resin layer is preferably 20 μm or less, more preferably 10 μm or less, still more preferably 5 μm or less, from the viewpoint of developability and resolvability.
＜形成方法＞
　熱可塑性樹脂層の形成方法は、上記の成分を含有する層を形成可能な方法であれば特に制限されない。 <Formation method>
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.
　熱可塑性樹脂層の形成方法としては、例えば、上記の成分と溶剤とを含有する熱可塑性樹脂組成物を調製し、仮支持体等の表面に熱可塑性樹脂組成物を塗布し、熱可塑性樹脂組成物の塗膜を乾燥させることにより形成する方法が挙げられる。 As a method for forming the thermoplastic resin layer, for example, a thermoplastic resin composition containing the above components and a solvent is prepared, and the thermoplastic resin composition is applied to the surface of a temporary support or the like to form the thermoplastic resin composition. Examples thereof include a method of forming by drying a coating film of an object.
　熱可塑性樹脂組成物は、熱可塑性樹脂組成物の粘度を調節し、熱可塑性樹脂層の形成を容易にするため、溶剤を含有することが好ましい。 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.
（溶剤）
　熱可塑性樹脂組成物に含有される溶剤としては、熱可塑性樹脂層に含有される上記成分を溶解又は分散可能であれば特に制限されない。 (solvent)
The solvent contained in the thermoplastic resin composition is not particularly limited as long as the above-mentioned components contained in the thermoplastic resin layer can be dissolved or dispersed.
　熱可塑性樹脂組成物に含有される溶剤としては、上述した感光性樹脂組成物が含有してもよい溶剤が挙げられ、好ましい態様も同じである。 Examples of the solvent contained in the thermoplastic resin composition include a solvent that may be contained in the above-mentioned photosensitive resin composition, and the preferred embodiment is also the same.
　熱可塑性樹脂組成物に含有される溶剤は、１種単独であってもよく、２種以上であってもよい。 The solvent contained in the thermoplastic resin composition may be one kind alone or two or more kinds.
　熱可塑性樹脂組成物における溶剤の含有量は、熱可塑性樹脂組成物中の全固形分１００質量部に対し、５０質量部～１，９００質量部が好ましく、１００質量部～９００質量部がより好ましい。 The content of the solvent in the thermoplastic resin composition is preferably 50 parts by mass to 1,900 parts by mass, more preferably 100 parts by mass to 900 parts by mass, based on 100 parts by mass of the total solid content in the thermoplastic resin composition. ..
　熱可塑性樹脂組成物の調製及び熱可塑性樹脂層の形成は、上述した感光性樹脂組成物の調製方法及び感光性樹脂層の形成方法に準じて行えばよい。 The preparation of the thermoplastic resin composition and the formation of the thermoplastic resin layer may be carried out according to the method for preparing the photosensitive resin composition and the method for forming the photosensitive resin layer described above.
　例えば、熱可塑性樹脂層に含有される各成分を上記溶剤に溶解させた溶液を予め調製し、得られた溶液を所定の割合で混合することにより、熱可塑性樹脂組成物が調製した後、得られた熱可塑性樹脂組成物を仮支持体の表面に塗布し、熱可塑性樹脂組成物の塗膜を乾燥させることにより、熱可塑性樹脂層が形成される。 For example, a solution in which each component contained in the thermoplastic resin layer is dissolved in the above solvent is prepared in advance, and the obtained solution is mixed at a predetermined ratio to prepare a thermoplastic resin composition, which is then obtained. The obtained thermoplastic resin composition is applied to the surface of the temporary support, and the coating film of the thermoplastic resin composition is dried to form the thermoplastic resin layer.
　また、後述するカバーフィルム上に、感光性樹脂層及び中間層を形成した後、中間層の表面に熱可塑性樹脂層を形成してもよい。 Further, after forming the photosensitive resin layer and the intermediate layer on the cover film described later, the thermoplastic resin layer may be formed on the surface of the intermediate layer.
〔中間層〕
　感光性転写材料は、熱可塑性樹脂層と感光性樹脂層との間に、中間層を備えることが好ましい。中間層を配置することにより、複数層を塗布する際及び塗布後の保存の際における成分の混合を抑制できる。 [Middle layer]
The photosensitive transfer material preferably has an intermediate layer between the thermoplastic resin layer and the photosensitive resin layer. By arranging the intermediate layer, it is possible to suppress the mixing of the components when the plurality of layers are applied and when the layers are stored after application.
　中間層は、現像性、並びに、複数層を塗布する際及び塗布後の保存の際における成分の混合を抑制する観点から、水溶性の層であることが好ましい。 The intermediate layer is preferably a water-soluble layer from the viewpoint of developability and suppressing mixing of components during application of the plurality of layers and storage after application.
　なお、本明細書において「水溶性」とは、液温が２２℃であるｐＨ７．０の水１００ｇへの溶解度が０．１ｇ以上であることを意味する。 In the present specification, "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.
　中間層としては、特開平５－７２７２４号公報に「分離層」として記載されている、酸素遮断機能のある酸素遮断層が挙げられる。中間層が酸素遮断層であると、露光時の感度が向上し、露光機の時間負荷が低減し、生産性が向上する。 Examples of the intermediate layer include an oxygen blocking layer having an oxygen blocking function, which is described as a "separation layer" in Japanese Patent Application Laid-Open No. 5-72724. When the intermediate layer is an oxygen blocking layer, the sensitivity at the time of exposure is improved, the time load of the exposure machine is reduced, and the productivity is improved.
　中間層として用いられる酸素遮断層は、上記公報等に記載された公知の層から適宜選択すればよい。中でも、中間層は、低い酸素透過性を示し、水又はアルカリ水溶液（２２℃の炭酸ナトリウムの１質量％水溶液）に分散又は溶解する酸素遮断層であることが好ましい。 The oxygen blocking layer used as the intermediate layer may be appropriately selected from the known layers described in the above publications and the like. Above all, the intermediate layer is preferably 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.).
　中間層は、樹脂を含有することが好ましい。
　中間層に含有される樹脂としては、例えば、ポリビニルアルコール系樹脂、ポリビニルピロリドン系樹脂、セルロース系樹脂、アクリルアミド系樹脂、ポリエチレンオキサイド系樹脂、ゼラチン、ビニルエーテル系樹脂、ポリアミド、及び、これらの共重合体等の樹脂が挙げられる。 The intermediate layer preferably contains a resin.
Examples of the resin contained in the intermediate layer include polyvinyl alcohol-based resin, polyvinylpyrrolidone-based resin, cellulose-based resin, acrylamide-based resin, polyethylene oxide-based resin, gelatin, vinyl ether-based resin, polyamide, and copolymers thereof. And other resins.
　中間層に含有される樹脂としては、水溶性樹脂が好ましい。
　また、中間層に含有される樹脂は、複数層間の成分の混合を抑制する観点から、感光性樹脂層に含有される重合体Ａ、及び、熱可塑性樹脂層に含有される熱可塑性樹脂（アルカリ可溶性樹脂）のいずれとも異なる樹脂であることが好ましい。 As the resin contained in the intermediate layer, a water-soluble resin is preferable.
Further, the resin contained in the intermediate layer includes the polymer A contained in the photosensitive resin layer and the thermoplastic resin (alkali) contained in the thermoplastic resin layer from the viewpoint of suppressing the mixing of the components between the plurality of layers. It is preferable that the resin is different from any of the soluble resins).
　中間層は、酸素遮断性、並びに、複数層を塗布する際及び塗布後の保存の際における成分の混合を抑制する観点から、ポリビニルアルコールを含有することが好ましく、ポリビニルアルコール及びポリビニルピロリドンの両者を含有することがより好ましい。 The intermediate layer preferably contains polyvinyl alcohol from the viewpoint of oxygen blocking property and suppressing mixing of components during application of the plurality of layers and storage after application, and contains both polyvinyl alcohol and polyvinylpyrrolidone. It is more preferable to contain it.
　中間層は、上記樹脂を１種単独で含有してもよく、２種以上を含有してもよい。 The intermediate layer may contain the above resin alone or in combination of two or more.
　中間層における樹脂の含有量は、特に制限されないが、酸素遮断性、並びに、複数層を塗布する際及び塗布後の保存の際における成分の混合を抑制する観点から、中間層の全質量に対し、５０質量％～１００質量％が好ましく、７０質量％～１００質量％がより好ましく、８０～１００質量％がさらに好ましく、９０質量％～１００質量％が特に好ましい。 The content of the resin in the intermediate layer is not particularly limited, but is based on the total mass of the intermediate layer from the viewpoint of oxygen blocking property and suppressing the mixing of components during application of the plurality of layers and storage after application. , 50% by mass to 100% by mass, more preferably 70% by mass to 100% by mass, further preferably 80 to 100% by mass, and particularly preferably 90% by mass to 100% by mass.
　また、中間層は、必要に応じて界面活性剤等の添加剤を含有してもよい。 Further, the intermediate layer may contain an additive such as a surfactant, if necessary.
　中間層の厚さは、特に制限されないが、０．１μｍ～５μｍが好ましく、０．５μｍ～３μｍがより好ましい。 The thickness of the intermediate layer is not particularly limited, but is preferably 0.1 μm to 5 μm, and more preferably 0.5 μm to 3 μm.
　中間層の厚さが上記の範囲内であると、酸素遮断性を低下させることがなく、複数層を塗布する際及び塗布後の保存の際における成分の混合を抑制できる。また、中間層の厚さが上記の範囲内であると、現像時の中間層除去時間の増大を抑制できる。 When the thickness of the intermediate layer is within the above range, the oxygen blocking property is not lowered, and the mixing of the components at the time of applying the plurality of layers and at the time of storage after application can be suppressed. Further, when the thickness of the intermediate layer is within the above range, an increase in the intermediate layer removal time during development can be suppressed.
　中間層の形成方法は、特に制限されず、例えば、上記樹脂及び任意の添加剤を含有する中間層組成物を調製し、熱可塑性樹脂層又は感光性樹脂層の表面に塗布し、中間層組成物の塗膜を乾燥させることにより、中間層を形成する方法が挙げられる。 The method for forming the intermediate layer is not particularly limited, and for example, an intermediate layer composition containing the above resin and any additive is prepared and applied to the surface of the thermoplastic resin layer or the photosensitive resin layer to form the intermediate layer composition. Examples thereof include a method of forming an intermediate layer by drying a coating film of an object.
　中間層組成物は、中間層組成物の粘度を調節し、中間層の形成を容易にするため、溶剤を含有することが好ましい。 The intermediate layer composition preferably contains a solvent in order to adjust the viscosity of the intermediate layer composition and facilitate the formation of the intermediate layer.
　中間層組成物に含有される溶剤としては、上記樹脂を溶解又は分散可能であれば特に制限されず、水及び水混和性の有機溶剤からなる群より選択される少なくとも１種が好ましく、水又は水と水混和性の有機溶剤との混合溶剤がより好ましい。 The solvent contained in the intermediate layer composition is not particularly limited as long as the above resin can be dissolved or dispersed, and at least one selected from the group consisting of water and a water-miscible organic solvent is preferable, and water or water or water is preferable. A mixed solvent of water and a water-miscible organic solvent is more preferable.
　水混和性の有機溶剤としては、例えば、炭素数１～３のアルコール、アセトン、エチレングリコール及びグリセリンが挙げられ、炭素数１～３のアルコールが好ましく、メタノール又はエタノールがより好ましい。 Examples of the water-miscible organic solvent include alcohols having 1 to 3 carbon atoms, acetone, ethylene glycol and glycerin, and alcohols having 1 to 3 carbon atoms are preferable, and methanol or ethanol is more preferable.
〔カバーフィルム〕
　感光性転写材料は、感光性樹脂層の仮支持体に対向していない面に接するカバーフィルムを備えることが好ましい。
　以下、本明細書において、感光性樹脂層の仮支持体に対向する面を「第１面」ともいい、第１面とは反対側の面を「第２面」ともいう。 [Cover film]
The photosensitive transfer material preferably includes a cover film that is in contact with a surface of the photosensitive resin layer that does not face the temporary support.
Hereinafter, in the present specification, the surface of the photosensitive resin layer facing the temporary support is also referred to as a "first surface", and the surface opposite to the first surface is also referred to as a "second surface".
　カバーフィルムを構成する材料としては、樹脂フィルム及び紙が挙げられる。中でも、カバーフィルムを構成する材料は、強度及び可撓性の観点から、樹脂フィルムであることが好ましい。 Examples of the material constituting the cover film include a resin film and paper. Above all, the material constituting the cover film is preferably a resin film from the viewpoint of strength and flexibility.
　樹脂フィルムとしては、ポリエチレンフィルム、ポリプロピレンフィルム、ポリエチレンテレフタレートフィルム、トリ酢酸セルロースフィルム、ポリスチレンフィルム、及び、ポリカーボネートフィルムが挙げられる。中でも、樹脂フィルムは、ポリエチレンフィルム、ポリプロピレンフィルム、又は、ポリエチレンテレフタレートフィルムであることが好ましい。 Examples of the resin film include polyethylene film, polypropylene film, polyethylene terephthalate film, cellulose triacetate film, polystyrene film, and polycarbonate film. Above all, the resin film is preferably a polyethylene film, a polypropylene film, or a polyethylene terephthalate film.
　カバーフィルムの厚さは、特に制限されないが、５μｍ～１００μｍが好ましく、１０μｍ～５０μｍがより好ましい。 The thickness of the cover film is not particularly limited, but is preferably 5 μm to 100 μm, and more preferably 10 μm to 50 μm.
　また、カバーフィルムの感光性樹脂層に接する面（以下単に「カバーフィルムの表面」ともいう）の算術平均粗さＲａ値は、解像性により優れる点から、０．３μｍ以下が好ましく、０．１μｍ以下がより好ましく、０．０５μｍ以下がさらに好ましい。カバーフィルムの表面のＲａ値が上記範囲であることにより、感光性樹脂層及び形成される樹脂パターンの層厚の均一性が向上すると考えられる。 Further, the arithmetic mean roughness Ra value of the surface of the cover film in contact with the photosensitive resin layer (hereinafter, also simply referred to as “the surface of the cover film”) is preferably 0.3 μm or less from the viewpoint of excellent resolution. 1 μm or less is more preferable, and 0.05 μm or less is further preferable. It is considered that when the Ra value on the surface of the cover film is within the above range, the uniformity of the layer thickness of the photosensitive resin layer and the formed resin pattern is improved.
　カバーフィルムの表面のＲａ値の下限値は特に制限されない。カバーフィルムの表面のＲａ値は、０．００１μｍ以上が好ましい。 The lower limit of the Ra value on the surface of the cover film is not particularly limited. The Ra value on the surface of the cover film is preferably 0.001 μm or more.
　カバーフィルムの表面のＲａ値は、以下の方法で測定される。
　３次元光学プロファイラー（Ｎｅｗ　Ｖｉｅｗ７３００、Ｚｙｇｏ社製）を用いて、以下の条件にてカバーフィルムの表面を測定し、光学フィルムの表面プロファイルを得る。測定・解析ソフトとしては、ＭｅｔｒｏＰｒｏ　ｖｅｒ８．３．２のＭｉｃｒｏｓｃｏｐｅ　Ａｐｐｌｉｃａｔｉｏｎを用いる。次に、上記解析ソフトにてＳｕｒｆａｃｅ　Ｍａｐ画面を表示し、Ｓｕｒｆａｃｅ　Ｍａｐ画面中でヒストグラムデータを得る。得られたヒストグラムデータから、算術平均粗さを算出し、カバーフィルムの表面のＲａ値を得る。
　カバーフィルムが感光性転写材料に貼り合わされている場合は、感光性転写材料からカバーフィルムを剥離して、剥離した側の表面のＲａ値を測定すればよい。 The Ra value on the surface of the cover film is measured by the following method.
Using a three-dimensional optical profiler (New View7300, manufactured by Zygo), the surface of the cover film is measured under the following conditions to obtain a surface profile of the optical film. As the measurement / analysis software, Microscope Application of MetroPro ver 8.3.2 is used. Next, the Surface Map screen is displayed with the above analysis software, and histogram data is obtained in the Surface Map screen. From the obtained histogram data, the arithmetic mean roughness is calculated to obtain the Ra value of the surface of the cover film.
When the cover film is attached to the photosensitive transfer material, the cover film may be peeled from the photosensitive transfer material and the Ra value of the surface on the peeled side may be measured.
　感光性転写材料は、上述した層以外の層（以下「その他の層」ともいう。）を備えてもよい。その他の層としては、例えば、コントラストエンハンスメント層が挙げられる。
　コントラストエンハンスメント層については、国際公開第２０１８／１７９６４０号の段落０１３４に記載されている。また、その他の層については特開２０１４－８５６４３号公報の段落０１９４～０１９６に記載されている。これらの公報の内容は本明細書に組み込まれる。 The photosensitive transfer material may include a layer other than the above-mentioned layer (hereinafter, also referred to as “other layer”). Other layers include, for example, a contrast enhancement layer.
The contrast enhancement layer is described in paragraph 0134 of WO 2018/179640. Further, other layers are described in paragraphs 0194 to 0196 of Japanese Patent Application Laid-Open No. 2014-85643. The contents of these publications are incorporated herein by reference.
〔感光性転写材料の製造方法〕
　本開示に係る感光性転写材料の製造方法は、特に制限されず、公知の製造方法、例えば、公知の各層の形成方法を用いることができる。 [Manufacturing method of photosensitive transfer material]
The method for producing the photosensitive transfer material according to the present disclosure is not particularly limited, and a known production method, for example, a known method for forming each layer can be used.
　以下、図１を参照しながら、本開示に係る感光性転写材料の製造方法について説明する。但し、本開示に係る感光性転写材料は、図１に示す構成を有するものに制限されない。 Hereinafter, the method for producing the photosensitive transfer material according to the present disclosure will be described with reference to FIG. However, the photosensitive transfer material according to the present disclosure is not limited to the one having the configuration shown in FIG.
　図１は、本開示に係る感光性転写材料の構成の一例を示す概略図である。図１に示す感光性転写材料１００は、仮支持体１０と、熱可塑性樹脂層１２と、中間層１４と、感光性樹脂層１６と、カバーフィルム１８とがこの順に積層された構成を有する。 FIG. 1 is a schematic view showing an example of the configuration of the photosensitive transfer material according to the present disclosure. The photosensitive transfer material 100 shown in FIG. 1 has a structure in which a temporary support 10, a thermoplastic resin layer 12, an intermediate layer 14, a photosensitive resin layer 16, and a cover film 18 are laminated in this order.
　上記の感光性転写材料１００の製造方法としては、例えば、仮支持体１０の表面に熱可塑性樹脂組成物を塗布した後、熱可塑性樹脂組成物の塗膜を乾燥させることにより、熱可塑性樹脂層１２を形成する工程と、熱可塑性樹脂層１２の表面に中間層組成物を塗布した後、中間層組成物の塗膜を乾燥させて中間層１４を形成する工程と、中間層１４の表面に感光性樹脂組成物を塗布した後、感光性樹脂組成物の塗膜を乾燥させて感光性樹脂層１６を形成する工程と、感光性樹脂層１６にカバーフィルム１８を圧着させる工程と、を含む方法が挙げられる。 As a method for producing the photosensitive transfer material 100, for example, a thermoplastic resin layer is applied by applying the thermoplastic resin composition to the surface of the temporary support 10 and then drying the coating film of the thermoplastic resin composition. A step of forming the intermediate layer 12, a step of applying the intermediate layer composition to the surface of the thermoplastic resin layer 12, and then drying the coating film of the intermediate layer composition to form the intermediate layer 14, and a step of forming the intermediate layer 14 on the surface of the intermediate layer 14. After applying the photosensitive resin composition, the step of drying the coating film of the photosensitive resin composition to form the photosensitive resin layer 16 and the step of pressing the cover film 18 against the photosensitive resin layer 16 are included. The method can be mentioned.
　仮支持体上に、感光性樹脂層を直接設ける場合には、仮支持体の表面に感光性樹脂組成物を塗布する。 When the photosensitive resin layer is directly provided on the temporary support, the photosensitive resin composition is applied to the surface of the temporary support.
　本開示に係る感光性転写材料の製造方法では、仮支持体の表面に感光性樹脂組成物（熱可塑性樹脂層を積層する場合には、熱可塑性樹脂組成物）を塗布する際、仮支持体を厚さ方向の中心で仮想的に２つの領域に分けたときに、異物の個数が少ない領域側の面に塗布する。これにより、仮支持体において、厚さ方向の中心より感光性樹脂層側の領域を第１領域とし、厚さ方向の中心より感光性樹脂層とは反対側の領域を第２領域としたとき、第１領域に含まれる異物の個数が第２領域に含まれる異物の個数よりも少ない感光性転写材料を製造することができる。 In the method for producing a photosensitive transfer material according to the present disclosure, when a photosensitive resin composition (in the case of laminating a thermoplastic resin layer, a thermoplastic resin composition) is applied to the surface of the temporary support, the temporary support is applied. Is virtually divided into two regions at the center in the thickness direction, and is applied to the surface on the region side where the number of foreign substances is small. As a result, in the temporary support, when the region on the photosensitive resin layer side from the center in the thickness direction is set as the first region and the region on the side opposite to the photosensitive resin layer from the center in the thickness direction is set as the second region. , It is possible to produce a photosensitive transfer material in which the number of foreign substances contained in the first region is smaller than the number of foreign substances contained in the second region.
　本発明者は、仮支持体を厚さ方向の中心で仮想的に２つの領域に分けたときに、異物の個数が少ない領域側の面とは、仮支持体の製造の際にキャスティングドラムと接触していない面であるという知見を得た。そのため、本開示の製造方法では、仮支持体の製造の際にキャスティングドラムと接触していない面に、感光性樹脂組成物（熱可塑性樹脂層を積層する場合には、熱可塑性樹脂組成物）を塗布することが好ましい。 According to the present inventor, when the temporary support is virtually divided into two regions at the center in the thickness direction, the surface on the region side where the number of foreign substances is small is the casting drum when the temporary support is manufactured. We obtained the finding that it is a non-contact surface. Therefore, in the manufacturing method of the present disclosure, the photosensitive resin composition (in the case of laminating the thermoplastic resin layer, the thermoplastic resin composition) on the surface that is not in contact with the casting drum during the manufacturing of the temporary support. Is preferably applied.
　上記の製造方法において、アルキレングリコールエーテル溶剤及びアルキレングリコールエーテルアセテート溶剤からなる群より選択される少なくとも１種を含有する熱可塑性樹脂組成物と、水及び水混和性の有機溶剤からなる群より選択される少なくとも１種を含有する中間層組成物と、重合体Ａ、重合性化合物Ｂ、並びに、アルキレングリコールエーテル溶剤及びアルキレングリコールエーテルアセテート溶剤からなる群より選択される少なくとも１種を含有する感光性樹脂組成物とを使用することが好ましい。これにより、
熱可塑性樹脂層１２の表面への中間層組成物の塗布、及び／又は、中間層組成物の塗膜を有する積層体の保存期間における、熱可塑性樹脂層１２に含有される成分と中間層１４に含有される成分との混合を抑制できる。また、中間層１４の表面への感光性樹脂組成物の塗布、及び／又は、感光性樹脂組成物の塗膜を有する積層体の保存期間における、中間層１４に含有される成分と感光性樹脂層１６に含有される成分との混合を抑制できる。 In the above production method, it is selected from the group consisting of a thermoplastic resin composition containing at least one selected from the group consisting of an alkylene glycol ether solvent and an alkylene glycol ether acetate solvent, and a water- and water-mixable organic solvent. A photosensitive resin containing at least one selected from the group consisting of an intermediate layer composition containing at least one of the above, polymer A, polymerizable compound B, and an alkylene glycol ether solvent and an alkylene glycol ether acetate solvent. It is preferable to use with the composition. This will
The components contained in the thermoplastic resin layer 12 and the intermediate layer 14 during the application of the intermediate layer composition to the surface of the thermoplastic resin layer 12 and / or the storage period of the laminate having the coating film of the intermediate layer composition. It is possible to suppress mixing with the components contained in. Further, the components and the photosensitive resin contained in the intermediate layer 14 during the application of the photosensitive resin composition to the surface of the intermediate layer 14 and / or the storage period of the laminate having the coating film of the photosensitive resin composition. Mixing with the components contained in the layer 16 can be suppressed.
　本開示に係る感光性転写材料の製造方法としては、感光性樹脂層１６の第２面に接するようにカバーフィルム１８を設ける工程を含むことにより、仮支持体１０、熱可塑性樹脂層１２、中間層１４、感光性樹脂層１６及びカバーフィルム１８を備える感光性転写材料１００を製造することが好ましい。 The method for producing a photosensitive transfer material according to the present disclosure includes a step of providing a cover film 18 so as to be in contact with the second surface of the photosensitive resin layer 16, thereby including a temporary support 10, a thermoplastic resin layer 12, and an intermediate. It is preferable to manufacture the photosensitive transfer material 100 including the layer 14, the photosensitive resin layer 16 and the cover film 18.
　感光性転写材料１００を製造した後、感光性転写材料１００を巻き取ることにより、ロール形態の感光性転写材料を作製し、保管してもよい。ロール形態の感光性転写材料は、後述するロールツーロール方式での基板との貼り合わせ工程にそのままの形態で提供できる。 After manufacturing the photosensitive transfer material 100, the photosensitive transfer material 100 in the form of a roll may be produced and stored by winding the photosensitive transfer material 100. The photosensitive transfer material in the form of a roll can be provided as it is in the process of bonding with a substrate in a roll-to-roll method described later.
［樹脂パターンの製造方法、及び、回路配線の製造方法］
　樹脂パターンの製造方法は、上記の感光性転写材料を用いる樹脂パターンの製造方法であれば、特に制限されない。 [Manufacturing method of resin pattern and manufacturing method of circuit wiring]
The method for producing the resin pattern is not particularly limited as long as it is the method for producing the resin pattern using the above-mentioned photosensitive transfer material.
　樹脂パターンの製造方法は、感光性転写材料における感光性樹脂層の仮支持体と対向していない側の面（すなわち、第２面）と基板とを貼り合わせる工程と（以下「貼り合わせ工程」ともいう。）と、感光性樹脂層をパターン露光する工程（以下「露光工程」ともいう。）と、パターン露光する工程後の感光性樹脂層を現像して樹脂パターンを形成する工程（以下「現像工程」ともいう。）と、をこの順に含む方法であることが好ましい。 The method for producing the resin pattern includes a step of bonding the surface (that is, the second surface) of the photosensitive resin layer on the photosensitive transfer material on the side not facing the temporary support and the substrate (hereinafter, "bonding step"). (Also also referred to as), a step of pattern-exposing the photosensitive resin layer (hereinafter, also referred to as “exposure step”), and a step of developing the photosensitive resin layer after the pattern exposure step to form a resin pattern (hereinafter, “exposed step”). It is preferable that the method includes "development step") in this order.
　回路配線の製造方法は、上記の感光性転写材料を用いる回路配線の製造方法であれば、特に制限されない。 The circuit wiring manufacturing method is not particularly limited as long as it is a circuit wiring manufacturing method using the above-mentioned photosensitive transfer material.
　回路配線の製造方法は、上記貼り合わせ工程と、上記露光工程と、上記現像工程と、樹脂パターンが配置されていない領域における基板をエッチング処理する工程（以下「エッチング工程」ともいう。）を含む方法であることが好ましい。 The circuit wiring manufacturing method includes the bonding step, the exposure step, the developing step, and the step of etching the substrate in the region where the resin pattern is not arranged (hereinafter, also referred to as “etching step”). The method is preferred.
　以下、樹脂パターンの製造方法及び回路配線の製造方法が含む各工程について説明する。特に言及した場合を除き、樹脂パターンの製造方法に含まれる各工程について説明した内容は、回路配線の製造方法に含まれる各工程についても適用されるものとする。 Hereinafter, each process included in the resin pattern manufacturing method and the circuit wiring manufacturing method will be described. Unless otherwise specified, the contents described for each step included in the resin pattern manufacturing method shall also be applied to each step included in the circuit wiring manufacturing method.
〔貼り合わせ工程〕
　樹脂パターンの製造方法は、貼り合わせ工程を含むことが好ましい。
　貼り合わせ工程においては、感光性樹脂層の第２面に基板（基板の表面に導電層が設けられている場合は導電層）を接触させ、感光性転写材料と基板とを圧着させることが好ましい。上記態様であると、感光性樹脂層の第２面と基板との密着性が向上するため、露光及び現像後のパターン形成された感光性樹脂層を、エッチングする際のエッチングレジストとして好適に用いることができる。 [Lasting process]
The method for producing the resin pattern preferably includes a bonding step.
In the bonding step, it is preferable that the substrate (or the conductive layer when the conductive layer is provided on the surface of the substrate) is brought into contact with the second surface of the photosensitive resin layer, and the photosensitive transfer material and the substrate are pressure-bonded. .. In the above aspect, since the adhesion between the second surface of the photosensitive resin layer and the substrate is improved, the patterned photosensitive resin layer after exposure and development is suitably used as an etching resist for etching. be able to.
　なお、感光性転写材料がカバーフィルムを備える場合は、感光性樹脂層の表面からカバーフィルムを除去した後、貼り合わせればよい。  When the photosensitive transfer material includes a cover film, the cover film may be removed from the surface of the photosensitive resin layer and then bonded.
　また、貼り合わせ工程は、感光性転写材料が感光性樹脂層の第２面にカバーフィルム以外の層（例えば、高屈折率層及び低屈折率層からなる群より選択される少なくとも１種の層）をさらに備える場合、感光性樹脂層の第２面と基板とがその層を介して貼り合わされる態様となる。 Further, in the bonding step, at least one layer in which the photosensitive transfer material is selected from the group consisting of a layer other than the cover film (for example, a high refractive index layer and a low refractive index layer) on the second surface of the photosensitive resin layer. ) Is further provided, the second surface of the photosensitive resin layer and the substrate are bonded to each other via the layer.
　基板と感光性転写材料とを圧着する方法としては、特に制限されず、公知の転写方法、及び、ラミネート方法を用いることができる。 The method of crimping the substrate and the photosensitive transfer material is not particularly limited, and a known transfer method and laminating method can be used.
　感光性転写材料の基板への貼り合わせは、感光性樹脂層の第２面側に基板を重ね、ロール等の手段を用いて加圧及び加熱を施すことにより行われることが好ましい。貼り合わせには、ラミネーター、真空ラミネーター、及び、より生産性を高めることができるオートカットラミネーター等の公知のラミネーターが使用できる。 It is preferable that the photosensitive transfer material is bonded to the substrate by stacking the substrate on the second surface side of the photosensitive resin layer and applying pressure and heating by means such as a roll. For bonding, a known laminator such as a laminator, a vacuum laminator, and an auto-cut laminator capable of further increasing productivity can be used.
　貼り合わせ工程を含む樹脂パターンの製造方法及び回路配線の製造方法は、ロールツーロール方式により行われることが好ましい。 The resin pattern manufacturing method including the bonding step and the circuit wiring manufacturing method are preferably performed by a roll-to-roll method.
　以下、ロールツーロール方式について説明する。
　ロールツーロール方式とは、基板として、巻き取り及び巻き出しが可能な基板を用い、樹脂パターンの製造方法又は回路配線の製造方法に含まれるいずれかの工程の前に、基板又は基板を含む構造体を巻き出す工程（「巻き出し工程」ともいう。）と、いずれかの工程の後に、基板又は基板を含む構造体を巻き取る工程（「巻き取り工程」ともいう。）と、を含み、少なくともいずれかの工程（好ましくは、全ての工程、又は加熱工程以外の全ての工程）を、基板又は基板を含む構造体を搬送しながら行う方式をいう。 Hereinafter, the roll-to-roll method will be described.
The roll-to-roll method is a structure in which a substrate that can be wound and unwound is used as the substrate, and the substrate or the substrate is included before any of the steps included in the resin pattern manufacturing method or the circuit wiring manufacturing method. It includes a step of unwinding a body (also referred to as a “unwinding step”) and a step of winding a substrate or a structure including the substrate (also referred to as a “winding step”) after any of the steps. A method in which at least one of the steps (preferably all steps or all steps other than the heating step) is performed while transporting the substrate or the structure including the substrate.
　巻き出し工程における巻き出し方法、及び巻き取り工程における巻取り方法としては、特に制限されず、ロールツーロール方式を適用する製造方法において、公知の方法を用いればよい。 The unwinding method in the unwinding process and the winding method in the winding process are not particularly limited, and a known method may be used in the manufacturing method to which the roll-to-roll method is applied.
＜基板＞
　本開示に係る感光性転写材料を用いる樹脂パターンの形成に用いる基板としては、公知の基板を用いることができる。基板は、導電層を有する基板であることが好ましく、基材の表面に導電層を有する基板であることがより好ましい。 <Board>
A known substrate can be used as the substrate used for forming the resin pattern using the photosensitive transfer material according to the present disclosure. The substrate is preferably a substrate having a conductive layer, and more preferably a substrate having a conductive layer on the surface of the base material.
　基板は、必要に応じて導電層以外の任意の層を有してもよい。 The substrate may have an arbitrary layer other than the conductive layer, if necessary.
　基板を構成する基材としては、例えば、ガラス、シリコン及び樹脂フィルムが挙げられる。
　基材は透明であることが好ましい。本明細書において「透明である」とは、波長４００ｎｍ～７００ｎｍの光の透過率が８０％以上であることを意味する。また、基材の屈折率は、１．５０～１．５２であることが好ましい。 Examples of the base material constituting the substrate include glass, silicon, and a resin film.
The substrate is preferably transparent. As used herein, the term "transparent" means that the transmittance of light having a wavelength of 400 nm to 700 nm is 80% or more. The refractive index of the base material is preferably 1.50 to 1.52.
　透明なガラス基材としては、コーニング社のゴリラガラスに代表される強化ガラスが挙げられる。また、透明なガラス基材としては、特開２０１０－８６６８４号公報、特開２０１０－１５２８０９号公報及び特開２０１０－２５７４９２号公報に記載の材料を用いることができる。 Examples of the transparent glass base material include tempered glass represented by Corning's gorilla glass. Further, as the transparent glass substrate, the materials described in JP-A-2010-86684, JP-A-2010-152809 and JP-A-2010-257492 can be used.
　基材として樹脂フィルムを用いる場合は、基材は、光学的に歪みが小さく、かつ／又は、透明度が高い樹脂フィルムであることが好ましい。そのような樹脂フィルムとしては、例えば、ポリエチレンテレフタレート（ＰＥＴ）フィルム、ポリエチレンナフタレートフィルム、ポリカーボネートフィルム、トリアセチルセルロースフィルム及びシクロオレフィンポリマーフィルムが挙げられる。 When a resin film is used as the base material, the base material is preferably a resin film having low optical distortion and / or high transparency. Examples of such resin films include polyethylene terephthalate (PET) films, polyethylene naphthalate films, polycarbonate films, triacetyl cellulose films and cycloolefin polymer films.
　ロールツーロール方式で製造する場合、基材は、樹脂フィルムであることが好ましい。また、ロールツーロール方式によりタッチパネル用の回路配線を製造する場合、基材は、樹脂シートであることが好ましい。 When manufacturing by the roll-to-roll method, the base material is preferably a resin film. Further, when the circuit wiring for the touch panel is manufactured by the roll-to-roll method, the base material is preferably a resin sheet.
　基板が有する導電層としては、一般的な回路配線又はタッチパネル配線に用いられる導電層が挙げられる。 Examples of the conductive layer contained in the substrate include a conductive layer used for general circuit wiring or touch panel wiring.
　導電層は、導電性及び細線形成性の観点から、金属層、導電性金属酸化物層、グラフェン層、カーボンナノチューブ層及び導電ポリマー層からなる群より選択される少なくとも１種の層であることが好ましく、金属層であることがより好ましく、銅層又は銀層であることがさらに好ましい。 The conductive layer may be at least one layer selected from the group consisting of a metal layer, a conductive metal oxide layer, a graphene layer, a carbon nanotube layer, and a conductive polymer layer from the viewpoint of conductivity and fine wire forming property. It is preferably a metal layer, more preferably a copper layer or a silver layer.
　基板は、導電層を１層単独で有してよく、２層以上有してもよい。基板が２層以上の導電層を有する場合は、基板は異なる２種以上の材質の導電層を有することが好ましい。 The substrate may have one conductive layer alone, or may have two or more conductive layers. When the substrate has two or more conductive layers, it is preferable that the substrate has two or more different conductive layers.
　導電層の材料としては、金属及び導電性金属酸化物が挙げられる。 Examples of the material of the conductive layer include metals and conductive metal oxides.
　金属としては、Ａｌ、Ｚｎ、Ｃｕ、Ｆｅ、Ｎｉ、Ｃｒ、Ｍｏ、Ａｇ及びＡｕが挙げられる。 Examples of the metal include Al, Zn, Cu, Fe, Ni, Cr, Mo, Ag and Au.
　導電性金属酸化物としては、ＩＴＯ（Ｉｎｄｉｕｍ　Ｔｉｎ　Ｏｘｉｄｅ）、ＩＺＯ（Ｉｎｄｉｕｍ　Ｚｉｎｃ　Ｏｘｉｄｅ）及びＳｉＯ２が挙げられる。なお、本明細書において「導電性」とは、体積抵抗率が１×１０６Ωｃｍ未満であることをいう。導電性金属酸化物の体積抵抗率は、１×１０４Ωｃｍ未満であることが好ましい。 Examples of the conductive metal oxide include ITO (Indium Tin Oxide), IZO (Indium Zinc Oxide) and SiO 2 . In addition, in this specification, "conductivity" means that the volume resistivity is less than 1 × 10 6 Ωcm. The volume resistivity of the conductive metal oxide is preferably less than 1 × 10 4 Ωcm.
　複数の導電層を有する基板を用いて樹脂パターンを製造する場合、複数の導電層のうち少なくとも一つの導電層は導電性金属酸化物を含有することが好ましい。 When a resin pattern is produced using a substrate having a plurality of conductive layers, it is preferable that at least one of the plurality of conductive layers contains a conductive metal oxide.
　導電層は、静電容量型タッチパネルに用いられる視認部のセンサーに相当する電極パターン又は周辺取り出し部の配線であることが好ましい。 The conductive layer is preferably an electrode pattern corresponding to the sensor of the visual recognition part used in the capacitive touch panel or the wiring of the peripheral extraction part.
〔露光工程〕
　樹脂パターンの製造方法は、上記貼り合わせ工程の後、感光性樹脂層をパターン露光する工程（露光工程）を含むことが好ましい。 [Exposure process]
The method for producing the resin pattern preferably includes a step (exposure step) of pattern-exposing the photosensitive resin layer after the bonding step.
　パターン露光におけるパターンの詳細な配置及び具体的なサイズは特に制限されない。パターンの少なくとも一部（好ましくはタッチパネルの電極パターン及び／又は取り出し配線の部分）は幅が２０μｍ以下の細線を含むことが好ましく、幅が１０μｍ以下の細線を含むことがより好ましい。回路配線の製造方法により製造される回路配線を有する入力装置を備えた表示装置（例えば、タッチパネル）の表示品質を高め、かつ、取り出し配線の占める面積を小さくすることができる。 The detailed arrangement and specific size of the pattern in the pattern exposure are not particularly limited. At least a part of the pattern (preferably the electrode pattern of the touch panel and / or the portion of the take-out wiring) preferably includes a thin wire having a width of 20 μm or less, and more preferably contains a thin wire having a width of 10 μm or less. It is possible to improve the display quality of a display device (for example, a touch panel) including an input device having a circuit wiring manufactured by a method of manufacturing a circuit wiring, and to reduce the area occupied by the take-out wiring.
　露光に使用する光源は、感光性樹脂層を露光可能な波長の光（例えば、３６５ｎｍ又は４０５ｎｍ）を照射する光源であれば特に制限されず、適宜選定して用いることができる。光源としては、超高圧水銀灯、高圧水銀灯、メタルハライドランプ及びＬＥＤ（Ｌｉｇｈｔ　Ｅｍｉｔｔｉｎｇ　Ｄｉｏｄｅ）が挙げられる。 The light source used for exposure is not particularly limited as long as it is a light source that irradiates the photosensitive resin layer with light having a wavelength that allows exposure (for example, 365 nm or 405 nm), and can be appropriately selected and used. Examples of the light source include an ultra-high pressure mercury lamp, a high pressure mercury lamp, a metal halide lamp, and an LED (Light Emitting Diode).
　露光量は、５ｍＪ／ｃｍ２～２００ｍＪ／ｃｍ２であることが好ましく、１０ｍＪ／ｃｍ２～１００ｍＪ／ｃｍ２であることがより好ましい。 The exposure amount is preferably 5 mJ / cm 2 to 200 mJ / cm 2 , and more preferably 10 mJ / cm 2 to 100 mJ / cm 2 .
　露光工程においては、感光性樹脂層から仮支持体を剥離した後にパターン露光してもよく、仮支持体を介してパターン露光した後に仮支持体を剥離してもよい。仮支持体を剥離した後に露光する場合には、マスクと感光性樹脂層とを接触させて露光してもよく、マスクと感光性樹脂層とを接触させずに近接させて露光してもよい。仮支持体を剥離せずに露光する場合には、マスクと仮支持体とを接触させて露光してもよく、マスクと仮支持体とを接触させずに近接させて露光してもよい。感光性樹脂層とマスクとの接触によるマスク汚染の防止、及びマスクに付着した異物による露光への影響を避けるためには、仮支持体を剥離せずにパターン露光することが好ましい。なお、露光方式は、接触露光の場合は、コンタクト露光方式、非接触露光方式の場合は、プロキシミティ露光方式、レンズ系もしくはミラー系のプロジェクション露光方式、又は、露光レーザー等を用いたダイレクト露光方式を適宜選択して用いることができる。レンズ系又はミラー系のプロジェクション露光方式の場合、必要な解像力及び焦点深度に応じて、適当なレンズの開口数（ＮＡ）を有する露光機を用いることができる。ダイレクト露光方式の場合は、感光性樹脂層に直接露光してもよく、レンズを介して感光性樹脂層に縮小投影露光をしてもよい。また、露光は大気下で行うだけでなく、減圧下、又は真空下で行ってもよい。また、光源と感光性樹脂層との間に水等の液体を介在させて露光してもよい。 In the exposure step, the temporary support may be peeled off from the photosensitive resin layer and then pattern-exposed, or the temporary support may be peeled off after pattern-exposure through the temporary support. When the temporary support is peeled off and then exposed, the mask and the photosensitive resin layer may be brought into contact with each other for exposure, or the mask and the photosensitive resin layer may be exposed without being brought into contact with each other. .. When the temporary support is exposed without being peeled off, the mask and the temporary support may be brought into contact with each other for exposure, or the mask and the temporary support may be exposed without being brought into contact with each other. In order to prevent mask contamination due to contact between the photosensitive resin layer and the mask and to avoid the influence of foreign matter adhering to the mask on the exposure, it is preferable to perform pattern exposure without peeling off the temporary support. The exposure method is a contact exposure method in the case of contact exposure, a proximity exposure method in the case of a non-contact exposure method, a lens-based or mirror-based projection exposure method, or a direct exposure method using an exposure laser or the like. Can be appropriately selected and used. In the case of a lens-based or mirror-based projection exposure method, an exposure machine having an appropriate numerical aperture (NA) of the lens can be used depending on the required resolution and depth of focus. In the case of the direct exposure method, the photosensitive resin layer may be directly exposed, or the photosensitive resin layer may be subjected to reduced projection exposure via a lens. Further, the exposure may be performed not only in the atmosphere but also under reduced pressure or vacuum. Further, a liquid such as water may be interposed between the light source and the photosensitive resin layer for exposure.
〔現像工程〕
　樹脂パターンの製造方法は、上記露光工程の後、露光された感光性樹脂層を現像して樹脂パターンを形成する工程（現像工程）を含むことが好ましい。 [Development process]
The method for producing a resin pattern preferably includes, after the above-mentioned exposure step, a step (development step) of developing the exposed photosensitive resin layer to form a resin pattern.
　感光性転写材料が熱可塑性樹脂及び中間層を有する場合、現像工程において、非露光部の熱可塑性樹脂層及び中間層も、非露光部の感光性樹脂層とともに除去される。また、現像工程において、露光部の熱可塑性樹脂層及び中間層も現像液に溶解又は分散する形で除去されてもよい。 When the photosensitive transfer material has a thermoplastic resin and an intermediate layer, the thermoplastic resin layer and the intermediate layer in the non-exposed portion are also removed together with the photosensitive resin layer in the non-exposed portion in the developing process. Further, in the developing step, the thermoplastic resin layer and the intermediate layer of the exposed portion may also be removed in a form of being dissolved or dispersed in the developing solution.
　露光された感光性樹脂層の現像は、現像液を用いて行うことができる。 The exposed photosensitive resin layer can be developed using a developing solution.
　現像液は、感光性樹脂層の非画像部（非露光部）を除去することができれば特に制限されず、例えば、特開平５－７２７２４号公報に記載の現像液等の公知の現像液が使用できる。 The developing solution is not particularly limited as long as the non-image portion (non-exposed portion) of the photosensitive resin layer can be removed, and for example, a known developing solution such as the developing solution described in JP-A-5-72724 is used. can.
　現像液は、ｐＫａが７～１３の化合物を０．０５ｍｏｌ／Ｌ（リットル）～５ｍｏｌ／Ｌの濃度で含むアルカリ水溶液であることが好ましい。現像液は、水溶性の有機溶剤及び界面活性剤からなる群より選択される少なくとも１種を含有してもよい。現像液は、国際公開第２０１５／０９３２７１号の段落０１９４に記載の現像液も好ましい。 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 (liter) to 5 mol / L. The developer may contain at least one selected from the group consisting of water-soluble organic solvents and surfactants. As the developer, the developer described in paragraph 0194 of International Publication No. 2015/093271 is also preferable.
　現像方式としては、特に制限されず、パドル現像、シャワー現像、シャワー及びスピン現像、並びに、ディップ現像のいずれであってもよい。シャワー現像とは、露光後の感光性樹脂層に現像液をシャワーにより吹き付けることにより、非露光部を除去する現像処理である。 The development method is not particularly limited, and may be any of paddle development, shower development, shower and spin development, and dip development. Shower development is a development process for removing a non-exposed portion by spraying a developing solution on the photosensitive resin layer after exposure by a shower.
　現像工程の後に、洗浄剤をシャワーにより吹き付け、ブラシで擦りながら、現像残渣を除去することが好ましい。 After the developing step, it is preferable to spray the cleaning agent with a shower and rub with a brush to remove the developing residue.
　現像液の液温は特に制限されないが、２０℃～４０℃が好ましい。 The temperature of the developing solution is not particularly limited, but is preferably 20 ° C to 40 ° C.
〔エッチング工程〕
　回路配線の製造方法は、上記貼り合わせ工程と、上記露光工程と、上記現像工程とを含む製造方法により製造された樹脂パターンがこの順で積層された積層体において、樹脂パターンが配置されていない領域における基板をエッチング処理する工程（エッチング工程）を含むことが好ましい。 [Etching process]
In the circuit wiring manufacturing method, the resin pattern is not arranged in the laminated body in which the resin patterns manufactured by the manufacturing method including the bonding step, the exposure step, and the developing step are laminated in this order. It is preferable to include a step (etching step) of etching the substrate in the region.
　エッチング工程では、感光性樹脂層から形成された樹脂パターンを、エッチングレジストとして使用し、基板のエッチング処理を行う。 In the etching process, the resin pattern formed from the photosensitive resin layer is used as an etching resist to etch the substrate.
　エッチング処理の方法としては、公知の方法を適用でき、例えば、特開２０１７－１２０４３５号公報の段落０２０９～段落０２１０に記載の方法、特開２０１０－１５２１５５号公報の段落００４８～段落００５４に記載の方法、エッチング液に浸漬するウェットエッチング法、及び、プラズマエッチング等のドライエッチングによる方法が挙げられる。 As a method of etching treatment, a known method can be applied, and for example, the method described in paragraphs 0209 to 0210 of JP2017-120435A and the method described in paragraphs 0048 to 0054 of JP2010-152155A. Examples thereof include a wet etching method in which the material is immersed in an etching solution, and a dry etching method such as plasma etching.
　ウェットエッチングに用いられるエッチング液は、エッチングの対象に合わせて酸性又はアルカリ性のエッチング液を適宜選択すればよい。  As the etching solution used for wet etching, an acidic or alkaline etching solution may be appropriately selected according to the etching target.
　酸性のエッチング液としては、例えば、塩酸、硫酸、硝酸、酢酸、フッ酸、シュウ酸及びリン酸から選択される酸性成分単独の水溶液、並びに、酸性成分と、塩化第２鉄、フッ化アンモニウム及び過マンガン酸カリウムから選択される塩との混合水溶液が挙げられる。酸性成分は、複数の酸性成分を組み合わせた成分であってもよい。  Examples of the acidic etching solution include an aqueous solution of an acidic component alone selected from hydrochloric acid, sulfuric acid, nitric acid, acetic acid, hydrofluoric acid, oxalic acid and phosphoric acid, and the acidic component, ferric chloride, ammonium fluoride and Examples thereof include a mixed aqueous solution with a salt selected from potassium permanganate. The acidic component may be a component in which a plurality of acidic components are combined.
　アルカリ性のエッチング液としては、水酸化ナトリウム、水酸化カリウム、アンモニア、有機アミン、及び、有機アミンの塩（テトラメチルアンモニウムハイドロオキサイド等）から選択されるアルカリ成分単独の水溶液、並びに、アルカリ成分と塩（例えば、過マンガン酸カリウム）との混合水溶液が挙げられる。アルカリ成分は、複数のアルカリ成分を組み合わせた成分であってもよい。 As the alkaline etching solution, an aqueous solution of an alkaline component alone selected from sodium hydroxide, potassium hydroxide, ammonia, an organic amine, and a salt of an organic amine (tetramethylammonium hydroxide, etc.), and an alkaline component and a salt. (For example, a mixed aqueous solution with (for example, potassium permanganate) can be mentioned. The alkaline component may be a component in which a plurality of alkaline components are combined.
〔除去工程〕
　回路配線の製造方法においては、残存する樹脂パターンを除去する工程（除去工程）を行うことが好ましい。 [Removal process]
In the circuit wiring manufacturing method, it is preferable to perform a step (removal step) of removing the remaining resin pattern.
　除去工程は、特に制限されず、必要に応じて行うことができるが、エッチング工程の後に行うことが好ましい。 The removal step is not particularly limited and can be performed as needed, but it is preferably performed after the etching step.
　残存する樹脂パターンを除去する方法としては特に制限されないが、薬品処理により除去する方法が挙げられる。残存する樹脂パターンを除去する方法は、除去液を用いて除去する方法が好ましい。 The method for removing the remaining resin pattern is not particularly limited, but a method for removing it by chemical treatment can be mentioned. As a method for removing the remaining resin pattern, a method of removing with a removing liquid is preferable.
　感光性樹脂層の除去方法としては、液温が好ましくは３０℃～８０℃、より好ましくは５０℃～８０℃である撹拌中の除去液に、残存する樹脂パターンを有する基板を、１分～３０分間浸漬する方法が挙げられる。 As a method for removing the photosensitive resin layer, a substrate having a residual resin pattern is placed in a removing liquid during stirring at a liquid temperature of preferably 30 ° C. to 80 ° C., more preferably 50 ° C. to 80 ° C. for 1 minute to. A method of immersing for 30 minutes can be mentioned.
　除去液としては、例えば、無機アルカリ成分又は有機アルカリ成分を、水、ジメチルスルホキシド、Ｎ－メチルピロリドン又はこれらの混合溶液に溶解させた除去液が挙げられる。無機アルカリ成分としては、例えば、水酸化ナトリウム及び水酸化カリウムが挙げられる。有機アルカリ成分としては、第１級アミン化合物、第２級アミン化合物、第３級アミン化合物及び第４級アンモニウム塩化合物が挙げられる。 Examples of the removing liquid include a removing liquid in which an inorganic alkaline component or an organic alkaline component is dissolved in water, dimethyl sulfoxide, N-methylpyrrolidone, or a mixed solution thereof. Examples of the inorganic alkaline component include sodium hydroxide and potassium hydroxide. Examples of the organic alkali component include a primary amine compound, a secondary amine compound, a tertiary amine compound and a quaternary ammonium salt compound.
　また、除去液を使用し、スプレー法、シャワー法及びパドル法等の公知の方法により、残存する樹脂パターンを除去してもよい。 Alternatively, the removing liquid may be used to remove the remaining resin pattern by a known method such as a spray method, a shower method and a paddle method.
〔その他の工程〕
　回路配線の製造方法は、上述した工程以外の任意の工程（その他の工程）を含んでもよい。例えば、以下の工程が挙げられるが、これらの工程に制限されない。 [Other processes]
The circuit wiring manufacturing method may include an arbitrary step (other steps) other than the above-mentioned steps. For example, the following steps can be mentioned, but the steps are not limited to these steps.
　また、回路配線の製造方法に適用可能な露光工程、現像工程、及びその他の工程としては、特開２００６－２３６９６号公報の段落００３５～００５１に記載の工程が挙げられる。 Further, examples of the exposure step, the developing step, and other steps applicable to the method for manufacturing the circuit wiring include the steps described in paragraphs 0035 to 0051 of JP-A-2006-23696.
＜カバーフィルム剥離工程＞
　感光性転写材料がカバーフィルムを備える場合、樹脂パターンの製造方法は、感光性転写材料からカバーフィルムを剥離する工程を含むことが好ましい。カバーフィルムを剥離する方法は、特に制限されず、公知の方法を適用することができる。 <Cover film peeling process>
When the photosensitive transfer material includes a cover film, the method for producing the resin pattern preferably includes a step of peeling the cover film from the photosensitive transfer material. The method for peeling the cover film is not particularly limited, and a known method can be applied.
＜可視光線反射率を低下させる工程＞
　回路配線の製造方法は、基板が備える導電層の一部又は全ての可視光線反射率を低下させる処理を行う工程を含んでいてもよい。 <Step to reduce visible light reflectance>
The method for manufacturing a circuit wiring may include a step of reducing the visible light reflectance of a part or all of the conductive layer provided on the substrate.
　可視光線反射率を低下させる処理としては、酸化処理が挙げられる。基板が銅を含有する導電層を備える場合、銅を酸化処理して酸化銅とし、導電層を黒化することにより、導電層の可視光線反射率を低下させることができる。 Oxidation treatment can be mentioned as a treatment for reducing the visible light reflectance. When the substrate includes a conductive layer containing copper, the visible light reflectance of the conductive layer can be reduced by oxidizing copper to copper oxide and blackening the conductive layer.
　可視光線反射率を低下させる処理については、特開２０１４－１５０１１８号公報の段落００１７～００２５、並びに、特開２０１３－２０６３１５号公報の段落００４１、段落００４２、段落００４８及び段落００５８に記載されており、これらの公報に記載の内容は本明細書に組み込まれる。 The treatment for lowering 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 these publications are incorporated herein by reference.
＜絶縁膜を形成する工程、絶縁膜の表面に新たな導電層を形成する工程＞
　回路配線の製造方法は、回路配線の表面に絶縁膜を形成する工程と、絶縁膜の表面に新たな導電層を形成する工程と、を含むことも好ましい。上記の工程により、第一の電極パターンと絶縁した第二の電極パターンを形成することができる。 <Step of forming an insulating film, step of forming a new conductive layer on the surface of the insulating film>
The method for manufacturing the circuit wiring preferably includes a step of forming an insulating film on the surface of the circuit wiring and a step of forming a new conductive layer on the surface of the insulating film. By the above steps, a second electrode pattern insulated from the first electrode pattern can be formed.
　絶縁膜を形成する工程としては、特に制限されず、公知の永久膜を形成する方法が挙げられる。また、絶縁性を有する感光性材料を用いて、フォトリソグラフィにより所望のパターンの絶縁膜を形成してもよい。 The step of forming the insulating film is not particularly limited, and examples thereof include a known method of forming a permanent film. Further, an insulating film having a desired pattern may be formed by photolithography using a photosensitive material having an insulating property.
　絶縁膜上に新たな導電層を形成する工程は、特に制限されず、例えば、導電性を有する感光性材料を用いて、フォトリソグラフィにより所望のパターンの新たな導電層を形成してもよい。 The step of forming a new conductive layer on the insulating film is not particularly limited, and for example, a new conductive layer having a desired pattern may be formed by photolithography using a photosensitive material having conductivity.
　回路配線の製造方法は、基材の両方の表面にそれぞれ複数の導電層を備える基板を用い、基材の両方の表面に形成された導電層に対して逐次又は同時に回路形成することも好ましい。このような構成により、基材の一方の表面に第一の導電パターン、もう一方の表面に第二の導電パターンを形成したタッチパネル用回路配線を形成できる。また、このような構成のタッチパネル用回路配線を、ロールツーロールで基材の両面から形成することも好ましい。 As a method for manufacturing a circuit wiring, it is also preferable to use a substrate having a plurality of conductive layers on both surfaces of the base material, and to form a circuit sequentially or simultaneously on the conductive layers formed on both surfaces of the base material. With such a configuration, a touch panel circuit wiring having a first conductive pattern formed on one surface of the base material and a second conductive pattern formed on the other surface can be formed. It is also preferable to form the touch panel circuit wiring having such a configuration from both sides of the base material by roll-to-roll.
〔回路配線の用途〕
　回路配線の製造方法により製造される回路配線は、種々の装置に適用することができる。上記の製造方法により製造される回路配線を備えた装置としては、例えば、入力装置が挙げられ、タッチパネルが好ましく、静電容量型タッチパネルがより好ましい。また、上記入力装置は、有機ＥＬ表示装置及び液晶表示装置等の表示装置に適用できる。 [Use of circuit wiring]
The circuit wiring manufactured by the method of manufacturing the circuit wiring can be applied to various devices. Examples of the device provided with the circuit wiring manufactured by the above manufacturing method include an input device, a touch panel is preferable, and a capacitance type touch panel is more preferable. Further, the input device can be applied to a display device such as an organic EL display device and a liquid crystal display device.
［タッチパネルの製造方法］
　タッチパネルの製造方法は、上記の感光性転写材料を用いるタッチパネルの製造方法であれば特に制限されない。 [Manufacturing method of touch panel]
The method for manufacturing the touch panel is not particularly limited as long as it is the method for manufacturing the touch panel using the above-mentioned photosensitive transfer material.
　タッチパネルの製造方法は、上記貼り合わせ工程と、上記露光工程と、上記現像工程と、樹脂パターンが配置されていない領域における基板をエッチング処理する工程（以下「エッチング工程」ともいう。）を含む方法であることが好ましい。 The touch panel manufacturing method includes the bonding step, the exposure step, the developing step, and the step of etching the substrate in the region where the resin pattern is not arranged (hereinafter, also referred to as “etching step”). Is preferable.
　タッチパネルの製造方法における、各工程の具体的な態様、及び、各工程を行う順序等の実施態様については、上述の「回路配線の製造方法」の項において説明したとおりであり、好ましい態様も同様である。
　タッチパネルの製造方法は、上記の方法によりタッチパネル用配線を形成すること以外は、公知のタッチパネルの製造方法を参照すればよい。また、タッチパネルの製造方法は、上記工程以外の任意の工程（その他の工程）を含んでもよい。 The specific embodiment of each step in the touch panel manufacturing method and the embodiment such as the order in which each step is performed are as described in the above-mentioned "Circuit wiring manufacturing method", and the preferred embodiments are also the same. Is.
As the method for manufacturing the touch panel, a known method for manufacturing the touch panel may be referred to except that the wiring for the touch panel is formed by the above method. Further, the touch panel manufacturing method may include an arbitrary step (other steps) other than the above steps.
　上記タッチパネルの製造方法により、タッチパネル用配線を少なくとも有するタッチパネルが製造される。タッチパネルは、透明基板と、電極と、絶縁層又は保護層とを有することが好ましい。 A touch panel having at least wiring for the touch panel is manufactured by the above-mentioned manufacturing method of the touch panel. The touch panel preferably has a transparent substrate, electrodes, and an insulating layer or a protective layer.
　タッチパネルにおける検出方法としては、抵抗膜方式、静電容量方式、超音波方式、電磁誘導方式、光学方式等の公知の方式が挙げられる。中でも、タッチパネルにおける検出方法は、静電容量方式であることが好ましい。 Examples of the detection method on the touch panel include known methods such as a resistive film method, a capacitance method, an ultrasonic method, an electromagnetic induction method, and an optical method. Above all, the detection method on the touch panel is preferably the capacitance method.
　以下に実施例を挙げて本発明の実施形態をさらに具体的に説明する。以下の実施例に示す材料、使用量、割合、処理内容、及び、処理手順は、本発明の実施形態の趣旨を逸脱しない限り、適宜、変更することができる。したがって、本発明の実施形態の範囲は以下に示す具体例に制限されない。なお、特に断りのない限り、「部」及び「％」は質量基準である。 Hereinafter, embodiments of the present invention will be described in more detail with reference to examples. The materials, amounts used, proportions, treatment contents, and treatment procedures shown in the following examples can be appropriately changed as long as they do not deviate from the gist of the embodiment of the present invention. Therefore, the scope of the embodiments of the present invention is not limited to the specific examples shown below. Unless otherwise specified, "parts" and "%" are based on mass.
＜感光性樹脂組成物の調製＞
　感光性樹脂組成物を調製するために用いた各成分は以下のとおりである。
〔重合体Ａ（アルカリ可溶性樹脂）〕
　以下の方法に従い、重合体Ａ－３を合成した。重合体Ａ－３の合成方法において、以下の略語は以下の化合物をそれぞれ表す。
　Ｓｔ：スチレン（富士フイルム和光純薬社製）
　ＭＡＡ：メタクリル酸（富士フイルム和光純薬社製）
　ＭＭＡ：メタクリル酸メチル（富士フイルム和光純薬社製）
　Ｖ－６０１：２，２’－アゾビス（イソ酪酸）ジメチル（富士フイルム和光純薬社製、重合開始剤）
　ＰＧＭＥＡ：プロピレングリコールモノメチルエーテルアセテート <Preparation of photosensitive resin composition>
The components used to prepare the photosensitive resin composition are as follows.
[Polymer A (alkali-soluble resin)]
Polymer A-3 was synthesized according to the following method. In the method for synthesizing polymer A-3, the following abbreviations represent the following compounds, respectively.
St: Styrene (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.)
MAA: Methacrylic acid (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.)
MMA: Methyl methacrylate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.)
V-601: 2,2'-azobis (isobutyric acid) dimethyl (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., polymerization initiator)
PGMEA: Propylene Glycol Monomethyl Ether Acetate
　３つ口フラスコにＰＧＭＥＡ（１１６．５部）を入れ、窒素雰囲気下において９０℃に昇温した。３つ口フラスコ内の液温を９０℃±２℃に維持しながら、Ｓｔ（５２．０部）、ＭＭＡ（１９．０部）、ＭＡＡ（２９．０部）、Ｖ－６０１（４．０部）及びＰＧＭＥＡ（１１６．５部）の混合液を、２時間かけて３つ口フラスコ内に滴下した。滴下終了後、液温を９０℃±２℃に維持しながら混合液を２時間撹拌することで、重合体Ａを３０．０質量％含有する組成物を得た。重合体Ａの酸価は１８９ｍｇＫＯＨ/ｇ、重量平均分子量は６０，０００、ガラス転移温度は１３１℃であった。 PGMEA (116.5 parts) was placed in a three-necked flask, and the temperature was raised to 90 ° C. in a nitrogen atmosphere. St (52.0 parts), MMA (19.0 parts), MAA (29.0 parts), V-601 (4.0 parts) while maintaining the liquid temperature in the three-necked flask at 90 ° C ± 2 ° C. Part) and PGMEA (116.5 parts) were added dropwise into a three-necked flask over 2 hours. After completion of the dropping, the mixed solution was stirred for 2 hours while maintaining the liquid temperature at 90 ° C. ± 2 ° C. to obtain a composition containing 30.0% by mass of the polymer A. The acid value of the polymer A was 189 mgKOH / g, the weight average molecular weight was 60,000, and the glass transition temperature was 131 ° C.
＜重合体Ａ－１、Ａ－２、Ａ－４及びＡ－５＞
　重合体の合成に使用するモノマーの種類及び量を下記表１に示すとおりに変更したこと以外は、重合体Ａ－３の合成方法と同様の方法で、重合体Ａ－１、Ａ－２、Ａ－４及びＡ－５を合成し、重合体を３０．０質量％含有する組成物を得た。
　なお、表１中、ＢｎＭＡはベンジルメタクリレート（三菱ガス化学社製）を意味する。
　また、表１に、得られた重合体の重量平均分子量（Ｍｗ）、酸価及びガラス転移温度（Ｔｇ）を記載した。 <Polymers A-1, A-2, A-4 and A-5>
Polymers A-1, A-2, and the same method as in the synthesis of polymer A-3, except that the type and amount of the monomers used in the synthesis of the polymer were changed as shown in Table 1 below. A-4 and A-5 were synthesized to obtain a composition containing 30.0% by mass of the polymer.
In Table 1, BnMA means benzyl methacrylate (manufactured by Mitsubishi Gas Chemical Company, Inc.).
In addition, Table 1 shows the weight average molecular weight (Mw), acid value and glass transition temperature (Tg) of the obtained polymer.
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
〔重合性化合物Ｂ〕
・重合性化合物Ｂ－１：ＮＫエステルＢＰＥ－５００（２，２－ビス（４－（メタクリロキシペンタエトキシ）フェニル）プロパン、新中村化学工業社製）
・重合性化合物Ｂ－２：ＮＫエステルＢＰＥ－２００（２，２－ビス（４－（メタクリロキシジエトキシ）フェニル）プロパン、新中村化学工業社製）
・重合性化合物Ｂ－３：ＮＫエステルＡ－ＴＭＰＴ（トリメチロールプロパントリアクリレート、新中村化学工業社製）
・重合性化合物Ｂ－４：アロニックス ＴＯ－２３４９（下記構造を有する化合物、東亞合成社製） [Polymerizable compound B]
-Polymerizable compound B-1: NK ester BPE-500 (2,2-bis (4- (methacryloxypentaethoxy) phenyl) propane, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.)
-Polymerizable compound B-2: NK ester BPE-200 (2,2-bis (4- (methacryloxydiethoxy) phenyl) propane, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.)
-Polymerizable compound B-3: NK ester A-TMPT (trimethylolpropane triacrylate, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.)
-Polymerizable compound B-4: Aronix TO-2349 (Compound having the following structure, manufactured by Toagosei Co., Ltd.)
Figure JPOXMLDOC01-appb-C000004
Figure JPOXMLDOC01-appb-C000004
〔光重合開始剤〕
・Ｂ－ＣＩＭ（光ラジカル重合開始剤、２－（２－クロロフェニル）－４，５－ジフェニルイミダゾール二量体、Ｈａｍｐｆｏｒｄ社製） [Photopolymerization initiator]
-B-CIM (photoradical polymerization initiator, 2- (2-chlorophenyl) -4,5-diphenylimidazole dimer, manufactured by Hampford)
〔増感剤〕
・ＳＢ－ＰＩ　７０１（４，４’－ビス（ジエチルアミノ）ベンゾフェノン、三洋貿易社製） [Sensitizer]
-SB-PI 701 (4,5'-bis (diethylamino) benzophenone, manufactured by Sanyo Trading Co., Ltd.)
〔色素Ｎ〕
・色素Ｎ－１：ＬＣＶ（ロイコクリスタルバイオレット、東京化成工業社製、ラジカルにより発色する
・色素Ｎ－２：ブリリアントグリーン（東京化成工業社製） [Dye N]
・ Dye N-1: LCV (Leuko Crystal Violet, manufactured by Tokyo Chemical Industry Co., Ltd., color is developed by radicals ・ Dye N-2: Brilliant Green (manufactured by Tokyo Chemical Industry Co., Ltd.)
〔防錆剤〕
・１－（２－ジ－ｎ－ブチルアミノメチル）－５－カルボキシベンゾトリアゾールと１－（２－ジ－ｎ－ブチルアミノメチル）－６－カルボキシベンゾトリアゾールの混合物（質量比１：１） 〔anti-rust〕
-A mixture of 1- (2-di-n-butylaminomethyl) -5-carboxybenzotriazole and 1- (2-di-n-butylaminomethyl) -6-carboxybenzotriazole (mass ratio 1: 1)
〔酸化防止剤〕
・Ｉｒｇａｎｏｘ２４５（エチレンビス（オキシエチレン）ビス－（３－（５－ｔｅｒｔ－ブチル－４－ヒドロキシ－ｍ－トリル）プロピオネート）、ＢＡＳＦ社製） 〔Antioxidant〕
-Irganox245 (ethylene bis (oxyethylene) bis- (3- (5-tert-butyl-4-hydroxy-m-tolyl) propionate), manufactured by BASF)
〔重合禁止剤〕
・Ｎ－ニトロソフェニルヒドロキシルアミンアルミニウム塩（富士フイルム和光純薬社製） [Polymerization inhibitor]
・ N-nitrosophenylhydroxylamine aluminum salt (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.)
　以下の成分を混合して感光性樹脂組成物を調製した。
・重合体Ａ－１（固形分濃度３０．０％）： ５３．２７部
・重合性化合物Ｂ－１：２２．５０部
・重合性化合物Ｂ－２：１０．００部
・重合性化合物Ｂ－３：１０．００部
・光重合開始剤： ３．００部
・増感剤： ０．３０部
・色素Ｎ－１：０．６０部
・色素Ｎ－２：０．０２部
・防錆剤：０．１０部
・酸化防止剤：０．２０部
・重合禁止剤：０．０１部
・メチルエチルケトン（三協化学社製）：１００．００部
・ＰＧＭＥＡ（昭和電工社製）：５０．００部
・メタノール（三菱ガス化学社製）：１０．００部 The following components were mixed to prepare a photosensitive resin composition.
-Polymer A-1 (solid content concentration 30.0%): 53.27 parts-Polymer compound B-1: 22.50 parts-Polymer compound B-2: 10.00 parts-Polymer compound B- 3: 10.00 parts ・ Photopolymerization initiator: 3.00 parts ・ Sensitizer: 0.30 parts ・ Dye N-1: 0.60 parts ・ Dye N-2: 0.02 parts ・ Rust preventive agent: 0.10 parts ・ Antioxidant: 0.20 parts ・ Polymerization inhibitor: 0.01 parts ・ Methyl ethyl ketone (manufactured by Sankyo Chemical Co., Ltd.): 100.00 parts ・ PGMEA (manufactured by Showa Denko Co., Ltd.): 50.00 parts ・Methanol (manufactured by Mitsubishi Gas Chemicals): 10.00 parts
＜感光性転写材料の作製＞
［実施例１］
　仮支持体として厚さ３０μｍのＰＥＴフィルムを用意した。仮支持体の表面に、スリット状ノズルを用いて塗布幅が１．０ｍ、かつ、乾燥後の層厚が５μｍとなるように感光性樹脂組成物を塗布した。感光性樹脂組成物の塗膜を８０℃で４０秒間かけて乾燥し、感光性樹脂層を形成し、感光性転写材料を得た。 <Preparation of photosensitive transfer material>
[Example 1]
A PET film having a thickness of 30 μm was prepared as a temporary support. A photosensitive resin composition was applied to the surface of the temporary support using a slit-shaped nozzle so that the coating width was 1.0 m and the layer thickness after drying was 5 μm. The coating film of the photosensitive resin composition was dried at 80 ° C. for 40 seconds to form a photosensitive resin layer, and a photosensitive transfer material was obtained.
［実施例２～実施例１３、比較例１、比較例２］
　感光性樹脂層の厚さ、感光性樹脂層に含まれる重合体Ａ及び重合性化合物Ｂの種類と量を、表２及び表３に記載の値に変更したこと以外は、実施例１と同様の方法で、感光性転写材料を得た。 [Examples 2 to 13, Comparative Example 1, Comparative Example 2]
Same as in Example 1 except that the thickness of the photosensitive resin layer and the types and amounts of the polymer A and the polymerizable compound B contained in the photosensitive resin layer were changed to the values shown in Tables 2 and 3. A photosensitive transfer material was obtained by the above method.
　表２及び表３中、「重合体Ａ」の「スチレン含有量」は、感光性樹脂層に含まれる重合体Ａの全質量に対するスチレンに由来する構成単位の含有量を示す。「重合体Ａ」の「含有量」は、感光性樹脂層の全質量に対する重合体Ａの含有量を示す。重合性化合物Ｂについては、感光性樹脂層の全質量に対する各重合性化合物の含有量（質量％）を記載した。また、「Ｍ／Ｂ比」は、重合体Ａの含有量に対する重合性化合物Ｂの含有量の比率を示す。 In Tables 2 and 3, the "styrene content" of "polymer A" indicates the content of the structural unit derived from styrene with respect to the total mass of the polymer A contained in the photosensitive resin layer. The "content" of the "polymer A" indicates the content of the polymer A with respect to the total mass of the photosensitive resin layer. For the polymerizable compound B, the content (mass%) of each polymerizable compound with respect to the total mass of the photosensitive resin layer is described. Further, "M / B ratio" indicates the ratio of the content of the polymerizable compound B to the content of the polymer A.
＜中間層組成物の調製＞
　以下の成分を混合して中間層組成物を調製した。
・イオン交換水：３８．１２部
・メタノール（三菱ガス化学社製）：５７．１７部
・クラレポバールＰＶＡ－２０５（ポリビニルアルコール、（株）クラレ製）：３．２２部
・ポリビニルピロリドンＫ－３０（日本触媒社製）：１．４９部
・メガファックＦ－４４４（フッ素系ノニオン性界面活性剤、ＤＩＣ社製）：０．０
０１５部 <Preparation of intermediate layer composition>
The following components were mixed to prepare an intermediate layer composition.
-Ion exchanged water: 38.12 parts-Methanol (manufactured by Mitsubishi Gas Chemical Company): 57.17 parts-Clarepovar PVA-205 (polyvinyl alcohol, manufactured by Kuraray Co., Ltd.): 3.22 parts-Polyvinylpyrrolidone K-30 (Manufactured by Nippon Catalyst Co., Ltd.): 1.49 parts, Megafuck F-444 (Fluorine-based nonionic surfactant, manufactured by DIC Co., Ltd.): 0.0
015 copies
＜熱可塑性樹脂組成物の調製＞
　以下の成分を混合して熱可塑性樹脂組成物を調製した。
・ベンジルメタクリレート、メタクリル酸及びアクリル酸の共重合体（固形分濃度３０．０％、Ｍｗ３００００、酸価１５３ｍｇＫＯＨ／ｇ）：４２．８５部
・ＮＫエステルＡ－ＤＣＰ（トリシクロデカンジメタノールジアクリレート、新中村化学工業社製）：４．６３部
・８ＵＸ－０１５Ａ（多官能ウレタンアクリレート化合物、大成ファインケミカル社製）：２．３１部
・アロニックスＴＯ－２３４９（東亞合成社製）：０．７７部
・下記に示す構造の化合物（光酸発生剤、特開２０１３－４７７６５号公報の段落０２２７に記載の方法に従って合成した化合物。）：０．３２部 <Preparation of thermoplastic resin composition>
The following components were mixed to prepare a thermoplastic resin composition.
・ Copolymer of benzyl methacrylate, methacrylic acid and acrylic acid (solid content concentration 30.0%, Mw30000, acid value 153 mgKOH / g): 42.85 parts ・ NK ester A-DCP (tricyclodecanedimethanol diacrylate, Shin-Nakamura Chemical Co., Ltd.): 4.63 parts, 8UX-015A (polyfunctional urethane acrylate compound, manufactured by Taisei Fine Chemical Co., Ltd.): 2.31 parts, Aronix TO-2349 (manufactured by Toa Synthetic Co., Ltd.): 0.77 parts, A compound having the structure shown below (a photoacid generator, a compound synthesized according to the method described in paragraph 0227 of JP2013-47765A): 0.32 parts.
Figure JPOXMLDOC01-appb-C000005
Figure JPOXMLDOC01-appb-C000005
・下記に示す構造の化合物（酸により発色する色素）：０．０８部 -Compounds with the structure shown below (dyes that develop color with acid): 0.08 parts
Figure JPOXMLDOC01-appb-C000006
Figure JPOXMLDOC01-appb-C000006
・メガファックＦ５５２（ＤＩＣ社製）：０．０３部
・メチルエチルケトン（三協化学社製）：３９．５０部
・ＰＧＭＥＡ（昭和電工社製）：９．５１部 ・ Megafuck F552 (manufactured by DIC): 0.03 parts ・ Methyl ethyl ketone (manufactured by Sankyo Chemical Co., Ltd.): 39.50 parts ・ PGMEA (manufactured by Showa Denko Co., Ltd.): 9.51 parts
＜感光性転写材料の作製＞
［実施例１４］
　仮支持体として厚さ３０μｍのＰＥＴフィルムを用意した。仮支持体の表面に、スリット状ノズルを用いて塗布幅が１．０ｍ、かつ、乾燥後の層厚が３．０μｍとなるように熱可塑性樹脂組成物を塗布した。形成された熱可塑性樹脂組成物の塗膜を８０℃で４０秒間かけて乾燥し、熱可塑性樹脂層を形成した。形成された熱可塑性樹脂層の表面に、スリット状ノズルを用いて塗布幅が１．０ｍ、かつ、乾燥後の層厚が１．２μｍとなるように中間層組成物を塗布した。中間層組成物の塗膜を８０℃で４０秒間かけて乾燥し、中間層を形成した。形成された中間層の表面に、スリット状ノズルを用いて塗布幅が１．０ｍ、かつ、乾燥後の層厚が２μｍとなるように感光性樹脂組成物を塗布した。感光性樹脂組成物の塗膜を８０℃で４０秒間かけて乾燥し、感光性樹脂層を形成し、感光性転写材料を得た。 <Preparation of photosensitive transfer material>
[Example 14]
A PET film having a thickness of 30 μm was prepared as a temporary support. A thermoplastic resin composition was applied to the surface of the temporary support using a slit-shaped nozzle so that the coating width was 1.0 m and the layer thickness after drying was 3.0 μm. The formed coating film of the thermoplastic resin composition was dried at 80 ° C. for 40 seconds to form a thermoplastic resin layer. An intermediate layer composition was applied to the surface of the formed thermoplastic resin layer using a slit-shaped nozzle so that the coating width was 1.0 m and the layer thickness after drying was 1.2 μm. The coating film of the intermediate layer composition was dried at 80 ° C. for 40 seconds to form an intermediate layer. A photosensitive resin composition was applied to the surface of the formed intermediate layer using a slit-shaped nozzle so that the coating width was 1.0 m and the layer thickness after drying was 2 μm. The coating film of the photosensitive resin composition was dried at 80 ° C. for 40 seconds to form a photosensitive resin layer, and a photosensitive transfer material was obtained.
　実施例及び比較例で得られた感光性転写材料を用いて、ヘイズを測定し、解像度、クッション性及びスカム発生の評価を行った。測定方法及び評価方法は以下のとおりである。評価結果を表２及び表３に示す。 The haze was measured using the photosensitive transfer materials obtained in Examples and Comparative Examples, and the resolution, cushioning property and scum generation were evaluated. The measurement method and evaluation method are as follows. The evaluation results are shown in Tables 2 and 3.
＜ヘイズ＞
　実施例及び比較例で得られた感光性転写材料から、それぞれ０．０２ｍ２の測定サンプルを得た。２００ｍＬの１質量％炭酸ナトリウム水溶液に０．０２ｍ２の測定サンプルを入れ、気泡を混入しないように注意しながら３０℃で４時間攪拌した。撹拌後、測定サンプルが溶解した溶液のヘイズを測定した。ヘイズは、ヘイズメーター（製品名「ＮＤＨ４０００」、日本電色工業社製）を用い、液体測定用ユニット及び光路長２０ｍｍの液体測定専用セルを用いて測定した。 <Haze>
From the photosensitive transfer materials obtained in Examples and Comparative Examples, 0.02 m 2 measurement samples were obtained, respectively. A 0.02 m 2 measurement sample was placed in 200 mL of a 1 mass% sodium carbonate aqueous solution, and the mixture was stirred at 30 ° C. for 4 hours, being careful not to mix air bubbles. After stirring, the haze of the solution in which the measurement sample was dissolved was measured. The haze was measured using a haze meter (product name "NDH4000", manufactured by Nippon Denshoku Kogyo Co., Ltd.) using a liquid measuring unit and a liquid measuring cell having an optical path length of 20 mm.
＜解像度＞
　まず、厚さ１００μｍのポリエチレンテレフタレート（ＰＥＴ）フィルム上に、スパッタ法にて厚さ２００ｎｍの銅層を形成することにより、銅層付きＰＥＴ基板を作製した。
　ロール形態の感光性転写材料を巻き出した後、感光性転写材料と銅層付きＰＥＴ基板とを、感光性樹脂層と銅層とが互いに接触するように貼り合わせて、積層体を得た。貼り合わせ工程は、ロール温度１２０℃、線圧１．０ＭＰａ、線速度０．５ｍ／ｍｉｎの条件で行った。
　得られた積層体の仮支持体側から、フォトマスクを介して超高圧水銀灯（露光主波長：３６５ｎｍ）を照射して、感光性樹脂層を露光した。露光に使用したフォトマスクは、透過領域と遮光領域の幅の比（Ｄｕｔｙ比）が１：１であり、かつ、ライン幅（及びスペース幅）が１μｍから２０μｍまで１μｍおきに段階的に変化するラインアンドスペースパターンを有していた。
　なお、フォトマスクのうち、ラインアンドスペースパターンのライン幅及びスペース幅が２０μｍである領域を通過した照射光によって露光されて形成される樹脂パターンのライン幅が２０μｍとなるように、感光性樹脂層に対する露光量を調整した。
　露光された積層体から仮支持体を剥離した後、積層体に対して、液温２５℃の１．０質量％炭酸ナトリウム水溶液を用いて３０秒間のシャワー現像を行った。この現像工程により、
積層体から、未露光の感光性樹脂層を除去し、銅層の表面に上記の段階的に変化するラインアンドスペースパターンを有する樹脂パターンを作製した。中間層及び熱可塑性樹脂層を積層した例では、この現像工程により、中間層及び熱可塑性樹脂層も除去した。 <Resolution>
First, a PET substrate with a copper layer was produced by forming a copper layer having a thickness of 200 nm on a polyethylene terephthalate (PET) film having a thickness of 100 μm by a sputtering method.
After unwinding the photosensitive transfer material in the form of a roll, the photosensitive transfer material and the PET substrate with a copper layer were bonded together so that the photosensitive resin layer and the copper layer were in contact with each other to obtain a laminate. The bonding step was performed under the conditions of a roll temperature of 120 ° C., a linear pressure of 1.0 MPa, and a linear velocity of 0.5 m / min.
The photosensitive resin layer was exposed by irradiating an ultra-high pressure mercury lamp (exposure main wavelength: 365 nm) from the temporary support side of the obtained laminate via a photomask. In the photomask used for exposure, the ratio of the widths of the transmission region and the light-shielding region (duty ratio) is 1: 1 and the line width (and space width) changes stepwise from 1 μm to 20 μm every 1 μm. It had a line and space pattern.
In the photomask, the photosensitive resin layer has a line width of a line-and-space pattern and a line width of a resin pattern formed by exposure by irradiation light passing through a region where the space width is 20 μm. The amount of exposure to light was adjusted.
After peeling the temporary support from the exposed laminate, the laminate was shower-developed for 30 seconds using a 1.0 mass% sodium carbonate aqueous solution at a liquid temperature of 25 ° C. By this development process
The unexposed photosensitive resin layer was removed from the laminate to prepare a resin pattern having the above-mentioned stepwise changing line-and-space pattern on the surface of the copper layer. In the example in which the intermediate layer and the thermoplastic resin layer were laminated, the intermediate layer and the thermoplastic resin layer were also removed by this developing step.
　形成された樹脂パターンについて、パターン形状及びスペース部における感光性樹脂層の残渣の有無を、走査型電子顕微鏡（製品名「Ｓ－４８００」、日立ハイテクノロジー社製）を用いて各線幅ごとに観察した。ライン部において硬化された感光性樹脂層が剥離せず、かつ、感光性樹脂層の残渣が無い樹脂パターンの線幅のうち最小の線幅を、解像度として判定した。評価基準は以下のとおりである。３以上は実用上問題ないレベルである。
　５：解像度が４μｍ以下である。
　４：解像度が５μｍ又は６μｍである。
　３：解像度が７μｍ又は８μｍである。
　２：解像度が９μｍ又は１０μｍである。
　１：解像度が１１μｍ以上である。 With respect to the formed resin pattern, the pattern shape and the presence or absence of residue of the photosensitive resin layer in the space portion are observed for each line width using a scanning electron microscope (product name "S-4800", manufactured by Hitachi High-Technology Co., Ltd.). bottom. The minimum line width of the resin pattern in which the cured photosensitive resin layer was not peeled off at the line portion and there was no residue of the photosensitive resin layer was determined as the resolution. The evaluation criteria are as follows. A level of 3 or higher is a level at which there is no problem in practical use.
5: The resolution is 4 μm or less.
4: The resolution is 5 μm or 6 μm.
3: The resolution is 7 μm or 8 μm.
2: The resolution is 9 μm or 10 μm.
1: The resolution is 11 μm or more.
＜クッション性＞
　まず、厚さ１００μｍのポリエチレンテレフタレート（ＰＥＴ）フィルム上に、スパッタ法にて厚さ２００ｎｍの銅層を形成することにより、銅層付きＰＥＴ基板を作製した。銅層付きＰＥＴ基板をエッチングし、高さ２００ｎｍ、幅１０００μｍのラインアンドスペースの銅パターンからなる段差を有する基板を作製した。ロール形態の感光性転写材料を巻き出した後、感光性転写材料と基板とを、感光性樹脂層と銅層とが互いに接触するように貼り合わせて、積層体を得た。貼り合わせ工程は、ロール温度を５℃おきに変化させながら、大気圧下で、線圧１．０ＭＰａ、線速度４ｍ／ｍｉｎの条件で行った。段差に対して、気泡が混入することなく貼り合わせることができる最も低い温度（以下、気泡なしラミネート可能温度」という）をクッション性の指標とした。気泡が混入することなく貼り合わせることができる温度が低いほど、クッション性に優れるといえる。評価基準は以下のとおりである。３以上は実用上問題ないレベルである。
　５：気泡なしラミネート可能温度が７０℃以下である。
　４：気泡なしラミネート可能温度が７５℃以上８５℃以下である。
　３：気泡なしラミネート可能温度が９０℃以上１００℃以下である。
　２：気泡なしラミネート可能温度が１０５℃以上１１５℃以下である。
　１：気泡なしラミネート可能温度が１２０℃以上である。　 <Cushioning>
First, a PET substrate with a copper layer was produced by forming a copper layer having a thickness of 200 nm on a polyethylene terephthalate (PET) film having a thickness of 100 μm by a sputtering method. A PET substrate with a copper layer was etched to prepare a substrate having a step having a line-and-space copper pattern having a height of 200 nm and a width of 1000 μm. After unwinding the photosensitive transfer material in the form of a roll, the photosensitive transfer material and the substrate were bonded together so that the photosensitive resin layer and the copper layer were in contact with each other to obtain a laminate. The bonding step was performed under atmospheric pressure under the conditions of a linear pressure of 1.0 MPa and a linear velocity of 4 m / min while changing the roll temperature every 5 ° C. The lowest temperature at which air bubbles can be bonded to the step without air bubbles (hereinafter referred to as "air bubble-free laminating temperature") was used as an index of cushioning property. It can be said that the lower the temperature at which they can be bonded without air bubbles being mixed, the better the cushioning property. The evaluation criteria are as follows. A level of 3 or higher is a level at which there is no problem in practical use.
5: The temperature at which bubbles can be laminated is 70 ° C. or lower.
4: Bubble-free laminating temperature is 75 ° C or higher and 85 ° C or lower.
3: The temperature at which bubbles can be laminated is 90 ° C. or higher and 100 ° C. or lower.
2: Bubble-free laminating temperature is 105 ° C or higher and 115 ° C or lower.
1: The temperature at which bubbles can be laminated is 120 ° C. or higher.
＜スカム発生＞
　実施例及び比較例で得られた感光性転写材料から、それぞれ０．５ｍ２の評価サンプルを得た。１Ｌの１質量％炭酸ナトリウム水溶液に０．５ｍ２の評価サンプルを溶解させた。評価サンプルが溶解した溶液を０．１５ＭＰａの圧力でスプレーしながら、３時間循環させた。３時間後、溶液を２００ｍＬ回収し、ポアサイズ０．４５μｍのポリプロピレン製メンブレンフィルター（ＨＤＣII　Ｐａｌｌ社製）を用いてろ過した。ろ過後、ろ過に用いたフィルターを８０℃で真空乾燥させ、水分を蒸発させた。ろ過前のフィルターの質量と、ろ過後のフィルターの質量から、ろ過残渣の質量を算出した。また、溶液の残りを２５℃の室内で２４時間静置させた。２４時間後、溶液の残りが入った槽内における凝集物（スカム）の発生状態を目視で観察した。評価基準は以下のとおりである。３以上は実用上問題ないレベルである。
　６：ろ過残渣の質量が１ｍｇ未満であり、かつ、槽内のスカム（凝集物）の発生も認められなかった。
　５：ろ過残渣の質量が１ｍｇ以上２ｍｇ未満であり、かつ、槽内のスカム（凝集物）の発生も認められなかった。
　４：ろ過残渣の質量が１ｍｇ以上２ｍｇ未満であるが、槽内にスカム（凝集物）の発生が認められた。
　３：ろ過残渣の質量が２ｍｇ以上５ｍｇ未満である。
　２：ろ過残渣の質量が５ｍｇ以上１０ｍｇ未満である。
　１：ろ過残渣の質量が１０ｍｇ以上であるか、又は、槽内に多量の固形状のスカム（凝集物）の発生が認められた。 <Scum generation>
From the photosensitive transfer materials obtained in Examples and Comparative Examples, 0.5 m 2 of evaluation samples were obtained, respectively. Was dissolved evaluation samples of 0.5 m 2 to 1% by weight aqueous sodium carbonate 1L. The solution in which the evaluation sample was dissolved was circulated for 3 hours while spraying at a pressure of 0.15 MPa. After 3 hours, 200 mL of the solution was collected and filtered using a polypropylene membrane filter (manufactured by HDCII Pall) having a pore size of 0.45 μm. After filtration, the filter used for filtration was vacuum dried at 80 ° C. to evaporate the water content. The mass of the filtration residue was calculated from the mass of the filter before filtration and the mass of the filter after filtration. The rest of the solution was allowed to stand in a room at 25 ° C. for 24 hours. After 24 hours, the state of occurrence of agglomerates (scums) in the tank containing the rest of the solution was visually observed. The evaluation criteria are as follows. A level of 3 or higher is a level at which there is no problem in practical use.
6: The mass of the filtration residue was less than 1 mg, and no scum (aggregate) was observed in the tank.
5: The mass of the filtration residue was 1 mg or more and less than 2 mg, and no scum (aggregate) was observed in the tank.
4: The mass of the filtration residue was 1 mg or more and less than 2 mg, but scum (aggregates) was observed in the tank.
3: The mass of the filtration residue is 2 mg or more and less than 5 mg.
2: The mass of the filtration residue is 5 mg or more and less than 10 mg.
1: The mass of the filtration residue was 10 mg or more, or a large amount of solid scum (aggregate) was observed in the tank.
Figure JPOXMLDOC01-appb-T000007
Figure JPOXMLDOC01-appb-T000007
Figure JPOXMLDOC01-appb-T000008
 
Figure JPOXMLDOC01-appb-T000008
 
　表２及び表３に示すように、実施例１～実施例１４は、１質量％炭酸ナトリウムの３０℃水溶液１リットルに０．１ｍ２の感光性転写材料を溶解させて得られる溶液のヘイズが６０％以下であるため、スカム（凝集物）の発生が少ないことが分かった。 As shown in Tables 2 and 3, in Examples 1 to 14, the haze of the solution obtained by dissolving 0.1 m 2 of the photosensitive transfer material in 1 liter of a 30 ° C. aqueous solution of 1 mass% sodium carbonate has a haze. Since it was 60% or less, it was found that the generation of scum (aggregate) was small.
　一方、表３に示すように、比較例１及び比較例２では、上記溶液のヘイズが１００％、６８．２％であり、スカム（凝集物）の発生が多いことが分かった。 On the other hand, as shown in Table 3, in Comparative Example 1 and Comparative Example 2, the haze of the above solution was 100% and 68.2%, and it was found that scum (aggregates) were frequently generated.
　実施例３は、感光性樹脂層に含まれるアルカリ可溶性樹脂の酸価が１２０ｍｇ／ＫＯＨ以上であるため、実施例１と比較すると、スカム（凝集物）の発生が少なく、解像度が優れる。 In Example 3, since the acid value of the alkali-soluble resin contained in the photosensitive resin layer is 120 mg / KOH or more, less scum (aggregates) is generated and the resolution is excellent as compared with Example 1.
　実施例３は、感光性樹脂層に含まれるアルカリ可溶性樹脂の含有量に対する重合性化合物の含有量の比率が、質量基準で０．８５以下であるため、実施例１３と比較すると、スカム（凝集物）の発生が少ない。 In Example 3, the ratio of the content of the polymerizable compound to the content of the alkali-soluble resin contained in the photosensitive resin layer is 0.85 or less on a mass basis, and therefore, as compared with Example 13, scum (aggregation) (aggregation). There are few things).
　実施例８は、感光性樹脂層に含まれるアルカリ可溶性樹脂が、スチレンに由来する構成単位を含むため、実施例７と比較すると、スカム（凝集物）の発生が少ない。 In Example 8, since the alkali-soluble resin contained in the photosensitive resin layer contains a structural unit derived from styrene, less scum (aggregates) is generated as compared with Example 7.
　実施例１０は、感光性樹脂層の厚さが１０μｍ以下であるため、実施例９と比較すると、スカム（凝集物）の発生が少ない。 In Example 10, since the thickness of the photosensitive resin layer is 10 μm or less, less scum (aggregates) is generated as compared with Example 9.
　実施例１１は、酸基を有する重合性化合物を含むため、実施例８と比較すると、スカム（凝集物）の発生が少ない。 Since Example 11 contains a polymerizable compound having an acid group, less scum (aggregates) is generated as compared with Example 8.
　本開示に係る感光性転写材料は、フォトリソグラフィーによる精密微細加工が必要な各種用途に好適に用いることができる。感光性樹脂層をパターニングした後に、感光性樹脂層を被膜としてエッチングをしてもよく、電気めっきを主体とするエレクトロフォーミングを行ってもよい。また、パターニングによって得られた硬化膜は、永久膜として使用してもよい。硬化膜は、例えば、層間絶縁膜、配線保護膜、又はインデックスマッチング層を有する配線保護膜として用いてもよい。また、本開示に係る感光性転写材料は、半導体パッケージ、プリント基板、センサー基板等の各種配線を形成するための材料、並びに、タッチパネル、電磁波シールド材、フィルムヒーターのような導電性フィルム、液晶シール材、マイクロマシン、及びマイクロエレクトロニクス分野における構造物を形成するための材料として好適に使用し得る。 The photosensitive transfer material according to the present disclosure can be suitably used for various applications requiring precision microfabrication by photolithography. After patterning the photosensitive resin layer, the photosensitive resin layer may be used as a coating for etching, or electroforming may be performed mainly by electroplating. Moreover, the cured film obtained by patterning may be used as a permanent film. The cured film may be used as, for example, an interlayer insulating film, a wiring protective film, or a wiring protective film having an index matching layer. The photosensitive transfer material according to the present disclosure includes materials for forming various wirings such as semiconductor packages, printed circuit boards, sensor substrates, touch panels, electromagnetic wave shielding materials, conductive films such as film heaters, and liquid crystal seals. It can be suitably used as a material for forming a structure in the field of materials, micromachines, and microelectronics.
　なお、２０２０年４月２８日に出願された日本国特許出願２０２０－０７９５３４号の開示は、その全体が参照により本明細書に取り込まれる。また、本明細書に記載された全ての文献、特許出願および技術規格は、個々の文献、特許出願、および技術規格が参照により取り込まれることが具体的かつ個々に記された場合と同程度に、本明細書中に参照により取り込まれる。  The entire disclosure of Japanese Patent Application No. 2020-079534 filed on April 28, 2020 is incorporated herein by reference in its entirety. Also, all documents, patent applications and technical standards described herein are to the same extent as if the individual documents, patent applications and technical standards were specifically and individually stated to be incorporated by reference. , Incorporated by reference herein.

Claims (11)

  1. 　仮支持体と、前記仮支持体上に配置された感光性樹脂層と、を備え、
    　１質量％炭酸ナトリウムの３０℃水溶液１リットルに０．１ｍ２の感光性転写材料を溶解させて得られる溶液のヘイズが６０％以下である、感光性転写材料。     A temporary support and a photosensitive resin layer arranged on the temporary support are provided.
    A photosensitive transfer material having a haze of 60% or less of a solution obtained by dissolving 0.1 m 2 of a photosensitive transfer material in 1 liter of a 30 ° C. aqueous solution of 1 mass% sodium carbonate.
  2. 　前記感光性樹脂層の厚さが１０μｍ以下である、請求項１に記載の感光性転写材料。 The photosensitive transfer material according to claim 1, wherein the photosensitive resin layer has a thickness of 10 μm or less.
  3. 　前記感光性樹脂層は、重合性化合物とアルカリ可溶性樹脂とを含み、
    　前記アルカリ可溶性樹脂の含有量に対する前記重合性化合物の含有量の比率が、質量基準で０．８５以下である、請求項１又は請求項２に記載の感光性転写材料。     The photosensitive resin layer contains a polymerizable compound and an alkali-soluble resin, and contains
    The photosensitive transfer material according to claim 1 or 2, wherein the ratio of the content of the polymerizable compound to the content of the alkali-soluble resin is 0.85 or less on a mass basis.
  4. 　前記感光性樹脂層は、アルカリ可溶性樹脂を含み、
    　前記アルカリ可溶性樹脂の酸価は１２０ｍｇ／ＫＯＨ以上である、請求項１～請求項３のいずれか１項に記載の感光性転写材料。     The photosensitive resin layer contains an alkali-soluble resin and contains an alkali-soluble resin.
    The photosensitive transfer material according to any one of claims 1 to 3, wherein the alkali-soluble resin has an acid value of 120 mg / KOH or more.
  5. 　前記感光性樹脂層は、アルカリ可溶性樹脂を含み、
    　前記アルカリ可溶性樹脂は、スチレンに由来する構成単位を含む、請求項１～請求項４のいずれか１項に記載の感光性転写材料。     The photosensitive resin layer contains an alkali-soluble resin and contains an alkali-soluble resin.
    The photosensitive transfer material according to any one of claims 1 to 4, wherein the alkali-soluble resin contains a structural unit derived from styrene.
  6. 　スチレンに由来する構成単位の含有量が、前記アルカリ可溶性樹脂の全質量に対して４０質量％以上である、請求項５に記載の感光性転写材料。 The photosensitive transfer material according to claim 5, wherein the content of the structural unit derived from styrene is 40% by mass or more with respect to the total mass of the alkali-soluble resin.
  7. 　前記感光性樹脂層は、酸基を有する重合性化合物を含む、請求項１～請求項６のいずれか１項に記載の感光性転写材料。 The photosensitive transfer material according to any one of claims 1 to 6, wherein the photosensitive resin layer contains a polymerizable compound having an acid group.
  8. 　前記仮支持体と前記感光性樹脂層との間に、熱可塑性樹脂層をさらに備える、請求項１～請求項７のいずれか１項に記載の感光性転写材料。 The photosensitive transfer material according to any one of claims 1 to 7, further comprising a thermoplastic resin layer between the temporary support and the photosensitive resin layer.
  9. 　請求項１～請求項８のいずれか１項に記載の感光性転写材料における前記感光性樹脂層の前記仮支持体と対向していない側の面と基板とを貼り合わせる工程と、
    　前記貼り合わせる工程後の感光性転写材料における前記感光性樹脂層をパターン露光する工程と、
    　前記パターン露光する工程後の感光性樹脂層を現像して樹脂パターンを形成する工程と、を含む、樹脂パターンの製造方法。     The step of bonding the surface of the photosensitive resin layer on the side of the photosensitive resin layer not facing the temporary support and the substrate in the photosensitive transfer material according to any one of claims 1 to 8.
    A step of pattern-exposing the photosensitive resin layer in the photosensitive transfer material after the bonding step, and a step of pattern-exposing the photosensitive resin layer.
    A method for producing a resin pattern, which comprises a step of developing a photosensitive resin layer after the step of pattern exposure to form a resin pattern.
  10. 　請求項１～請求項８のいずれか１項に記載の感光性転写材料における前記感光性樹脂層の前記仮支持体と対向していない側の面と基板とを貼り合わせる工程と、
    　前記貼り合わせる工程後の感光性転写材料における前記感光性樹脂層をパターン露光する工程と、
    　前記パターン露光する工程後の感光性樹脂層を現像して樹脂パターンを形成する工程と、
    　前記樹脂パターンが配置されていない領域における基板をエッチング処理する工程と、を含む、回路配線の製造方法。     The step of bonding the surface of the photosensitive resin layer on the side of the photosensitive resin layer not facing the temporary support and the substrate in the photosensitive transfer material according to any one of claims 1 to 8.
    A step of pattern-exposing the photosensitive resin layer in the photosensitive transfer material after the bonding step, and a step of pattern exposure.
    A step of developing a photosensitive resin layer after the step of pattern exposure to form a resin pattern, and a step of forming a resin pattern.
    A method for manufacturing a circuit wiring, which comprises a step of etching a substrate in a region where the resin pattern is not arranged.
  11. 　請求項１～請求項８のいずれか１項に記載の感光性転写材料における前記感光性樹脂層の前記仮支持体と対向していない側の面と基板とを貼り合わせる工程と、
    　前記貼り合わせる工程後の感光性転写材料における前記感光性樹脂層をパターン露光する工程と、
    　前記パターン露光する工程後の感光性樹脂層を現像して樹脂パターンを形成する工程と、
    　前記樹脂パターンが配置されていない領域における基板をエッチング処理する工程と、を含む、タッチパネルの製造方法。     The step of bonding the surface of the photosensitive resin layer on the side of the photosensitive resin layer not facing the temporary support and the substrate in the photosensitive transfer material according to any one of claims 1 to 8.
    A step of pattern-exposing the photosensitive resin layer in the photosensitive transfer material after the bonding step, and a step of pattern-exposing the photosensitive resin layer.
    A step of developing a photosensitive resin layer after the step of pattern exposure to form a resin pattern, and a step of forming a resin pattern.
    A method for manufacturing a touch panel, which comprises a step of etching a substrate in a region where the resin pattern is not arranged.
PCT/JP2021/016522 2020-04-28 2021-04-23 Photosensitive transfer material, method for producing resin pattern, method for producing circuit wiring, and method for producing touch panel WO2021220980A1 (en)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012086371A1 (en) * 2010-12-24 2012-06-28 旭化成イーマテリアルズ株式会社 Photosensitive resin composition
JP2017003641A (en) * 2015-06-05 2017-01-05 日油株式会社 Urethane (meth)acrylate and photosensitive resin composition for dry film resist
WO2017043544A1 (en) * 2015-09-11 2017-03-16 旭化成株式会社 Photosensitive resin composition

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012086371A1 (en) * 2010-12-24 2012-06-28 旭化成イーマテリアルズ株式会社 Photosensitive resin composition
JP2017003641A (en) * 2015-06-05 2017-01-05 日油株式会社 Urethane (meth)acrylate and photosensitive resin composition for dry film resist
WO2017043544A1 (en) * 2015-09-11 2017-03-16 旭化成株式会社 Photosensitive resin composition

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