Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
  • B32B7/04—Interconnection of layers
  • B32B7/06—Interconnection of layers permitting easy separation
• • 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
  • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/20—Exposure; Apparatus therefor
• • H—ELECTRICITY
  • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
  • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
  • H05K3/00—Apparatus or processes for manufacturing printed circuits
  • H05K3/02—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding
  • H05K3/06—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding the conductive material being removed chemically or electrolytically, e.g. by photo-etch process
• • H—ELECTRICITY
  • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
  • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
  • H05K3/00—Apparatus or processes for manufacturing printed circuits
  • H05K3/10—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern
  • H05K3/18—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using precipitation techniques to apply the conductive material
• • H—ELECTRICITY
  • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
  • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
  • H05K3/00—Apparatus or processes for manufacturing printed circuits
  • H05K3/10—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern
  • H05K3/20—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern by affixing prefabricated conductor pattern

Definitions

• the present disclosure relates to a transfer film and a conductor pattern forming method.
• a method of manufacturing a printed wiring board having a predetermined conductor pattern As a method of manufacturing a printed wiring board having a predetermined conductor pattern, a method of forming a seed layer on a substrate, forming a resist pattern on the seed layer, and forming a metal layer on the exposed seed layer is known. ing.
• Formation of the seed layer on the base material is carried out by methods such as a sputtering method, application of a composition for forming a seed layer to the base material, and heating.
• a composition containing a metal salt and a reducing agent is applied onto a substrate to form a layer containing the metal salt, and the layer containing the metal salt is heated. , reducing a metal salt to form a seed layer containing a simple metal.
• Japanese Patent Application Laid-Open No. 2014-27211 proposes subjecting the base material to roughening treatment for the purpose of improving the adhesion between the base material and the seed layer.
• the present inventors have recently found that a seed layer formed by a sputtering method, a method of applying a seed layer-forming composition to a substrate and a heating method, or the like has good adhesion to a substrate (particularly, a liquid crystal polymer substrate). It was found that there is room for improvement in terms of sex. In addition, the present inventors have found that when the base material is roughened, the transmission loss in the high-frequency region increases, and the applicability to the printed wiring board may deteriorate.
• the problem to be solved by one embodiment of the present disclosure is to improve the adhesion between a substrate and a layer containing a metal such as a seed layer without roughening the substrate.
• An object of the present invention is to provide a transfer film and a method of forming a conductor pattern using the transfer film.
• the photosensitive composition layer contains an alkali-soluble resin, a polymerizable compound, and a photopolymerization initiator.
• the layer containing the metal salt has a thickness of 10 nm to 1000 nm.
• ⁇ 5> The transfer film according to any one of ⁇ 1> to ⁇ 4>, wherein the metal salt is a metal carboxylate.
• the layer containing the metal salt contains a reducing agent.
• the layer containing the metal salt is a layer for forming a seed layer.
• a method for forming a conductor pattern comprising: ⁇ 9> The method comprising, after the step of forming a metal layer on the exposed seed layer, removing the resist pattern and removing the seed layer exposed by removing the resist pattern in this order.
• the transfer film and the above-described transfer film can improve the adhesion between the substrate and a layer containing a metal such as a seed layer without roughening the substrate.
• a method of forming a conductor pattern using a transfer film can be provided.
• FIG. 1 is a schematic cross-sectional view showing one embodiment of the transfer film of the present disclosure.
• the numerical range indicated using “-" includes the numerical values before and after "-" as the minimum and maximum values, respectively.
• the upper limit or lower limit described in one numerical range may be replaced with the upper limit or lower limit of another numerical range described step by step.
• the upper or lower limits of the numerical ranges may be replaced with the values shown in the examples.
• each component may contain multiple types of applicable substances.
• layer includes the case where the layer or film is formed in the entire region when the region where the layer or film is present is formed only in a part of the region. case is also included.
• process includes not only an independent process but also a process that cannot be clearly distinguished from other processes as long as the intended purpose of the process is achieved.
• “transparent” means that the average transmittance of visible light with a wavelength of 400 nm to 700 nm is 80% or more, preferably 90% or more.
• the transmittance is a value measured using a spectrophotometer, and can be measured using, for example, a spectrophotometer U-3310 manufactured by Hitachi, Ltd.
• the weight-average molecular weight (Mw) and number-average molecular weight (Mn) are measured as columns of TSKgel GMHxL, TSKgel G4000HxL, or TSKgel G2000HxL (all products manufactured by Tosoh Corporation). name), THF (tetrahydrofuran) as an eluent, a differential refractometer as a detector, and polystyrene as a standard substance, measured by a gel permeation chromatography (GPC) analyzer, converted using polystyrene as a standard substance is.
• GPC gel permeation chromatography
• the ratio of polymer constitutional units is the mass ratio.
• the molecular weight of compounds having a molecular weight distribution is the weight average molecular weight (Mw).
• (meth)acrylic is a concept that includes both acrylic and methacrylic.
• a "(meth)acryloxy group” is a concept that includes both an acryloxy group and a methacryloxy group.
• a “(meth)acryloyl group” is a concept that includes both an acryloyl group and a methacryloyl group.
• alkali-soluble means that the solubility in 100 g of a 1% by mass aqueous solution of sodium carbonate at 22°C is 0.1 g or more.
• water-soluble means that the solubility in 100 g of water at pH 7.0 at a liquid temperature of 22°C is 0.1 g or more.
• water-soluble resin is intended a resin that satisfies the solubility conditions set forth above.
• the “solid content” of the composition means a component that forms a composition layer formed using the composition, and when the composition contains a solvent (organic solvent, water, etc.), the solvent means all ingredients except In addition, as long as it is a component that forms a composition layer, a liquid component is also regarded as a solid content.
• a solvent organic solvent, water, etc.
• thickness is calculated as an average value of arbitrary five points measured by cross-sectional observation of a target using a SEM (Scanning Electron Microscope).
• the transfer film 1 of the present disclosure includes a temporary support 10, a photosensitive composition layer 11, and a layer 12 containing a metal salt (hereinafter also referred to as a "metal salt-containing layer"). and , in that order.
• the transfer film 1 of the present disclosure may include an intermediate layer 13 between the temporary support 10 and the photosensitive composition layer 11, as shown in FIG.
• the transfer film 1 of the present disclosure may include a thermoplastic resin layer 14 between the temporary support 10 and the photosensitive composition layer 11 or between the intermediate layer 13 and the photosensitive composition layer 11. .
• the structure provided with the thermoplastic resin layer 14 between the intermediate layer 13 and the photosensitive composition layer 11 was shown.
• the transfer film 1 of the present disclosure may include a protective film 15 on the metal salt-containing layer 12, as shown in FIG.
• a temporary support, a photosensitive composition layer, a metal salt-containing layer, and the like are laminated in this order.
• the transfer film has a temporary support.
• a temporary support is a member that supports a photosensitive composition layer and the like, and is finally removed by a peeling treatment.
• the temporary support may have a single layer structure or a multilayer structure.
• the temporary support is preferably a film, more preferably a resin film.
• the temporary support is preferably a film that has flexibility and does not undergo significant deformation, shrinkage, or elongation under pressure or under pressure and heat.
• the resin film include polyethylene terephthalate film, polymethyl methacrylate film, cellulose triacetate film, polystyrene film, polyimide film, and polycarbonate film, with polyethylene terephthalate film being preferred.
• the resin film may be stretched, may be a uniaxially stretched resin film, or may be a biaxially stretched resin film. In addition, it is preferable that the film used as the temporary support does not have deformation such as wrinkles, scratches, or the like.
• Exposure of the photosensitive composition layer may be performed after peeling the temporary support, it may be performed before peeling, but when the exposure is performed before peeling the temporary support, the pattern through the temporary support.
• the temporary support preferably has high transparency from the viewpoint of being able to be exposed to light.
• the temporary support has a transmittance of light at wavelengths of 313 nm, 365 nm, 313 nm, 405 nm and 436 nm, preferably 60% or more, more preferably 70% or more, even more preferably 80% or more, and 90% or more. is most preferred.
• Preferred transmittance values include, for example, 87%, 92%, and 98%.
• the haze value of the temporary support is preferably as small as possible from the viewpoints of the conductor pattern formability and the transparency of the temporary support when exposure is performed before peeling of the temporary support.
• the haze value of the temporary support is preferably 2% or less, more preferably 0.5% or less, and even more preferably 0.1% or less.
• a haze value is measured by a method according to JIS K 7105 (1981) using a haze meter.
• the haze value described in this disclosure is a value measured using a haze meter (NDH-2000, manufactured by Nippon Denshoku Industries Co., Ltd.).
• the number of fine particles, foreign matters and defects contained in the temporary support is preferably as small as possible.
• the number of fine particles having a diameter of 1 ⁇ m or more, foreign matter and defects in the temporary support is preferably 50/10 mm 2 or less, more preferably 10/10 mm 2 or less, further preferably 3/10 mm 2 or less, and 0/ 10 mm 2 is particularly preferred.
• the thickness of the temporary support is not particularly limited, it is preferably 5 ⁇ m to 200 ⁇ m, more preferably 5 ⁇ m to 150 ⁇ m, still more preferably 5 ⁇ m to 50 ⁇ m, most preferably 5 ⁇ m to 25 ⁇ m from the viewpoint of ease of handling and versatility.
• the surface of the temporary support that is in contact with the composition layer may be modified by UV irradiation, corona discharge, plasma, or the like.
• the exposure dose is preferably 10 mJ/cm 2 to 2000 mJ/cm 2 , more preferably 50 mJ/cm 2 to 1000 mJ/cm 2 .
• Light sources for UV irradiation include low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, carbon arc lamps, metal halide lamps, xenon lamps, chemical lamps, electrodeless discharge lamps, and light-emitting diodes that emit light in the wavelength band of 150 nm to 450 nm. (LED) etc. can be mentioned. As long as the amount of light irradiation can be within this range, there are no particular restrictions on the lamp output, illuminance, and the like.
• Examples of the temporary support include a biaxially stretched polyethylene terephthalate (PET) film with a thickness of 16 ⁇ m, a biaxially stretched PET film with a thickness of 12 ⁇ m, and a biaxially stretched PET film with a thickness of 9 ⁇ m.
• PET polyethylene terephthalate
• Preferred forms of the temporary support include, for example, paragraphs [0017] to [0018] of JP-A-2014-085643, paragraphs [0019] to [0026] of JP-A-2016-027363, International Publication No. 2012/ No. 081680, paragraphs [0041] to [0057], and WO 2018/179370, paragraphs [0029] to [0040], the contents of these publications are incorporated herein.
• a layer containing fine particles may be provided on the surface of the temporary support in terms of imparting handleability.
• the lubricant layer may be provided on one side or both sides of the temporary support.
• the diameter of the particles contained in the lubricant layer is preferably 0.05 ⁇ m to 0.8 ⁇ m.
• the film thickness of the lubricant layer is preferably 0.05 ⁇ m to 1.0 ⁇ m.
• Temporary supports may be commercially available products, such as Lumirror (registered trademark) 16KS40, Lumirror (registered trademark) 16FB40, Lumirror (registered trademark) #38-U48, Lumirror (registered trademark) #75-U34 (the above, Toray Co., Ltd.), Cosmoshine (registered trademark) A4100, Cosmoshine (registered trademark) A4160, Cosmoshine (registered trademark) A4300, Cosmoshine (registered trademark) A4360, Cosmoshine (registered trademark) A8300 (above, Toyobo ( Co., Ltd.) and the like.
• the temporary support may be a recycled product.
• recycled products include films made from washed and chipped used films and the like.
• Ecouse registered trademark
• the photosensitive composition layer may be a negative photosensitive composition layer or a positive photosensitive composition layer.
• a display device organic electroluminescence (EL) display device, liquid crystal display device, etc.
• the electrode pattern corresponding to the sensor in the visible part the wiring of the peripheral wiring part and the lead-out wiring part
• a conductive layer pattern such as is provided inside the touch panel.
• a negative photosensitive composition layer photosensitive layer
• the photosensitive composition layer is preferably a negative photosensitive composition layer.
• the photosensitive composition layer is a negative photosensitive composition layer, the formed pattern corresponds to the cured layer.
• the photosensitive composition layer is a negative photosensitive composition layer
• the negative photosensitive composition layer preferably contains a resin, a polymerizable compound, and a polymerization initiator.
• an alkali-soluble resin Polymer A, which is an alkali-soluble resin, etc.
• the photosensitive composition layer preferably contains a resin containing an alkali-soluble resin, a polymerizable compound, and a polymerization initiator (preferably a photopolymerization initiator).
• Such a photosensitive composition layer (that is, a negative photosensitive composition layer) is based on the total weight of the photosensitive composition layer, resin: 10% to 90% by weight; polymerizable compound: 5% by weight to 70% by mass; polymerization initiator: preferably 0.01% to 20% by mass. Below, each component is demonstrated in order.
• the resin contained in the photosensitive composition layer is also referred to as polymer A.
• the polymer A include (meth)acrylic resins, styrene resins, epoxy resins, amide resins, amide epoxy resins, alkyd resins, phenol resins, ester resins, urethane resins, and epoxy acrylate resins and acid anhydrides. Examples include acid-modified epoxy acrylate resins obtained by reaction. It is not limited to this.
• (meth)acrylic resin means resin which has a structural unit derived from a (meth)acrylic compound.
• the content of structural units derived from the (meth)acrylic compound is preferably 30% by mass or more, more preferably 50% by mass or more, based on the total structural units of the (meth)acrylic resin. 60% by mass or more is more preferable.
• a polymer having a structural unit derived from a (meth)acrylic compound and a structural unit derived from a styrene compound is also preferable.
• Polymer A is preferably an alkali-soluble resin.
• the acid value of the polymer A is preferably 220 mgKOH/g or less, more preferably less than 200 mgKOH/g, from the viewpoint of better resolution by suppressing swelling of the negative photosensitive composition layer due to the developer. More preferably less than 190 mg KOH/g.
• the lower limit of the acid value of polymer A is not particularly limited, but from the viewpoint of better developability, it is preferably 60 mgKOH/g or more, more preferably 70 mgKOH/g or more, still more preferably 80 mgKOH/g or more, and 90 mgKOH/g or more. Especially preferred.
• the acid value (mgKOH/g) is the mass [mg] of potassium hydroxide required to neutralize 1 g of the sample.
• the acid value can be calculated, for example, from the average content of acid groups in the compound.
• the acid value of the polymer A may be adjusted according to the type of structural units constituting the polymer A and the content of structural units containing acid groups.
• the weight average molecular weight of polymer A is preferably 5,000 to 500,000.
• a weight-average molecular weight of 500,000 or less is preferable from the viewpoint of improving resolution and developability.
• the weight average molecular weight is more preferably 100,000 or less, even more preferably 60,000 or less.
• the properties of development aggregates and the properties of unexposed films such as edge fuse properties and cut-chip properties when formed into negative photosensitive resin laminates are controlled.
• the weight average molecular weight is more preferably 10,000 or more, still more preferably 12,000 or more, and particularly preferably 15,000 or more.
• Edge fuseability refers to the degree of ease with which the negative photosensitive composition layer protrudes from the end face of the roll when the transfer film provided with the negative photosensitive composition layer is wound into a roll.
• the cut chip property refers to the degree of easiness of chip flying when the unexposed film is cut with a cutter. If this chip adheres to the upper surface of the transfer film provided with the negative photosensitive composition layer, etc., it will be transferred to the mask in the subsequent exposure process or the like, resulting in defective products.
• the degree of dispersion of polymer A is preferably 1.0 to 6.0, more preferably 1.0 to 5.0, even more preferably 1.0 to 4.0, and particularly preferably 1.0 to 3.0. .
• dispersity is the ratio of weight average molecular weight to number average molecular weight (weight average molecular weight/number average molecular weight).
• the polymer A is a composition based on a monomer having an aromatic hydrocarbon group. It preferably contains units. Examples of such aromatic hydrocarbon groups include substituted or unsubstituted phenyl groups and substituted or unsubstituted aralkyl groups.
• the content of structural units based on the monomer having an aromatic hydrocarbon group in the polymer A is preferably 20% by mass or more, more preferably 30% by mass or more, relative to the total mass of the polymer A.
• the upper limit is not particularly limited, it is preferably 95% by mass or less, more preferably 85% by mass or less.
• the average value of the content of the constituent units based on the monomer having an aromatic hydrocarbon group is within the above range.
• monomers having an aromatic hydrocarbon group examples include monomers having an aralkyl group, styrene, and polymerizable styrene derivatives (e.g., methylstyrene, vinyltoluene, tert-butoxystyrene, acetoxystyrene, 4-vinylbenzoyl acids, styrene dimers, styrene trimers, etc.).
• a monomer having an aralkyl group or styrene is preferred.
• the content of structural units based on styrene is 20% by mass to 70% by mass with respect to the total mass of the polymer A. % by mass is preferable, 25% by mass to 65% by mass is more preferable, 30% by mass to 60% by mass is still more preferable, and 30% by mass to 55% by mass is particularly preferable.
• the photosensitive composition layer contains a plurality of types of polymer A, the content of structural units having an aromatic hydrocarbon group is obtained as a weight average value.
• Aralkyl groups include substituted or unsubstituted phenylalkyl groups (excluding benzyl groups), substituted or unsubstituted benzyl groups, and the like, with substituted or unsubstituted benzyl groups being preferred.
• Examples of monomers having a phenylalkyl group include phenylethyl (meth)acrylate.
• Examples of monomers having a benzyl group include (meth)acrylates having a benzyl group, such as benzyl (meth)acrylate and chlorobenzyl (meth)acrylate; vinyl monomers having a benzyl group, such as vinylbenzyl chloride, and vinyl benzyl alcohol and the like. Among them, benzyl (meth)acrylate is preferred.
• the content of structural units based on benzyl (meth) acrylate is the total mass of the polymer A
• 50% by mass to 95% by mass is preferable, 60% by mass to 90% by mass is more preferable, 70% by mass to 90% by mass is still more preferable, and 75% by mass to 90% by mass is particularly preferable.
• Polymer A containing a structural unit based on a monomer having an aromatic hydrocarbon group is a monomer having an aromatic hydrocarbon group and at least one of the first monomers described later and / or It is preferably obtained by polymerizing at least one of the second monomers.
• the polymer A that does not contain a structural unit based on a monomer having an aromatic hydrocarbon group is preferably obtained by polymerizing at least one of the first monomers described later, and the first monomer It is more preferably obtained by copolymerizing at least one of the monomers and at least one of the second monomers described below.
• a 1st monomer is a monomer which has a carboxyl group in a molecule
• the first monomer include (meth)acrylic acid, fumaric acid, cinnamic acid, crotonic acid, itaconic acid, 4-vinylbenzoic acid, maleic anhydride, and maleic acid half ester. .
• (meth)acrylic acid is preferred.
• the content of the structural unit based on the first monomer in the polymer A is preferably 5% by mass to 50% by mass, more preferably 10% by mass to 40% by mass, based on the total mass of the polymer A. 14% by mass to 30% by mass is more preferable.
• Setting the content to 5% by mass or more is preferable from the viewpoint of exhibiting good developability, controlling edge fuse properties, and the like.
• Setting the content to 50% by mass or less is preferable from the viewpoints of high resolution and groove shape of the resist pattern, and further from the viewpoint of chemical resistance of the resist pattern.
• the second monomer is a monomer that is non-acidic and has at least one polymerizable unsaturated group in the molecule.
• Examples of the second monomer include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, and isobutyl (meth) acrylate.
• tert-butyl (meth)acrylate 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, cyclohexyl (meth)acrylate, and 2-ethylhexyl (meth)acrylate; acetic acid; ester compounds of vinyl alcohol such as vinyl; and (meth)acrylonitrile.
• methyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, or n-butyl (meth)acrylate is preferred, and methyl (meth)acrylate is more preferred.
• the content of the structural unit based on the second monomer in the polymer A is preferably 5% by mass to 60% by mass, more preferably 15% by mass to 50% by mass, based on the total mass of the polymer A. 17% by mass to 45% by mass is more preferable.
• the polymer A contains a structural unit based on a monomer having an aralkyl group and/or a structural unit based on a styrene monomer, thickening of the line width and deterioration of the resolution when the focal point shifts during exposure are suppressed.
• a copolymer containing a structural unit based on methacrylic acid, a structural unit based on benzyl methacrylate, and a structural unit based on styrene a structural unit based on methacrylic acid, a structural unit based on methyl methacrylate, a structural unit based on benzyl methacrylate, and a structural unit based on styrene.
• a copolymer or the like containing a structural unit based on is preferable.
• the polymer A contains 25% to 55% by mass of structural units based on a monomer having an aromatic hydrocarbon group, and 20% to 35% by mass of structural units based on the first monomer.
• a polymer containing 15% by mass to 45% by mass of structural units based on the second monomer preferably a polymer containing 15% by mass to 45% by mass of structural units based on the second monomer.
• Polymer A may have any one of a linear structure, a branched structure, and an alicyclic structure in the side chain.
• a branched structure or an alicyclic structure can be introduced into the side chain of the polymer A 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. .
• the group having an alicyclic structure may be monocyclic or polycyclic
• Specific examples of the monomer containing a group having a branched structure in the side chain include isopropyl (meth)acrylate, isobutyl (meth)acrylate, (meth)acrylate ) sec-butyl acrylate, tert-butyl (meth)acrylate, isoamyl (meth)acrylate, tert-amyl (meth)acrylate, sec-amyl (meth)acrylate, 2-octyl (meth)acrylate, Examples include 3-octyl (meth)acrylate and tert-octyl (meth)acrylate.
• isopropyl (meth)acrylate, isobutyl (meth)acrylate, and tert-butyl methacrylate are preferred, and isopropyl methacrylate and tert-butyl methacrylate are more preferred.
• the monomer containing a group having an alicyclic structure in its side chain include a monomer having a monocyclic aliphatic hydrocarbon group and a monomer having a polycyclic aliphatic hydrocarbon group.
• (Meth)acrylates having an alicyclic hydrocarbon group with 5 to 20 carbon atoms are also included.
• More specific examples include (meth)acrylic acid (bicyclo[2.2.1]heptyl-2), (meth)acrylate-1-adamantyl, (meth)acrylate-2-adamantyl, (meth) 3-methyl-1-adamantyl acrylate, 3,5-dimethyl-1-adamantyl (meth)acrylate, 3-ethyladamantyl (meth)acrylate, 3-methyl-5-(meth)acrylate Ethyl-1-adamantyl, (meth)acrylate-3,5,8-triethyl-1-adamantyl, (meth)acrylate-3,5-dimethyl-8-ethyl-1-adamantyl, (meth)acrylic acid 2 -methyl-2-adamantyl, 2-ethyl-2-adamantyl (meth)acrylate, 3-hydroxy-1-adamantyl (meth)acrylate, octahydro-4,7-mentanoindene-5- (meth
• cyclohexyl (meth)acrylate, (nor)bornyl (meth)acrylate, isobornyl (meth)acrylate, 1-adamantyl (meth)acrylate, (meth)acrylic acid -2-adamantyl, fenchyl (meth)acrylate, 1-menthyl (meth)acrylate, or tricyclodecane (meth)acrylate is preferred, cyclohexyl (meth)acrylate, (nor)bornyl (meth)acrylate, Isobornyl (meth)acrylate, 2-adamantyl (meth)acrylate, or tricyclodecane (meth)acrylate are more preferred.
• Polymer A also preferably contains a structural unit having a polymerizable group.
• a structural unit having a polymerizable group a structural unit represented by formula (P) is preferable.
• R P represents a hydrogen atom or a methyl group.
• LP represents a divalent linking group.
• P represents a polymerizable group.
• R P represents a hydrogen atom or a methyl group.
• R 2 P is preferably a hydrogen atom.
• LP represents a divalent linking group.
• the divalent linking group include -CO-, -O-, -S-, -SO-, -SO 2 -, -NR N -, divalent hydrocarbon groups and divalent group.
• RN represents a substituent.
• the hydrocarbon group include an alkylene group, a cycloalkylene group and an arylene group.
• the alkylene group may be linear or branched.
• the alkylene group preferably has 1 to 10 carbon atoms, more preferably 2 to 8 carbon atoms, and still more preferably 3 to 5 carbon atoms.
• the alkylene group may have a heteroatom, and the methylene group in the alkylene group may be replaced with a heteroatom.
• the heteroatom is preferably an oxygen atom, a sulfur atom or a nitrogen atom, more preferably an oxygen atom.
• the cycloalkylene group may be either monocyclic or polycyclic.
• the cycloalkylene group preferably has 3 to 20 carbon atoms, more preferably 5 to 10 carbon atoms, and still more preferably 6 to 8 carbon atoms.
• the arylene group may be monocyclic or polycyclic.
• the arylene group preferably has 6 to 20 carbon atoms, more preferably 6 to 15 carbon atoms, and even more preferably 6 to 10 carbon atoms.
• a phenylene group is preferable as the arylene group.
• the cycloalkylene group and the arylene group may have a heteroatom as a ring member atom.
• the heteroatom is preferably an oxygen atom, a sulfur atom or a nitrogen atom, more preferably an oxygen atom.
• the hydrocarbon group may further have a substituent. Examples of the substituent include halogen atoms (eg, fluorine atoms), hydroxy groups, nitro groups, cyano groups, alkyl groups, alkoxy groups, alkoxycarbonyl groups and alkenyl groups, with hydroxy groups being preferred.
• L P an alkylene group optionally having a heteroatom is preferable.
• P represents a polymerizable group.
• the polymerizable group is as described above.
• Rx and Ry each independently represent a hydrogen atom or a methyl group.
• Polymer A may be used alone or in combination of two or more.
• a mixture of two types of polymer A containing a structural unit based on a monomer having an aromatic hydrocarbon group, or based on a monomer having an aromatic hydrocarbon group It is preferable to use a mixture of a polymer A containing structural units and a polymer A containing no structural units based on a monomer having an aromatic hydrocarbon group.
• the use ratio of the polymer A containing a structural unit based on a monomer having an aromatic hydrocarbon group is preferably 50% by mass or more, and preferably 70% by mass or more, relative to the total mass of the polymer A. It is more preferably 80% by mass or more, and more preferably 90% by mass or more.
• Polymer A is synthesized by adding a radical polymerization initiator such as benzoyl peroxide and azoisobutyronitrile to a solution of the above-described single or multiple monomers diluted with a solvent such as acetone, methyl ethyl ketone, and isopropanol. is preferably added in an appropriate amount and heated and stirred. In some cases, the synthesis is performed while part of the mixture is added dropwise to the reaction solution. After completion of the reaction, a solvent may be further added to adjust the desired concentration. As a means of synthesis, bulk polymerization, suspension polymerization, or emulsion polymerization may be used in addition to solution polymerization.
• a radical polymerization initiator such as benzoyl peroxide and azoisobutyronitrile
• the glass transition temperature Tg of polymer A is preferably 30°C to 135°C.
• the Tg of the polymer A is preferably 130° C. or lower, more preferably 120° C. or lower, and particularly preferably 110° C. or lower.
• the polymer A having a Tg of 30° C. or more from the viewpoint of improving the edge fuse resistance. From this viewpoint, the Tg of the polymer A is more preferably 40°C or higher, still more preferably 50°C or higher, particularly preferably 60°C or higher, and most preferably 70°C or higher.
• the negative photosensitive composition layer may contain other resins as the polymer A than those described above.
• Other resins include acrylic resins, styrene-acrylic copolymers, polyurethane resins, polyvinyl alcohol, polyvinyl formal, polyamide resins, polyester resins, polyamide resins, epoxy resins, polyacetal resins, polyhydroxystyrene resins, polyimide resins, poly Benzoxazole resins, polysiloxane resins, polyethyleneimines, polyallylamines, and polyalkylene glycols.
• an alkali-soluble resin which will be described later in the description of the thermoplastic resin layer, may be used.
• the content of polymer A is preferably 10% by mass to 90% by mass, more preferably 20% by mass to 80% by mass, and further 30% by mass to 70% by mass, based on the total mass of the negative photosensitive composition layer. 40 to 60 mass % is particularly preferred. It is preferable from the viewpoint of controlling the developing time that the content of the polymer A is 90% by mass or less. On the other hand, setting the content of the polymer A to 10% by mass or more is preferable from the viewpoint of improving the edge fuse resistance.
• the photosensitive composition layer is a negative photosensitive composition layer
• the negative photosensitive composition layer preferably contains a polymerizable compound having a polymerizable group.
• the polymerizable compound contained in the photosensitive composition layer is also called polymerizable compound B in particular.
• the term "polymerizable compound” means a compound that polymerizes under the action of a polymerization initiator, which will be described later, and that is different from the polymer A described above.
• the polymerizable group possessed by the polymerizable compound is not particularly limited as long as it is a group involved in the polymerization reaction.
• it has an ethylenically unsaturated group such as a vinyl group, an acryloyl group, a methacryloyl group, a styryl group and a maleimide group. groups; and groups having cationic polymerizable groups such as epoxy groups and oxetane groups.
• a group having an ethylenically unsaturated group is preferable, and an acryloyl group or a methacryloyl group is more preferable.
• a compound having one or more ethylenically unsaturated groups is preferable in terms of better photosensitivity of the negative photosensitive composition layer, and two in one molecule.
• Compounds having the above ethylenically unsaturated groups are more preferred.
• the number of ethylenically unsaturated groups that the ethylenically unsaturated compound has in one molecule is preferably 6 or less, more preferably 3 or less, and 2 or less. More preferred.
• a bifunctional or trifunctional ethylenically unsaturated group having two or three ethylenically unsaturated groups in one molecule is considered to have a better balance between the photosensitivity, resolution, and releasability of the negative photosensitive composition layer. It preferably contains a saturated compound, and more preferably contains a bifunctional ethylenically unsaturated compound having two ethylenically unsaturated groups in one molecule. From the viewpoint of excellent peelability, the content of the bifunctional ethylenically unsaturated compound relative to the total mass of the polymerizable compound is preferably 20% by mass or more, more preferably more than 40% by mass, and still more preferably 55% by mass or more.
• the upper limit is not particularly limited, and may be 100% by mass. That is, all polymerizable compounds may be difunctional ethylenically unsaturated compounds. Moreover, as the ethylenically unsaturated compound, a (meth)acrylate compound having a (meth)acryloyl group as a polymerizable group is preferable.
• the negative photosensitive composition layer also preferably contains a polymerizable compound B1 having an aromatic ring and two ethylenically unsaturated groups.
• Polymerizable compound B1 is a bifunctional ethylenically unsaturated compound having one or more aromatic rings in one molecule among the polymerizable compounds B described above.
• the mass ratio of the content of the polymerizable compound B1 to the total mass of the polymerizable compound B is preferably 40% or more, more preferably 50% or more, from the viewpoint of better resolution. It is preferably 55% by mass or more, more preferably 60% by mass or more.
• the upper limit is not particularly limited, from the viewpoint of peelability, it is, for example, 100% by mass or less, preferably 99% by mass or less, more preferably 95% by mass or less, further preferably 90% by mass or less, and particularly 85% by mass or less. preferable.
• aromatic ring of the polymerizable compound B1 examples include aromatic hydrocarbon rings such as benzene ring, naphthalene ring and anthracene ring; aromatic rings such as thiophene ring, furan ring, pyrrole ring, imidazole ring, triazole ring and pyridine ring; Heterocyclic rings and condensed rings thereof are included, with aromatic hydrocarbon rings being preferred, and benzene rings being more preferred.
• the said aromatic ring may have a substituent.
• Polymerizable compound B1 may have only one aromatic ring, or may have two or more aromatic rings.
• Polymerizable compound B1 preferably has a bisphenol structure from the viewpoint of improving resolution by suppressing swelling of the photosensitive composition layer due to a developer.
• the bisphenol structure includes, for example, a bisphenol A structure derived from bisphenol A (2,2-bis(4-hydroxyphenyl)propane) and a bisphenol derived from bisphenol F (2,2-bis(4-hydroxyphenyl)methane).
• the F structure and the bisphenol B structure derived from bisphenol B (2,2-bis(4-hydroxyphenyl)butane) are included, with the bisphenol A structure being preferred.
• Examples of the polymerizable compound B1 having a bisphenol structure include compounds having a bisphenol structure and two polymerizable groups (preferably (meth)acryloyl groups) bonded to both ends of the bisphenol structure. Both ends of the bisphenol structure and the two polymerizable groups may be directly bonded or bonded via one or more alkyleneoxy groups.
• the alkyleneoxy group added to both ends of the bisphenol structure is preferably an ethyleneoxy group or a propyleneoxy group, more preferably an ethyleneoxy group.
• the number of alkyleneoxy groups to be added to the bisphenol structure is not particularly limited, but is preferably 4 to 16, more preferably 6 to 14 per molecule.
• the polymerizable compound B1 having a bisphenol structure is described in paragraphs 0072 to 0080 of JP-A-2016-224162, and the contents described in this publication are incorporated herein.
• polymerizable compound B1 a bifunctional ethylenically unsaturated compound having a bisphenol A structure is preferable, and 2,2-bis(4-((meth)acryloxypolyalkoxy)phenyl)propane is more preferable.
• Examples of 2,2-bis(4-((meth)acryloxypolyalkoxy)phenyl)propane examples include 2,2-bis(4-(methacryloxydiethoxy)phenyl)propane (FA-324M, Showa Denko Materials Co., Ltd.), 2,2-bis(4-(methacryloxyethoxypropoxy)phenyl)propane, 2,2-bis(4-(methacryloxypentaethoxy)phenyl)propane (BPE-500, Shin-Nakamura Chemical Kogyo Co., Ltd.), 2,2-bis(4-(methacryloxide decaethoxytetrapropoxy)phenyl)propane (FA-3200MY, Showa Denko Materials Co., Ltd.), 2,2-bis(4-( methacryloxypentadecaethoxy)phenyl)propane (BPE-1300, manufactured by Shin-Nakamura Chemical Co., Ltd.), 2,2-bis(4-(methacryloxydiethoxy)phen
• a compound represented by the following general formula (B1) is also preferable as the polymerizable compound B1.
• R 1 and R 2 each independently represent a hydrogen atom or a methyl group.
• A represents C2H4 .
• B represents C3H6 .
• n1 and n3 are each independently an integer of 1-39, and n1+n3 is an integer of 2-40.
• n2 and n4 are each independently an integer of 0-29, and n2+n4 is an integer of 0-30.
• the arrangement of -(AO)- and -(B-O)- constitutional units may be random or block. In the case of a block, either -(AO)- or -(B-O)- may be on the side of the biphenyl group.
• n1+n2+n3+n4 is preferably 2 to 20, more preferably 2 to 16, and even more preferably 4 to 12. Further, n2+n4 is preferably 0 to 10, more preferably 0 to 4, still more preferably 0 to 2, and particularly preferably 0.
• the content of the polymerizable compound B1 is preferably 10% by mass or more, more preferably 20% by mass or more, relative to the total mass of the negative photosensitive composition layer, from the viewpoint of better resolution.
• the upper limit is not particularly limited, it is preferably 70% by mass or less, more preferably 60% by mass or less, from the viewpoint of transferability and edge fusion (a phenomenon in which the photosensitive resin oozes out from the edge of the transfer film).
• the negative photosensitive composition layer may contain a polymerizable compound other than the polymerizable compound B1 described above.
• Polymerizable compounds other than polymerizable compound B1 are not particularly limited and can be appropriately selected from known compounds. For example, a compound having one ethylenically unsaturated group in one molecule (monofunctional ethylenically unsaturated compound), a bifunctional ethylenically unsaturated compound having no aromatic ring, and a trifunctional or higher ethylenically unsaturated compound are mentioned.
• Examples of monofunctional ethylenically unsaturated compounds include ethyl (meth)acrylate, ethylhexyl (meth)acrylate, 2-(meth)acryloyloxyethyl succinate, polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate. , and phenoxyethyl (meth)acrylate.
• Examples of bifunctional ethylenically unsaturated compounds having no aromatic ring include alkylene glycol di(meth)acrylate, polyalkylene glycol di(meth)acrylate, urethane di(meth)acrylate, and trimethylolpropane diacrylate.
• Alkylene glycol di(meth)acrylates include, for example, tricyclodecanedimethanol diacrylate (A-DCP, manufactured by Shin-Nakamura Chemical Co., Ltd.), tricyclodecanedimethanol dimethacrylate (DCP, Shin-Nakamura Chemical Co., Ltd.
• Polyalkylene glycol di(meth)acrylates include, for example, polyethylene glycol di(meth)acrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, and polypropylene glycol di(meth)acrylate.
• Urethane di(meth)acrylates include, for example, propylene oxide-modified urethane di(meth)acrylates, and ethylene oxide and propylene oxide-modified urethane di(meth)acrylates.
• 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.). be done.
• trifunctional or higher ethylenically unsaturated compounds include dipentaerythritol (tri/tetra/penta/hexa) (meth) acrylate, pentaerythritol (tri/tetra) (meth) acrylate, trimethylolpropane tri(meth) Acrylate, ditrimethylolpropane tetra(meth)acrylate, trimethylolethane tri(meth)acrylate, isocyanurate tri(meth)acrylate, glycerin tri(meth)acrylate, and alkylene oxide-modified products thereof.
• (tri/tetra/penta/hexa) (meth)acrylate is a concept including tri(meth)acrylate, tetra(meth)acrylate, penta(meth)acrylate, and hexa(meth)acrylate.
• (tri/tetra)(meth)acrylate” is a concept including tri(meth)acrylate and tetra(meth)acrylate.
• the negative photosensitive composition layer preferably contains the above-described polymerizable compound B1 and a trifunctional or higher ethylenically unsaturated compound, and the above-described polymerizable compound B1 and two or more trifunctional or higher functional More preferably, it contains an ethylenically unsaturated compound.
• the negative photosensitive composition layer preferably contains the polymerizable compound B1 and two or more trifunctional ethylenically unsaturated compounds described above.
• alkylene oxide-modified trifunctional or higher ethylenically unsaturated compounds examples include caprolactone-modified (meth)acrylate compounds (KAYARAD (registered trademark) DPCA-20 manufactured by Nippon Kayaku Co., Ltd., manufactured by Shin-Nakamura Chemical Co., Ltd.
• alkylene oxide-modified (meth) acrylate compounds (KAYARAD (registered trademark) RP-1040 manufactured by Nippon Kayaku Co., Ltd., ATM-35E and A- manufactured by Shin-Nakamura Chemical Co., Ltd.) 9300, EBECRYL (registered trademark) 135 manufactured by Daicel Allnex Co., Ltd.), ethoxylated glycerin triacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., A-GLY-9E, etc.), Aronix (registered trademark) TO-2349 (manufactured by Toagosei Co., Ltd.), Aronix M-520 (manufactured by Toagosei Co., Ltd.), and Aronix M-510 (manufactured by Toagosei Co., Ltd.).
• the polymerizable compound which has an acid group may form an acid anhydride group.
• the polymerizable compound having an acid group examples include Aronix (registered trademark) TO-2349 (manufactured by Toagosei Co., Ltd.), Aronix (registered trademark) M-520 (manufactured by Toagosei Co., Ltd.), and Aronix (registered trademark). M-510 (manufactured by Toagosei Co., Ltd.) can be mentioned.
• the polymerizable compound having an acid group for example, polymerizable compounds having an acid group described in paragraphs 0025 to 0030 of JP-A-2004-239942 may be used.
• a polymerizable compound may be used individually by 1 type, and may be used 2 or more types.
• the content of the polymerizable compound is preferably 10% by mass to 70% by mass, more preferably 15% by mass to 70% by mass, and 20% by mass to 70% by mass, based on the total mass of the negative photosensitive composition layer. More preferred.
• the molecular weight (weight average molecular weight when having a molecular weight distribution) of the polymerizable compound (including the polymerizable compound B1) is preferably 200 to 3,000, more preferably 280 to 2,200, and 300 to 2,200. More preferred.
• the negative photosensitive composition layer also preferably contains a polymerization initiator.
• the polymerization initiator is selected according to the type of polymerization reaction, and examples thereof include thermal polymerization initiators and photopolymerization initiators.
• the polymerization initiator may be a radical polymerization initiator or a cationic polymerization initiator.
• the negative photosensitive composition layer preferably contains a photopolymerization initiator.
• a photopolymerization initiator is a compound that initiates polymerization of a polymerizable compound upon exposure to actinic rays such as ultraviolet rays, visible rays, and X-rays.
• the photopolymerization initiator is not particularly limited, and known photopolymerization initiators can be used. Examples of photopolymerization initiators include radical photopolymerization initiators and cationic photopolymerization initiators, and radical photopolymerization initiators are preferred.
• photoradical polymerization initiators examples include photopolymerization initiators having an oxime ester structure, photopolymerization initiators having an ⁇ -aminoalkylphenone structure, photopolymerization initiators having an ⁇ -hydroxyalkylphenone structure, and acylphosphine oxide. structure and a photopolymerization initiator having an N-phenylglycine structure.
• the negative photosensitive composition layer contains 2,4,5-triarylimidazole dimer as a photoradical polymerization initiator. It preferably contains at least one selected from the group consisting of derivatives and derivatives thereof.
• the two 2,4,5-triarylimidazole structures in the 2,4,5-triarylimidazole dimer and its derivative may be the same or different.
• 2,4,5-triarylimidazole dimer examples include, for example, 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer, 2-(o-chlorophenyl)-4,5-di (Methoxyphenyl)imidazole dimer, 2-(o-fluorophenyl)-4,5-diphenylimidazole dimer, 2-(o-methoxyphenyl)-4,5-diphenylimidazole dimer, and 2- (p-Methoxyphenyl)-4,5-diphenylimidazole dimer.
• radical photopolymerization initiator for example, polymerization initiators described in paragraphs 0031 to 0042 of JP-A-2011-95716 and paragraphs 0064-0081 of JP-A-2015-14783 may be used.
• photoradical polymerization initiators examples include ethyl dimethylaminobenzoate (DBE, CAS No. 10287-53-3), benzoin methyl ether, anisyl (p,p'-dimethoxybenzyl), TAZ-110 (trade name: Midori Chemical Co., Ltd.), benzophenone, 4,4′-bis(diethylamino)benzophenone, TAZ-111 (trade name: Midori Chemical Co., Ltd.), Irgacure (registered trademark) OXE01, OXE02, OXE03, OXE04 (BASF company), Omnirad (registered trademark) 651 and 369 (trade name: IGM Resins B.V.), and 2,2′-bis(2-chlorophenyl)-4,4′,5,5′-tetra Phenyl-1,2'-biimidazole (manufactured by Tokyo Chemical Industry Co., Ltd.) can be mentioned.
• DBE ethy
• radical photopolymerization initiators examples include 1-[4-(phenylthio)]-1,2-octanedione-2-(O-benzoyloxime) (trade name: IRGACURE (registered trademark) OXE-01).
• a photocationic polymerization initiator is a compound that generates an acid upon receiving an actinic ray.
• the photocationic polymerization initiator is preferably a compound that responds to an actinic ray with a wavelength of 300 nm or more, preferably 300 to 450 nm, and generates an acid, but its chemical structure is not limited.
• the sensitizer can be used.
• the photocationic polymerization initiator is preferably a photocationic polymerization initiator that generates an acid with a pKa of 4 or less, more preferably a photocationic polymerization initiator that generates an acid with a pKa of 3 or less, and an acid with a pKa of 2 or less.
• Photocationic polymerization initiators generated are particularly preferred.
• the lower limit of pKa is not particularly defined, it is preferably -10.0 or more, for example.
• photocationic polymerization initiators examples include ionic photocationic polymerization initiators and nonionic photocationic polymerization initiators.
• Ionic photocationic polymerization initiators include, for example, onium salt compounds such as diaryliodonium salts and triarylsulfonium salts, and quaternary ammonium salts.
• the ionic photocationic polymerization initiator the ionic photocationic polymerization initiators described in paragraphs 0114 to 0133 of JP-A-2014-085643 may be used.
• nonionic photocationic polymerization initiators include trichloromethyl-s-triazine compounds, diazomethane compounds, imidosulfonate compounds, and oximesulfonate compounds.
• trichloromethyl-s-triazine compound, diazomethane compound and imidosulfonate compound compounds described in paragraphs 0083 to 0088 of JP-A-2011-221494 may be used.
• oxime sulfonate compound compounds described in paragraphs 0084 to 0088 of WO 2018/179640 may be used.
• the negative photosensitive composition layer preferably contains a photoradical polymerization initiator, and more preferably contains at least one selected from the group consisting of 2,4,5-triarylimidazole dimers and derivatives thereof. preferable.
• a polymerization initiator may be used individually by 1 type, and may be used 2 or more types.
• the content of the polymerization initiator (preferably a photopolymerization initiator) is not particularly limited, but is preferably 0.1% by mass or more, and 0.5% by mass or more, based on the total mass of the negative photosensitive composition layer. More preferably, 1.0% by mass or more is even more preferable.
• the upper limit is not particularly limited, it is preferably 20% by mass or less, more preferably 15% by mass or less, and more preferably 10% by mass or less, relative to the total mass of the negative photosensitive composition layer.
• the photosensitive composition layer has a maximum absorption wavelength of 450 nm or more in a wavelength range of 400 nm to 780 nm during color development, from the viewpoints of visibility of exposed and unexposed areas, pattern visibility after development, and resolution.
• a dye also referred to as “dye N”
• the adhesion to the adjacent layer for example, the water-soluble resin layer
• the resolution is improved.
• the expression that the dye "changes the maximum absorption wavelength due to an acid, a base, or a radical” means that the dye in a colored state is decolored by an acid, a base, or a radical, and the dye in a decolored state is It may mean any one of a mode in which a color is developed by an acid, a base, or a radical, and a mode in which a dye in a coloring state changes to a coloring state of another hue.
• the dye N may be a compound that changes from a decolored state to develop color upon exposure, or may be a compound that changes from a colored state to decolor upon exposure.
• it may be a dye that changes the state of coloring or decoloring due to the action of acid, base, or radicals generated in the photosensitive composition layer by exposure. It may be a dye that changes its coloring or decoloring state by changing the state (for example, pH) in the layer. Moreover, it may be a dye that changes its coloring or decoloring state by being directly stimulated by an acid, a base, or a radical without being exposed to light.
• the dye N is preferably a dye whose maximum absorption wavelength is changed by acid or radicals, more preferably a dye whose maximum absorption wavelength is changed by radicals.
• the photosensitive composition layer is a negative photosensitive composition layer
• the negative photosensitive composition layer from the viewpoint of the visibility and resolution of the exposed and unexposed areas, has the maximum It is preferable to contain both a dye whose absorption wavelength changes and a photoradical polymerization initiator.
• the dye N is preferably a dye that develops color with an acid, a base, or a radical.
• a photoradical polymerization initiator, a photocationic polymerization initiator (photoacid generator), or a photobase generator is added to the photosensitive composition layer, and photoradical polymerization is initiated after exposure.
• a radical-reactive dye, an acid-reactive dye, or a base-reactive dye develops color by radicals, acids, or bases generated from the agent, photocationic polymerization initiator, or photobase generator. be done.
• the dye N preferably has a maximum absorption wavelength of 550 nm or more in a wavelength range of 400 nm to 780 nm during color development, more preferably 550 nm to 700 nm, and 550 nm. More preferably ⁇ 650 nm.
• the dye N may have only one maximum absorption wavelength in the wavelength range of 400 nm to 780 nm during color development, or may have two or more.
• the maximum absorption wavelength with the highest absorbance among the two or more maximum absorption wavelengths may be 450 nm or more.
• the maximum absorption wavelength of Dye N is measured in the range of 400 nm to 780 nm using a spectrophotometer: UV3100 (manufactured by Shimadzu Corporation) in an air atmosphere. and detecting the wavelength (maximum absorption wavelength) at which the light intensity becomes minimum.
• Examples of dyes that develop or decolorize upon exposure include leuco compounds.
• Examples of dyes that are decolorized by exposure include leuco compounds, diarylmethane-based dyes, oxazine-based dyes, xanthene-based dyes, iminonaphthoquinone-based dyes, azomethine-based dyes, and anthraquinone-based dyes.
• As the dye N a leuco compound is preferable from the viewpoint of the visibility of the exposed area and the non-exposed area.
• leuco compounds include leuco compounds having a triarylmethane skeleton (triarylmethane dyes), leuco compounds having a spiropyran skeleton (spiropyran dyes), leuco compounds having a fluorane skeleton (fluoran dyes), and diarylmethane skeletons.
• a leuco compound (leuco auramine dye) can be mentioned.
• triarylmethane-based dyes or fluoran-based dyes are preferable, and leuco compounds having a triphenylmethane skeleton (triphenylmethane-based dyes) or fluoran-based dyes are more preferable.
• the leuco compound preferably has a lactone ring, a sultine ring, or a sultone ring from the viewpoint of the visibility of the exposed area and the non-exposed area.
• the lactone ring, sultine ring, or sultone ring of the leuco compound is reacted with a radical generated from a radical photopolymerization initiator or an acid generated from a photocationic polymerization initiator to change the leuco compound into a ring-closed state.
• the color can be developed by changing the leuco compound into a ring-opened state.
• the leuco compound is preferably a compound that has a lactone ring, a sultine ring, or a sultone ring and develops a color due to the opening of the lactone ring, sultine ring, or sultone ring by a radical or an acid.
• a compound that develops color by opening the lactone ring with an acid is more preferable.
• dye N examples include the following dyes and leuco compounds. Specific examples of dyes among dyes N include brilliant green, ethyl violet, methyl green, crystal violet, basic fuchsine, methyl violet 2B, quinaldine red, rose bengal, methanil yellow, thymolsulfophtalein, xylenol blue, methyl Orange, Paramethyl Red, Congo Fred, Benzopurpurin 4B, ⁇ -Naphthyl Red, Nile Blue 2B, Nile Blue A, Methyl Violet, Malachite Green, Parafuchsin, Victoria Pure Blue-Naphthalene Sulfonate, Victoria Pure Blue BOH (protective Tsuchiya Chemical Industry Co., Ltd.), Oil Blue #603 (Orient Chemical Industry Co., Ltd.), Oil Pink #312 (Orient Chemical Industry Co., Ltd.), Oil Red 5B (Orient Chemical Industry Co., Ltd.), Oil Scarlet #308 (manufactured by Orient Chemical Industry Co., Ltd.), Oil Red
• leuco compound of the dye N include p,p′,p′′-hexamethyltriaminotriphenylmethane (leuco crystal violet), Pergascript Blue SRB (manufactured by Ciba-Geigy), crystal violet lactone, malachite green lactone, benzoyl leucomethylene blue, 2-(N-phenyl-N-methylamino)-6-(Np-tolyl-N-ethyl)aminofluorane, 2-anilino-3-methyl-6-(N-ethyl-p -toluidino)fluorane, 3,6-dimethoxyfluorane, 3-(N,N-diethylamino)-5-methyl-7-(N,N-dibenzylamino)fluorane, 3-(N-cyclohexyl-N-methyl amino)-6-methyl-7-anilinofluorane, 3-(N,N-diethylamino)-6-
• Dye N is preferably a dye whose maximum absorption wavelength is changed by radicals from the viewpoint of visibility of exposed and unexposed areas, pattern visibility after development, and resolution, and is a dye that develops color by radicals. It is more preferable to have Preferred dyes N are leuco crystal violet, crystal violet lactone, brilliant green, or victoria pure blue-naphthalene sulfonate.
• the pigment N may be used singly or in combination of two or more.
• the content of dye N is 0.1% by mass or more with respect to the total mass of the photosensitive composition layer, from the viewpoints of visibility of exposed and unexposed areas, pattern visibility after development, and resolution. is preferred, 0.1% by mass to 10% by mass is more preferred, 0.1% by mass to 5% by mass is even more preferred, and 0.1% by mass to 1% by mass is particularly preferred.
• the content of the dye N means the content of the dye when all the dyes N contained in the total weight of the photosensitive composition layer are in a colored state.
• a method for quantifying the content of dye N will be described below using a dye that develops color by radicals as an example.
• a solution of 0.001 g and 0.01 g of dye in 100 mL of methyl ethyl ketone is prepared.
• a radical photopolymerization initiator Irgacure (registered trademark) OXE01 manufactured by BASF Japan Co., Ltd.
• radicals are generated by irradiation with light of 365 nm to bring all the dyes into a colored state. .
• the absorbance of each solution having a liquid temperature of 25° C. is measured using a spectrophotometer (UV3100, manufactured by Shimadzu Corporation) in an air atmosphere to create a calibration curve.
• UV3100 UV3100, manufactured by Shimadzu Corporation
• the absorbance of the solution in which all the dyes are developed is measured in the same manner as described above except that 3 g of the photosensitive composition layer is dissolved in methyl ethyl ketone instead of the dyes. From the absorbance of the obtained solution containing the photosensitive composition layer, the content of the dye contained in the photosensitive composition layer is calculated based on the calibration curve. 3 g of the photosensitive composition layer is the same as 3 g of the total solid content in the photosensitive resin composition.
• the photosensitive composition layer is a negative photosensitive composition layer, it preferably contains a thermal crosslinkable compound from the viewpoint of the strength of the resulting cured film and the adhesiveness of the resulting uncured film.
• a thermally crosslinkable compound having an ethylenically unsaturated group which will be described later, is not treated as a polymerizable compound, but as a thermally crosslinkable compound.
• Thermally crosslinkable compounds include methylol compounds and blocked isocyanate compounds. Among them, a blocked isocyanate compound is preferable from the viewpoint of the strength of the cured film to be obtained and the adhesiveness of the uncured film to be obtained.
• the blocked isocyanate compound reacts with the hydroxy group and the carboxy group, for example, when the resin and/or the polymerizable compound has at least one of the hydroxy group and the carboxy group, the hydrophilicity of the formed film is lowered. , the function tends to be enhanced when a film obtained by curing a negative photosensitive composition layer is used as a protective film.
• the blocked isocyanate compound refers to "a compound having a structure in which the isocyanate group of isocyanate is protected (so-called masked) with a blocking agent".
• the dissociation temperature of the blocked isocyanate compound is not particularly limited, but is preferably 100 to 160°C, more preferably 130 to 150°C.
• the dissociation temperature of the blocked isocyanate means "the temperature of the endothermic peak associated with the deprotection reaction of the blocked isocyanate when measured by DSC (Differential Scanning Calorimetry) analysis using a differential scanning calorimeter".
• DSC Different Scanning Calorimetry
• a differential scanning calorimeter for example, a differential scanning calorimeter (model: DSC6200) manufactured by Seiko Instruments Inc. can be suitably used. However, the differential scanning calorimeter is not limited to this.
• Blocking agents having a dissociation temperature of 100° C. to 160° C. include active methylene compounds [malonic acid diesters (dimethyl malonate, diethyl malonate, di-n-butyl malonate, di-2-ethylhexyl malonate, etc.)] and oxime compounds.
• malonic acid diesters dimethyl malonate, diethyl malonate, di-n-butyl malonate, di-2-ethylhexyl malonate, etc.
• the blocking agent having a dissociation temperature of 100° C. to 160° C. is preferably at least one selected from oxime compounds from the viewpoint of storage stability.
• the blocked isocyanate compound preferably has an isocyanurate structure from the viewpoint of, for example, improving the brittleness of the film and improving the adhesive strength with the transferred material.
• a blocked isocyanate compound having an isocyanurate structure can be obtained, for example, by converting hexamethylene diisocyanate into an isocyanurate for protection.
• a compound having an oxime structure using an oxime compound as a blocking agent tends to have a dissociation temperature within a preferable range and produces less development residue than a compound having no oxime structure. It is preferable from the viewpoint that it is easy to
• the blocked isocyanate compound may have a polymerizable group.
• the polymerizable group is not particularly limited, and any known polymerizable group can be used, and a radically polymerizable group is preferred.
• Polymerizable groups include ethylenically unsaturated groups such as (meth)acryloxy groups, (meth)acrylamide groups, and styryl groups, and groups having epoxy groups such as glycidyl groups. Among them, the polymerizable group is preferably an ethylenically unsaturated group, more preferably a (meth)acryloxy group, and still more preferably an acryloxy group.
• a commercial item can be used as a block isocyanate compound.
• blocked isocyanate compounds include Karenz (registered trademark) AOI-BM, Karenz (registered trademark) MOI-BM, Karenz (registered trademark) MOI-BP, etc. (manufactured by Showa Denko K.K.), block type Duranate series (eg, Duranate (registered trademark) TPA-B80E, Duranate (registered trademark) WT32-B75P, etc., manufactured by Asahi Kasei Chemicals Corporation).
• the compound of the following structure can also be used as a blocked isocyanate compound.
• the thermally crosslinkable compounds may be used singly or in combination of two or more.
• the content of the heat-crosslinkable compound is preferably 1% by mass to 50% by mass, and 5% by mass to 30% by mass, based on the total mass of the photosensitive composition layer. % by mass is more preferred.
• the photosensitive composition layer may contain known additives, if necessary, in addition to the above components.
• additives include radical polymerization inhibitors, sensitizers, plasticizers, heterocyclic compounds (triazole, etc.), benzotriazole compounds, carboxybenzotriazole compounds, pyridine compounds (isonicotinamide, etc.), purine bases (adenine, etc.). ), and surfactants.
• Each additive may be used individually by 1 type, and may be used 2 or more types.
• the photosensitive composition layer may contain a radical polymerization inhibitor.
• radical polymerization inhibitors include thermal polymerization inhibitors described in paragraph 0018 of Japanese Patent No. 4502784. Among them, phenothiazine, phenoxazine and 4-methoxyphenol are preferred.
• Other radical polymerization inhibitors include naphthylamine, cuprous chloride, nitrosophenylhydroxyamine aluminum salt, and diphenylnitrosamine. In order not to impair the sensitivity of the photosensitive composition layer, it is preferred to use a nitrosophenylhydroxyamine aluminum salt as a radical polymerization inhibitor.
• the content of the polymerization inhibitor is preferably 0.001% by mass to 5.0% by mass, based on the total mass of the photosensitive composition layer, and 0.01% by mass. % to 3.0% by mass, more preferably 0.02% to 2.0% by mass.
• the content of the polymerization inhibitor is preferably 0.005% by mass to 5.0% by mass, more preferably 0.01% by mass to 3.0% by mass, relative to the total mass of the polymerizable compound, and 0.01% by mass. % by mass to 1.0% by mass is more preferred.
• Benzotriazole compounds include, for example, 1,2,3-benzotriazole, 1-chloro-1,2,3-benzotriazole, bis(N-2-ethylhexyl)aminomethylene-1,2,3-benzotriazole, bis(N-2-ethylhexyl)aminomethylene-1,2,3-tolyltriazole, bis(N-2-hydroxyethyl)aminomethylene-1,2,3-benzotriazole and the like.
• Carboxybenzotriazole compounds include, for example, 4-carboxy-1,2,3-benzotriazole, 5-carboxy-1,2,3-benzotriazole, N-(N,N-di-2-ethylhexyl)aminomethylene Carboxybenzotriazole, N-(N,N-di-2-hydroxyethyl)aminomethylene carboxybenzotriazole, N-(N,N-di-2-ethylhexyl)aminoethylene carboxybenzotriazole and the like.
• the carboxybenzotriazole compound for example, commercially available products such as CBT-1 (Johoku Chemical Industry Co., Ltd.) can be used.
• the total content of the benzotriazole compound and the carboxybenzotriazole compound is preferably 0.01% by mass to 3% by mass, more preferably 0.05% by mass to 1% by mass, based on the total mass of the photosensitive composition layer. % by mass is more preferred.
• the content is 0.01% by mass or more, the storage stability of the photosensitive composition layer is more excellent.
• the content is 3% by mass or less, the maintenance of sensitivity and suppression of decolorization of the dye are more excellent.
• the photosensitive composition layer may contain a sensitizer.
• the sensitizer is not particularly limited, and known sensitizers, dyes and pigments can be used.
• Sensitizers include, for example, dialkylaminobenzophenone compounds, pyrazoline compounds, anthracene compounds, coumarin compounds, xanthone compounds, thioxanthone compounds, acridone compounds, oxazole compounds, benzoxazole compounds, thiazole compounds, benzothiazole compounds, triazole compounds (e.g., 1,2,4-triazoles), stilbene compounds, triazine compounds, thiophene compounds, naphthalimide compounds, triarylamine compounds, and aminoacridine compounds.
• a sensitizer may be used alone or in combination of two or more.
• the content of the sensitizer can be appropriately selected depending on the purpose, but from the viewpoint of improving the sensitivity to the light source and improving the curing speed due to the balance between the polymerization speed and the chain transfer. , preferably 0.01% to 5% by mass, more preferably 0.05% to 1% by mass, based on the total mass of the photosensitive composition layer.
• the photosensitive composition layer may contain at least one selected from the group consisting of plasticizers and heterocyclic compounds.
• Plasticizers and heterocyclic compounds include compounds described in paragraphs 0097-0103 and 0111-0118 of WO2018/179640.
• the photosensitive composition layer may contain a surfactant.
• surfactants include those described in paragraph [0017] of Japanese Patent No. 4502784 and paragraphs [0060] to [0071] of JP-A-2009-237362.
• surfactants examples include hydrocarbon-based surfactants, fluorine-based surfactants, and silicone-based surfactants. From the viewpoint of improving environmental friendliness, the surfactant preferably does not contain a fluorine atom. As the surfactant, a hydrocarbon-based surfactant or a silicone-based surfactant is preferred.
• fluorosurfactants include, for example, Megafac (registered trademark) F-171, F-172, F-173, F-176, F-177, F-141, F-142, F-143 , F-144, F-437, F-475, F-477, F-479, F-482, F-551-A, F-552, F-554, F-555-A, F-556, F -557, F-558, F-559, F-560, F-561, F-565, F-563, F-568, F-575, F-780, EXP.MFS-330, EXP. MFS-578, EXP . MFS-578-2, EXP. MFS-579, EXP.
• an acrylic compound that has a molecular structure with a functional group containing a fluorine atom and in which the portion of the functional group containing the fluorine atom is cleaved and the fluorine atom volatilizes when heat is applied can also be suitably used.
• a fluorosurfactant Megafac (registered trademark) DS series manufactured by DIC Corporation (Chemical Daily (February 22, 2016), Nikkei Sangyo Shimbun (February 23, 2016)) , for example, Megafac® DS-21.
• the fluorosurfactant 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 fluorosurfactant.
• the fluorine-based surfactant has a structural unit derived from a (meth)acrylate compound having a fluorine atom and 2 or more (preferably 5 or more) alkyleneoxy groups (preferably ethyleneoxy groups and propyleneoxy groups).
• a fluorine-containing polymer compound containing a structural unit derived from a (meth)acrylate compound can also be preferably used.
• a fluorosurfactant a fluoropolymer having an ethylenically unsaturated bond-containing group in a side chain can also be used.
• Megafac registered trademark
• RS-101, RS-102, RS-718K, RS-72-K manufactured by DIC Corporation
• fluorosurfactant from the viewpoint of improving environmental friendliness, compounds having linear perfluoroalkyl groups having 7 or more carbon atoms, such as perfluorooctanoic acid (PFOA) and perfluorooctane sulfonic acid (PFOS), are used.
• PFOA perfluorooctanoic acid
• PFOS perfluorooctane sulfonic acid
• Hydrocarbon surfactants include glycerol, trimethylolpropane, trimethylolethane, their ethoxylates and propoxylates (e.g., glycerol propoxylate, glycerol ethoxylate, etc.), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether , polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester, and the like.
• Pluronic (registered trademark) L10, L31, L61, L62, 10R5, 17R2, 25R2, Tetronic (registered trademark) 304, 701, 704, 901, 904, 150R1, HYDROPALAT WE 3323 above, BASF Corporation
• Solsperse 20000 manufactured by Nippon Lubrizol Co., Ltd.
• NCW-101, NCW-1001, NCW-1002 manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.
• Pionin D-1105, D-6112 , D-6112-W, D-6315 manufactured by Takemoto Oil & Fat Co., Ltd.
• Olfine E1010, Surfynol 104, 400, 440 manufactured by Nissin Chemical Industry Co., Ltd.
• silicone-based surfactants include straight-chain polymers composed of siloxane bonds, and modified siloxane polymers in which organic groups are introduced into side chains and terminals.
• silicone-based surfactants include EXP. S-309-2, EXP. S-315, EXP. S-503-2, EXP. S-505-2 (manufactured by DIC Corporation), DOWSIL 8032 ADDITIVE, Toray Silicone DC3PA, Toray Silicone SH7PA, Toray Silicone DC11PA, Toray Silicone SH21PA, Toray Silicone SH28PA, Toray Silicone SH29PA, Toray Silicone SH30PA, Toray Silicone SH8400 (above, manufactured by Dow Corning Toray Co., Ltd.) and 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, KF-6001, KF-6002, KP-101KP-103, KP-104, KP-105, KP-106,
• nonionic surfactants are preferred as surfactants.
• Surfactants may be used singly or in combination of two or more.
• the content of the surfactant is preferably 0.01% by mass to 3.0% by mass, based on the total mass of the photosensitive composition layer, and 0.01% by mass. % to 1.0% by mass, more preferably 0.05% to 0.80% by mass.
• the photosensitive composition layer contains metal oxide particles, antioxidants, dispersants, acid multipliers, development accelerators, conductive fibers, ultraviolet absorbers, thickeners, cross-linking agents, and organic or inorganic precipitates. It may further contain known additives such as inhibitors. Additives contained in the photosensitive composition layer are described in paragraphs 0165 to 0184 of JP-A-2014-085643, and the contents of this publication are incorporated herein.
• the water content in the photosensitive composition layer is preferably 0.01% by mass to 1.0% by mass, more preferably 0.05% by mass to 0.5% by mass, from the viewpoint of improving reliability and lamination properties. preferable.
• the photosensitive composition layer may contain a certain amount of impurities.
• impurities include sodium, potassium, magnesium, calcium, iron, manganese, copper, aluminum, titanium, chromium, cobalt, nickel, zinc, tin, halogens and ions thereof.
• halide ions, sodium ions, and potassium ions are likely to be mixed as impurities, so the following contents are preferable.
• the content of impurities in the photosensitive composition layer is preferably 80 ppm or less, more preferably 10 ppm or less, and even more preferably 2 ppm or less on a mass basis.
• the content of impurities can be 1 ppb or more, and may be 0.1 ppm or more, on a mass basis.
• the amount of impurities can be made within the above range.
• Impurities can be quantified by known methods such as ICP (Inductively Coupled Plasma) emission spectroscopy, atomic absorption spectroscopy, and ion chromatography.
• ICP Inductively Coupled Plasma
• the content of compounds such as benzene, formaldehyde, trichlorethylene, 1,3-butadiene, carbon tetrachloride, chloroform, N,N-dimethylformamide, N,N-dimethylacetamide, and hexane in the photosensitive composition layer is small. is preferred.
• the content of these compounds with respect to the total mass of the photosensitive composition layer is preferably 100 ppm or less, more preferably 20 ppm or less, and even more preferably 4 ppm or less, based on mass.
• the lower limit can be 10 ppb or more, and can be 100 ppb or more based on the total weight of the photosensitive composition layer.
• the content of these compounds can be suppressed in the same manner as the metal impurities described above. Moreover, it can quantify by a well-known measuring method.
• the water content in the photosensitive composition layer is preferably 0.01% by mass to 1.0% by mass, more preferably 0.05% by mass to 0.5% by mass, from the viewpoint of improving reliability and lamination properties. preferable.
• the photosensitive composition layer may be a colored resin layer containing a pigment.
• liquid crystal display windows of electronic devices have a cover glass with a black frame-shaped light-shielding layer formed on the periphery of the back surface of a transparent glass base material, etc., in order to protect the liquid crystal display window.
• a colored resin layer may be used to form such a light shielding layer.
• the pigment may be appropriately selected according to the desired hue, and may be selected from black pigments, white pigments, and chromatic pigments other than black and white. Among them, when forming a black pattern, a black pigment is preferably selected as the pigment.
• black pigment a known black pigment (organic pigment, inorganic pigment, etc.) can be appropriately selected as long as it does not impair the effects of the transfer film of the present disclosure.
• black pigments include, for example, carbon black, titanium oxide, titanium carbide, iron oxide, titanium oxide, and graphite, and carbon black is particularly preferred.
• carbon black from the viewpoint of surface resistance, carbon black having at least a part of the surface coated with a resin is preferable.
• the number average particle size of the black pigment is preferably 0.001 ⁇ m to 0.1 ⁇ m, more preferably 0.01 ⁇ m to 0.08 ⁇ m.
• the particle size refers to the diameter of a circle obtained by obtaining the area of a pigment particle from a photographic image of the pigment particle taken with an electron microscope and considering a circle having the same area as the area of the pigment particle. is an average value obtained by obtaining the above particle size for 100 arbitrary particles and averaging the obtained 100 particle sizes.
• White pigments described in paragraphs 0015 and 0114 of JP-A-2005-007765 can be used as pigments other than black pigments.
• inorganic pigments are preferably titanium oxide, zinc oxide, lithopone, light calcium carbonate, white carbon, aluminum oxide, aluminum hydroxide, or barium sulfate, and more preferably titanium oxide or zinc oxide. Preferred, and more preferred is titanium oxide.
• titanium oxide rutile-type or anatase-type titanium oxide is more preferable, and rutile-type titanium oxide is particularly preferable.
• the surface of titanium oxide may be subjected to silica treatment, alumina treatment, titania treatment, zirconia treatment, or organic substance treatment, or may be subjected to two or more treatments.
• the catalytic activity of titanium oxide is suppressed, and the heat resistance, fade resistance, and the like are improved.
• the surface treatment of the titanium oxide surface is preferably at least one of alumina treatment and zirconia treatment, and particularly preferably both alumina treatment and zirconia treatment.
• the photosensitive composition layer when the photosensitive composition layer is a colored resin layer, from the viewpoint of transferability, the photosensitive composition layer preferably further contains a chromatic pigment other than the black pigment and the white pigment.
• a chromatic pigment when a chromatic pigment is included, the particle size of the chromatic pigment is preferably 0.1 ⁇ m or less, more preferably 0.08 ⁇ m or less, from the viewpoint of better dispersibility.
• chromatic pigments include Victoria Pure Blue BO (Color Index (hereinafter C.I.) 42595), Auramine (C.I. 41000), Fat Black HB (C.I. 26150), and Monolite. ⁇ Yellow GT (C.I. Pigment Yellow 12), Permanent Yellow GR (C.I. Pigment Yellow 17), Permanent Yellow HR (C.I.
• Pigment Yellow 83 Permanent Carmine FBB (C) Pigment Red 146), Hoster Balm Red ESB (C.I. Pigment Violet 19), Permanent Ruby FBH (C.I. Pigment Red 11), Fastel Pink B Spra (C.I. Pigment Red 81), Monastral Fast Blue (C.I. Pigment Blue 15), Monolite Fast Black B (C.I. Pigment Black 1) and Carbon, C.I. I. Pigment Red 97, C.I. I. Pigment Red 122, C.I. I. Pigment Red 149, C.I. I. Pigment Red 168, C.I. I. Pigment Red 177, C.I. I. Pigment Red 180, C.I. I. Pigment Red 192, C.I. I.
• C.I. I. Pigment Red 177 is preferred.
• the content of the pigment is preferably more than 3% by mass and 40% by mass or less, and more than 3% by mass and 35% by mass or less with respect to the total mass of the photosensitive composition layer. More preferably, it is more than 5% by mass and 35% by mass or less, and particularly preferably 10% by mass or more and 35% by mass or less.
• the content of pigments other than black pigments is preferably 30% by mass or less, and 1% by mass, relative to the black pigment. ⁇ 20% by mass is more preferable, and 3% by mass to 15% by mass is even more preferable.
• the black pigment preferably carbon black
• the dispersion liquid may be prepared by adding a mixture obtained by previously mixing a black pigment and a pigment dispersant to an organic solvent (or vehicle) and dispersing the mixture with a dispersing machine.
• a pigment dispersant may be selected according to the pigment and solvent, and for example, a commercially available dispersant can be used.
• the vehicle refers to the part of the medium in which the pigment is dispersed when it is made into a pigment dispersion, and is a liquid binder component that holds the black pigment in a dispersed state, and a solvent component that dissolves and dilutes the binder component. (organic solvent) and
• dispersants include urethane-based dispersants such as polyurethane, polycarboxylic acid esters such as polyacrylate, unsaturated polyamides, polycarboxylic acids, polycarboxylic acid (partial) amine salts, polycarboxylic acid ammonium salts, and polycarboxylic acid alkyls.
• Amine salts polysiloxanes, long-chain polyaminoamide phosphates, hydroxyl group-containing polycarboxylic acid esters, modified products thereof, amides formed by the reaction of poly(lower alkyleneimine) with polyesters having free carboxyl groups, and their Oily dispersants such as salts, (meth)acrylic acid-styrene copolymers, (meth)acrylic acid-(meth)acrylic acid ester copolymers, styrene-maleic acid copolymers, polyvinyl alcohols, polyvinylpyrrolidone, etc.
• Oily dispersants such as salts, (meth)acrylic acid-styrene copolymers, (meth)acrylic acid-(meth)acrylic acid ester copolymers, styrene-maleic acid copolymers, polyvinyl alcohols, polyvinylpyrrolidone, etc.
• the aspect of the dispersant may be selected from items described in paragraphs [0021] to [0065] of JP-A-2021-012355.
• Preferred dispersants include, for example, basic polymeric dispersants.
• Basic polymeric dispersants include, for example, polymers containing nitrogen atoms. The nitrogen atoms may be included in the main chain of the polymer. The nitrogen atom may be contained in the side chain of the polymer. Nitrogen atoms may be included in the main chain and side chains of the polymer.
• the basic polymeric dispersant is preferably a polymer containing nitrogen atoms in side chains. Since the surface of carbon black is generally acidic, a basic polymer-type dispersant is particularly preferred as the dispersant when carbon black is used as the pigment.
• Polymers containing nitrogen atoms include, for example, primary amino groups, secondary amino groups, tertiary amino groups, quaternary ammonium bases and nitrogen-containing Examples thereof include polymers containing at least one atomic group selected from the group consisting of heterocyclic groups.
• polymers containing quaternary ammonium bases are preferred.
• the atomic group is preferably introduced into the side chain of the polymer.
• Counter ions for the quaternary ammonium cation in the quaternary ammonium base include, for example, carboxylate ions.
• Carboxylate ions include, for example, aliphatic carboxylate ions and aromatic carboxylate ions.
• a polymer containing a nitrogen atom is preferably a polymer containing a structural unit derived from styrene and a structural unit derived from a maleimide derivative.
• a copolymer with a maleimide derivative is more preferred.
• a maleimide derivative has a structure in which at least one hydrogen atom of maleimide is substituted with a substituent.
• the maleimide derivative includes, for example, at least one atomic group selected from the group consisting of primary amino groups, secondary amino groups, tertiary amino groups, quaternary ammonium bases and nitrogen-containing heterocyclic groups. and maleimide derivatives containing The maleimide derivative is preferably a maleimide derivative containing a quaternary ammonium base.
• the dispersant may be a commercially available dispersant, such as BYK-2012 (manufactured by BYK-Chemie Japan Co., Ltd.).
• the photosensitive composition layer may contain a dispersing aid (also referred to as a pigment dispersing aid) in addition to the pigment.
• Dispersing aids may be selected from known dispersing aids.
• Dispersing aids include, for example, compounds having organic dye residues.
• organic dyes include phthalocyanine-based pigments, diketopyrrolopyrrole-based pigments, anthraquinone-based pigments, quinacridone-based pigments, dioxazine-based pigments, perinone-based pigments, perylene-based pigments, thiazineindigo-based pigments, triazine-based pigments, benzimidazo Ron-based pigments, indole-based pigments such as benzoisoindole, isoindoline-based pigments, isoindolinone-based pigments, quinophthalone-based pigments, naphthol-based pigments, threne-based pigments, metal complex-based pigments, azo-based pigments such as azo, disazo, and polyazo A pigment etc.
• a compound having an organic dye residue may have an acidic substituent, a basic substituent or a neutral substituent.
• Acidic substituents include, for example, sulfo groups, carboxy groups and phosphate groups.
• Basic substituents include, for example, sulfonamide groups and amino groups.
• Neutral substituents include, for example, phenyl groups and phthalimidoalkyl groups. Aspects of the dispersing aid may be selected from items described in paragraphs [0067] to [0084] of JP-A-2021-012355.
• Preferred dispersing aids include, for example, compounds having phthalocyanine residues.
• the dispersing aid is preferably a phthalocyanine pigment derivative or a salt thereof having an acidic substituent, and at least one acidic substituent selected from the group consisting of a sulfo group, a carboxyl group and a phosphoric acid group. or a salt thereof, and more preferably a phthalocyanine pigment derivative having a sulfo group or a salt thereof.
• Phthalocyanine pigment derivatives are described, for example, in JP-A-2007-226161, WO-A-2016/163351, JP-A-2017-165820 and JP-A-5753266. These publications are incorporated herein by reference.
• the disperser is not particularly limited, and includes known dispersers such as kneaders, roll mills, attritors, super mills, dissolvers, homomixers, and sand mills. Furthermore, it may be finely pulverized using frictional force by mechanical grinding. Regarding the dispersing machine and the fine pulverization, reference can be made to the description in "Encyclopedia of Pigment” (Kunizo Asakura, 1st edition, Asakura Shoten, 2000, pp. 438, 310).
• the layer thickness (film thickness) of the photosensitive composition layer is generally 0.1 ⁇ m to 300 ⁇ m, preferably 0.2 ⁇ m to 100 ⁇ m, more preferably 0.5 ⁇ m to 50 ⁇ m, and further preferably 0.5 ⁇ m to 15 ⁇ m.
• 0.5 ⁇ m to 10 ⁇ m is particularly preferred, and 0.5 ⁇ m to 8 ⁇ m is most preferred.
• the thickness is preferably 0.5 ⁇ m to 5 ⁇ m, more preferably 0.5 ⁇ m to 4 ⁇ m, even more preferably 0.5 ⁇ m to 3 ⁇ m.
• the transmittance of the photosensitive composition layer for light with a wavelength of 365 nm is preferably 10% or more, more preferably 30% or more, and even more preferably 50% or more.
• the upper limit is not particularly limited, 99.9% or less is preferable.
• the metal-containing layer may be a layer for forming a seed layer.
• a seed layer is an electrode layer used when forming a conductor pattern, and the conductor pattern is formed on the seed layer.
• Metal ions in the metal salt contained in the metal salt-containing layer are reduced by heat or a reducing agent to become an elemental metal, and the formed seed layer can exhibit conductivity.
• a metal salt is a compound in which a hydrogen atom of an acid is replaced with a metal ion.
• the metal salt is an ionically binding compound.
• Metal oxides are not included in metal salts in the present invention.
• the metal salt is not particularly limited as long as it is a compound containing a metal ion. Examples thereof include a metal salt composed of a metal ion and at least one of an inorganic anion and an organic anion. From the viewpoint of solubility, the metal salt is preferably a metal salt composed of a metal ion and an organic anion, and is one or more selected from the group consisting of metal carboxylates and complex salts of metal ions and acetylacetone derivatives.
• an acetylacetone derivative refers to a compound having an acetylacetone skeleton, and includes, for example, acetylacetonate, which is a conjugate base of acetylacetone.
• Carboxylic acids constituting the metal carboxylates include formic acid, acetic acid, trifluoroacetic acid, propionic acid, butyric acid, isobutyric acid, 2-methylbutyric acid, 2-ethylbutyric acid, valeric acid, isovaleric acid, pivalic acid, and hexane.
• Fatty carboxylic acids such as acids, heptanoic acid, octanoic acid, 2-ethylhexanoic acid, nonanoic acid, decanoic acid and neodecanoic acid, dicarboxylic acids such as malonic acid, succinic acid and maleic acid, aromatics such as benzoic acid and salicylic acid Carboxylic acid, hydroxyacetic acid, glyoxylic acid, lactic acid, oxalic acid, tartaric acid, malic acid, citric acid and the like.
• Complex salts of metals and acetylacetone derivatives include, for example, acetylacetonate metal salt, 1,1,1-trimethylacetylacetonate metal salt, and 1,1,1,5,5,5-hexamethylacetylacetonate.
• metal salts, 1,1,1-trifluoroacetylacetonate metal salts and 1,1,1,5,5,5-hexafluoroacetylacetonate metal salts, and the like are examples of complex salts of metals and acetylacetonate metal salt, 1,1,1-trimethylacetylacetonate metal salt, and 1,1,1,5,5,5-hexafluoroacetylacetonate metal salts, and the like.
• metal ions examples include copper ions, silver ions, tin ions, nickel ions, antimony ions, and indium ions, with copper ions or silver ions being preferred, and silver ions being more preferred.
• the metal salt is preferably copper carboxylate or silver carboxylate, and more preferably silver carboxylate, from the viewpoint of adhesion to the substrate and resistance properties of the formed seed layer.
• copper salts or silver salts of carboxylic acids selected from the group consisting of formic acid, acetic acid, propionic acid, isobutyric acid, valeric acid, isovaleric acid, glyoxylic acid, 2-ethylhexanoic acid and neodecanoic acid are preferred. Salt is more preferred.
• the content of the metal salt with respect to the total mass of the metal salt-containing layer is preferably 10% by mass to 70% by mass, more preferably 15% by mass to 60% by mass, and 20% by mass to 50% by mass is more preferred.
• the content of the metal salt within the above numerical range, when forming a conductive pattern using the transfer film of the present disclosure, the ratio of the line width at the bottom of the pattern to the line width at the top of the pattern can be reduced. It is possible to form a good conductor pattern (hereinafter also referred to as conductor pattern formability).
• the metal salt-containing layer may contain a reducing agent for the purpose of reducing the metal ion contained in the metal salt into a simple metal.
• the reducing agent is not particularly limited as long as it has a reducing property with respect to the metal ions contained in the metal salt of the metal salt-containing layer.
• the reducing agent include compounds having one or more functional groups selected from the group consisting of thiol groups, nitrile groups, amino groups, hydroxy groups, and hydroxycarbonyl groups, nitrogen atoms, oxygen atoms and sulfur.
• Examples thereof include compounds having one or more heteroatoms selected from the group consisting of atoms in the molecular structure.
• Examples of compounds having the above functional groups include alkanethiol compounds, amine compounds, hydrazine compounds, monoalcohol compounds, diol compounds, hydroxyamine compounds, ⁇ -hydroxyketone compounds, carboxylic acid compounds, salts of carboxylic acid compounds, and the like. .
• Compounds having heteroatoms in their molecular structures include polyvinylpyrrolidone, polyethyleneimine, polyaniline, polypyrrole, polythiophene, polyacrylamide, polyacrylic acid, carboxymethylcellulose, polyvinyl alcohol, polyethylene oxide, and the like.
• the reducing agent is one selected from the group consisting of alkanethiol compounds, amine compounds, carboxylic acid compounds, and salts of carboxylic acid compounds, or Two or more are preferable, and one or two or more selected from the group consisting of amine compounds, carboxylic acid compounds and salts of carboxylic acid compounds are more preferable.
• Alkanethiol compounds include ethanethiol, n-propanethiol, i-propanethiol, n-butanethiol, i-butanethiol, t-butanethiol, n-pentanethiol, n-hexanethiol, cyclohexanethiol, and n-heptane.
• Amine compounds include ethylamine, n-propylamine, i-propylamine, n-butylamine, i-butylamine, t-butylamine, n-pentylamine, n-hexylamine, cyclohexylamine, n-heptylamine, n-octyl amines, 2-ethylhexylamine, 2-ethylhexylpropylamine, 3-methoxypropylamine, 3-ethoxypropylamine, n-nonylamine, n-decylamine, n-undecylamine, n-dodecylamine, n-tridecylamine, n-tetradecylamine, n-pentadecylamine, n-hexadecylamine, benzylamine, monoamine compounds such as aminoacetaldehyde diethyl acetal, ethylene
• the carboxylic acid compound is not particularly limited as long as it has a reducing property with respect to metal salts, and examples thereof include formic acid, hydroxyacetic acid, glyoxylic acid, lactic acid, oxalic acid, tartaric acid, malic acid, and citric acid.
• Examples of the salt of the carboxylic acid compound include the ammonium salts of the carboxylic acid compounds described above.
• the metal salt-containing layer can contain one or more reducing agents capable of reducing the metal salt by appropriately selecting or combining them.
• the content of the reducing agent with respect to the total weight of the metal salt-containing layer is preferably 1% by mass to 99% by mass, more preferably 10% by mass to 90% by mass. , more preferably 30% to 90% by mass, particularly preferably 40% to 85% by mass, most preferably 45% to 80% by mass.
• the metal salt-containing layer may contain additives other than metal salts and reducing agents, such as surfactants, plasticizers, and sensitizers.
• the thickness of the metal salt-containing layer is preferably 10 nm to 1000 nm, more preferably 100 nm to 500 nm, and even more preferably 150 nm to 400 nm, from the viewpoint of adhesion to the substrate and conductive pattern formability.
• the transfer film of the present disclosure can comprise an intermediate layer.
• the intermediate layer can be provided between the temporary support and the photosensitive composition layer, or between the thermoplastic resin layer and the photosensitive composition layer, which will be described later. Due to the presence of an intermediate layer between the thermoplastic resin layer and the photosensitive composition layer, components that may occur during coating formation of the thermoplastic resin layer and the photosensitive composition layer and during storage after coating formation. Mixing can be suppressed.
• a water-soluble resin layer containing a water-soluble resin can be used as the intermediate layer.
• an oxygen-blocking layer having an oxygen-blocking function which is described as a "separation layer" in JP-A-5-072724, can also be used. It is preferable that the intermediate layer is an oxygen-blocking layer because the sensitivity during 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 known layers described in the above publications. Among them, an oxygen-blocking layer that exhibits low oxygen permeability and is dispersed or dissolved in water or an alkaline aqueous solution (a 1% by mass aqueous solution of sodium carbonate at 22° C.) is preferred.
• the water-soluble resin layer contains a resin.
• the resin includes a water-soluble resin as part or all of it.
• resins that can be used as water-soluble resins include polyvinyl alcohol-based resins, polyvinylpyrrolidone-based resins, cellulose-based resins, acrylamide-based resins, polyethylene oxide-based resins, gelatin, vinyl ether-based resins, polyamide resins, and copolymers thereof. Resins such as coalescence can be mentioned.
• a (meth)acrylic acid/vinyl compound copolymer or the like can also be used as the water-soluble resin.
• the (meth)acrylic acid/vinyl compound copolymer As the (meth)acrylic acid/vinyl compound copolymer, a (meth)acrylic acid/allyl (meth)acrylate copolymer is preferable, and a methacrylic acid/allyl methacrylate copolymer is more preferable.
• the water-soluble resin is a (meth)acrylic acid/vinyl compound copolymer
• the composition ratio (mol%) is preferably 90/10 to 20/80, and preferably 80/20 to 30/70. more preferred.
• the lower limit of the weight average molecular weight of the water-soluble resin is preferably 5,000 or more, more preferably 7,000 or more, and even more preferably 10,000 or more. Moreover, the upper limit thereof is preferably 200,000 or less, more preferably 100,000 or less, and even more preferably 50,000 or less.
• the dispersity (Mw/Mn) of the water-soluble resin is preferably 1-10, more preferably 1-5.
• the resin in the water-soluble resin layer (intermediate layer) is arranged on one side of the water-soluble resin layer (intermediate layer). It is preferable that the resin contained in the layer on which the second surface is arranged is different from the resin contained in the layer arranged on the other surface side.
• the resin of the water-soluble resin layer (intermediate layer) is the polymer A and thermoplastic resin (alkali-soluble resin).
• the water-soluble resin preferably contains polyvinyl alcohol, and more preferably contains both polyvinyl alcohol and polyvinylpyrrolidone, from the viewpoint of further improving the oxygen-blocking property and the ability to suppress interlayer mixing.
• One type of water-soluble resin may be used alone, or two or more types may be used.
• the content of the water-soluble resin is not particularly limited, it is preferably 50% by mass or more with respect to the total mass of the water-soluble resin layer (intermediate layer) in order to further improve the oxygen barrier property and the ability to suppress interlayer mixing. , more preferably 70% by mass or more, still more preferably 80% by mass or more, and particularly preferably 90% by mass or more.
• the upper limit is not particularly limited, for example, 99.9% by mass or less is preferable, and 99.8% by mass or less is more preferable.
• the intermediate layer may contain known additives such as surfactants, if necessary.
• the layer thickness of the water-soluble resin layer (intermediate layer) is not particularly limited, it is preferably 0.1 ⁇ m to 5 ⁇ m, more preferably 0.5 ⁇ m to 3 ⁇ m.
• the inter-layer mixing suppression ability is excellent without lowering the oxygen barrier properties. Furthermore, it is possible to suppress the increase in the time required for removing the water-soluble resin layer (intermediate layer) during development.
• the transfer film may have a protective film.
• a resin film having heat resistance and solvent resistance can be used. Examples thereof include polyolefin films such as polypropylene films and polyethylene films, polyester films such as polyethylene terephthalate films, polycarbonate films, and polystyrene films. be done.
• a resin film made of the same material as the temporary support may be used.
• the protective film is preferably a polyolefin film, more preferably a polypropylene film or a polyethylene film, and still more preferably a polyethylene film.
• the thickness of the protective film is preferably 1 ⁇ m to 100 ⁇ m, more preferably 5 ⁇ m to 50 ⁇ m, still more preferably 5 ⁇ m to 40 ⁇ m, particularly preferably 15 ⁇ m to 30 ⁇ m.
• the thickness of the protective film is preferably 1 ⁇ m or more from the viewpoint of excellent mechanical strength, and preferably 100 ⁇ m or less from the viewpoint of being relatively inexpensive.
• the number of fisheyes having a diameter of 80 ⁇ m or more contained in the protective film is preferably 5/m 2 or less.
• fish eye refers to foreign matter, undissolved matter, and oxidative degradation products of the material when producing a film by methods such as heat melting, kneading, extrusion, biaxial stretching and casting. is captured in the film.
• the number of particles having a diameter of 3 ⁇ m or more contained in the protective film is preferably 30 particles/mm 2 or less, more preferably 10 particles/mm 2 or less, and even more preferably 5 particles/mm 2 or less. This makes it possible to suppress defects caused by the unevenness caused by the particles contained in the protective film being transferred to the photosensitive composition layer or the conductive layer.
• the surface of the protective film opposite to the surface in contact with the composition layer preferably has an arithmetic mean roughness Ra of 0.01 ⁇ m or more, more preferably 0.02 ⁇ m or more, and 0.03 ⁇ m.
• the above is more preferable.
• it is preferably less than 0.50 ⁇ m, more preferably 0.40 ⁇ m or less, and even more preferably 0.30 ⁇ m or less.
• the surface roughness Ra of the protective film in contact with the composition layer is preferably 0.01 ⁇ m or more, more preferably 0.02 ⁇ m or more, and still more preferably 0.03 ⁇ m or more, from the viewpoint of suppressing defects during transfer.
• it is preferably less than 0.50 ⁇ m, more preferably 0.40 ⁇ m or less, and even more preferably 0.30 ⁇ m or less.
• the protective film may be a recycled product.
• recycled products include films made from washed and chipped used films and the like.
• Ecouse registered trademark
• the cured film obtained by curing the photosensitive composition layer has a breaking elongation at 120 ° C. of 15% or more, and the arithmetic average roughness Ra of the surface of the temporary support on the photosensitive composition layer side is 50 nm. and the arithmetic mean roughness Ra of the surface of the protective film on the photosensitive composition layer side is preferably 150 nm or less.
• the transfer film of the present disclosure preferably satisfies the following formula (1).
• X represents the value (%) of the elongation at break at 120 ° C. of the cured film obtained by curing the photosensitive composition layer
• Y is the photosensitive composition layer of the temporary support.
• the elongation at break at 120°C is at least twice as large as the elongation at break at 23°C of the cured film obtained by curing the photosensitive composition layer.
• the elongation at break was measured by exposing a photosensitive composition layer having a thickness of 20 ⁇ m to 120 mJ/cm 2 with an ultra-high pressure mercury lamp and curing it, then further exposing it to 400 mJ/cm 2 with a high pressure mercury lamp, and heating at 145° C. for 30 minutes. Post-cured films are measured by a tensile test.
• the transfer film of the present disclosure preferably satisfies the following formula (2).
• Y ⁇ Z formula (2)
• Y represents the value (nm) of the arithmetic mean roughness Ra of the surface of the temporary support on the photosensitive composition layer side
• Z represents the photosensitive composition layer side of the protective film.
• the transfer film of the present disclosure can comprise a thermoplastic resin layer.
• the thermoplastic resin layer is usually provided between the temporary support and the photosensitive composition layer.
• the thermoplastic resin layer contains resin.
• the resin includes a thermoplastic resin in part or in whole. That is, in one aspect, it is also preferable that the resin of the thermoplastic resin layer is a thermoplastic resin.
• the thermoplastic resin is preferably an alkali-soluble resin.
• alkali-soluble resins include acrylic resins, polystyrene resins, styrene-acrylic copolymers, polyurethane resins, polyvinyl alcohol, polyvinyl formal, polyamide resins, polyester resins, polyamide resins, epoxy resins, polyacetal resins, and polyhydroxystyrene resins. , polyimide resins, polybenzoxazole resins, polysiloxane resins, polyethyleneimines, polyallylamines, and polyalkylene glycols.
• an acrylic resin is preferable from the viewpoint of developability and adhesion to adjacent layers.
• the acrylic resin is at least selected from the group consisting of structural units derived from (meth)acrylic acid, structural units derived from (meth)acrylic acid esters, and structural units derived from (meth)acrylic acid amide. It means a resin having one kind of constitutional unit.
• the acrylic resin the total content of structural units derived from (meth)acrylic acid, structural units derived from (meth)acrylic acid ester, and structural units derived from (meth)acrylic acid amide is the total content of the acrylic resin. It is preferably 50% by mass or more based on the mass. Among them, the total content of structural units derived from (meth) acrylic acid and structural units derived from (meth) acrylic acid ester is preferably 30 to 100% by mass, based on the total mass of the acrylic resin, and 50 to 100% by mass is more preferred.
• the alkali-soluble resin is preferably a polymer having an acid group.
• the acid group includes a carboxy group, a sulfo group, a phosphoric acid group, and a phosphonic acid group, with the carboxy group being preferred.
• the alkali-soluble resin is more preferably an alkali-soluble resin having an acid value of 60 mgKOH/g or more, and more preferably a carboxy group-containing acrylic resin having an acid value of 60 mgKOH/g or more.
• the upper limit of the acid value of the alkali-soluble resin is not particularly limited, it is preferably 300 mgKOH/g or less, more preferably 250 mgKOH/g or less, still more preferably 200 mgKOH/g or less, and particularly preferably 150 mgKOH/g or less.
• the carboxy group-containing acrylic resin having an acid value of 60 mgKOH/g or more is not particularly limited, and can be appropriately selected from known resins and used.
• an alkali-soluble resin that is a carboxy group-containing acrylic resin having an acid value of 60 mgKOH/g or more, described in paragraphs 0033 to 0052 of JP-A-2010-237589 A carboxy group-containing acrylic resin having an acid value of 60 mgKOH/g or more among the polymers, and a carboxy group-containing acrylic resin having an acid value of 60 mgKOH/g or more among the binder polymers described in paragraphs 0053 to 0068 of JP-A-2016-224162.
• the copolymerization ratio of the structural unit having a carboxy group in the carboxy group-containing acrylic resin is preferably 5 to 50% by mass, more preferably 10 to 40% by mass, and 12 to 30% by mass with respect to the total mass of the acrylic resin. is more preferred.
• an acrylic resin having a structural unit derived from (meth)acrylic acid is particularly preferable from the viewpoint of developability and adhesion to an adjacent layer.
• the alkali-soluble resin may have a reactive group.
• the reactive group may be any group capable of addition polymerization, and includes an ethylenically unsaturated group; a polycondensable group such as a hydroxy group and a carboxyl group; a polyaddition reactive group such as an epoxy group and a (blocked) isocyanate group. mentioned.
• the weight average molecular weight (Mw) of the alkali-soluble resin is preferably 1,000 or more, more preferably 10,000 to 100,000, and even more preferably 20,000 to 50,000.
• Alkali-soluble resin may be used individually by 1 type, and may be used 2 or more types.
• the content of the alkali-soluble resin is preferably 10% to 99% by mass, preferably 20% to 90% by mass, based on the total mass of the thermoplastic resin layer, from the viewpoint of developability and adhesion to adjacent layers. is more preferable, 40% by mass to 80% by mass is more preferable, and 50% by mass to 75% by mass is particularly preferable.
• thermoplastic resin layer has a maximum absorption wavelength of 450 nm or more in a wavelength range of 400 nm to 780 nm during color development, and contains a dye whose maximum absorption wavelength is changed by an acid, a base, or a radical (also simply referred to as "dye B"). is preferred.
• Preferred embodiments of the dye B are the same as preferred embodiments of the dye N described above, except for the points described later.
• Dye B is preferably a dye whose maximum absorption wavelength changes with acid or radicals, more preferably a dye whose maximum absorption wavelength changes with acid, from the viewpoint of visibility and resolution of exposed and unexposed areas.
• the thermoplastic resin layer contains both a dye whose maximum absorption wavelength is changed by an acid as the dye B and a compound that generates an acid by light, which will be described later. preferably included.
• the dye B may be used alone or in combination of two or more.
• the content of the dye B is preferably 0.2% by mass or more, and 0.2% to 6% by mass, based on the total mass of the thermoplastic resin layer, from the viewpoint of visibility of the exposed and unexposed areas. It is more preferably 0.2% by mass to 5% by mass, and particularly preferably 0.25% by mass to 3.0% by mass.
• the content of the dye B means the content of the dye when all of the dye B contained in the thermoplastic resin layer is in a colored state.
• a method for quantifying the content of the dye B will be described below using a dye that develops color by radicals as an example.
• a solution of 0.001 g and 0.01 g of dye in 100 mL of methyl ethyl ketone is prepared.
• a radical photopolymerization initiator Irgacure (registered trademark) OXE01 (trade name, BASF Japan Co., Ltd.) is added to each solution obtained, and radicals are generated by irradiation with light of 365 nm, and all dyes are brought into a colored state.
• the absorbance of each solution having a liquid temperature of 25° C. is measured using a spectrophotometer (UV3100, manufactured by Shimadzu Corporation) in an air atmosphere to create a calibration curve.
• UV3100 UV3100, manufactured by Shimadzu Corporation
• the absorbance of the solution in which all the dyes are developed is measured in the same manner as described above except that 0.1 g of the thermoplastic resin layer is dissolved in methyl ethyl ketone instead of the dyes. From the absorbance of the obtained solution containing the thermoplastic resin layer, the amount of dye contained in the thermoplastic resin layer is calculated based on the calibration curve. 3 g of the thermoplastic resin layer is the same as 3 g of the solid content of the composition.
• the thermoplastic resin layer may contain a compound that generates an acid, a base, or a radical upon exposure to light (also simply referred to as “compound C”).
• Compound C is preferably a compound that generates an acid, a base, or a radical upon receiving actinic rays such as ultraviolet rays and visible rays.
• known photoacid generators, photobase generators, and photoradical polymerization initiators photoradical generators
• thermoplastic resin layer may contain a photoacid generator from the viewpoint of resolution.
• photoacid generator include photocationic polymerization initiators that may be included in the negative photosensitive composition layer described above, and preferred embodiments are the same except for the points described later.
• the photoacid generator preferably contains at least one compound selected from the group consisting of onium salt compounds and oxime sulfonate compounds. From the viewpoint of compatibility, it is more preferable to contain an oxime sulfonate compound. Moreover, as a photo-acid generator, the photo-acid generator which has the following structures is also preferable.
• thermoplastic resin layer may contain a radical photopolymerization initiator.
• photoradical polymerization initiator include photoradical polymerization initiators that may be included in the negative photosensitive composition layer described above, and preferred embodiments are also the same.
• the thermoplastic resin layer may contain a photobase generator.
• the photobase generator is not particularly limited as long as it is a known photobase generator. Examples include 2-nitrobenzylcyclohexylcarbamate, triphenylmethanol, O-carbamoylhydroxylamide, O-carbamoyloxime, [[(2, 6-dinitrobenzyl)oxy]carbonyl]cyclohexylamine, bis[[(2-nitrobenzyl)oxy]carbonyl]hexane 1,6-diamine, 4-(methylthiobenzoyl)-1-methyl-1-morpholinoethane, (4 -morpholinobenzoyl)-1-benzyl-1-dimethylaminopropane, N-(2-nitrobenzyloxycarbonyl)pyrrolidine, hexaamminecobalt (III) tris(triphenylmethylborate), 2-benzyl-2-dimethylamino- 1-(4-morpholinophenyl)-butanone
• Compound C may be used alone or in combination of two or more.
• the content of compound C is preferably 0.1% by mass to 10% by mass, and 0.5% by mass, based on the total mass of the thermoplastic resin layer, from the viewpoint of visibility and resolution of exposed and unexposed areas. % by mass to 5% by mass is more preferred.
• the thermoplastic resin layer preferably contains a plasticizer from the viewpoints of resolution, adhesion to adjacent layers, and developability.
• the plasticizer preferably has a smaller molecular weight (weight average molecular weight if it is an oligomer or polymer and has a molecular weight distribution) than the alkali-soluble resin.
• the molecular weight (weight average 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 exhibits plasticity by being compatible with the alkali-soluble resin, but from the viewpoint of imparting plasticity, the plasticizer preferably has an alkyleneoxy group in the molecule, such as polyalkylene glycol. Compounds are more preferred.
• the alkyleneoxy group contained in the plasticizer more preferably has a polyethyleneoxy structure or a polypropyleneoxy structure.
• the plasticizer preferably contains a (meth)acrylate compound from the viewpoint of resolution and storage stability.
• the alkali-soluble resin is an acrylic resin and the plasticizer contains a (meth)acrylate compound.
• the (meth)acrylate compound used as the plasticizer include the (meth)acrylate compounds described above as the polymerizable compound contained in the negative photosensitive composition layer.
• both the thermoplastic resin layer and the negative photosensitive composition layer contain the same (meth)acrylate compound. is preferred. This is because when the same (meth)acrylate compound is included in the thermoplastic resin layer and the negative photosensitive composition layer, the diffusion of components between layers is suppressed and the storage stability is improved.
• the thermoplastic resin layer contains a (meth)acrylate compound as a plasticizer
• the (meth)acrylate compound should not be polymerized even in the exposed areas after exposure.
• the (meth)acrylate compound used as a plasticizer has two or more (meth) Polyfunctional (meth)acrylate compounds having acryloyl groups are preferred.
• a (meth)acrylate compound or a urethane (meth)acrylate compound having an acid group is also preferable.
• a plasticizer may be used individually by 1 type, and may be used 2 or more types.
• the content of the plasticizer is 1% by mass to 70% by mass with respect to the total mass of the thermoplastic resin layer from the viewpoints of the resolution of the thermoplastic resin layer, the adhesion with adjacent layers, and the developability. It is preferably 10% by mass to 60% by mass, and even more preferably 20% by mass to 50% by mass.
• the thermoplastic resin layer may contain a sensitizer.
• the sensitizer is not particularly limited, and includes sensitizers that may be included in the negative photosensitive composition layer described above.
• a sensitizer may be used alone or in combination of two or more.
• the content of the sensitizer can be appropriately selected depending on the purpose, but from the viewpoint of improving the sensitivity to the light source and visibility of the exposed area and the non-exposed area, it is 0.01 with respect to the total mass of the thermoplastic resin layer. % to 5% by mass is preferable, and 0.05% to 1% by mass is more preferable.
• thermoplastic resin layer may contain known additives such as surfactants, if necessary, in addition to the above components. Further, the thermoplastic resin layer is described in paragraphs 0189 to 0193 of JP-A-2014-085643, and the contents described in this publication are incorporated herein.
• the layer thickness of the thermoplastic resin layer is not particularly limited, it is preferably 1 ⁇ m or more, more preferably 2 ⁇ m or more, from the viewpoint of adhesion to adjacent layers.
• the upper limit is not particularly limited, it is preferably 20 ⁇ m or less, more preferably 10 ⁇ m or less, and even more preferably 8 ⁇ m or less from the viewpoint of developability and resolution.
• a method for producing the transfer film is not particularly limited, and a known method can be used.
• a method for producing a transfer film for example, a step of applying a thermoplastic resin composition to the surface of a temporary support to form a coating film, and further drying this coating film to form a thermoplastic resin layer; a step of applying a water-soluble resin composition to the surface of the plastic resin layer to form a coating film, and drying the coating film to form an intermediate layer; and applying a photosensitive composition to the surface of the intermediate layer.
• a coating film and drying the coating film to form a photosensitive composition layer for example, a step of applying a thermoplastic resin composition to the surface of a temporary support to form a coating film, and further drying this coating film to form a thermoplastic resin layer; a step of applying a water-soluble resin composition to the surface of the plastic resin layer to form a coating film, and drying the coating film to form an intermediate layer; and applying a photosensitive composition to the surface of the intermediate layer.
• a protective film may be attached onto the metal salt-containing layer of the laminate produced by the above-described production method.
• a method for producing a transfer film includes a step of providing a protective film so as to be in contact with the surface of the metal salt-containing layer opposite to the temporary support side, whereby the temporary support, the thermoplastic resin layer, the intermediate layer, the photosensitive It is preferred to produce a transfer film comprising a composition layer, a metal salt-containing layer and a protective film. After producing the transfer film by the above production method, the transfer film may be wound up to produce and store a roll-shaped transfer film. The roll-shaped transfer film can be provided as it is to the lamination step with the base material by the roll-to-roll method, which will be described later.
• the method for producing the above-mentioned transfer film is a method of forming a metal salt-containing layer, a photosensitive composition layer and an intermediate layer on a cover film, and then forming a thermoplastic resin layer on the surface of the intermediate layer.
• the method for forming the thermoplastic resin layer on the temporary support is not particularly limited, and known methods can be used. For example, it can be formed by applying a composition for forming a thermoplastic resin layer onto a temporary support and drying it if necessary.
• the composition for forming a thermoplastic resin layer preferably contains the above-described various components for forming the thermoplastic resin layer and a solvent.
• the preferred range of the content of each component with respect to the total solid content of the composition is the same as the preferred range of the content of each component with respect to the total mass of the thermoplastic resin layer. be.
• the solvent is not particularly limited as long as it can dissolve or disperse each component other than the solvent, and known solvents can be used.
• Examples of the solvent include those similar to the solvent contained in the photosensitive composition described later, and the preferred embodiments are also the same.
• the content of the solvent 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 of the composition.
• 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.
• known coating methods slit coating, spin coating, curtain coating, inkjet coating, etc. mentioned.
• the water-soluble resin composition preferably contains various components and a solvent for forming the intermediate layer (water-soluble resin layer) described above.
• the preferred range of the content of each component with respect to the total solid content of the composition is the same as the preferred range of the content of each component with respect to the total mass of the water-soluble resin layer described above.
• the solvent is not particularly limited as long as it can dissolve or disperse the water-soluble resin, preferably at least one selected from the group consisting of water and water-miscible organic solvents, water or water and water-miscible organic solvents A mixed solvent with a solvent is more preferable.
• water-miscible organic solvents include alcohols having 1 to 3 carbon atoms, acetone, ethylene glycol, and glycerin, with alcohols having 1 to 3 carbon atoms being preferred, and methanol or ethanol being more preferred.
• a solvent may be used individually by 1 type, and may be used 2 or more types.
• the content of the solvent is preferably 50 parts by mass to 2,500 parts by mass, more preferably 50 parts by mass to 1,900 parts by mass, and 100 parts by mass to 900 parts by mass with respect to 100 parts by mass of the total solid content of the composition. Part is more preferred.
• the method for forming the water-soluble resin layer is not particularly limited as long as it is a method capable of forming a layer containing the above components.
• known coating methods slit coating, spin coating, curtain coating, inkjet coating, etc. mentioned.
• Photosensitive composition and method for forming photosensitive composition layer In terms of excellent productivity, components constituting the photosensitive composition layer described above (e.g., binder polymer, polymerizable compound, and polymerization initiator, etc.), and coating using a photosensitive composition containing a solvent preferably formed by law.
• the transfer film is produced by coating a photosensitive composition on the intermediate layer to form a coating film, and drying the coating film at a predetermined temperature to form a photosensitive composition layer. It is preferably a method of forming.
• the photosensitive composition preferably contains various components and a solvent for forming the photosensitive composition layer described above.
• the preferred range of the content of each component with respect to the total solid content of the composition is the same as the preferred range of the content of each component with respect to the total mass of the photosensitive composition layer described above.
• the solvent is not particularly limited as long as it can dissolve or disperse each component other than the solvent, and known solvents can be used.
• alkylene glycol ether solvents for example, alkylene glycol ether solvents, alkylene glycol ether acetate solvents, alcohol solvents (methanol, ethanol, etc.), ketone solvents (acetone, methyl ethyl ketone, etc.), aromatic hydrocarbon solvents (toluene, etc.), aprotic polar Examples include solvents (N,N-dimethylformamide, etc.), cyclic ether solvents (tetrahydrofuran, etc.), ester solvents (n-propyl acetate, etc.), amide solvents, lactone solvents, and mixed solvents containing two or more of these.
• the solvent preferably contains at least one selected from the group consisting of alkylene glycol ether solvents and alkylene glycol ether acetate solvents.
• a mixed solvent containing at least one selected from the group consisting of alkylene glycol ether solvents and alkylene glycol ether acetate solvents and at least one selected from the group consisting of ketone solvents and cyclic ether solvents is more preferable.
• a mixed solvent containing at least one selected from the group consisting of alkylene glycol ether solvents and alkylene glycol ether acetate solvents, and at least a ketone solvent is more preferable.
• alkylene glycol ether solvents include ethylene glycol monoalkyl ether, ethylene glycol dialkyl ether, propylene glycol monoalkyl ether (propylene glycol monomethyl ether, etc.), propylene glycol dialkyl ether, diethylene glycol dialkyl ether, dipropylene glycol monoalkyl ether, and Dipropylene glycol dialkyl ethers may be mentioned.
• Alkylene glycol ether acetate solvents include, for example, ethylene glycol monoalkyl ether acetate, propylene glycol monoalkyl ether acetate, diethylene glycol monoalkyl ether acetate, and dipropylene glycol monoalkyl ether acetate.
• Ketone solvents include acetone, 2-butanone, 2-heptanone, cyclohexanone and the like, with 2-butanone being preferred.
• the solvent the solvent described in paragraphs 0092 to 0094 of WO 2018/179640, and the solvent described in paragraph 0014 of JP 2018-177889 may be used, the contents of which are herein. incorporated into.
• a solvent may be used individually by 1 type, and may be used 2 or more types.
• the content of the solvent is preferably 50 parts by mass to 1,900 parts by mass, more preferably 100 parts by mass to 1200 parts by mass, and further 100 parts by mass to 900 parts by mass with respect to 100 parts by mass of the total solid content of the composition. preferable.
• Examples of methods for applying the photosensitive composition include printing, spraying, roll coating, bar coating, curtain coating, spin coating, and die coating (that is, slit coating).
• Heat drying and reduced pressure drying are preferable as a method for drying the coating film of the photosensitive composition.
• the drying temperature is preferably 80° C. or higher, more preferably 90° C. or higher.
• the upper limit thereof is preferably 130° C. or lower, more preferably 120° C. or lower. Drying can also be performed by changing the temperature continuously.
• the drying time is preferably 20 seconds or longer, more preferably 40 seconds or longer, and even more preferably 60 seconds or longer.
• the upper limit is not particularly limited, it is preferably 600 seconds or less, more preferably 300 seconds or less.
• the metal salt-containing composition preferably contains various components and a solvent for forming the metal salt-containing layer described above.
• the preferred range of the content of each component with respect to the total solid content of the composition is the same as the preferred range of the content of each component with respect to the total mass of the metal salt-containing layer.
• the metal salt-containing composition preferably contains a solvent from the viewpoint of adjusting the viscosity of the composition to improve productivity and from the viewpoint of obtaining a uniform conductive layer with low resistance.
• the boiling point of the solvent is preferably 200°C or lower, more preferably 180°C or lower, and even more preferably 150°C or lower.
• the boiling point of the solvent having a large mass ratio is preferably within the above range, and it is more preferable that the boiling points of all the solvents used are within the above range.
• alcohol compounds include methanol, ethanol, isopropanol, butanol, 2-butanol, t-butanol, methoxyethanol, and alcohols having an ether group (ethylene glycol, diethylene glycol monomethyl ether, 1-methoxy-2-propanol, etc.).
• Amide compounds include N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, N-ethylpyrrolidone and the like.
• Ketone compounds include acetone, 2-butanone, methyl isobutyl ketone, cyclohexanone, etc.
• Ether compounds include, for example, hexylmethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, triethylene glycol dimethyl ether, triethylene glycol diethyl ether, tetrahydrofuran. , tetrahydropyran, 1,4-dioxane and the like.
• ester compounds include methyl formate, ethyl formate, butyl formate, methyl acetate, ethyl acetate, butyl acetate, methyl propionate, ethyl propionate, butyl propionate, ⁇ -butyrolactone, and ethyl lactate.
• aliphatic hydrocarbon compounds examples include n-pentane, n-hexane, n-heptane, n-octane, n-nonane, n-decane, n-undecane, n-dodecane, cyclohexane, and decalin.
• aromatic hydrocarbon compounds examples include benzene, toluene, xylene, ethylbenzene, n-propylbenzene, i-propylbenzene, n-butylbenzene, mesitylene, chlorobenzene, and dichlorobenzene.
• a solvent containing water is preferred, a mixed solvent of water and a water-soluble organic solvent is preferred, and a mixed solvent of water and alcohol is more preferred.
• the content of the solvent contained in the metal salt-containing composition of the present embodiment ranges from 0% by mass to 99.5% by mass, and It is preferably in the mass % range.
• the solvent is not particularly limited as long as it can dissolve or disperse the water-soluble resin, preferably at least one selected from the group consisting of water and water-miscible organic solvents, water or water and water-miscible organic solvents A mixed solvent with a solvent is more preferable.
• the method for forming the metal salt-containing layer is not particularly limited as long as it is a method capable of forming a layer containing the above components.
• known coating methods slit coating, spin coating, curtain coating, inkjet coating, etc. mentioned.
• a protective film may be attached to the metal salt-containing layer.
• a method for laminating the protective film to the metal salt-containing layer is not particularly limited, and includes known methods. Apparatuses for bonding the protective film to the metal salt-containing layer include known laminators such as a vacuum laminator and an autocut laminator. Preferably, the laminator is equipped with any heatable roller, such as a rubber roller, and can be applied with pressure and heat.
• the method for forming a conductor pattern of the present disclosure includes the steps of preparing a transfer film having a temporary support, a photosensitive composition layer, and a layer containing a metal salt in this order, and laminating the transfer film on a substrate. Then, a step of forming a laminate having a substrate, a layer containing a metal salt, a photosensitive composition layer and the temporary support in this order, a step of patternwise exposing the photosensitive composition layer, and a photosensitive composition forming a resist pattern by developing the layer to expose a portion of the layer containing the metal salt or the seed layer; and forming a metal layer on the exposed seed layer, in this order.
• the method for forming a conductor pattern of the present disclosure includes the steps of preparing a transfer film having, in this order, a temporary support, a photosensitive composition layer, and a layer containing a metal salt (metal salt-containing layer); is laminated on a substrate to form a laminate having a substrate, a layer containing a metal salt, a photosensitive composition layer and a temporary support in this order, and the metal salt contained in the metal salt-containing layer is a step of reducing to form a seed layer; a step of patternwise exposing the photosensitive composition layer; and a step of developing the photosensitive composition layer to form a resist pattern and expose a portion of the seed layer. , and forming a metal layer on the exposed seed layer, in this order.
• the method of forming a conductor pattern according to the present disclosure comprises the steps of: removing the resist pattern after the step of forming a metal layer on the exposed seed layer; and removing the seed layer exposed by removing the resist pattern. You can have in order.
• the method for forming a conductor pattern of the present disclosure can have a step of peeling off the temporary support before or after the step of patternwise exposing the photosensitive composition layer.
• the transfer film can be produced by the method described above.
• the method for forming a conductor pattern of the present disclosure includes the steps of laminating a transfer film on a substrate to form a laminate having a substrate, a metal salt-containing layer, a photosensitive composition layer, and a temporary support in this order.
• the transfer film has a thermoplastic resin layer and an intermediate layer
• the laminate has a substrate, a metal salt-containing layer, a photosensitive composition layer, an intermediate layer, a thermoplastic resin layer and a temporary support in this order
• Transfer film is provided with a protective film, lamination is performed after peeling off the protective film.
• the lamination method is not particularly limited, and for example, it is preferable to stack the surface of the metal salt-containing layer on the base material, and apply pressure and heat using rolls or the like.
• a known laminator such as a vacuum laminator, an autocut laminator, etc. can be used for lamination.
• the lamination temperature is not particularly limited, it is preferably 70° C. to 130° C., for example.
• Examples of base materials include resin base materials, glass base materials, and semiconductor base materials.
• Examples of resin substrates include polyimide substrates, polyester substrates (eg, polyethylene terephthalate substrates and polyethylene naphthalate substrates), polycarbonate substrates, acrylic resin substrates, and the like.
• the resin base material may be a liquid crystal polymer (LCP) base material.
• LCP substrates tend to have poor adhesion to seed layers.
• the metal salt contained in the metal salt-containing layer is reduced to form a seed layer. do. According to the above method, the adhesion between the LCP substrate and the seed layer can be improved.
• the thickness of the substrate is preferably 5 ⁇ m to 200 ⁇ m, more preferably 10 ⁇ m to 100 ⁇ m.
• the seed layer is formed by reducing the metal salt contained in the metal salt-containing layer after the step of forming the laminate and before the step of forming the metal layer. have a process.
• the step of forming the seed layer may be performed after the step of forming the laminate and before the step of forming the metal layer, for example, after the step of forming the laminate and after the photosensitive composition It may be carried out before the step of pattern-exposing the layer, or may be carried out after the step of exposing a portion of the metal salt-containing layer and before the step of forming the metal layer.
• Reduction of the metal salt can be performed by heating.
• the heating temperature of the metal salt-containing layer is preferably 80°C to 200°C, more preferably 100°C to 150°C.
• the heating time of the metal salt-containing layer is preferably 5 to 60 minutes, more preferably 10 to 40 minutes.
• the method of forming a conductor pattern of the present disclosure has a step of patternwise exposing a photosensitive composition layer.
• patterned exposure refers to exposure in a patterned form, that is, exposure in which an exposed portion and a non-exposed portion are present.
• the positional relationship between the exposed area and the unexposed area in pattern exposure is not particularly limited, and is adjusted as appropriate.
• the exposure of the photosensitive composition layer may be performed from the side opposite to the substrate side, or may be performed from the substrate side.
• the light source for pattern exposure can be appropriately selected and used as long as it can irradiate at least light in a wavelength range capable of curing the photosensitive composition layer (for example, 365 nm or 405 nm).
• the dominant wavelength of the exposure light for pattern exposure is preferably 365 nm. Note that the dominant wavelength is the wavelength with the highest intensity.
• Examples of light sources include various lasers, light emitting diodes (LEDs), ultrahigh pressure mercury lamps, high pressure mercury lamps, and metal halide lamps.
• the exposure amount is preferably 5 mJ/cm 2 to 200 mJ/cm 2 , more preferably 10 mJ/cm 2 to 200 mJ/cm 2 .
• pattern exposure may be performed after peeling off the temporary support or before peeling off the temporary support. That is, the pattern exposure may be performed without intervening the temporary support, or the pattern exposure may be performed through the temporary support.
• the temporary support should be peeled off. It is preferable to expose without From the viewpoint of improving resolution by suppressing scattering of exposure light by the temporary support and suppressing diffraction of light transmitted through the mask, exposure is preferably performed after peeling off the temporary support.
• the pattern exposure may be exposure through a mask, or may be direct exposure using a laser or the like.
• mask substrates for exposure through an exposure mask include quartz masks, soda-lime glass masks, and film masks.
• the quartz mask is preferable because it has excellent dimensional accuracy
• the film mask is preferable because it is easy to increase the size.
• a polyester film is preferable, and a polyethylene terephthalate film is more preferable.
• a specific example of the film mask substrate is XPR-7S SG (manufactured by FUJIFILM Global Graphic Systems Co., Ltd.).
• the method for forming a conductor pattern of the present disclosure includes the step of forming a resist pattern by developing a photosensitive composition layer to expose a portion of the layer containing the metal salt or the seed layer.
• the exposed layer is the seed layer, and when performed after the development of the photosensitive composition layer, the exposed The layer is a metal salt-containing layer.
• Alkaline compounds that can be contained in the alkaline aqueous solution include, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, and choline (2-hydroxyethyltrimethylammonium hydroxide).
• Development methods include, for example, puddle development, shower development, spin development, and dip development.
• Examples of the developer suitably used in the present specification include the developer described in paragraph [0194] of International Publication No. 2015/093271. Examples include the development method described in paragraph [0195] of 2015/093271.
• the resist pattern obtained by the above development may be exposed (hereinafter also referred to as post-exposure) and/or heated (hereinafter also referred to as post-baking).
• post-exposure When performing both post-exposure and post-baking, post-baking is preferably performed after post-exposure.
• the exposure amount of post-exposure is preferably 100 mJ/cm 2 to 5000 mJ/cm 2 , more preferably 200 mJ/cm 2 to 3000 mJ/cm 2 .
• the post-baking temperature is preferably 80°C to 250°C, more preferably 90°C to 160°C.
• the post-baking time is preferably 1 minute to 180 minutes, more preferably 10 minutes to 60 minutes.
• the method of forming a conductor pattern of the present disclosure includes forming a metal layer on the exposed seed layer.
• a patterned interconnect can be formed by forming a metal layer over the exposed seed layer.
• Metal layers include metals such as copper, silver, tin, nickel, antimony, indium, etc., with copper or silver being preferred.
• the metal content in the metal layer is preferably 70% by mass or more, more preferably 80% by mass or more, and even more preferably 90% by mass or more.
• the upper limit of the metal content is not particularly limited, and may be 100% by mass or less.
• the formation of the metal layer is not particularly limited, and can be carried out using conventionally known methods such as electroplating and electroless plating.
• the method of forming a conductor pattern of the present disclosure can have the step of removing the resist pattern after the step of forming the metal layer on the exposed seed layer.
• a method for removing the resist pattern is not particularly limited, and a conventionally known stripping solution can be used.
• the liquid temperature of the stripping solution is preferably 30°C to 80°C, more preferably 50°C to 80°C.
• stripping solutions include removal solutions obtained by dissolving an inorganic alkaline component or an organic alkaline component in water, dimethylsulfoxide, N-methylpyrrolidone, or a mixed solution thereof.
• inorganic alkaline components include sodium hydroxide and potassium hydroxide.
• Organic alkali components include primary amine compounds, secondary amine compounds, tertiary amine compounds and quaternary ammonium salt compounds.
• the method of forming a conductor pattern according to the present disclosure can include a step of removing the seed layer exposed by removing the resist pattern (hereinafter also referred to as an etching step).
• an etching step known methods can be applied, for example, the method described in paragraphs [0209] to [0210] of JP-A-2017-120435, paragraphs [0048] to JP-A-2010-152155. [0054], etc., a wet etching method in which the substrate is immersed in an etchant, and a dry etching method such as plasma etching.
• an acidic or alkaline etchant may be appropriately selected according to the object to be etched.
• acidic etching solutions include aqueous solutions of acidic components alone selected from hydrochloric acid, sulfuric acid, nitric acid, acetic acid, hydrofluoric acid, oxalic acid and phosphoric acid, and acidic components, ferric chloride, ammonium fluoride and A mixed aqueous solution with a salt selected from potassium permanganate can be mentioned.
• the acidic component may be a combination of multiple acidic components.
• Alkaline etchants include aqueous solutions of alkali components alone selected from sodium hydroxide, potassium hydroxide, ammonia, organic amines, and salts of organic amines (tetramethylammonium hydroxide, etc.), and alkali components and salts. (potassium permanganate, etc.).
• the alkaline component may be a component obtained by combining a plurality of alkaline components.
• the method for forming a conductive pattern of the present disclosure has a step of peeling off the temporary support after the step of forming the laminate and before the step of exposing the layer containing the metal salt or the seed layer. can be done.
• the peeling method is not particularly limited, and a mechanism similar to the cover film peeling mechanism described in paragraphs [0161] to [0162] of JP-A-2010-072589 can be used.
• the method of forming a conductor pattern according to the present disclosure may include arbitrary steps (other steps) other than the steps described above.
• steps other steps
• the step of forming a new conductive layer on the insulating film described in paragraph [0172] of International Publication No. WO2019/022089 may be mentioned, but is not limited to these steps.
• the method of forming a conductor pattern of the present disclosure preferably includes the steps of forming an insulating film on the surface of the conductor pattern formed as described above, and forming a new seed layer on the surface of the insulating film. .
• the first conductor pattern and the second conductor pattern insulated from the first conductor pattern can be formed.
• the process of forming the insulating film is not particularly limited, and a known method of forming a permanent film can be used.
• an insulating film having a desired pattern may be formed by photolithography using an insulating photosensitive material.
• the step of forming a new seed layer on the insulating film is not particularly limited, and may be performed by using the transfer film described above.
• a conductor pattern formed by the method for forming a conductor pattern of the present disclosure can be applied to various devices.
• the device provided with the conductor pattern include a display device, a printed wiring board, a semiconductor package, an input device, and a touch panel, and a printed wiring board and a semiconductor package are preferable.
• the input device can be applied to display devices such as an organic EL display device and a liquid crystal display device.
• V-601 was added three times at intervals of 1 hour. After that, the reaction was further continued for 3 hours. After that, it was diluted with 160.7 g of propylene glycol monomethyl ether acetate and 233.3 g of propylene glycol monomethyl ether. The temperature of the reaction solution was raised to 100° C. under an air stream, and 1.8 g of tetraethylammonium bromide and 0.86 g of p-methoxyphenol were added. 71.9 g of glycidyl methacrylate (manufactured by NOF Corporation, Blenmer GH) was added dropwise to this over 20 minutes. This was reacted at 100° C. for 7 hours.
• glycidyl methacrylate manufactured by NOF Corporation, Blenmer GH
• Propylene glycol monomethyl ether acetate/propylene glycol monomethyl ether (mass ratio 50/50) was diluted to a solid content concentration of 30.0 mass % to obtain a solution of alkali-soluble resin A-2.
• the weight average molecular weight in terms of standard polystyrene in GPC was 18,000.
• Resin A-2, resin A-4 and resin A-5 were synthesized using the same method as the above method (30.0% by mass solution, solvent: propylene glycol monomethyl ether acetate/propylene glycol monomethyl ether (mass ratio 50/50)).
• the amount of residual monomers measured using gas chromatography on the obtained resin was less than 0.1% by mass based on the solid content of the resin for any monomer.
• Resins A1 to A5 Represented by the following chemical formulas, and Mw, Mw/Mn, and acid values are as follows. The number written next to the parentheses in each chemical formula indicates the content (% by mass) of each structural unit.
• Example 1 [Production of transfer film]
• a temporary support (16 ⁇ m thick polyethylene terephthalate (PET) film (product name “Lumirror (registered trademark) 16KS40”, manufactured by Toray Industries, Inc.)
• the intermediate layer-forming composition was applied using a bar coater, after drying. was applied to a thickness of 1.0 ⁇ m to form a coating film, which was dried at 90° C. using an oven to form an intermediate layer.
• the photosensitive composition K1 was applied to the surface of the intermediate layer using a bar coater so that the thickness after drying was 3.0 ⁇ m to form a coating film.
• the coating film was dried at 80° C. using an oven to form a photosensitive composition layer (negative photosensitive composition layer).
• the metal salt-containing composition S1 is applied to the surface of the photosensitive composition layer so that the thickness after drying is 300 nm, dried at 80° C. for 1 minute, and brought into direct contact with the photosensitive composition layer.
• a metal salt-containing layer (layer for seed layer formation) was formed.
• a 16 ⁇ m thick PET film (product name “Lumirror (registered trademark) 16KS40” manufactured by Toray Industries, Inc.) was pressed onto the seed layer forming layer to form a protective film and obtain a transfer film.
• the protective film is peeled off from the transfer film, and a substrate containing a liquid crystal polymer (trade name “Vecstar (registered trademark) CTQ-50” manufactured by Kuraray Co., Ltd., thickness 50 ⁇ m, hereinafter referred to as LCP substrate).
• LCP substrate a substrate containing a liquid crystal polymer (trade name “Vecstar (registered trademark) CTQ-50” manufactured by Kuraray Co., Ltd., thickness 50 ⁇ m, hereinafter referred to as LCP substrate).
• LCP substrate liquid crystal polymer
• the lamination conditions were a lamination roll temperature of 100° C., a linear pressure of 3 N/cm, and a conveying speed of 2 m/min.
• the laminate A1 was heated in an oven at 120° C.
• Example 25 A transfer film and a laminate were produced in the same manner as in Example 1, except that at least one of the photosensitive composition and the metal salt-containing composition was changed as shown in Table 4.
• Example 23 and Example 24> A transfer film and a laminate were produced in the same manner as in Example 1, except that the thickness of the photosensitive composition layer and the thickness of the seed layer forming layer were changed as shown in Table 4.
• a transfer film (hereinafter referred to as a comparative transfer film) was produced in the same manner as in Example 1, except that the seed layer forming layer was not formed.
• a copper seed layer (thickness: 300 nm) was formed on the LCP substrate by sputtering.
• the protective film was peeled off from the comparative transfer film and laminated on the seed layer to obtain a laminate B having a laminated structure of temporary support/intermediate layer/photosensitive composition layer/seed layer/LCP substrate.
• the lamination conditions were the same as in Example 1.
• the protective film is peeled off from the comparative transfer film, laminated on the seed layer forming layer, and a laminate having a laminated structure of temporary support/intermediate layer/photosensitive composition layer/seed layer forming layer/LCP substrate Body C1 was obtained.
• the lamination conditions were the same as in Example 1.
• the laminate C1 was heated in an oven at 120° C. for 20 minutes under a nitrogen stream to reduce the metal salt in the seed layer forming layer to obtain a seed layer.
• a laminate C2 having a laminate structure of temporary support/intermediate layer/photosensitive composition layer/seed layer/LCP substrate was obtained.
• B The ratio of the area of the seed layer separated from the LCP substrate to the total area of the seed layer was more than 0% and less than 5%.
• C The ratio of the area of the seed layer separated from the LCP substrate to the total area of the seed layer was 5% or more and less than 15%.
• D The ratio of the area of the seed layer separated from the LCP substrate to the total area of the seed layer was 15% or more and less than 35%.
• E The ratio of the area of the seed layer separated from the LCP substrate to the total area of the seed layer was 35% or more.
• the laminate is irradiated with light using a high-pressure mercury lamp exposure machine (product name “MAP-1200L”, manufactured by Dainippon Kaken Co., Ltd., main wavelength: 365 nm), and a photosensitive composition is obtained.
• the layer was patternwise exposed. The exposure amount was adjusted so that the resist pattern obtained after development was a line-and-space pattern (line line width 2 ⁇ m, space line width 4 ⁇ m).
• the photosensitive composition layer was developed using a 1.0% by mass sodium carbonate aqueous solution at 28° C. as a developer. Specifically, shower processing using the developer was performed for 30 seconds, AirKnife processing was performed, shower processing using pure water was performed for 30 seconds, and AirKnife processing was performed. As a result, a laminate having a resist pattern of a line-and-space pattern (line width 2 ⁇ m, space line width 4 ⁇ m) was obtained. In addition, it was confirmed that the seed layer included in the laminate was exposed in the space region of the pattern.
• the laminate having the resist pattern was immersed in a copper sulfate plating solution (copper sulfate 75 g/L, sulfuric acid 190 g/L, chloride ion 50 ppm by mass, copper glimmer PCM (manufactured by Meltex) 5 mL/L) at 1 A/dm.
• a metal layer was formed on the surface of the laminate by performing a copper plating treatment under the conditions of No. 2 .
• the resist pattern was removed by immersing it in a 1% by mass potassium hydroxide aqueous solution (pH 13.5) at 50°C.
• the seed layer exposed by removing the resist pattern was removed using an aqueous solution containing 0.1% by mass sulfuric acid and 0.1% by mass hydrogen peroxide to form a conductor pattern.
• the cross-sectional shape of the conductor pattern composed of the metal layer is observed with a scanning electron microscope, and the ratio of the line width at the bottom of the pattern to the line width at the top of the pattern (line width at the bottom of the pattern/line width at the top of the pattern) is determined.
• the conductive pattern formability was evaluated according to the following evaluation criteria. The evaluation results are summarized in Table 4. The closer the value is to 1, the smaller the line width difference between the pattern bottom and the pattern top, indicating that the conductor pattern is well formed. (Evaluation criteria) A: The line width at the bottom of the pattern/the line width at the top of the pattern was 0.95 or more and 1.00 or less.
• B The line width at the bottom of the pattern/the line width at the top of the pattern was 0.9 or more and less than 0.95.
• C The line width at the bottom of the pattern/the line width at the top of the pattern was 0.8 or more and less than 0.9.
• D The line width at the bottom of the pattern/the line width at the top of the pattern was less than 0.8.
• the conductor pattern of the example manufactured by using the transfer film having the temporary support, the photosensitive composition layer, and the seed layer forming layer in this order has the seed layer forming layer.
• Examples 1A to 25A> A transfer film and a laminate were produced in the same manner as in Example 1, except that the temporary support and protective film used in the production of the transfer film were changed to the following materials. Adhesion and conductor pattern formability were evaluated in the same manner as in Example 1, and the results are summarized in Table 5.
• Temporary support product name “Cosmo Shine (registered trademark) A4160”, manufactured by Toyobo Co., Ltd., thickness 50 ⁇ m
• PET film Protective film product name “Alphan (registered trademark) E-210F”, Oji F-Tex Co., Ltd., thickness 50 ⁇ m
• Examples 1B to 25B> A transfer film and a laminate were produced in the same manner as in Example 1, except that the temporary support and protective film used in the production of the transfer film were changed to the following materials. Adhesion and conductor pattern formability were evaluated in the same manner as in Example 1, and the results are summarized in Table 6.
• Temporary support product name “Cosmo Shine (registered trademark) A4360”, manufactured by Toyobo Co., Ltd., thickness 38 ⁇ m
• PET film Protective film product name “Alphan (registered trademark) FG-201”, Oji F-Tex Co., Ltd., thickness 30 ⁇ m
• Examples 1C to 25C> A transfer film and a laminate were produced in the same manner as in Example 1, except that the temporary support and protective film used in the production of the transfer film were changed to the following materials. Adhesion and conductor pattern formability were evaluated in the same manner as in Example 1, and the results are summarized in Table 7.
• Temporary support product name “Lumirror (registered trademark) #38-U48”, manufactured by Toray Industries, Inc., thickness 38 ⁇ m, PET film
• Protective film product name “Alphan (registered trademark) E-210F”, Oji F-Tex Co., Ltd., thickness 50 ⁇ m, polypropylene film
• Examples 1D to 25D> A transfer film and a laminate were produced in the same manner as in Example 1, except that the temporary support and protective film used in the production of the transfer film were changed to the following materials. Adhesion and conductor pattern formability were evaluated in the same manner as in Example 1, and the results are summarized in Table 8.
• Temporary support product name “Lumirror (registered trademark) #75-U34”, manufactured by Toray Industries, Inc., thickness 75 ⁇ m
• PET film ⁇
• Protective film product name “Alphan (registered trademark) FG-201”, Oji F-Tex Co., Ltd., thickness 30 ⁇ m, polypropylene film
• Examples 1E to 25E> A transfer film and a laminate were produced in the same manner as in Example 1, except that the temporary support and protective film used in the production of the transfer film were changed to the following materials. Adhesion and conductor pattern formability were evaluated in the same manner as in Example 1, and the results are summarized in Table 9.
• Temporary support product name “Lumirror (registered trademark) 16FB40”, manufactured by Toray Industries, Inc., thickness 16 ⁇ m, PET film
• Protective film product name “Alphan (registered trademark) E-210F”, Oji F-Tex ( Co., Ltd., thickness 50 ⁇ m, polypropylene film
• Examples 1F to 25F> A transfer film and a laminate were produced in the same manner as in Example 1, except that the temporary support and protective film used in the production of the transfer film were changed to the following materials. Adhesion and conductor pattern formability were evaluated in the same manner as in Example 1, and the results are summarized in Table 10.
• Temporary support Product name “Lumirror (registered trademark) 16FB40”, manufactured by Toray Industries, Inc., thickness 16 ⁇ m, PET film
• Protective film Product name “Alphan (registered trademark) FG-201”, Oji F-Tex ( Co., Ltd., thickness 30 ⁇ m, polypropylene film
• Examples 1G to 25G> A transfer film and a laminate were produced in the same manner as in Example 1, except that the temporary support and protective film used in the production of the transfer film were changed to the following materials. Adhesion and conductor pattern formability were evaluated in the same manner as in Example 1, and the results are summarized in Table 11.
• Temporary support Product name “Lumirror (registered trademark) 16KS40”, manufactured by Toray Industries, Inc., thickness 16 ⁇ m, PET film
• Protective film Product name “Alphan (registered trademark) FG-201”, Oji F-Tex ( Co., Ltd., thickness 30 ⁇ m, polypropylene film

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• 2022
  • 2022-10-17 JP JP2023576618A patent/JPWO2023145156A1/ja not_active Abandoned
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