Classifications

• • 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
• • H—ELECTRICITY
  • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
  • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
  • H05K3/00—Apparatus or processes for manufacturing printed circuits
  • H05K3/02—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding
  • H05K3/06—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding the conductive material being removed chemically or electrolytically, e.g. by photo-etch process

Definitions

• the present invention relates to a transfer film, a laminate, a method for manufacturing a laminate having a resist pattern, and a method for manufacturing a laminate having a conductor pattern.
• a method for obtaining circuit wiring and the like it is common to use a method of performing an etching process using a resist pattern formed from a photosensitive composition. Specifically, for example, a photosensitive composition layer is formed on a substrate having a conductive layer, the photosensitive composition layer is exposed to light in a pattern, and then developed to form a pattern on the conductive layer, and the pattern is formed. An example of this method is to etch the exposed portion of the conductive layer.
• Patent Document 1 discloses a photosensitive element (transfer film) comprising a support film (temporary support), an intermediate layer, and a photosensitive layer (photosensitive composition layer) in this order, and the thickness of the support film is is 20 ⁇ m or more, and the number of particles with a diameter of 5 ⁇ m or more contained in the support film is 30 particles/mm 2 or less.
• the photosensitive composition layer of the transfer film and the object to be etched (object to be laminated) are laminated so that they are in contact with each other.
• a photosensitive composition layer is formed on the object to be laminated.
• the adhesion between the object to be laminated and the photosensitive composition layer is high in terms of handling and the like.
• exposure and development are performed to form a resist pattern. When carrying out the development process, it is required that the generation of residues (development residues) in the photosensitive composition layer be suppressed in order to obtain a designed pattern.
• the present inventors investigated the transfer film described in Patent Document 1 and found that it meets the standards required these days in terms of adhesion between the object to be laminated and the photosensitive composition layer and suppression of the generation of development residue. It was discovered that this had not been achieved. In particular, when the object to be laminated contains silver, further improvements have been sought in achieving both of the above properties.
• the present invention provides excellent adhesion between the photosensitive composition layer and the object to be laminated when laminated to the object, and suppresses the generation of residue in the development process performed when forming the resist pattern.
• Our goal is to provide transfer films.
• Another object of the present invention is to provide a laminate, a method for manufacturing a laminate having a resist pattern, and a method for manufacturing a laminate having a conductor pattern.
• the present inventor has completed the present invention as a result of intensive studies to solve the above problems. That is, it has been found that the above problem can be solved by the following configuration.
• a transfer film having a temporary support and a photosensitive composition layer contains an alkali-soluble resin, a polymerizable compound having an ethylenically unsaturated group, and a photopolymerization initiator, A transfer film, wherein the content of phosphate ions in the photosensitive composition layer is 10.0 mass ppm or less based on the total mass of the photosensitive composition layer.
• a transfer film comprising a temporary support and a photosensitive composition layer,
• the photosensitive composition layer contains an alkali-soluble resin, a polymerizable compound having an ethylenically unsaturated group, and a photopolymerization initiator,
• a transfer film wherein the content of nitrate ions in the photosensitive composition layer is 10.0 mass ppm or less based on the total mass of the photosensitive composition layer.
• a transfer film having a temporary support and a photosensitive composition layer contains an alkali-soluble resin, a polymerizable compound having an ethylenically unsaturated group, and a photopolymerization initiator, A transfer film, wherein the content of iodide ions in the photosensitive composition layer is 2.0 to 20.0 ppm by mass based on the total mass of the photosensitive composition layer.
• a transfer film having a temporary support and a photosensitive composition layer contains an alkali-soluble resin, a polymerizable compound having an ethylenically unsaturated group, and a photopolymerization initiator, A transfer film, wherein the content of bromide ions in the photosensitive composition layer is 4.0 to 20.0 ppm by mass based on the total mass of the photosensitive composition layer.
• a laminate comprising the transfer film according to any one of [1] to [13], a conductive layer, and a substrate in this order.
• the surface of the photosensitive composition layer of the transfer film according to any one of [1] to [13] on the side opposite to the temporary support side is the conductive layer of the substrate having a conductive layer on the surface.
• a laminate having a resist pattern further comprising a temporary support peeling process of peeling off the temporary support between the lamination process and the exposure process, or between the exposure process and the development process.
• the adhesion between the photosensitive composition layer and the object to be laminated is excellent when the photosensitive composition layer is laminated to the object, and the generation of residues is suppressed in the development process performed when forming a resist pattern.
• a laminate, a method for manufacturing a laminate having a resist pattern, and a method for manufacturing a laminate having a conductor pattern can also be provided.
• FIG. 1 is a schematic diagram showing an example of the structure of a transfer film used in the manufacturing method of the present invention.
• a numerical range expressed using " ⁇ " means a range that includes the numerical values written before and after " ⁇ " as lower and upper limits.
• the upper limit or lower limit of a certain numerical range may be replaced with the upper or lower limit of another numerical range described in stages. .
• the upper limit or lower limit described in a certain numerical range may be replaced with the value shown in the Examples.
• process is used not only to refer to an independent process, but also to include it in the term even if the process cannot be clearly distinguished from other processes, as long as the intended purpose of the process is achieved. .
• transmittance means that the average transmittance of visible light with a wavelength of 400 to 700 nm is 80% or more, preferably 90% or more.
• transmittance is a value measured using a spectrophotometer, and can be measured using, for example, a spectrophotometer U-3310 manufactured by Hitachi, Ltd.
• weight average molecular weight (Mw) and number average molecular weight (Mn) are expressed as columns such as TSKgel GMHxL, TSKgel G4000HxL, or TSKgel G2000HxL (all brand names manufactured by Tosoh Corporation). ), using THF (tetrahydrofuran) as the eluent, a differential refractometer as the detector, and polystyrene as the standard material, and the value converted using polystyrene as the standard material measured with a gel permeation chromatography (GPC) analyzer.
• GPC gel permeation chromatography
• the ratio of the constituent units of a polymer is a mass ratio.
• the molecular weight of a compound having a molecular weight distribution is the weight average molecular weight (Mw).
• Mw weight average molecular weight
• the content of metal elements is a value measured using an inductively coupled plasma (ICP) spectrometer.
• ICP inductively coupled plasma
• (meth)acrylic is a concept that includes both acryl and methacryl
• (meth)acryloxy group is a concept that includes both acryloxy and methacryloxy groups.
• 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 and a liquid temperature of 22° C. is 0.1 g or more. Therefore, for example, water-soluble resin is intended to be a resin that satisfies the above-mentioned solubility conditions.
• the "solid content" of a photosensitive composition means a component forming a photosensitive composition layer formed using the photosensitive composition
• the "solid content” of the photosensitive composition means a component that forms a photosensitive composition layer formed using the photosensitive composition.
• water, etc. means all components excluding the solvent.
• liquid components are also considered solid components as long as they form a photosensitive composition layer.
• the transfer film of the present invention includes a first embodiment, a second embodiment, a third embodiment, and a fourth embodiment. Each embodiment will be described in detail below.
• excellent adhesion the fact that the adhesion between the photosensitive composition layer and the object to be laminated when laminated to the object to be laminated is simply referred to as "excellent adhesion.”
• the fact that the generation of residues is further suppressed in the development process performed when forming the resist pattern is also simply referred to as "the generation of residues is suppressed.”
• a first embodiment of the transfer film of the present invention is a transfer film having a temporary support and a photosensitive composition layer, wherein the photosensitive composition layer is an alkali-soluble resin, a polymer having an ethylenically unsaturated group, and a photosensitive composition layer. and a photopolymerization initiator, and the content of phosphate ions in the photosensitive composition layer is 10.0 mass ppm or less with respect to the total mass of the photosensitive composition layer. The content of phosphate ions will be detailed later. It is thought that the first embodiment of the transfer film of the present invention has excellent adhesion and suppresses the generation of residues for the following reasons by having the above configuration.
• the content of phosphate ions is less than or equal to a predetermined amount, so it is thought that the surface of the object to be laminated is less likely to be altered and has excellent adhesion. Moreover, it is considered that since the content of phosphate ions is less than or equal to a predetermined amount, ions derived from the object to be bonded are less likely to be generated. It is thought that when the generation of ions derived from the object to be laminated is small, the components of the photosensitive composition layer are less susceptible to effects such as coordination, and as a result, the generation of residue is suppressed.
• the first embodiment of the transfer film may have other layers in addition to the temporary support and the photosensitive composition layer. Examples of other layers include an intermediate layer and a thermoplastic resin layer, which will be described later. Further, the first embodiment of the transfer film may include other members (for example, a protective film, etc.) described below.
• Examples of the configuration of the first embodiment of the transfer film include the following configurations (1) to (3), with configuration (2) being preferred.
• a negative photosensitive composition layer described below or a colored resin layer described below is preferable.
• the maximum width of the undulations in the first embodiment of the transfer film is preferably 300 ⁇ m or less, more preferably 200 ⁇ m or less, and even more preferably 60 ⁇ m or less.
• the lower limit of the maximum width of the waviness is 0 ⁇ m or more, preferably 0.1 ⁇ m or more, and more preferably 1 ⁇ m or more.
• the maximum width of waviness of the first embodiment of the transfer film is a value measured by the following procedure. First, a test sample is prepared by cutting the transfer film in a direction perpendicular to the main surface to a size of 20 cm in length x 20 cm in width.
• the transfer film has a protective film
• the protective film is peeled off.
• the test sample is placed on a stage with a smooth and horizontal surface so that the surface of the temporary support faces the stage.
• the surface of the test sample was scanned with a laser microscope (for example, VK-9700SP manufactured by Keyence Corporation) for a 10 cm square area at the center of the test sample to obtain a three-dimensional surface image. Subtract the minimum concavity height from the maximum convexity height observed in the dimensional surface image.
• the above operation is performed on 10 test samples, and the arithmetic mean value thereof is defined as the "maximum waviness of the transfer film".
• the total thickness of the other composition layers is the same as the photosensitive composition layer. It is preferably 0.1 to 30%, more preferably 0.1 to 20%, based on the total thickness of the material layer.
• the transmittance of the photosensitive composition layer for light at 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 preferably 99.9% or less, more preferably 99.0% or less.
• the transfer film 10 shown in FIG. 1 includes a temporary support 11, a composition layer 17 including an intermediate layer 13 and a photosensitive composition layer 15, and a protective film 19 in this order.
• the transfer film 10 shown in FIG. 1 has an intermediate layer 13 and a protective film 19, it may not have the intermediate layer 13 and the protective film 19.
• the transfer film 10 may have a thermoplastic resin layer between the temporary support 11 and the intermediate layer 13.
• each layer (for example, a photosensitive composition layer, an intermediate layer, etc.) other than the protective film 19 that may be placed on the temporary support 11 is also referred to as a "composition layer.”
• the first embodiment of the transfer film has a temporary support.
• the temporary support is a member that supports the composition layer, and is finally removed by a peeling process.
• 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 is flexible and does not undergo significant deformation, shrinkage, or elongation under pressure or under pressure and heat.
• the film include polyethylene terephthalate film (for example, biaxially oriented polyethylene terephthalate film), polymethyl methacrylate film, cellulose triacetate film, polystyrene film, polyimide film, and polycarbonate film.
• a polyethylene terephthalate film is preferable, and a biaxially stretched polyethylene terephthalate film is more preferable.
• the film used as the temporary support is preferably free from deformation such as wrinkles and scratches.
• the temporary support preferably has high transparency from the viewpoint that pattern exposure can be performed through the temporary support, and the transmittance at wavelengths of 313 nm, 365 nm, 313 nm, 405 nm, and 436 nm is preferably 60% or more. , more preferably 70% or more, still more preferably 80% or more, and most preferably 90% or more. Preferred values of transmittance include, for example, 87%, 92%, 98%, and the like. From the viewpoints of pattern formation properties during pattern exposure through the temporary support and transparency of the temporary support, it is preferable that the haze of the temporary support is small.
• 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.
• the haze of the temporary support is preferably 0.05% or more, more preferably 0.1% or more, from the viewpoint of transportability during production of the temporary support.
• the above haze is total light haze (%) in accordance with JIS K 7136:2000, and can be measured as total light haze using a haze meter (equipment name: HZ-2, manufactured by Suga Test Instruments Co., Ltd.). . From the viewpoints of pattern formation during pattern exposure through the temporary support and transparency of the temporary support, it is preferable that the number of fine particles, foreign matter, and defects contained in the temporary support be small.
• the number of fine particles, foreign matter, and defects with a diameter of 1 ⁇ m or more in the temporary support is preferably 50 pieces/10 mm 2 or less, more preferably 10 pieces/10 mm 2 or less, even more preferably 3 pieces/10 mm 2 or less, and 0. pieces/10 mm 2 is particularly preferred.
• the thickness of the temporary support is not particularly limited, but is preferably 5 to 200 ⁇ m, more preferably 5 to 150 ⁇ m, even more preferably 5 to 50 ⁇ m, and most preferably 5 to 25 ⁇ m from the viewpoint of ease of handling and versatility.
• the thickness of the temporary support is calculated as the average value of five arbitrary points measured by cross-sectional observation using a SEM (Scanning Electron Microscope).
• the surface of the temporary support in contact with the composition layer may be surface-modified by UV irradiation, corona discharge, plasma, etc.
• the exposure amount is preferably 10 mJ/cm 2 to 2000 mJ/cm 2 , more preferably 50 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 Examples include light emitting diodes (LEDs). There are no particular restrictions on the lamp output or illuminance as long as the amount of light irradiation can be within this range.
• the temporary support may be a recycled product. Examples of recycled products include those that have been washed and made into chips from used films, etc., and made into films using these as materials. A specific example of a recycled product is Toray's Ecouse series.
• Examples of the temporary support include a biaxially stretched polyethylene terephthalate film with a thickness of 16 ⁇ m, a biaxially stretched polyethylene terephthalate film with a thickness of 12 ⁇ m, and a biaxially stretched polyethylene terephthalate film with a thickness of 9 ⁇ m.
• Preferred forms of the temporary support include, for example, paragraphs [0017] to [0018] of JP 2014-085643, paragraphs [0019] to [0026] of JP 2016-027363, and International Publication No. 2012/ The descriptions are given in paragraphs [0041] to [0057] of No. 081680 and paragraphs [0029] to [0040] of International Publication No. 2018/179370, and the contents of these publications are incorporated herein.
• a layer containing fine particles may be provided on the surface of the temporary support in order to impart handling properties.
• 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 to 0.8 ⁇ m. Further, the thickness of the lubricant layer is preferably 0.05 to 1.0 ⁇ m.
• Commercially available temporary supports include Lumirror 16KS40, Lumirror 16FB40 (all manufactured by Toray Industries, Inc.), Cosmoshine A4100, Cosmoshine A4160, Cosmoshine A4300, Cosmoshine A4360, and Cosmoshine A8300 (all manufactured by Toyobo Co., Ltd.). can be mentioned.
• the first embodiment of the transfer film has a photosensitive composition layer. After transferring the photosensitive composition layer onto the transfer target, a pattern can be formed on the transfer target by performing exposure and development.
• a photosensitive composition layer a negative type is preferable. Note that the negative photosensitive composition layer is a photosensitive composition layer whose exposed areas have reduced solubility in a developer upon exposure. When the photosensitive composition layer is a negative photosensitive composition layer, the pattern formed corresponds to a cured layer.
• the photosensitive composition layer When the photosensitive composition layer is a negative photosensitive composition layer, the negative photosensitive composition layer contains an alkali-soluble resin, a polymerizable compound having an ethylenically unsaturated group, and a photopolymerization initiator.
• a photosensitive composition layer (negative photosensitive composition layer) is composed of an alkali-soluble resin: 10 to 90% by mass, based on the total mass of the photosensitive composition layer; a polymerizable resin having an ethylenically unsaturated group; Compound: 5 to 70% by mass; photopolymerization initiator: 0.01 to 20% by mass.
• the content of phosphate ions is 10.0 mass ppm or less with respect to the total mass of the photosensitive composition layer.
• the photosensitive composition layer contains an alkali-soluble resin (hereinafter also referred to as "resin A").
• the resin A include (meth)acrylic resins, styrene resins, epoxy resins, amide resins, amide epoxy resins, alkyd resins, phenol resins, ester resins, urethane resins, and reactions between epoxy acrylate resins and acid anhydrides. Examples include, but are not limited to, acid-modified epoxy acrylate resins obtained in .
• (meth)acrylic resin is preferable.
• a (meth)acrylic resin means resin which has a structural unit derived from a (meth)acrylic compound.
• the content of the structural units derived from the (meth)acrylic compound is preferably 30% by mass or more, more preferably 50% by mass or more, based on the total structural units of the (meth)acrylic resin. More preferably 60% by mass or more.
• a polymer having a structural unit derived from a (meth)acrylic compound and a structural unit derived from a styrene compound is also preferable.
• the acid value of resin A is preferably 220 mgKOH/g or less, and 200 mgKOH/g or less, from the viewpoint of improving the resolution of the photosensitive composition layer by suppressing swelling of the negative photosensitive composition layer by the developer. It is more preferably less than 190 mgKOH/g, and even more preferably less than 190 mgKOH/g.
• the lower limit of the acid value of resin A is not particularly limited, but from the viewpoint of better developability, it is preferably 60 mgKOH/g or more, more preferably 100 mgKOH/g or more, even more preferably 120 mgKOH/g or more, and especially 150 mgKOH/g or more. Preferably, 170 mgKOH/g or more is most preferable.
• the acid value (mgKOH/g) is the mass [mg] of potassium hydroxide required to neutralize 1 g of sample.
• the acid value can be calculated, for example, from the average content of acid groups in the compound.
• the acid value of resin A may be adjusted depending on the type of structural units constituting resin A and the content of structural units containing acid groups, which will be described later. Note that, hereinafter, the resolution of the photosensitive composition layer is also simply referred to as "resolution.”
• the weight average molecular weight of resin A is preferably 5,000 to 500,000.
• a weight average molecular weight of 500,000 or less is preferred from the viewpoint of improving resolution and developability.
• the weight average molecular weight is more preferably 100,000 or less, and even more preferably 60,000 or less.
• the weight average molecular weight is 5,000 or more, the properties of the developed aggregate and the properties of the unexposed film such as edge fusing property and cut chip property when formed into a negative photosensitive composition laminate are controlled. Preferable from this point of view.
• the weight average molecular weight is more preferably 10,000 or more, even more preferably 20,000 or more, and particularly preferably 30,000 or more.
• Edge fusing property refers to the degree of ease with which the negative photosensitive composition layer protrudes from the end surface of the roll when the negative photosensitive composition laminate is wound into a roll.
• the cut chip property refers to the degree to which chips easily fly when an unexposed film is cut with a cutter. If this chip adheres to the upper surface of the negative photosensitive composition laminate, it will be transferred to a mask in a subsequent exposure step, etc., resulting in defective products.
• the degree of dispersion of resin 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 resin A contains a structural unit derived from a monomer having an aromatic hydrocarbon group.
• aromatic hydrocarbon groups include, for example, substituted or unsubstituted phenyl groups and substituted or unsubstituted aralkyl groups.
• the content of structural units derived from monomers having aromatic hydrocarbon groups in resin A is preferably 20% by mass or more, more preferably 30% by mass or more, based on the total mass of resin A.
• the upper limit is not particularly limited, but is preferably 95% by mass or less, more preferably 85% by mass or less.
• the average value of the content of structural units derived from monomers having aromatic hydrocarbon groups falls within the above range.
• monomers having an aromatic hydrocarbon group examples include monomers having an aralkyl group, styrene, and polymerizable styrene derivatives (for example, methylstyrene, vinyltoluene, tert-butoxystyrene, acetoxystyrene, styrene dimer, and styrene trimmer, etc.).
• monomers having an aralkyl group or styrene are preferred.
• the content of the structural unit based on styrene is preferably 20 to 70% by mass, more preferably 25 to 65% by mass, based on the total mass of resin A. It is preferably 30 to 60% by weight, more preferably 40 to 60% by weight.
• the photosensitive composition layer contains a plurality of types of resins A
• the content rate of the structural unit having an aromatic hydrocarbon group is determined as a weight average value.
• aralkyl group examples include a phenylalkyl group that may have a substituent, and a benzyl group that may have a substituent is preferred.
• Examples of the monomer having a phenylalkyl group which may have a substituent include phenylethyl (meth)acrylate and the like.
• Examples of monomers having a benzyl group which may have a substituent include (meth)acrylates having a benzyl group such as benzyl (meth)acrylate and chlorobenzyl (meth)acrylate; vinylbenzyl chloride and vinylbenzyl Examples include vinyl monomers having a benzyl group such as alcohol, preferably (meth)acrylates having a benzyl group, and more preferably benzyl (meth)acrylates.
• the monomer having an aromatic hydrocarbon group is benzyl (meth)acrylate
• the content of the structural unit based on benzyl (meth)acrylate is preferably 50 to 95% by mass based on the total mass of resin A. , more preferably 60 to 90% by weight, even more preferably 70 to 90% by weight, particularly preferably 75 to 90% by weight.
• the resin A containing a structural unit derived from a monomer having an aromatic hydrocarbon group includes at least one of a monomer having an aromatic hydrocarbon group, a monomer having a carboxyl group described below, and/or Alternatively, it is preferably obtained by polymerizing with at least one non-acidic monomer described below.
• Resin A that does not contain a structural unit derived from a monomer having an aromatic hydrocarbon group is preferably obtained by polymerizing at least one monomer having a carboxyl group, which will be described later. More preferably, it is obtained by copolymerizing at least one monomer and at least one non-acidic monomer described below.
• resin A contains a structural unit having a carboxy group.
• the structural unit having a carboxy group is derived from a monomer having a carboxy group in the molecule.
• monomers having a carboxyl group include (meth)acrylic acid, fumaric acid, cinnamic acid, crotonic acid, itaconic acid, 4-vinylbenzoic acid, maleic anhydride, and maleic acid half ester. It will be done. Among these, (meth)acrylic acid is preferred.
• the content of the structural unit having a carboxyl group in resin A is preferably 5 to 50% by mass, more preferably 10 to 40% by mass, and even more preferably 15 to 30% by mass, based on the total mass of resin A. It is preferable that the content be 5% by mass or more from the viewpoint of achieving good developability and controlling edge fusing properties. It is preferable that the content be 50% by mass or less from the viewpoint of high resolution and groove shape of the resist pattern, and further from the viewpoint of acid resistance.
• Non-acidic structural unit- Resin A may contain non-acidic structural units.
• the non-acidic structural unit is non-acidic and is derived from a monomer having at least one polymerizable unsaturated group in the molecule. Examples of the above monomer (non-acidic monomer) include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, and n-butyl (meth)acrylate.
• vinyl alcohol such as vinyl acetate
• the content of non-acidic structural units in resin A is preferably 0.5 to 60% by mass, more preferably 1 to 50% by mass, and even more preferably 1 to 30% by mass, based on the total mass of resin A.
• -Other constituent units- Resin A may have a structural unit having either a linear structure, a branched structure, or an alicyclic structure in its side chain.
• main chain refers to the relatively longest bonding chain in the molecules of the polymer compound that constitutes the resin
• side chain refers to the atomic group branching from the main chain. represent.
• the alicyclic structure may be monocyclic or polycyclic.
• monomers containing a group having a branched structure in the side chain include isopropyl (meth)acrylate, isobutyl (meth)acrylate, sec-butyl (meth)acrylate, and tert-butyl (meth)acrylate. , isoamyl (meth)acrylate, tert-amyl (meth)acrylate, sec-amyl (meth)acrylate, 2-octyl (meth)acrylate, 3-octyl (meth)acrylate and tert-(meth)acrylate -Octyl etc.
• isopropyl (meth)acrylate, isobutyl (meth)acrylate, and tert-butyl methacrylate are preferred, and isopropyl methacrylate or tert-butyl methacrylate is more preferred.
• monomers containing a group having an alicyclic structure in the side chain include monomers having a monocyclic aliphatic hydrocarbon group and monomers having a polycyclic aliphatic hydrocarbon group. Can be mentioned. Also included are (meth)acrylates having an alicyclic hydrocarbon group having 5 to 20 carbon atoms.
• More specific examples include (meth)acrylic acid (bicyclo[2.2.1]heptyl-2), (meth)acrylic acid-1-adamantyl, (meth)acrylic acid-2-adamantyl, (meth)acrylic acid-2-adamantyl; 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)acrylic acid-3,5,8-triethyl-1-adamantyl, (meth)acrylic acid-3,5-dimethyl-8-ethyl-1-adamantyl, (meth)acrylic acid 2 -Methyl-2-adamantyl, 2-ethyl-2-adamantyl (meth)acrylate, 3-hydroxy-1-adamantyl (meth)acrylate, oct
• cyclohexyl (meth)acrylate, (nor)bornyl (meth)acrylate, isobornyl (meth)acrylate, 1-adamantyl (meth)acrylate, (meth)acrylic acid -2-adamantyl, fentyl (meth)acrylate, 1-menthyl (meth)acrylate, or tricyclodecane (meth)acrylate are preferred, and cyclohexyl (meth)acrylate, (nor)bornyl (meth)acrylate, More preferred are isobornyl (meth)acrylate, 2-adamantyl (meth)acrylate, or tricyclodecane (meth)acrylate.
• Resin A may be used alone or in combination of two or more. When using two or more types, use a mixture of two types of resin A containing structural units derived from monomers having aromatic hydrocarbon groups, or use monomers having aromatic hydrocarbon groups. It is preferable to use a mixture of resin A containing a structural unit derived from an aromatic hydrocarbon group and resin A containing no structural unit derived from a monomer having an aromatic hydrocarbon group. In the latter case, the proportion of resin A containing a structural unit derived from a monomer having an aromatic hydrocarbon group is preferably 50% by mass or more, more preferably 70% by mass or more, based on the total mass of resin A. It is preferably at least 80% by mass, more preferably at least 90% by mass.
• Resin A is synthesized by combining the above-mentioned monomer or monomers with radicals such as a peroxide polymerization initiator (e.g. benzoyl peroxide) and an azo polymerization initiator (e.g. azobisisobutyronitrile).
• a peroxide polymerization initiator e.g. benzoyl peroxide
• an azo polymerization initiator e.g. azobisisobutyronitrile
• the polymerization method involves dropping a monomer solution and a radical polymerization initiator solution into a heated solvent (preferably acetone, methyl ethyl ketone, cyclohexanone, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, and isopropanol) under a nitrogen stream.
• a heated solvent preferably acetone, methyl ethyl ketone, cyclohexanone, propylene glycol monomethyl
• a solvent may be further added to adjust the concentration to a desired level.
• synthesis means in addition to solution polymerization, bulk polymerization, suspension polymerization, or emulsion polymerization may be used.
• the photosensitive composition layer contains a polymerizable compound having an ethylenically unsaturated group.
• a polymerizable compound having an ethylenically unsaturated group will also be simply referred to as a polymerizable compound.
• the term “polymerizable compound having an ethylenically unsaturated group” refers to a compound that polymerizes under the action of a photopolymerization initiator, which will be described later, and which is different from the resin A described above. .
• Examples of the ethylenically unsaturated group that the polymerizable compound has include a vinyl group, an acryloyl group, a methacryloyl group, a styryl group, and a maleimide group, with an acryloyl group or a methacryloyl group being preferred.
• a compound having one or more ethylenically unsaturated groups is preferable in that the photosensitivity of the negative photosensitive composition layer is better, and two or more ethylenically unsaturated groups are used in one molecule.
• Compounds having the above ethylenically unsaturated groups are more preferred.
• the number of ethylenically unsaturated groups in one molecule of the ethylenically unsaturated compound is preferably 6 or less, more preferably 3 or less, and 2 or less. More preferred.
• a difunctional or trifunctional ethylenically unsaturated group having two or three ethylenically unsaturated groups in one molecule has a better balance between photosensitivity, resolution, and removability of the negative photosensitive composition layer. It is preferable to contain a saturated compound, and more preferably to contain a bifunctional ethylenically unsaturated compound having two ethylenically unsaturated groups in one molecule.
• the content of the bifunctional ethylenically unsaturated compound with respect to the total mass of the polymerizable compound is preferably 20% by mass or more, and 40% by mass with respect to the total mass of the negative photosensitive composition layer, from the viewpoint of excellent releasability.
• the content is more preferably greater than 55% by mass, and even more preferably 55% by mass or more.
• the upper limit is not particularly limited and may be 100% by mass. That is, all of the polymerizable compounds may be difunctional ethylenically unsaturated compounds.
• a (meth)acrylate compound having a (meth)acryloyl group as a polymerizable group is preferable.
• the negative photosensitive composition layer 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 mentioned above.
• the mass ratio of the content of polymerizable compound B1 to the total mass of polymerizable compounds is preferably 40% or more, more preferably 50% by mass or more, from the viewpoint of better resolution. , more preferably 55% by mass or more, particularly preferably 60% by mass or more.
• the upper limit is not particularly limited, but from the viewpoint of releasability, it is, for example, 100% by mass or less, preferably 99% by mass or less, more preferably 95% by mass or less, even more preferably 90% by mass or less, particularly 85% by mass or less. preferable.
• aromatic ring possessed by the polymerizable compound B1 examples include aromatic hydrocarbon rings such as a benzene ring, naphthalene ring, and anthracene ring; aromatic rings such as a thiophene ring, a furan ring, a pyrrole ring, an imidazole ring, a triazole ring, and a pyridine ring; Examples include heterocycles and fused rings thereof, with aromatic hydrocarbon rings being preferred and benzene rings being more preferred. Note that the aromatic ring may have a substituent. Polymerizable compound B1 may have only one aromatic ring, or may have two or more aromatic rings.
• the polymerizable compound B1 preferably has a bisphenol structure from the viewpoint of improving resolution by suppressing swelling of the photosensitive composition layer caused by the developer.
• bisphenol structures include bisphenol A structure derived from bisphenol A (2,2-bis(4-hydroxyphenyl)propane) and bisphenol A structure derived from bisphenol F (2,2-bis(4-hydroxyphenyl)methane). F structure and bisphenol B structure derived from bisphenol B (2,2-bis(4-hydroxyphenyl)butane), and bisphenol A structure is preferred.
• Examples of the polymerizable compound B1 having a bisphenol structure include a compound having a bisphenol structure and two polymerizable groups (preferably (meth)acryloyl groups) bonded to both ends of the bisphenol structure. Both ends of the bisphenol structure and the two polymerizable groups may be bonded directly or may be 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, and more preferably an ethyleneoxy group.
• the number of alkyleneoxy groups added to the bisphenol structure is not particularly limited, but is preferably 4 to 16, more preferably 6 to 14 per molecule.
• Polymerizable compound B1 having a bisphenol structure is described in paragraphs [0072] to [0080] of JP-A-2016-224162, and the content described in this publication is 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.
• 2,2-bis(4-((meth)acryloxypolyalkoxy)phenyl)propane for example, 2,2-bis(4-(methacryloxydiethoxy)phenyl)propane (FA-324M, Hitachi Chemical Co., Ltd.
• polymerizable compound B1 a compound represented by the following general formula (B1) is also preferable.
• R 1 and R 2 each independently represent a hydrogen atom or a methyl group.
• A represents C 2 H 4 .
• B represents C3H6 .
• n1 and n3 are each independently an integer of 1 to 39, and n1+n3 is an integer of 2 to 40.
• n2 and n4 are each independently an integer of 0 to 29, and n2+n4 is an integer of 0 to 30.
• the arrangement of the constituent units of -(AO)- and -(BO)- may be random or block. In the case of a block, either -(AO)- or -(BO)- may be on the bisphenyl group side.
• n1+n2+n3+n4 is preferably 2 to 20, more preferably 2 to 16, and even more preferably 4 to 12. Further, n2+n4 is preferably 0 to 10, more preferably 0 to 4, even more preferably 0 to 2, and particularly preferably 0.
• One type of polymerizable compound B1 may be used alone, or two or more types may be used.
• the content of the polymerizable compound B1 is preferably 10% by mass or more, more preferably 20% by mass or more, based on the total mass of the negative photosensitive composition layer.
• the upper limit is not particularly limited, but from the viewpoint of transferability and edge fusion (a phenomenon in which the photosensitive composition oozes out from the edges of the transfer member), it is preferably 70% by mass or less, and more preferably 60% by mass or less.
• the negative photosensitive composition layer may contain a polymerizable compound other than the above-mentioned polymerizable compound B1.
• Polymerizable compounds other than polymerizable compound B1 are not particularly limited, and can be appropriately selected from known compounds. For example, compounds that have one ethylenically unsaturated group in one molecule (monofunctional ethylenically unsaturated compounds), bifunctional ethylenically unsaturated compounds that do not have an aromatic ring, and trifunctional or higher functional ethylenically unsaturated compounds. can be mentioned.
• Examples of monofunctional ethylenically unsaturated compounds include ethyl (meth)acrylate, ethylhexyl (meth)acrylate, 2-(meth)acryloyloxyethyl succinate, polyethylene glycol mono(meth)acrylate, and polypropylene glycol mono(meth)acrylate. , and phenoxyethyl (meth)acrylate.
• bifunctional ethylenically unsaturated compounds having no aromatic ring examples include alkylene glycol di(meth)acrylate, polyalkylene glycol di(meth)acrylate, urethane di(meth)acrylate, and trimethylolpropane diacrylate. .
• alkylene glycol di(meth)acrylate examples include tricyclodecane dimethanol diacrylate (A-DCP, manufactured by Shin Nakamura Chemical Co., Ltd.), tricyclodecane dimethanol dimethacrylate (DCP, manufactured by Shin Nakamura Chemical Co., Ltd.), 1,9-nonanediol diacrylate (A-NOD-N, manufactured by Shin Nakamura Chemical Co., Ltd.), 1,6-hexanediol diacrylate (A-HD-N, manufactured by Shin Nakamura Chemical Co., Ltd.), ethylene glycol dimethacrylate , 1,10-decanediol diacrylate, and neopentyl glycol di(meth)acrylate.
• A-DCP tricyclodecane dimethanol diacrylate
• DCP manufactured by Shin Nakamura Chemical Co., Ltd.
• 1,9-nonanediol diacrylate A-NOD-N, manufactured by Shin Nakamura
• polyalkylene glycol di(meth)acrylate examples include polyethylene glycol di(meth)acrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, and polypropylene glycol di(meth)acrylate.
• urethane di(meth)acrylates examples include propylene oxide-modified urethane di(meth)acrylates, and ethylene oxide- and propylene oxide-modified urethane di(meth)acrylates.
• the content of the bifunctional ethylenically unsaturated compound is preferably 20% by mass or more, and 30% by mass or more based on the total mass of the negative photosensitive composition layer, from the viewpoint of better resolution and resist removability. is more preferable, and even more preferably 40% by mass or more.
• the upper limit 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 composition oozes out from the edge of the transfer member).
• the content of the bifunctional ethylenically unsaturated compound is preferably 40% by mass or more, based on the total mass of the polymerizable compound having an ethylenically unsaturated group, from the viewpoint of better resolution and resist removability. It is more preferably at least 80% by mass, and even more preferably at least 80% by mass.
• the upper limit is preferably 100% by mass or less, more preferably 90% by mass or less, from the viewpoints of transferability and edge fusion (a phenomenon in which the photosensitive composition oozes out from the edges of the transfer member).
• trifunctional or more ethylenically unsaturated compounds include dipentaerythritol (tri/tetra/penta/hexa) (meth)acrylate, pentaerythritol (tri/tetra)(meth)acrylate, trimethylolpropane tri(meth) Examples include acrylate, ditrimethylolpropane tetra(meth)acrylate, trimethylolethane tri(meth)acrylate, isocyanuric acid tri(meth)acrylate, glycerin tri(meth)acrylate, and alkylene oxide modified products thereof.
• (tri/tetra/penta/hexa)(meth)acrylate is a concept that includes tri(meth)acrylate, tetra(meth)acrylate, penta(meth)acrylate, and hexa(meth)acrylate.
• (tri/tetra)(meth)acrylate” is a concept that includes tri(meth)acrylate and tetra(meth)acrylate.
• the negative photosensitive composition layer preferably contains the above-mentioned polymerizable compound B1 and a trifunctional or more functional ethylenically unsaturated compound, and the above-mentioned polymerizable compound B1 and two or more trifunctional or more functional ethylenically unsaturated compounds. More preferably, it contains an ethylenically unsaturated compound.
• the negative photosensitive composition layer contains the polymeric compound B1 mentioned above and 2 or more types of trifunctional ethylenically unsaturated compounds.
• alkylene oxide-modified compounds of trifunctional or higher-functional ethylenically unsaturated compounds include caprolactone-modified (meth)acrylate compounds (KAYARAD (registered trademark) DPCA-20 manufactured by Nippon Kayaku Co., Ltd., A-9300-1CL manufactured by Shin Nakamura Chemical Co., Ltd.
• alkylene oxide-modified (meth)acrylate compounds (KAYARAD RP-1040 manufactured by Nippon Kayaku Co., Ltd., ATM-35E and A-9300 manufactured by Shin-Nakamura Chemical Co., Ltd., EBECRYL (registered trademark) 135 manufactured by Daicel Allnex Co., Ltd., etc.), Ethoxylated glycerin triacrylate (A-GLY-9E, etc.
• the polymeric 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.). manufactured by Toagosei Co., Ltd.).
• the polymerizable compound having an acid group for example, the polymerizable compound having an acid group described in paragraphs [0025] to [0030] of JP-A No. 2004-239942 may be used.
• One type of polymerizable compound may be used alone, or two or more types may be used.
• the content of the polymerizable compound is preferably 10 to 70% by weight, more preferably 15 to 70% by weight, and even more preferably 20 to 70% by weight, based on the total weight of the negative photosensitive composition layer.
• the molecular weight (weight average molecular weight if it has a molecular weight distribution) of the polymerizable compound (including polymerizable compound B1) is preferably 200 to 3,000, more preferably 280 to 2,200, and 300 to 2,200. More preferred.
• the photosensitive composition layer contains a photopolymerization initiator.
• a photopolymerization initiator is a compound that initiates polymerization of a polymerizable compound upon receiving actinic rays such as ultraviolet rays, visible rays, and X-rays.
• the photopolymerization initiator is not particularly limited, and any known photopolymerization initiator can be used. Examples of the photopolymerization initiator include radical photopolymerization initiators and cationic photopolymerization initiators, with radical photopolymerization initiators being preferred.
• radical photopolymerization initiator examples include a photopolymerization initiator having an oxime ester structure, a photopolymerization initiator having an ⁇ -aminoalkylphenone structure, a photopolymerization initiator having an ⁇ -hydroxyalkylphenone structure, and acylphosphine oxide.
• examples include a photopolymerization initiator having a structure and a photopolymerization initiator having an N-phenylglycine structure.
• the negative photosensitive composition layer uses 2,4,5-triarylimidazole dimer as a photoradical polymerization initiator. It is preferable to include at least one selected from the group consisting of esters and derivatives thereof. Note that the two 2,4,5-triarylimidazole structures in the 2,4,5-triarylimidazole dimer and its derivatives may be the same or different. Examples of derivatives of 2,4,5-triarylimidazole dimer include 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer and 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer.
• photoradical polymerization initiator examples include the polymerization initiators described in paragraphs [0031] to [0042] of JP-A No. 2011-95716 and paragraphs [0064] to [0081] of JP-A No. 2015-14783. may also be used.
• Examples of the photoradical polymerization initiator include ethyl dimethylaminobenzoate (DBE, CAS No. 10287-53-3), benzoin methyl ether, anisyl (p,p'-dimethoxybenzyl), and TAZ-110 (trade name: Midori Kagaku Co., Ltd.), benzophenone, 4,4'-bis(diethylamino)benzophenone, TAZ-111 (product name: Midori Kagaku Co., Ltd.), Irgacure OXE01, OXE02, OXE03, OXE04 (BASF Co., Ltd.), Omnirad651 and 369 (product name: Midori Kagaku Co., Ltd.) Name: IGM Resins manufactured by B.V.), and 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole (Tokyo Chemical Industry Co., Ltd.) (manu
• photoradical polymerization initiators include, for example, 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 acid upon receiving actinic rays.
• the photocationic polymerization initiator is preferably a compound that is sensitive to actinic rays 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 as a sensitizer.
• a photocationic polymerization initiator that generates an acid with a pKa of 4 or less is preferable
• a photocationic polymerization initiator that generates an acid with a pKa of 3 or less is more preferable
• a photocationic polymerization initiator that generates an acid with a pKa of 2 or less is preferable.
• Particularly preferred are photocationic polymerization initiators that are generated.
• the lower limit of pKa is not particularly determined, it is preferably -10.0 or more, for example.
• Examples of the cationic photopolymerization initiator include ionic cationic photopolymerization initiators and nonionic cationic photopolymerization initiators.
• Examples of the ionic photocationic polymerization initiator include onium salt compounds such as diaryliodonium salts and triarylsulfonium salts, and quaternary ammonium salts.
• the ionic photocationic polymerization initiator described in paragraphs [0114] to [0133] of JP 2014-085643A may be used.
• nonionic photocationic polymerization initiator examples include trichloromethyl-s-triazines, diazomethane compounds, imidosulfonate compounds, and oxime sulfonate compounds.
• trichloromethyl-s-triazines, diazomethane compounds, and imidosulfonate compounds compounds described in paragraphs [0083] to [0088] of JP-A-2011-221494 may be used.
• oxime sulfonate compound compounds described in paragraphs [0084] to [0088] of International Publication No. 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 dimer and derivatives thereof. preferable.
• One type of photopolymerization initiator may be used alone, or two or more types of photopolymerization initiators may be used.
• the content of the photopolymerization initiator is not particularly limited, but is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and 1.0% by mass based on the total mass of the negative photosensitive composition layer. % or more is more preferable.
• the upper limit is not particularly limited, but is preferably 20% by mass or less, more preferably 15% by mass or less, and even more preferably 10% by mass or less, based on the total mass of the negative photosensitive composition layer.
• the content of phosphate ions in the photosensitive composition layer is 10.0 mass ppm or less based on the total mass of the photosensitive composition layer.
• the lower limit is not particularly limited, and may be 0.0 mass ppm, and may be 0.0 mass ppm.
• the content of phosphate ions is preferably 0.1 to 7.0 ppm by mass based on the total mass of the photosensitive composition layer, from the viewpoints of better adhesion and better suppression of residue generation. Note that the content of phosphate ions in the photosensitive composition layer refers to the content of phosphate ions when the photosensitive composition layer is analyzed by ion chromatography. Analysis by chromatography will be detailed later.
• the content of phosphate ions mentioned above refers to the total content of the content of phosphate ions derived from the salt containing phosphate ions and the content of ionized phosphate ions.
• the photosensitive composition layer contains phosphate ions or phosphate ions. This means that it contains salts that contain.
• a phosphate ion is an anion obtained by removing one or more hydrogen atoms contained in phosphoric acid (H 3 PO 4 ).
• a salt containing a phosphate ion is a compound consisting of a phosphate ion and a counter cation.
• the counter cation is not particularly limited and includes known cations.
• the cation may be either an organic cation or an inorganic cation.
• organic cations include quaternary ammonium cations and quaternary phosphonium cations.
• inorganic cations include alkali metal ions such as lithium ions and potassium ions.
• the content of phosphate ions is measured by ion chromatography according to the following procedure.
• 100 mg of a sample is taken from the photosensitive composition layer of the transfer film, and 100 mg of the sample is dissolved in 1 g of ethyl acetate.
• 2.00 g of 0.0200 mol/L potassium hydroxide aqueous solution is added and sufficiently stirred to form a mixed solution, and then the mixed solution is allowed to stand for 1 hour.
• the aqueous phase is extracted from the mixture and subjected to cation exchange treatment to remove potassium ions.
• anions are concentrated in the aqueous phase from which potassium ions have been removed using an anion concentration column.
• the content of phosphate ions is measured by ion chromatography using the anion-concentrated aqueous phase under the following conditions. Measuring equipment: DIONEX INTEGRION HPIC (Thermo Fisher Scientific Co., Ltd.) Column: Dionex IonPac AS22 (anion analysis column, size: 4 x 250 mm) Flow rate: 1mL/min Temperature: 35°C From the above measurement results, the content of phosphate ions with respect to the sample is determined, and is taken as the content of phosphate ions with respect to the total mass of the photosensitive composition layer.
• the photosensitive composition layer may contain ions other than phosphate ions, or salts containing ions other than phosphate ions.
• Other ions include nitrate, iodide, and bromide ions.
• salts containing other ions include compounds consisting of any one of nitrate ions, iodide ions, and bromide ions and a counter cation. Examples of the counter cation include the cations exemplified above as counter cations contained in the salt containing phosphate ions.
• the content of nitrate ions in the photosensitive composition layer is preferably 10.0 mass ppm or less, based on the total mass of the photosensitive composition layer, in terms of better adhesion and better suppression of residue generation. More preferably 0.1 to 7.0 mass ppm. Note that the content of nitrate ions may be 0.0 mass ppm.
• the ratio of the nitrate ion content to the phosphate ion content is preferably 0.3 to 2.0, more preferably 0.5 to 1.5.
• the content of iodide ions in the photosensitive composition layer is 2.0 to 20.0 mass based on the total mass of the photosensitive composition layer, since it has better adhesion and suppresses generation of residue. ppm is preferable, and 3.0 to 10.0 ppm by mass is more preferable.
• the ratio of the iodide ion content to the phosphate ion content is preferably 1.0 to 50.0, more preferably 1.4 to 30.0.
• the content of bromide ions in the photosensitive composition layer is 4.0 to 20.0 mass ppm based on the total mass of the photosensitive composition layer, in that it has better adhesion and further suppresses the generation of residue. is preferable, and 6.0 to 10.0 mass ppm is more preferable.
• the ratio of the bromide ion content to the phosphate ion content is preferably 1.0 to 100.0, more preferably 1.4 to 60.0.
• each of the other ions mentioned above refers to the total content of the content of other ions derived from the salt containing the other ions and the content of ionized other ions.
• the nitrate ion content refers to the total content of the nitrate ion content derived from the salt containing nitrate ions and the content of ionized nitrate ions.
• the content of the other ions is measured in the same manner as the content of phosphate ions.
• the photosensitive composition layer has a maximum absorption wavelength of 450 nm or more in a wavelength range of 400 to 780 nm during color development, from the viewpoint of visibility of exposed areas and non-exposed areas, pattern visibility after development, and resolution,
• a dye also referred to as "dye N"
• dye N although the detailed mechanism is unknown, adhesion with adjacent layers (for example, a water-soluble resin layer) is improved, resulting in better resolution.
• the phrase "the maximum absorption wavelength of a dye changes due to an acid, a base, or a radical” refers to a state in which a dye in a colored state is decolored by an acid, a base, or a radical, or a state in which a dye in a decolored state is It may refer to either an aspect in which color is developed by an acid, a base, or a radical, or an aspect 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 decolorized state and develops color upon exposure to light, or may be a compound that changes from a color developed state and decolorizes upon exposure.
• it may be a dye that changes its coloring or decoloring state when acids, bases, or radicals are generated within the photosensitive composition layer and act upon exposure; It may be a dye whose coloring or decoloring state changes depending on the state (for example, pH) within the layer. It may also be a dye that changes its coloring or decoloring state when directly stimulated by an acid, base, or radical without being exposed to light.
• the dye N is preferably a dye whose maximum absorption wavelength changes with acid or radicals, and more preferably a dye whose maximum absorption wavelength changes with radicals.
• the photosensitive composition layer is a negative photosensitive composition layer
• the negative photosensitive composition layer is It is preferable to include both a dye whose absorption wavelength changes and a photoradical polymerization initiator.
• the dye N is a dye that develops color with an acid, a base, or a radical.
• a photoradical polymerization initiator As an example of the coloring mechanism of dye N, a photoradical polymerization initiator, a photocationic polymerization initiator (photoacid generator), or a photobase generator is added to the photosensitive composition layer to initiate photoradical polymerization after exposure.
• examples include embodiments in which radical-reactive dyes, acid-reactive dyes, or base-reactive dyes (e.g., leuco dyes) are colored by radicals, acids, or bases generated from agents, photocationic polymerization initiators, or photobase generators. It will be done.
• the dye N preferably has a maximum absorption wavelength of 550 nm or more in the wavelength range of 400 to 780 nm during color development, more preferably 550 to 700 nm, and 550 nm or more. More preferably, the wavelength is 650 nm. Further, the dye N may have only one maximum absorption wavelength in the wavelength range of 400 to 780 nm during color development, or may have two or more. When the dye N has two or more maximum absorption wavelengths in the wavelength range of 400 to 780 nm during color development, it is sufficient that the maximum absorption wavelength with the highest absorbance among the two or more maximum absorption wavelengths is 450 nm or more.
• the maximum absorption wavelength of dye N is determined by the transmission spectrum of a solution containing dye N (liquid temperature 25°C) in the range of 400 to 780 nm under atmospheric conditions using a spectrophotometer: UV3100 (manufactured by Shimadzu Corporation). It can be obtained by measuring the wavelength and detecting the wavelength at which the light intensity is minimum (maximum absorption wavelength).
• Examples of dyes that develop or discolor when exposed to light include leuco compounds.
• Examples of dyes that disappear upon exposure to light include leuco compounds, diarylmethane dyes, oxazine dyes, xanthene dyes, iminonaphthoquinone dyes, azomethine dyes, and anthraquinone dyes.
• As the dye N a leuco compound is preferable from the viewpoint of visibility of exposed areas and non-exposed areas.
• leuco compounds examples include leuco compounds having a triarylmethane skeleton (triarylmethane dyes), leuco compounds having a spiropyran skeleton (spiropyran dyes), leuco compounds having a fluorane skeleton (fluoran dyes), and diarylmethane skeletons.
• leuco compounds leuco auramine pigments.
• triarylmethane dyes or fluoran dyes are preferred, and leuco compounds having a triphenylmethane skeleton (triphenylmethane dyes) or fluoran dyes are more preferred.
• the leuco compound preferably has a lactone ring, a sultine ring, or a sultone ring from the viewpoint of visibility of exposed and non-exposed areas.
• the lactone ring, sultine ring, or sultone ring of the leuco compound is reacted with the radical generated from the photoradical polymerization initiator or the acid generated from the photocationic polymerization initiator, and the leuco compound is changed into a ring-closed state.
• the color can be removed by changing the leuco compound to an open ring state, or the color can be developed by changing the leuco compound to an open ring state.
• the leuco compound is preferably a compound that has a lactone ring, a sultine ring, or a sultone ring, and develops color when the lactone ring, sultine ring, or sultone ring opens with a radical or an acid. More preferred are compounds that develop color when the lactone ring opens with an acid.
• Examples of the dye N include the following dyes and leuco compounds. Specific examples of dyes among the dyes N include brilliant green, ethyl violet, methyl green, crystal violet, basic fuchsin, methyl violet 2B, quinaldine red, rose bengal, methanil yellow, thymol sulfophthalein, xylenol blue, and methyl.
• leuco compounds among the dyes N include p, p', p''-hexamethyltriaminotriphenylmethane (leuco crystal violet), Pergascript Blue SRB (manufactured by Ciba Geigy), crystal violet lactone, malachite green lactone, Benzoylleucomethylene blue, 2-(N-phenyl-N-methylamino)-6-(N-p-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-diethyla
• the dye N is preferably a dye whose maximum absorption wavelength changes with radicals, from the viewpoint of visibility of exposed areas and non-exposed areas, pattern visibility after development, and resolution, and is preferably a dye that develops color due to radicals. It is more preferable that there be.
• As the dye N leuco crystal violet, crystal violet lactone, brilliant green, or Victoria Pure Blue-naphthalene sulfonate is preferable.
• One type of dye N may be used alone, or two or more types may be used.
• the content of dye N is 0.1% by mass or more based on the total mass of the photosensitive composition layer, from the viewpoint of visibility of exposed areas and non-exposed areas, pattern visibility after development, and resolution. is preferable, 0.1 to 10% by weight is more preferable, even more preferably 0.1 to 5% by weight, and particularly preferably 0.1 to 1% by weight.
• the content of the dye N means the content of the dye when all the dye N contained in the total mass of the photosensitive composition layer is brought into a colored state.
• a method for quantifying the content of the dye N will be explained using a dye that develops color due to radicals as an example.
• a solution is prepared by dissolving 0.001 g and 0.01 g of the dye in 100 mL of methyl ethyl ketone.
• a photoradical polymerization initiator, Irgacure OXE01 (trade name, BASF Japan Ltd.), is added to each of the obtained solutions, and irradiation with 365 nm light generates radicals, causing all the dyes to become colored.
• the absorbance of each solution at a liquid temperature of 25° C. is measured using a spectrophotometer (UV3100, manufactured by Shimadzu Corporation) under atmospheric conditions, and a calibration curve is created.
• the absorbance of the solution in which all the dyes are colored is measured in the same manner as above except that 3 g of the photosensitive composition layer is dissolved in methyl ethyl ketone instead of the dye. 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 a calibration curve. Note that 3 g of the photosensitive composition layer is the same as 3 g of the solid content of the photosensitive composition layer.
• thermally crosslinkable compound When the photosensitive composition layer is a negative photosensitive composition layer, it is preferable to contain a thermally crosslinkable compound from the viewpoint of the strength of the obtained cured film and the tackiness of the obtained uncured film.
• the 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 these, blocked isocyanate compounds are preferred from the viewpoint of the strength of the cured film obtained and the adhesiveness of the uncured film obtained.
• Blocked isocyanate compounds react with hydroxy groups and carboxy groups, so if the resin and/or polymerizable compound has at least one of a hydroxy group and a carboxy group, the hydrophilicity of the formed film decreases.
• 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 differential scanning calorimetry
• a differential scanning calorimeter model: DSC6200 manufactured by Seiko Instruments, Inc. can be suitably used.
• the differential scanning calorimeter is not limited to this.
• the blocked isocyanate compound preferably has an isocyanurate structure, for example, from the viewpoint of improving the brittleness of the film and further improving the adhesion to the transfer target.
• a blocked isocyanate compound having an isocyanurate structure can be obtained, for example, by converting hexamethylene diisocyanate into isocyanurate and protecting it.
• a compound having an oxime structure using an oxime compound as a blocking agent is easier to maintain the dissociation temperature in a preferable range than a compound without an oxime structure, and produces less development residue. This is preferable from the viewpoint of ease of use.
• the blocked isocyanate compound may have a polymerizable group.
• the polymerizable group is not particularly limited, and any known polymerizable group can be used, with radically polymerizable groups being preferred.
• the polymerizable group include ethylenically unsaturated groups such as a (meth)acryloxy group, (meth)acrylamide group, and styryl group, and groups having an epoxy group such as a glycidyl group.
• the polymerizable group is preferably an ethylenically unsaturated group, more preferably a (meth)acryloxy group, and even more preferably an acryloxy group.
• blocked isocyanate compound commercially available products can be used.
• block isocyanate compounds include Karenz (registered trademark) AOI-BM, Karenz (registered trademark) MOI-BM, Karenz (registered trademark) MOI-BP (all manufactured by Showa Denko), block type Examples include the Duranate series (eg, Duranate (registered trademark) TPA-B80E, Duranate (registered trademark) WT32-B75P, etc., manufactured by Asahi Kasei Chemicals).
• a compound having the following structure can also be used as the blocked isocyanate compound.
• thermally crosslinkable compound may be used alone, or two or more types may be used.
• the content of the thermally crosslinkable compound is preferably 1 to 50% by mass, more preferably 5 to 30% by mass, based on the total mass of the photosensitive composition layer. preferable.
• the photosensitive composition layer may contain known additives as necessary.
• additives include radical polymerization inhibitors, antioxidants (e.g., phenidone, etc.), rust inhibitors (e.g., benzotriazoles and carboxybenzotriazoles, etc.), sensitizers, surfactants, plasticizers, Examples include heterocyclic compounds (eg, triazole, etc.), pyridines (eg, isonicotinamide, etc.), and purine bases (eg, adenine, etc.).
• additives include, for example, metal oxide particles, chain transfer agents, antioxidants, dispersants, acid multiplying agents, development accelerators, conductive fibers, ultraviolet absorbers, thickeners, crosslinking agents, organic or an inorganic suspending agent and paragraphs [0165] to [0184] of JP 2014-085643A, the contents of which are incorporated herein.
• Each additive may be used alone or in combination of two or more.
• the photosensitive composition layer may contain a polymerization inhibitor.
• the polymerization inhibitor include radical polymerization inhibitors.
• the radical polymerization inhibitor include thermal polymerization inhibitors described in paragraph [0018] of Japanese Patent No. 4502784. Among these, phenothiazine, phenoxazine, 1-phenyl-3-pyrazolidone or 4-methoxyphenol are preferred.
• Other radical polymerization inhibitors include naphthylamine, cuprous chloride, nitrosophenylhydroxyamine aluminum salt, diphenylnitrosamine, and the like. In order not to impair the sensitivity of the photosensitive composition layer, it is preferable to use nitrosophenylhydroxyamine aluminum salt as the radical polymerization inhibitor.
• the content of the radical polymerization inhibitor is preferably 0.005 to 5.0% by mass, more preferably 0.01 to 3.0% by mass, and more preferably 0.01 to 1.0% by mass based on the total mass of the polymerizable compound. More preferably, it is 0% by mass.
• benzotriazoles include 1,2,3-benzotriazole, 1-chloro-1,2,3-benzotriazole, bis(N-2-ethylhexyl)aminomethylene-1,2,3-benzotriazole, Examples include bis(N-2-ethylhexyl)aminomethylene-1,2,3-tolyltriazole and bis(N-2-hydroxyethyl)aminomethylene-1,2,3-benzotriazole.
• carboxybenzotriazoles include 4-carboxy-1,2,3-benzotriazole, 5-carboxy-1,2,3-benzotriazole, and N-(N,N-di-2-ethylhexyl)aminomethylene.
• Examples include carboxybenzotriazole, N-(N,N-di-2-hydroxyethyl)aminomethylenecarboxybenzotriazole, and N-(N,N-di-2-ethylhexyl)aminoethylenecarboxybenzotriazole.
• carboxybenzotriazole for example, commercially available products such as CBT-1 (trade name, manufactured by Johoku Kagaku Kogyo Co., Ltd.) can be used.
• the total content of benzotriazoles and carboxybenzotriazoles is preferably 0.01 to 3% by mass, more preferably 0.05 to 1% by mass, based on the total mass of the photosensitive composition layer.
• the content is 0.01% by mass or more, the storage stability of the photosensitive composition layer is better.
• the content is 3% by mass or less, sensitivity can be maintained and dye decolorization can be suppressed more effectively.
• the photosensitive composition layer may contain a sensitizer.
• the sensitizer is not particularly limited, and known sensitizers, dyes, and pigments can be used.
• Examples of the sensitizer include dialkylaminobenzophenone compounds, pyrazoline compounds, coumarin compounds, xanthone compounds, thioxanthone compounds, acridone compounds, oxazole compounds, benzoxazole compounds, thiazole compounds, benzothiazole compounds, triazole compounds (for example, 1,2 , 4-triazole), stilbene compounds, triazine compounds, thiophene compounds, naphthalimide compounds, triarylamine compounds, and aminoacridine compounds.
• One type of sensitizer may be used alone, or two or more types of sensitizers may be used.
• the content of the sensitizer can be selected as appropriate depending on the purpose, but from the viewpoint of improving the sensitivity to the light source and improving the curing rate by balancing the polymerization rate and chain transfer.
• the amount is preferably 0.01 to 5% by weight, more preferably 0.05 to 1% by weight, based on the total weight of the photosensitive composition layer.
• the photosensitive composition layer may also contain a surfactant.
• the surfactant include the surfactants described in paragraph [0017] of Japanese Patent No. 4502784 and paragraphs [0060] to [0071] of JP-A-2009-237362.
• the surfactant examples include hydrocarbon surfactants, fluorine surfactants, and silicone surfactants. From the viewpoint of improving environmental suitability, the surfactant preferably does not contain fluorine atoms. As the surfactant, hydrocarbon surfactants or silicone surfactants are preferred. Furthermore, as the surfactant, nonionic surfactants are preferred.
• fluorosurfactants include Megafac 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. MFS-586, EXP.
• fluorine-based surfactants include acrylic compounds that have a molecular structure with a functional group containing a fluorine atom, and when heat is applied, the functional group containing the fluorine atom is severed and the fluorine atom evaporates.
• fluorine-based surfactants include the Megafac DS series manufactured by DIC Corporation (Kagaku Kogyo Nippo (February 22, 2016), Nikkei Sangyo Shimbun (February 23, 2016)); An example is DS-21.
• the fluorine-based surfactant it is also preferable to use a polymer of a fluorine atom-containing vinyl ether compound having a fluorinated alkyl group or a fluorinated alkylene ether group and a hydrophilic vinyl ether compound.
• block polymers 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 two or more (preferably five or more) alkyleneoxy groups (preferably ethyleneoxy groups, propyleneoxy groups).
• a fluorine-containing polymer compound containing a structural unit derived from a (meth)acrylate compound can also be preferably used.
• fluorine-containing surfactant a fluorine-containing polymer having an ethylenically unsaturated bond-containing group in its side chain can also be used.
• fluorine-containing polymer having an ethylenically unsaturated bond-containing group in its side chain examples include Megafac RS-101, RS-102, RS-718K, and RS-72-K (manufactured by DIC Corporation).
• fluorosurfactants from the viewpoint of improving environmental suitability, compounds having a linear perfluoroalkyl group having 7 or more carbon atoms, such as perfluorooctanoic acid (PFOA) and perfluorooctane sulfonic acid (PFOS), are used.
• PFOA perfluorooctanoic acid
• PFOS perfluorooctane sulfonic acid
• Surfactants derived from alternative materials are preferred.
• hydrocarbon surfactants include glycerol, trimethylolpropane, trimethylolethane, and their ethoxylates and propoxylates (e.g., glycerol propoxylate, glycerol ethoxylate, etc.), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether , polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester, and the like.
• silicone surfactants include linear polymers consisting of siloxane bonds and modified siloxane polymers with organic groups introduced into side chains or terminals.
• silicone surfactants include EXP. S-309-2, EXP. S-315, EXP. S-503-2, EXP. S-505-2 (manufactured by DIC Corporation), DOWSIL 8032 ADDITIVE, Tore Silicone DC3PA, Tore Silicone SH7PA, Tore Silicone DC11PA, Tore Silicone SH21PA, Tore Silicone SH28PA, Tore Silicone SH29PA, Tore Silicone SH30 PA, Toray silicone SH8400 ( (manufactured by Dow Corning Toray Co., Ltd.), X-22-4952, X-22-4272, -642, KF-643, -109, KP-109, KP-112, KP-120, KP-121, KP-124, KP-125, KP-301, KP-306, KP-310, KP-322, KP-323, KP-327 , KP-341, KP-368, KP-369, KP-611, KP-620, KP
• the surfactants may be used alone or in combination of two or more.
• the content of the surfactant is preferably 0.01 to 3.0% by mass, and 0.01 to 1.0% by mass, based on the total mass of the photosensitive composition layer. 0% by mass is more preferred, and 0.05 to 0.80% by mass is even more preferred.
• the photosensitive composition layer also contains metal oxide particles, an antioxidant, a dispersant, an acid multiplying agent, a development accelerator, a conductive fiber, an ultraviolet absorber, a thickener, a crosslinking agent, and an organic or inorganic precipitate. It may further contain known additives such as inhibitors.
• the 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 content of water in the photosensitive composition layer is preferably 0.01 to 1.0% by mass, more preferably 0.05 to 0.5% by mass, from the viewpoint of improving reliability and lamination properties.
• the layer thickness (film thickness) of the photosensitive composition layer is generally 0.1 to 300 ⁇ m, preferably 0.2 to 100 ⁇ m, more preferably 0.5 to 50 ⁇ m, and even more preferably 0.5 to 15 ⁇ m.
• 0.5 to 10 ⁇ m is particularly preferred, and most preferably 0.5 to 8 ⁇ m.
• the thickness is preferably 0.5 to 5 ⁇ m, more preferably 0.5 to 4 ⁇ m, and even more preferably 0.5 to 3 ⁇ m.
• the transmittance of the photosensitive composition layer for light at 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, but is preferably 99.9% or less.
• the photosensitive composition layer may contain a predetermined amount of impurities.
• impurities include sodium, potassium, magnesium, calcium, iron, manganese, copper, aluminum, titanium, chromium, cobalt, nickel, zinc, tin, and ions thereof.
• sodium ions and potassium ions are likely to be mixed in as impurities, so it is preferable to have the following content.
• 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, based on mass.
• the content of impurities in the photosensitive composition layer can be 1 ppb or more or 0.1 ppm or more on a mass basis.
• a specific example of the content of impurities in the photosensitive composition layer includes an embodiment in which all of the above impurities are 0.6 ppm on a mass basis.
• Methods for keeping impurities within the above range include selecting materials with a low content of impurities as raw materials for the photosensitive composition layer, preventing contamination of impurities during formation of the photosensitive composition layer, and cleaning.
• One example is removal.
• 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, trichloroethylene, 1,3-butadiene, carbon tetrachloride, chloroform, N,N-dimethylformamide, N,N-dimethylacetamide, and hexane in the photosensitive composition layer is as follows: Preferably less.
• the content of these compounds in 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 on a mass basis.
• the content of these compounds can be suppressed in the same manner as the above-mentioned metal impurities. Moreover, it can be quantified by a known measuring method.
• the content of water in the photosensitive composition layer is preferably 0.01 to 1.0% by mass, more preferably 0.05 to 0.5% by mass, from the viewpoint of improving reliability and lamination properties.
• the photosensitive composition layer may be a colored resin layer containing a pigment.
• a cover glass with a black frame-shaped light-shielding layer formed on the periphery of the back surface of a transparent glass substrate, etc. is sometimes attached to the liquid crystal display window of recent electronic devices.
• a colored resin layer may be used to form such a light-blocking layer.
• the pigment may be appropriately selected depending on the desired hue, and can be selected from black pigments, white pigments, and chromatic pigments other than black and white. Among these, when forming a black pattern, a black pigment is preferably selected as the pigment.
• any known black pigment such as an organic pigment or an inorganic pigment
• suitable examples of the black pigment include carbon black, titanium oxide, titanium carbide, iron oxide, titanium oxide, and graphite, with carbon black being particularly preferred.
• carbon black whose surface is at least partially coated with resin is preferable as carbon black.
• the number average particle size of the black pigment is preferably 0.001 to 0.1 ⁇ m, more preferably 0.01 to 0.08 ⁇ m.
• the particle size refers to the diameter of a circle when the area of the pigment particle is determined from a photographic image of the pigment particle taken with an electron microscope and the area is the same as the area of the pigment particle, and the number average particle size is the average value obtained by determining the above particle size for 100 arbitrary particles and averaging the 100 determined particle sizes.
• the white pigment described in paragraphs [0015] and [0114] of JP-A-2005-007765 can be used.
• white pigments titanium oxide, zinc oxide, lithopone, light calcium carbonate, white carbon, aluminum oxide, aluminum hydroxide, or barium sulfate are preferable as inorganic pigments, and titanium oxide or zinc oxide is more preferable.
• titanium oxide is more preferable.
• inorganic pigment 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 two or more treatments may be performed. This suppresses the catalytic activity of titanium oxide and improves heat resistance, fading resistance, and the like.
• the surface treatment of the titanium oxide is preferably at least one of alumina treatment and zirconia treatment, and both alumina treatment and zirconia treatment are particularly preferred.
• the photosensitive composition layer when the photosensitive composition layer is a colored resin layer, from the viewpoint of transferability, it is also preferable that the photosensitive composition layer 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, in terms of better dispersibility.
• chromatic pigments include Victoria Pure Blue BO (Color Index (hereinafter referred to as C.I.) 42595), Auramine (C.I. 41000), Fat Black HB (C.I. 26150), and Monolight.
• C.I. Color Index
• Auramine C.I. 41000
• Fat Black HB C.I. 26150
• Monolight - 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 Splatter (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. Pigment Red 122, C. I. Pigment Red 149, C. I. Pigment Red 168, C. I. Pigment Red 177, C. I. Pigment Red 180, C. I. Pigment Red 192, C. I.
• C. I. Pigment Red 177 is preferred.
• the content of the pigment is preferably more than 3% by mass and not more than 40% by mass, and more than 3% by mass and not more than 35% by mass, based on the total mass of the photosensitive composition layer. More preferably, more than 5% by mass and 35% by mass or less, and particularly preferably 10% by mass or more and 35% by mass or less.
• the content of pigments other than black pigments is preferably 30% by mass or less, and 1 to 20% by mass based on the black pigment. It is more preferably % by mass, and even more preferably 3-15% by mass.
• the black pigment preferably carbon black
• the dispersion liquid may be prepared by adding a mixture obtained by premixing a black pigment and a pigment dispersant to an organic solvent (or vehicle) and dispersing the mixture using a dispersion machine.
• the pigment dispersant may be selected depending on the pigment and the solvent, and for example, commercially available dispersants 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 liquid, and includes a binder component that holds the black pigment in a dispersed state and a solvent component that dissolves and dilutes the binder component. (organic solvent).
• dispersants include urethane 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 acids.
• Alkylamine salts such as their salts, (meth)acrylic acid-styrene copolymers, (meth)acrylic acid-(meth)acrylic acid ester copolymers, styrene-maleic acid copolymers, polyvinyl alcohol, polyvinylpyrrolidone Examples include water-soluble resins and water-soluble polymer compounds such as, polyester systems, modified polyacrylate systems, ethylene oxide/propylene oxide adducts, and phosphate ester systems.
• the aspect of the dispersant may be selected from the items described in paragraphs [0021] to [0065] of JP-A-2021-012355.
• Preferred dispersants include, for example, basic polymer type dispersants.
• the basic polymer type dispersant include a polymer containing a nitrogen atom.
• the nitrogen atom may be contained in the main chain of the polymer, may be contained in the side chain of the polymer, or may be contained in the main chain and side chains of the polymer.
• the basic polymer type dispersant is preferably a polymer containing a nitrogen atom in a side chain. Since the surface of carbon black is generally acidic, when carbon black is used as a pigment, a basic polymer type dispersant is particularly preferred as the dispersant.
• Examples of the polymer containing a nitrogen atom include a primary amino group, a secondary amino group, a tertiary amino group, a quaternary ammonium base, and a nitrogen-containing polymer.
• Examples include polymers containing at least one atomic group selected from the group consisting of heterocyclic groups.
• a polymer containing a quaternary ammonium base is preferred.
• the atomic group is preferably introduced into the side chain of the polymer.
• the counter ion of the quaternary ammonium cation in the quaternary ammonium base include carboxylic acid ions.
• carboxylic acid ions include aliphatic carboxylic acid ions and aromatic carboxylic acid ions.
• the 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 of is more preferred.
• a maleimide derivative has a structure in which at least one hydrogen atom of maleimide is substituted with a substituent.
• a maleimide derivative for example, at least one atomic group selected from the group consisting of a primary amino group, a secondary amino group, a tertiary amino group, a quaternary ammonium base, and a nitrogen-containing heterocyclic group is used. Examples include 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 (BYK-Chemie Japan Co., Ltd.).
• the dispersion liquid may contain a dispersion aid (also referred to as a pigment dispersion aid) in addition to the pigment.
• the dispersion aid may be selected from known dispersion aids.
• the dispersion aid include compounds having organic dye residues.
• organic pigments include phthalocyanine pigments, diketopyrrolopyrrole pigments, anthraquinone pigments, quinacridone pigments, dioxazine pigments, perinone pigments, perylene pigments, thiazine indigo pigments, triazine pigments, and benzimidazo pigments.
• Ron pigments indole pigments such as benzoisoindole, isoindoline pigments, isoindolinone pigments, quinophthalone pigments, naphthol pigments, threne pigments, metal complex pigments, azo pigments such as azo, disazo, polyazo, etc.
• Examples include pigments.
• the compound having an organic dye residue may have an acidic substituent, a basic substituent, or a neutral substituent.
• acidic substituents include sulfo groups, carboxy groups, and phosphoric acid groups.
• Examples of the basic substituent include a sulfonamide group and an amino group.
• neutral substituents include phenyl groups and phthalimidoalkyl groups.
• the aspect of the dispersion aid may be selected from the items described in paragraphs [0067] to [0084] of JP-A-2021-012355.
• Preferred dispersion aids include, for example, compounds having phthalocyanine residues.
• the dispersion 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 carboxy group, and a phosphoric acid group.
• a phthalocyanine pigment derivative having a sulfo group or a salt thereof is more preferable, and a phthalocyanine pigment derivative having a sulfo group or a salt thereof is even more preferable.
• Phthalocyanine pigment derivatives are described, for example, in JP 2007-226161A, WO 2016/163351, JP 2017-165820, and Patent No. 5753266. These publications are incorporated herein by reference.
• the dispersing machine is not particularly limited, and examples thereof include known dispersing machines such as a kneader, roll mill, attritor, super mill, dissolver, homomixer, and sand mill. Furthermore, it may be finely pulverized by mechanical grinding using frictional force. Regarding the dispersing machine and fine pulverization, reference can be made to the description in "Encyclopedia of Pigments" (written by Kunizo Asakura, 1st edition, Asakura Shoten, 2000, pages 438 and 310).
• the first embodiment of the transfer film may include a protective film.
• a resin film having heat resistance and solvent resistance can be used, and examples thereof include polyolefin films such as polypropylene films and polyethylene films, polyester films such as polyethylene terephthalate films, polycarbonate films, and polystyrene films. It will be done.
• a resin film made of the same material as the above-mentioned temporary support may be used as the protective film.
• the protective film is preferably a polyolefin film, more preferably a polypropylene film or a polyethylene film, and even more preferably a polyethylene film.
• the thickness of the protective film is preferably 1 to 100 ⁇ m, more preferably 5 to 50 ⁇ m, even more preferably 5 to 40 ⁇ m, and particularly preferably 15 to 30 ⁇ m.
• the thickness of the protective film is preferably 1 ⁇ m or more in terms of excellent mechanical strength, and preferably 100 ⁇ m or less in terms of being relatively inexpensive.
• the number of fish eyes with a diameter of 80 ⁇ m or more contained in the protective film is 5 pieces/m 2 or less.
• fish eyes refers to foreign matter, undissolved matter, oxidized deterioration products, etc. of materials when manufacturing films by methods such as heat-melting, kneading, extrusion, biaxial stretching, and casting methods. was captured in the film.
• the number of particles with 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 transfer of unevenness caused by particles contained in the protective film onto the photosensitive composition layer or the conductive layer.
• the arithmetic mean roughness Ra of the surface of the protective film opposite to the surface in contact with the composition layer is preferably 0.01 ⁇ m or more, more preferably 0.02 ⁇ m or more, and 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 surface 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 even more preferably 0.03 ⁇ m or more.
• the elongation at break of the cured film obtained by curing the photosensitive composition layer at 120° C. is 15% or more, and the arithmetic mean roughness Ra of the surface of the temporary support on the photosensitive composition layer side is is 50 nm or less, and it is also preferable that the arithmetic mean roughness Ra of the surface of the photosensitive composition layer side of the protective film is 150 nm or less.
• the transfer film 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 represents the value (%) of the elongation at break on the photosensitive composition layer side of the temporary support. It represents the value (nm) of the arithmetic mean roughness Ra of the surface.
• the above-mentioned X ⁇ Y is more preferably 750 or less. Specific numerical values for the above-mentioned X include 18%, 25%, 30%, and 35%.
• Specific numerical values of the above-mentioned X ⁇ Y include 4 nm, 8 nm, 15 nm, and 30 nm. Specific numerical values of the above-mentioned X ⁇ Y include 150, 200, 300, 360, and 900.
• 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 determined by exposing a photosensitive composition layer with a thickness of 20 ⁇ m to 120 mJ/cm 2 using an ultra-high pressure mercury lamp and curing it, then additionally exposing it to 400 mJ/cm 2 using a high-pressure mercury lamp, and heating it at 145° C. for 30 minutes. The cured film is then measured by a tensile test.
• the transfer film satisfies the following formula (2).
• Y represents the value (nm) of the arithmetic mean roughness Ra of the surface on the photosensitive composition layer side of the temporary support
• Z represents the value (nm) of the surface on the photosensitive composition layer side of the protective film.
• R represents the value (nm) of the arithmetic mean roughness Ra of the surface.
• the first embodiment of the transfer film may include a thermoplastic resin layer.
• the thermoplastic resin layer is usually arranged between the temporary support and the photosensitive composition layer.
• the thermoplastic resin layer contains resin.
• the resin includes a thermoplastic resin as part or all of the resin. That is, in one embodiment, it is also preferable that the resin in the thermoplastic resin layer is a thermoplastic resin.
• alkali-soluble resin thermoplastic resin
• thermoplastic resin an alkali-soluble resin is preferable.
• alkali-soluble resins include acrylic resin, polystyrene resin, styrene-acrylic copolymer, polyurethane resin, polyvinyl alcohol, polyvinyl formal, polyamide resin, polyester resin, polyamide resin, epoxy resin, polyacetal resin, and polyhydroxystyrene resin.
• acrylic resin is preferable from the viewpoint of developability and adhesion with adjacent layers.
• the acrylic resin is at least one selected from the group consisting of structural units derived from (meth)acrylic acid, structural units derived from (meth)acrylic esters, and structural units derived from (meth)acrylic acid amide. It means a resin having one type of structural unit.
• the total content of structural units derived from (meth)acrylic acid, structural units derived from (meth)acrylic esters, and structural units derived from (meth)acrylic amide is the total content of the acrylic resin. It is preferable that the amount is 50% by mass or more based on the mass.
• 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, and 50 to 100% by mass, based on the total mass of the acrylic resin. 100% by mass is more preferred.
• the alkali-soluble resin is a polymer having an acid group.
• the acid group include a carboxy group, a sulfo group, a phosphoric acid group, and a phosphonic acid group, with a 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 even more preferably a carboxyl group-containing acrylic resin having an acid value of 60 mgKOH/g or more.
• the upper limit of the acid value of the alkali-soluble resin is not particularly limited, but is preferably 300 mgKOH/g or less, more preferably 250 mgKOH/g or less, even more preferably 200 mgKOH/g or less, and particularly preferably 150 mgKOH/g or less.
• the carboxyl 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.
• an alkali-soluble resin that is a carboxy group-containing acrylic resin with an acid value of 60 mgKOH/g or more paragraph [0033] of JP-A No.
• Examples include carboxy group-containing acrylic resins having a value of 60 mgKOH/g or more.
• the copolymerization ratio of structural units having a carboxyl group in the above carboxyl group-containing acrylic resin is preferably 5 to 50% by mass, more preferably 10 to 40% by mass, and 12 to 30% by mass based on the total mass of the acrylic resin. is even more preferable.
• an acrylic resin having a structural unit derived from (meth)acrylic acid is particularly preferable from the viewpoint of developability and adhesion with 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 ethylenically unsaturated groups; polycondensable groups such as hydroxy groups and carboxy groups; polyaddition reactive groups such as epoxy groups and (block) isocyanate groups. Can be mentioned.
• the weight average molecular weight (Mw) of the alkali-soluble resin is preferably 1,000 or more, more preferably 10,000 to 100,000, and even more preferably 20,000 to 50,000.
• alkali-soluble resin may be used alone, or two or more types may be used.
• the content of the alkali-soluble resin is preferably 10 to 99% by mass, more preferably 20 to 90% by mass, based on the total mass of the thermoplastic resin layer, from the viewpoint of developability and adhesion with adjacent layers. More preferably 40 to 80% by weight, particularly preferably 50 to 75% by weight.
• the thermoplastic resin layer may contain a compound (also simply referred to as "compound C") that generates an acid, a base, or a radical when exposed to light.
• 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.
• the photoacid generator include the photocationic polymerization initiator that may be included in the above-mentioned negative photosensitive composition layer, and preferred embodiments are the same except for the points described below.
• 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 properties, it is more preferable to include an oxime sulfonate compound. Further, as the photoacid generator, a photoacid generator having the following structure is also preferable.
• thermoplastic resin layer may contain a photoradical polymerization initiator.
• radical photopolymerization initiator include the radical photopolymerization initiator that may be included in the above-mentioned negative photosensitive composition layer, and the preferred embodiments are also the same.
• the thermoplastic resin composition may also include a photobase generator.
• the photobase generator is not particularly limited as long as it is a known photobase generator, and examples thereof include 2-nitrobenzylcyclohexylcarbamate, triphenylmethanol, O-carbamoylhydroxylamide, O-carbamoyloxime, [[(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)-
• Compound C may be used alone or in combination of two or more.
• the content of compound C is preferably 0.1 to 10% by mass, and 0.5 to 5% by mass, based on the total mass of the thermoplastic resin layer, from the viewpoint of visibility and resolution of exposed and unexposed regions. Mass% is more preferred.
• thermoplastic resin layer contains a dye (also simply referred to as "dye B") whose maximum absorption wavelength is 450 nm or more in the wavelength range of 400 to 780 nm during color development, and whose maximum absorption wavelength changes with acid, base, or radical. It is preferable.
• dye B are the same as the preferred embodiments of dye N described above, except for the points described below.
• dye B is preferably a dye whose maximum absorption wavelength changes with acid or radicals, and more preferably a dye whose maximum absorption wavelength changes with acid.
• the thermoplastic resin layer contains both a dye as dye B whose maximum absorption wavelength changes depending on an acid, and a compound that generates an acid when exposed to light, which will be described later. It is preferable to include.
• dye B may be used alone, or two or more types may be used.
• the content of dye B is preferably 0.2% by mass or more, more preferably 0.2 to 6% by mass, based on the total mass of the thermoplastic resin layer, from the viewpoint of visibility of exposed areas and non-exposed areas. , more preferably 0.2 to 5% by weight, particularly preferably 0.25 to 3.0% by weight.
• 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 brought into a colored state.
• a method for quantifying the content of dye B will be explained using a dye that develops color due to radicals as an example.
• a solution is prepared by dissolving 0.001 g and 0.01 g of the dye in 100 mL of methyl ethyl ketone.
• a photoradical polymerization initiator, Irgacure OXE01 (trade name, BASF Japan Ltd.), is added to each of the obtained solutions, and irradiation with 365 nm light generates radicals to bring all the dyes into a colored state. Thereafter, the absorbance of each solution at a liquid temperature of 25° C.
• thermoplastic resin layer is measured using a spectrophotometer (UV3100, manufactured by Shimadzu Corporation) under atmospheric conditions, and a calibration curve is created.
• UV3100 UV3100, manufactured by Shimadzu Corporation
• the absorbance of the solution in which all the dyes are colored is measured in the same manner as above except that 0.1 g of the thermoplastic resin layer is dissolved in methyl ethyl ketone instead of the dye. From the absorbance of the obtained solution containing the thermoplastic resin layer, the amount of dye contained in the thermoplastic resin layer is calculated based on a calibration curve. Note that 3 g of the thermoplastic resin layer is the same as 3 g of the solid content of the assembled thermoplastic resin layer.
• the thermoplastic resin layer preferably contains a plasticizer from the viewpoints of resolution, adhesion with 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 is compatible with the alkali-soluble resin and exhibits plasticity, but from the viewpoint of imparting plasticity, the plasticizer preferably has an alkyleneoxy group in the molecule, and polyalkylene glycol Compounds are more preferred. It is more preferable that the alkyleneoxy group contained in the plasticizer has a polyethyleneoxy structure or a polypropyleneoxy structure.
• a plasticizer contains a (meth)acrylate compound from a viewpoint of resolution and storage stability.
• the alkali-soluble resin is an acrylic resin and that the plasticizer contains a (meth)acrylate compound.
• the (meth)acrylate compound used as a plasticizer include the (meth)acrylate compound described above as a 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. It is preferable. This is because the thermoplastic resin layer and the negative photosensitive composition layer each contain the same (meth)acrylate compound, thereby suppressing component diffusion between the layers and improving storage stability.
• thermoplastic resin layer contains a (meth)acrylate compound as a plasticizer
• a (meth)acrylate compound as a plasticizer
• (meth)acrylate compounds used as plasticizers should contain two or more (meth)acrylates in one molecule.
• a polyfunctional (meth)acrylate compound having an acryloyl group is preferred.
• a (meth)acrylate compound or a urethane (meth)acrylate compound having an acid group is also preferable.
• the content of the plasticizer is preferably 1 to 70% by mass based on the total mass of the thermoplastic resin layer, from the viewpoint of resolution of the thermoplastic resin layer, adhesion with adjacent layers, and developability. More preferably 10 to 60% by weight, even more preferably 20 to 50% by weight.
• the thermoplastic resin layer may contain a sensitizer.
• the sensitizer is not particularly limited, and includes the sensitizers that may be included in the negative photosensitive composition layer described above.
• One type of sensitizer may be used alone, or two or more types of sensitizers may be used.
• the content of the sensitizer can be selected as appropriate depending on the purpose, but from the viewpoint of improving sensitivity to light sources and visibility of exposed and non-exposed areas, the content of the sensitizer should be 0.01% based on the total mass of the thermoplastic resin layer. ⁇ 5% by weight is preferred, and 0.05 ⁇ 1% by weight is more preferred.
• thermoplastic resin layer may also contain known additives such as surfactants, if necessary. Further, the thermoplastic resin layer is described in paragraphs [0189] to [0193] of JP-A No. 2014-085643, and the contents of this publication are incorporated herein.
• the thickness of the thermoplastic resin layer is not particularly limited, but from the viewpoint of adhesion with adjacent layers, it is preferably 1 ⁇ m or more, more preferably 2 ⁇ m or more.
• the upper limit is not particularly limited, but from the viewpoint of developability and resolution, it is preferably 20 ⁇ m or less, more preferably 10 ⁇ m or less, and even more preferably 8 ⁇ m or less.
• the first embodiment of the transfer film may have an intermediate layer.
• the intermediate layer 13 between the thermoplastic resin layer and the photosensitive composition layer 15
• the intermediate layer 13 is provided between the thermoplastic resin layer and the photosensitive composition layer 15. Mixing of components that may occur during storage can be suppressed.
• a water-soluble resin layer containing a water-soluble resin can be used.
• an oxygen barrier layer having an oxygen barrier 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 barrier layer because sensitivity during exposure is improved, time load on the exposure machine is reduced, and productivity is improved.
• the oxygen barrier layer used as the intermediate layer may be appropriately selected from the known layers described in the above-mentioned publications. Among these, an oxygen barrier 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 resin.
• the above resin includes a water-soluble resin as part or all of it.
• resins that can be used as water-soluble resins include polyvinyl alcohol resins, polyvinylpyrrolidone resins, cellulose resins, acrylamide resins, polyethylene oxide resins, gelatin, vinyl ether resins, polyamide resins, and copolymers thereof. Examples include resins such as coalescence. Further, as the water-soluble resin, a copolymer of (meth)acrylic acid/vinyl compound, etc. can also be used.
• the (meth)acrylic acid/vinyl compound copolymer As the (meth)acrylic acid/vinyl compound copolymer, a (meth)acrylic acid/allyl (meth)acrylate copolymer is preferred, and a methacrylic acid/allyl methacrylate copolymer is more preferred.
• the water-soluble resin is a copolymer of (meth)acrylic acid/vinyl compound, each composition ratio (mol%) is preferably 90/10 to 20/80, and 80/20 to 30/70, for example. 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. Further, 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 degree of dispersion (Mw/Mn) of the water-soluble resin is preferably 1 to 10, more preferably 1 to 5.
• the resin in the water-soluble resin layer (intermediate layer) is placed on one side of the water-soluble resin layer (intermediate layer). It is preferable that the resin contained in the layer disposed on the other surface is different from the resin contained in the layer disposed on the other surface side.
• the resin of the water-soluble resin layer (intermediate layer) is a polymer. It is preferable that the resin is different from A and the 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 oxygen barrier properties and interlayer mixing suppression ability.
• 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, but is preferably 50% by mass or more based on the total mass of the water-soluble resin layer (intermediate layer) in order to further improve oxygen barrier properties and ability to suppress interlayer mixing. , more preferably 70% by mass or more, still more preferably 80% by mass or more, particularly preferably 90% by mass or more.
• the upper limit is not particularly limited, but is preferably 99.9% by mass or less, and more preferably 99.8% by mass or less.
• 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, but is preferably 0.1 to 5 ⁇ m, more preferably 0.5 to 3 ⁇ m.
• the thickness of the water-soluble resin layer (intermediate layer) is within the above range, the oxygen barrier property is not reduced and the ability to suppress interlayer mixing is excellent. Furthermore, an increase in the time required to remove the water-soluble resin layer (intermediate layer) during development can also be suppressed.
• a second embodiment of the transfer film of the present invention is a transfer film having a temporary support and a photosensitive composition layer, wherein the photosensitive composition layer is an alkali-soluble resin and a polymeric material having an ethylenically unsaturated group.
• the content of nitrate ions in the photosensitive composition layer is 10.0 mass ppm or less based on the total mass of the photosensitive composition layer. The content of nitrate ions will be detailed later. It is thought that the second embodiment of the transfer film of the present invention has excellent adhesion and suppresses the generation of residues for the following reasons by having the above configuration.
• the content of nitrate ions is less than or equal to a predetermined amount, it is considered that the surface of the object to be laminated is less likely to be altered and has excellent adhesion. Moreover, it is considered that since the content of nitrate ions is less than or equal to a predetermined amount, ions originating from the object to be bonded are less likely to be generated. It is thought that when the generation of ions derived from the object to be laminated is small, the components of the photosensitive composition layer are less susceptible to effects such as coordination, and as a result, the generation of residue is suppressed.
• the second embodiment of the transfer film of the present invention is different from the first embodiment of the transfer film in that the content of nitrate ions is defined instead of the content of phosphate ions in the photosensitive composition layer. It's different.
• other points are the same as the first embodiment, and preferred aspects are also the same, so only the differences with the first embodiment will be explained, and the similar points will be explained. The explanation will be omitted.
• the photosensitive composition layer of the second embodiment of the transfer film has a nitrate ion content of 10.0 mass ppm or less based on the total mass of the photosensitive composition layer.
• the content of nitrate ions in the photosensitive composition layer is 10.0 mass ppm or less based on the total mass of the photosensitive composition layer.
• the lower limit is not particularly limited, and may be 0.0 mass ppm, and may be 0.0 mass ppm.
• the content of nitrate ions is preferably 0.1 to 7.0 ppm by mass based on the total mass of the photosensitive composition layer, from the viewpoints of better adhesion and better suppression of residue generation.
• the content of nitrate ions in the photosensitive composition layer refers to the content of nitrate ions when the photosensitive composition layer is analyzed by ion chromatography. Analysis by chromatography will be detailed later.
• the above-mentioned content of nitrate ions refers to the total content of the content of nitrate ions derived from the salt containing nitrate ions and the content of ionized nitrate ions.
• the photosensitive composition layer contains nitrate ions or a salt containing nitrate ions. It means to include.
• Nitrate ion refers to an anion represented by NO 3 - .
• a salt containing a nitrate ion is a compound consisting of a nitrate ion and a counter cation. Examples of the counter cation include the cations exemplified above as counter cations contained in the salt containing phosphate ions.
• the content of nitrate ions is measured by ion chromatography.
• the details of the measurement method using ion chromatography are the same as the method for measuring the content of phosphate ions.
• the photosensitive composition layer may contain ions other than nitrate ions, or salts containing ions other than nitrate ions.
• Other ions include phosphate, iodide, and bromide ions.
• examples of salts containing other ions include compounds consisting of a phosphate ion, an iodide ion, or a bromide ion and a counter cation.
• Examples of the counter cation include the cations exemplified above as counter cations contained in the salt containing phosphate ions.
• the content of phosphate ions in the photosensitive composition layer is preferably 10.0 mass ppm or less based on the total mass of the photosensitive composition layer, since it has better adhesion and further suppresses the generation of residue. , 0.1 to 7.0 mass ppm is more preferable. Note that the content of phosphate ions may be 0.0 mass ppm.
• the ratio of the phosphate ion content to the nitrate ion content is preferably 0.5 to 3.3, more preferably 0.7 to 2.0.
• the iodide ion content in the photosensitive composition layer is 2.0 to 20.0 mass based on the total mass of the photosensitive composition layer, since it has better adhesion and suppresses generation of residue. ppm is preferable, and 3.0 to 10.0 ppm by mass is more preferable.
• the ratio of the iodide ion content to the nitrate ion content is preferably 1.0 to 120.0, more preferably 1.4 to 30.0.
• the content of bromide ions in the photosensitive composition layer is 4.0 to 20.0 mass ppm based on the total mass of the photosensitive composition layer, in that it has better adhesion and further suppresses the generation of residue. is preferable, and 6.0 to 10.0 mass ppm is more preferable.
• the ratio of the bromide ion content to the nitrate ion content is preferably 1.0 to 230.0, more preferably 1.4 to 55.0.
• the content of each of the other ions mentioned above refers to the total content of the content of other ions derived from the salt containing the other ions and the content of ionized other ions.
• the content of the other ions mentioned above is measured in the same manner as the content of nitrate ions.
• a third embodiment of the transfer film of the present invention is a transfer film having a temporary support and a photosensitive composition layer, wherein the photosensitive composition layer is an alkali-soluble resin, a polymer having an ethylenically unsaturated group.
• the content of iodide ions in the photosensitive composition layer is 2.0 to 20.0 ppm by mass based on the total mass of the photosensitive composition layer. The content of iodide ions will be detailed later. It is thought that the third embodiment of the transfer film of the present invention has excellent adhesion and suppresses the generation of residues for the following reasons by having the above configuration.
• the content of iodide ions is at least a predetermined amount, it is thought that the iodide ions interact with the surface of the object to be laminated, resulting in excellent adhesion. Moreover, it is considered that since the content of iodide ions is below a predetermined amount, ions derived from the object to be bonded are less likely to be generated. It is thought that when the generation of ions derived from the object to be laminated is small, the components of the photosensitive composition layer are less susceptible to effects such as coordination, and as a result, the generation of residue is suppressed.
• the third embodiment of the transfer film of the present invention is different from the first embodiment of the transfer film in that the content of iodide ions is defined instead of the content of phosphate ions in the photosensitive composition layer. They differ in some respects.
• other points are the same as the first embodiment, and preferred aspects are also the same, so only the differences with the first embodiment will be explained, and the similar points will be explained. The explanation will be omitted.
• the photosensitive composition layer of the third embodiment of the transfer film has an iodide ion content of 2.0 to 20.0 ppm by mass based on the total mass of the photosensitive composition layer.
• the content of iodide ions in the photosensitive composition layer is 2.0 to 20.0 ppm by mass based on the total mass of the photosensitive composition layer.
• the content of iodide ions is preferably 3.0 to 10.0 ppm by mass based on the total mass of the photosensitive composition layer, since it has better adhesion and further suppresses the generation of residue.
• the iodide ion content in the photosensitive composition layer refers to the iodide ion content when the photosensitive composition layer is analyzed by ion chromatography. Analysis by chromatography will be detailed later.
• iodide ion content refers to the total content of the iodide ion content derived from the salt containing iodide ions and the content of ionized iodide ions.
• the photosensitive composition layer contains iodide ions or iodide ions. This means that it contains salts that contain.
• Iodide ion refers to an anion represented by I - .
• a salt containing an iodide ion is a compound consisting of an iodide ion and a counter cation.
• Examples of the counter cation include the cations exemplified above as counter cations contained in the salt containing phosphate ions.
• the iodide ion content is measured by ion chromatography.
• the details of the measurement method using ion chromatography are the same as the method for measuring the content of phosphate ions.
• the photosensitive composition layer may contain ions other than iodide ions, or salts containing ions other than iodide ions.
• Other ions include phosphate ions, nitrate ions, and bromide ions.
• salts containing other ions include compounds consisting of phosphate ions, nitrate ions, and bromide ions, and a counter cation. Examples of the counter cation include the cations exemplified above as counter cations contained in the salt containing phosphate ions.
• the content of phosphate ions in the photosensitive composition layer is preferably 10.0 mass ppm or less based on the total mass of the photosensitive composition layer, since it has better adhesion and further suppresses the generation of residue. , 0.1 to 7.0 mass ppm is more preferable. Note that the content of phosphate ions may be 0.0 mass ppm.
• the ratio of the phosphate ion content to the iodide ion content is preferably 0.0 to 1.0, more preferably 0.03 to 0.7.
• the content of nitrate ions in the photosensitive composition layer is preferably 10.0 mass ppm or less, based on the total mass of the photosensitive composition layer, in terms of better adhesion and better suppression of residue generation. More preferably 0.1 to 7.0 ppm by mass. Note that the content of nitrate ions may be 0.0 mass ppm.
• the ratio of the nitrate ion content to the iodide ion content is preferably 0.0 to 1.0, more preferably 0.03 to 0.7.
• the content of bromide ions in the photosensitive composition layer is 4.0 to 20.0 mass ppm based on the total mass of the photosensitive composition layer, in that it has better adhesion and further suppresses the generation of residue. is preferable, and 6.0 to 10.0 mass ppm is more preferable.
• the ratio of the bromide ion content to the iodide ion content is preferably 0.8 to 2.5, more preferably 0.9 to 2.1.
• the content of each of the other ions mentioned above refers to the total content of the content of other ions derived from the salt containing the other ions and the content of ionized other ions.
• the content of the other ions mentioned above is measured in the same manner as the content of iodide ions.
• a fourth embodiment of the transfer film of the present invention is a transfer film having a temporary support and a photosensitive composition layer, wherein the photosensitive composition layer is an alkali-soluble resin, a polymer having an ethylenically unsaturated group.
• the content of bromide ions in the photosensitive composition layer is 4.0 to 20.0 ppm by mass based on the total mass of the photosensitive composition layer.
• the content of iodide ions will be detailed later. It is thought that the fourth embodiment of the transfer film of the present invention has excellent adhesion and suppresses the generation of residue due to the following reasons.
• the content of bromide ions is at least a predetermined amount, it is thought that the bromide ions interact with the surface of the object to be laminated, resulting in excellent adhesion. Moreover, it is considered that since the content of bromide ions is less than or equal to a predetermined amount, ions derived from the object to be bonded are less likely to be generated. It is thought that when the generation of ions derived from the object to be laminated is small, the components of the photosensitive composition layer are less susceptible to effects such as coordination, and as a result, the generation of residue is suppressed.
• the fourth embodiment of the transfer film of the present invention is different from the first embodiment of the transfer film in that the content of bromide ions is defined instead of the content of phosphate ions in the photosensitive composition layer. It's different. Regarding the fourth embodiment of the transfer film, other points are the same as the first embodiment, and preferred aspects are also the same, so only the differences with the first embodiment will be explained, and the similar points will be explained. The explanation will be omitted.
• the photosensitive composition layer of the fourth embodiment of the transfer film has a bromide ion content of 4.0 to 20.0 ppm by mass based on the total mass of the photosensitive composition layer.
• the content of bromide ions in the photosensitive composition layer is 4.0 to 20.0 ppm by mass based on the total mass of the photosensitive composition layer.
• the content of bromide ions is preferably 6.0 to 10.0 ppm by mass based on the total mass of the photosensitive composition layer, from the viewpoints of better adhesion and better suppression of residue generation.
• the content of bromide ions in the photosensitive composition layer refers to the content of bromide ions when the photosensitive composition layer is analyzed by ion chromatography. Analysis by chromatography will be detailed later.
• the content of bromide ions mentioned above refers to the total content of the content of bromide ions derived from the salt containing bromide ions and the content of ionized bromide ions.
• the photosensitive composition layer contains bromide ions or a salt containing bromide ions. It means to include.
• Bromide ion refers to an anion represented by Br - .
• a salt containing a bromide ion is a compound consisting of a bromide ion and a counter cation. Examples of the counter cation include the cations exemplified above as counter cations contained in the salt containing phosphate ions.
• the content of bromide ions is measured by ion chromatography.
• the details of the measurement method using ion chromatography are the same as the method for measuring the content of phosphate ions.
• the photosensitive composition layer may contain ions other than bromide ions, or salts containing ions other than bromide ions.
• Other ions include phosphate ions, nitrate ions, and iodide ions.
• salts containing other ions include compounds consisting of phosphate ions, nitrate ions, and iodide ions and a counter cation. Examples of the counter cation include the cations exemplified above as counter cations contained in the salt containing phosphate ions.
• the content of phosphate ions in the photosensitive composition layer is preferably 10.0 mass ppm or less based on the total mass of the photosensitive composition layer, since it has better adhesion and further suppresses the generation of residue. , 0.1 to 7.0 mass ppm is more preferable. Note that the content of phosphate ions may be 0.0 mass ppm.
• the ratio of the phosphate ion content to the bromide ion content is preferably 0.0 to 1.0, more preferably 0.015 to 0.7.
• the content of nitrate ions in the photosensitive composition layer is preferably 10.0 mass ppm or less, based on the total mass of the photosensitive composition layer, in terms of better adhesion and better suppression of residue generation. More preferably 0.1 to 7.0 ppm by mass. Note that the content of nitrate ions may be 0.0 mass ppm.
• the ratio of the nitrate ion content to the bromide ion content is preferably 0.0 to 1.0, more preferably 0.018 to 0.7.
• the iodide ion content in the photosensitive composition layer is 4.0 to 20.0 mass based on the total mass of the photosensitive composition layer, since it has better adhesion and suppresses generation of residue. ppm is preferable, and 6.0 to 10.0 ppm by mass is more preferable.
• the ratio of the iodide ion content to the bromide ion content is preferably 0.4 to 1.25, more preferably 0.47 to 1.1.
• the content of each of the other ions mentioned above refers to the total content of the content of other ions derived from the salt containing the other ions and the content of ionized other ions.
• the content of the other ions mentioned above is measured in the same manner as the content of bromide ions.
• the method for producing the transfer film (first embodiment to fourth embodiment) is not particularly limited, and known methods may be used.
• the method for producing the transfer film 10 includes, for example, a step of coating the surface of the temporary support 11 with an intermediate layer forming composition to form a coating film, and further drying this coating film to form the intermediate layer 13. and a step of applying a photosensitive composition to the surface of the intermediate layer 13 to form a coating film, and further drying this coating film to form a photosensitive composition layer 15, and a temporary support. Examples include a method including the steps of applying a photosensitive composition to the surface of the body 11 to form a coating film, and further drying this coating film to form the photosensitive composition layer 15.
• thermoplastic resin composition is applied to the surface of the temporary support 11 to form a coating film, and this coating film is further dried.
• the intermediate layer 13 may be formed in the same manner as described above.
• the protective film 19 may be pressure-bonded onto the composition layer 17 of the transfer film 10 manufactured by the above manufacturing method.
• the method for manufacturing the transfer film 10 includes the step of providing a protective film 19 in contact with the surface of the composition layer 17 opposite to the temporary support 11 side, so that the temporary support 11, the intermediate layer 13, and the photosensitive It is preferable to manufacture a transfer film 10 comprising a sexual composition layer 15 and a protective film 19.
• the transfer film 10 may be wound up to produce and store a roll-shaped transfer film.
• the transfer film 10 in the form of a roll can be provided as is for the step of bonding with a substrate in a roll-to-roll method described later.
• the method for manufacturing the transfer film 10 may be a method of forming the composition layer 17 on the protective film 19.
• the intermediate layer 13 may be further formed.
• thermoplastic resin layer and method for forming thermoplastic resin layer
• the method for forming the thermoplastic resin layer on the temporary support is not particularly limited, and any known method 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 various components for forming the thermoplastic resin layer described above and a solvent.
• the preferred range of the content of each component relative to the total solid content of the composition is the same as the preferred range of the content of each component relative to the total mass of the thermoplastic resin layer described above. be.
• the solvent is not particularly limited as long as it can dissolve or disperse components other than the solvent, and any known solvent can be used.
• Examples of the solvent include those similar to those contained in the photosensitive composition described below, and preferred embodiments are also the same.
• the content of the solvent is preferably 50 to 1,900 parts by mass, more preferably 100 to 900 parts by mass, based on 100 parts by mass of the total solid content of the composition.
• thermoplastic resin layer is not particularly limited as long as it can form a layer containing the above components, and for example, known coating methods (slit coating, spin coating, curtain coating, inkjet coating, etc.) may be used. Can be mentioned.
• the water-soluble resin composition preferably contains various components forming the above-mentioned intermediate layer (water-soluble resin layer) and a solvent.
• the preferred range of the content of each component relative to the total solid content of the composition is the same as the preferred range of the content of each component relative to the total mass of the water-soluble resin layer described above.
• the solvent is not particularly limited as long as it is capable of dissolving or dispersing the water-soluble resin, and is preferably at least one selected from the group consisting of water and water-miscible organic solvents; A mixed solvent with a solvent is more preferable.
• water-miscible organic solvent examples include alcohols having 1 to 3 carbon atoms, acetone, ethylene glycol, and glycerin, with alcohols having 1 to 3 carbon atoms being preferred, and methanol or ethanol being more preferred.
• One kind of solvent may be used alone, or two or more kinds of solvents may be used.
• the content of the solvent is preferably 50 to 2,500 parts by weight, more preferably 50 to 1,900 parts by weight, and even more preferably 100 to 900 parts by weight, based on 100 parts by weight of the total solid content of the composition.
• the method of forming the water-soluble resin layer is not particularly limited as long as it can form a layer containing the above components, and for example, known coating methods (slit coating, spin coating, curtain coating, inkjet coating, etc.) can be used. Can be mentioned.
• Photosensitive composition and method for forming a photosensitive composition layer Components constituting the above-mentioned photosensitive composition layer (for example, binder polymer, polymerizable compound, polymerization initiator, etc.) have excellent productivity and easy formation of the above-mentioned photosensitive composition layer. It is preferable that the photosensitive composition is formed by a coating method using a photosensitive composition containing , and a solvent. Specifically, the method for producing a transfer film involves coating a photosensitive composition on an intermediate layer to form a coating film, and drying the coating film at a predetermined temperature to form a photosensitive composition layer. Preferably, it is a method of forming.
• the photosensitive composition preferably contains the various components that form the photosensitive composition layer described above and a solvent.
• the preferred range of the content of each component relative to the total solid content of the composition is the same as the preferred range of the content of each component relative 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 components other than the solvent, and any known solvent 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, a ketone solvent, and a cyclic ether solvent is more preferred.
• alkylene glycol ether solvent examples include ethylene glycol monoalkyl ether, ethylene glycol dialkyl ether, propylene glycol monoalkyl ether (propylene glycol monomethyl ether acetate, etc.), propylene glycol dialkyl ether, diethylene glycol dialkyl ether, dipropylene glycol monoalkyl ether, and dipropylene glycol dialkyl ether.
• alkylene glycol ether acetate solvent include ethylene glycol monoalkyl ether acetate, propylene glycol monoalkyl ether acetate, diethylene glycol monoalkyl ether acetate, and dipropylene glycol monoalkyl ether acetate.
• the solvents described in paragraphs [0092] to [0094] of International Publication No. 2018/179640 and the solvents described in paragraph [0014] of JP2018-177889 may be used, and these The content of is incorporated herein.
• One kind of solvent may be used alone, or two or more kinds of solvents may be used.
• the content of the solvent is preferably 50 to 1,900 parts by weight, more preferably 100 to 1,200 parts by weight, and even more preferably 100 to 900 parts by weight, based on 100 parts by weight of the total solid content of the composition.
• each ion in the photosensitive composition layer of the transfer film of the first embodiment to the fourth embodiment can be adjusted, for example, by the following method.
• a method may be mentioned in which the content of each ion in the composition forming the photosensitive composition layer is reduced and then a compound containing each ion is added.
• the components and solvent constituting the photosensitive composition layer are each subjected to ion removal treatment, mixed to form a composition, and a predetermined salt is added to adjust the ion content.
• the components and solvent constituting the composition layer are each subjected to ion removal treatment, they are mixed to form a composition, the composition is subjected to ion removal treatment, and a prescribed salt is added to reduce the ion content.
• Examples of the above-mentioned predetermined salts include salts of each ion and a cation (eg, hydrogen ion, alkali metal ion).
• the above ion removal treatment methods include a method of bringing the object to be treated into contact with ion-exchanged water, a method of bringing the object to be treated into contact with an anion exchange resin, and a method of bringing the object to be treated into contact with an anion adsorbent.
• the method for bringing the object to be treated and ion-exchanged water into contact is a method of mixing the object to be treated and ion-exchanged water and then separating the object and ion-exchanged water (for example, liquid separation, mixing with a water-absorbing agent, etc.). contact, distillation, etc.).
• the method of bringing the object to be treated into contact with an anion exchange resin and the method of bringing the object to be treated into contact with an anion adsorbent include mixing a solid anion exchange resin or an anion adsorbent with the object to be treated.
• examples include a method in which the material is separated from the object to be treated, and a method in which the object to be treated is passed through a filter containing a solid anion exchange resin or an anion adsorbent.
• cation removal treatment may be performed using a cation exchange resin, a cation adsorbent, or the like.
• Examples of methods for applying the photosensitive composition include printing, spraying, roll coating, bar coating, curtain coating, spin coating, and die coating (ie, slit coating).
• the drying temperature is preferably 80°C or higher, more preferably 90°C or higher.
• the upper limit thereof is preferably 130°C or less, more preferably 120°C or less. Drying can also be carried out by continuously changing the temperature.
• the drying time is preferably 20 seconds or more, more preferably 40 seconds or more, and even more preferably 60 seconds or more. Further, the upper limit thereof is not particularly limited, but is preferably 600 seconds or less, and more preferably 300 seconds or less.
• a transfer film having a protective film can be manufactured by laminating the protective film to the photosensitive composition layer.
• the method of bonding the protective film to the photosensitive composition layer is not particularly limited, and known methods may be used.
• Examples of the device for bonding the protective film to the photosensitive composition layer include known laminators such as a vacuum laminator and an auto-cut laminator.
• the laminator is preferably equipped with any heatable roller such as a rubber roller and capable of applying pressure and heating.
• the photosensitive composition layer can be transferred to the object to be transferred.
• the transfer film of the present invention can be applied to various uses. For example, it can be applied to etching resists, plating members, etc. A more specific example is an etching resist for forming wiring.
• a laminate having a conductor pattern can be manufactured using the above-described transfer film (first embodiment to fourth embodiment).
• the method for manufacturing a laminate having a conductor pattern is not particularly limited as long as it uses the above-mentioned transfer film, but the following manufacturing method is preferably mentioned as the method for manufacturing a laminate having a conductor pattern of the present invention. That is, a bonding step of bonding the transfer film and the substrate such that the surface of the photosensitive composition layer of the transfer film on the side opposite to the temporary support comes into contact with the conductive layer of the substrate having a conductive layer on the surface.
• an exposure step of exposing the photosensitive composition layer to pattern light A developing step of performing a developing treatment on the exposed photosensitive composition layer to form a resist pattern; an etching step of etching the conductive layer in a region where the resist pattern is not formed;
• a method for manufacturing a laminate having a conductor pattern further includes a temporary support peeling process of peeling off the temporary support between the lamination process and the exposure process, or between the exposure process and the development process. It will be done.
• the conductive layer preferably contains silver.
• the laminate having the resist pattern has a substrate, a conductive layer, and a resist pattern in this order. That is, as a method for manufacturing a laminate having a resist pattern, the following manufacturing method is preferably mentioned. That is, a bonding step of bonding the transfer film and the substrate such that the surface of the photosensitive composition layer of the transfer film on the side opposite to the temporary support comes into contact with the conductive layer of the substrate having a conductive layer on the surface.
• a developing step of performing a developing treatment on the exposed photosensitive composition layer to form a resist pattern
• a method for manufacturing a laminate having a conductor pattern further includes a temporary support peeling process of peeling off the temporary support between the lamination process and the exposure process, or between the exposure process and the development process. It will be done.
• peeling process When the transfer film has a protective film, it is preferable to carry out a peeling process of peeling the protective film from the transfer film before carrying out the above-mentioned bonding process. When the peeling step is performed, the surface of the photosensitive composition layer of the transfer film is exposed.
• the method for peeling off the protective film is not particularly limited, and any known method can be used.
• the protective film can be peeled off while being wound up into a roll.
• the bonding step is a step of bonding the transfer film and the substrate having the conductive layer so that the surface of the photosensitive composition layer is in contact with the conductive layer of the substrate having the conductive layer on the surface.
• a laminate (a substrate with a photosensitive composition layer) having a substrate, a conductive layer, a photosensitive composition layer, and a temporary support in this order is obtained.
• a substrate having a conductive layer has a conductive layer on the substrate, and an arbitrary layer may be formed as necessary. That is, the substrate having a conductive layer is a conductive substrate having at least a substrate and a conductive layer disposed on the substrate.
• the substrate examples include a resin substrate, a glass substrate, and a semiconductor substrate.
• a preferred embodiment of the substrate is described, for example, in paragraph [0140] of International Publication No. 2018/155193, the contents of which are incorporated herein.
• the material for the resin substrate cycloolefin polymers and polyimides are preferred.
• the thickness of the resin substrate is preferably 5 to 200 ⁇ m, more preferably 10 to 100 ⁇ m.
• the conductive layer is at least one layer selected from the group consisting of a metal layer, a conductive metal oxide layer, a graphene layer, a carbon nanotube layer, and a conductive polymer layer in terms of conductivity and fine line formation. It is preferable to have one. It is also preferable that the conductive layer contains silver, and the transfer film (first to fourth embodiments) of the present invention can be suitably applied to a conductive substrate in which the conductive layer contains silver. Furthermore, only one conductive layer or two or more conductive layers may be disposed on the substrate. When two or more conductive layers are arranged, it is preferable to have conductive layers made of different materials. A preferred embodiment of the conductive layer is described, for example, in paragraph [0141] of International Publication No. 2018/155193, the content of which is incorporated herein.
• the conductive layer may be a transparent conductive layer that can form a transparent electrode through the steps described below.
• the transparent conductive layer is preferably composed of a metal oxide film such as ITO (indium tin oxide) and IZO (indium zinc oxide), a metal mesh, and thin metal wires such as metal nanowires.
• the thin metal wire include thin wires made of silver, copper, and the like. Among these, silver conductive materials such as silver mesh and silver nanowires are preferred, and silver nanowires are more preferred.
• the thickness of the conductive layer is not particularly limited, and is preferably 50 nm or more, more preferably 100 nm or more.
• the upper limit is preferably 10 ⁇ m or less, more preferably 2 ⁇ m or less.
• the conductive layer and the surface of the photosensitive composition layer are in contact with each other.
• pressure bonding there are no particular limitations on the method of pressure bonding, and known transfer methods and lamination methods can be used. Among these, it is preferable that the surface of the photosensitive composition layer is placed on a substrate having a conductive part, and then pressure and heating are performed using a roll or the like.
• a known laminator such as a vacuum laminator and an auto-cut laminator can be used.
• the lamination temperature is not particularly limited, but is preferably, for example, 70 to 130°C.
• the exposure step is a step of exposing the photosensitive composition layer to light in a pattern.
• a resist pattern that protects at least a portion of the conductive layer is formed on the conductive layer on the substrate by performing an exposure step and a development step described below.
• pattern exposure refers to a form of exposure in a pattern, that is, a form of exposure in which exposed areas and non-exposed areas exist.
• the positional relationship between the exposed area and the unexposed area in pattern exposure is not particularly limited and may be adjusted as appropriate.
• the photosensitive composition layer may be exposed to light from the side opposite to the substrate, or the photosensitive composition layer may be exposed to light from the substrate side.
• the light source for pattern exposure can be appropriately selected and used as long as it can irradiate light in a wavelength range that can at least cure the photosensitive composition layer (for example, 365 nm or 405 nm).
• the main wavelength of exposure light for pattern exposure is preferably 365 nm.
• the dominant wavelength is the wavelength with the highest intensity.
• Examples of the light source include various lasers, light emitting diodes (LEDs), ultra-high-pressure mercury lamps, high-pressure mercury lamps, and metal halide lamps.
• the exposure amount is preferably 5 to 200 mJ/cm 2 , more preferably 10 to 200 mJ/cm 2 .
• the temporary support peeling process is a process of peeling the temporary support from the photosensitive composition layer-coated substrate between the bonding process and the exposure process, or between the exposure process and the development process described below.
• 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 developing step is a step of developing the exposed photosensitive composition layer to form a resist pattern.
• the photosensitive composition layer can be developed using a developer.
• an alkaline aqueous solution is preferred.
• alkaline compounds that can be contained in the alkaline aqueous solution include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, tetramethylammonium hydroxide, tetraethylammonium hydroxide, and tetrapropylammonium hydroxy. and choline (2-hydroxyethyltrimethylammonium hydroxide).
• development methods include paddle development, shower development, spin development, and dip development.
• Examples of the developer suitably used herein include the developer described in paragraph [0194] of International Publication No. 2015/093271, and examples of the development method suitably used include, for example, the developer described in International Publication No. 2015/093271, paragraph [0194].
• the development method described in paragraph [0195] of No. 2015/093271 can be mentioned.
• a rinsing treatment to remove the developer remaining on the conductive layer-coated substrate before proceeding to the next step.
• Water or the like can be used for rinsing.
• a drying treatment may be performed to remove excess liquid from the conductive layer-coated substrate.
• the etching process In the etching process, the conductive layer in the area where the resist pattern is not placed is etched. Through the etching process, a conductor pattern corresponding to the pattern of the resist pattern is formed, and a laminate having a conductor pattern is obtained.
• known methods can be applied, such as the method described in paragraphs [0209] to [0210] of JP2017-120435A, and paragraphs [0048] to [0048] of JP2010-152155A. Examples include the method described in [0054], a wet etching method using immersion in an etching solution, and a dry etching method such as plasma etching.
• an acidic or alkaline etching liquid may be appropriately selected depending on the object to be etched.
• the acidic etching solution include an aqueous solution of an acidic component alone selected from hydrochloric acid, sulfuric acid, nitric acid, acetic acid, hydrofluoric acid, oxalic acid, and phosphoric acid, and an aqueous solution of an acidic component selected from hydrochloric acid, sulfuric acid, nitric acid, acetic acid, hydrofluoric acid, oxalic acid, and phosphoric acid; Mention may be made of mixed aqueous solutions with salts selected from potassium permanganate.
• the acidic component may be a combination of multiple acidic components.
• the alkaline etching solution include an aqueous solution of an alkaline component alone selected from sodium hydroxide, potassium hydroxide, ammonia, organic amines, and salts of organic amines (such as tetramethylammonium hydroxide), and alkaline components and salts. (potassium permanganate, etc.).
• the alkaline component may be a combination of a plurality of alkaline components.
• the method for manufacturing a laminate having a conductor pattern may include a resist pattern stripping step of stripping off the remaining resist pattern after the etching step.
• the method for removing the remaining resist pattern is not particularly limited, but includes a method of removing it by chemical treatment, and a method of removing it using a removal liquid is preferable.
• the substrate having the remaining resist pattern is immersed for 1 to 30 minutes in a stirring removal solution whose temperature is preferably 30 to 80°C, more preferably 50 to 80°C. can be mentioned.
• the removal liquid examples include a removal liquid in which an inorganic alkali component or an organic alkali component is dissolved in water, dimethyl sulfoxide, N-methylpyrrolidone, or a mixed solution thereof.
• the inorganic alkali component examples include sodium hydroxide and potassium hydroxide.
• the organic alkali component examples include primary amine compounds, secondary amine compounds, tertiary amine compounds, and quaternary ammonium salt compounds. Alternatively, it may be removed by a known method such as a spray method, a shower method, or a paddle method using a removal solution.
• the method for manufacturing a laminate having a conductor pattern may include any steps (other steps) other than the steps described above.
• steps other steps
• Examples include a step of forming, but are not limited to these steps.
• the method for manufacturing a laminate having a conductive pattern may include a step of performing a treatment to reduce the visible light reflectance of some or all of the plurality of conductive layers included in the base material.
• An example of the treatment for reducing visible light reflectance is oxidation treatment.
• the visible light reflectance of the conductive layer can be reduced by oxidizing the copper to form copper oxide and blackening the conductive layer.
• the method for manufacturing a laminate having a conductive pattern includes the steps of forming an insulating film on the surface of the conductive pattern and forming a new conductive layer on the surface of the insulating film. Through the above steps, it is possible to form a second electrode pattern that is insulated from the first electrode pattern.
• the step of forming the insulating film is not particularly limited, and includes known methods for forming a permanent film.
• an insulating film having a desired pattern may be formed by photolithography using a photosensitive material having insulating properties.
• the process of forming a new conductive layer on the insulating film is not particularly limited, and for example, a new conductive layer with a desired pattern may be formed by photolithography using a conductive photosensitive material.
• a method for producing a laminate having a conductive pattern uses a substrate having a plurality of conductive layers on both surfaces of the base material, and sequentially or simultaneously forms a circuit on the conductive layers formed on both surfaces of the base material. It is also preferable. With such a configuration, it is possible to form a laminate having a conductor pattern for a touch panel in which the first conductor pattern is formed on one surface of the base material and the second conductor pattern is formed on the other surface. Moreover, it is also preferable to form a laminate having a conductor pattern for a touch panel having such a configuration from both sides of the base material by roll-to-roll.
• the laminate having a conductor pattern manufactured by the above manufacturing method can be applied to various devices.
• Examples of the device including a laminate having a conductive pattern manufactured by the above manufacturing method include a display device, a printed wiring board, a semiconductor package, and an input device, and a touch panel is preferable, and a capacitive touch panel is more preferable. preferable.
• the input device can be applied to display devices such as organic EL display devices and liquid crystal display devices.
• Temporary support The following temporary support A was used as the temporary support.
• Temporary support A polyethylene terephthalate film (16KS40, manufactured by Toray Industries, thickness: 16 ⁇ m, haze: 0.4%)
• composition for forming photosensitive composition layer The composition for forming a photosensitive composition layer used in each Example and Comparative Example was obtained by the following procedure. First, a pre-treatment composition A1 and a pre-treatment composition B1 were prepared using raw materials subjected to ion removal treatment. Ion removal treatment was performed on pre-treatment composition A1 and pre-treatment composition B1 according to the procedure described below to obtain composition A and composition B. Next, the following compounds I1 to I4 were added to Composition A or Composition B so that the content of each ion in the photosensitive composition layer to be formed was as shown in the table below, and each Example Photosensitive composition layer forming compositions A1 to A7 and B1 to B7 used in the above were obtained.
• ⁇ I1 Potassium phosphate (manufactured by Tokyo Kasei Co., Ltd.)
• I2 Potassium iodide (manufactured by Tokyo Kasha)
• I3 Potassium bromide (manufactured by Tokyo Kasei Co., Ltd.)
• I4 Potassium nitrate (manufactured by Wako Pure Chemical Industries) The method for measuring the content of each ion in the photosensitive composition layer is as described above.
• the alkali-soluble resin shown in the latter part was subjected to ion removal treatment according to the following procedure.
• PGME propylene glycol-1-monomethyl ether
• copolymer A solid content concentration 30.0%
• acetone 250 g of acetone
• NK Ester BPE-500 manufactured by Shin-Nakamura Chemical Industry Co., Ltd.
• 50 g of NK ester BPE-500 was dissolved in 200 g of ethyl acetate, then 100 g of ion-exchanged water was added and stirred for 5 minutes. After stirring, the mixture was allowed to stand to separate an aqueous phase and an organic phase, and the organic phase was extracted. Ion-exchanged water (100 g) was added to the extracted organic phase, and the organic phase was extracted in the same manner as above.
• the photopolymerization initiator (2-(o-chlorophenyl)-4,5-diphenylimidazole dimer, hereinafter also referred to as BIMD) shown in the latter part was subjected to ion removal treatment according to the following procedure. 10 g of BIMD was dissolved in 400 g of ethyl acetate, then 100 g of ion-exchanged water was added and stirred for 5 minutes. After stirring, the mixture was allowed to stand to separate an aqueous phase and an organic phase, and the organic phase was extracted. Ion-exchanged water (100 g) was added to the extracted organic phase, and the organic phase was extracted in the same manner as above. This treatment was carried out again to wash the organic phase. After washing, the solvent was removed under conditions of a temperature of 50° C. and a pressure of 30 Torr to obtain BIMD after ion removal treatment.
• composition A before adding the above-mentioned compounds I1 to I4 and composition B were obtained by performing the following ion removal treatment.
• a method for obtaining composition A will be described.
• the composition of the pre-treatment composition A1 used for the treatment is as follows. Note that the alkali-soluble resin, polymerizable compound, and photopolymerization initiator used in the preparation of pre-treatment composition A1 were subjected to the treatment described in the ion removal treatment of the raw materials.
• a zeolite adsorbent which will be described later as a metal ion adsorbent
• an anion exchange resin Amberlyst A21 manufactured by Rohm and Haas
• the mixture was stirred for 24 hours and subjected to ion adsorption treatment using a metal ion adsorbent and an anion exchange resin.
• the zeolite adsorbent and anion exchange resin were filtered off to obtain a composition A for forming a photosensitive composition layer.
• the metal ion adsorbent used in the above ion removal treatment was obtained by the following procedure. According to the synthesis method described in Japanese Patent Publication No. 42-008129, 100 g of Mizuga Sieves Y-500 (synthetic zeolite) manufactured by Mizusawa Chemical Industry Co., Ltd. was added to an aqueous solution obtained by dissolving 300 g of ammonium sulfate in 1500 g of ion-exchanged water. The mixture was treated at 100° C. for 30 minutes with stirring. The synthetic zeolite was filtered through a Teflon (registered trademark) filter to recover the synthetic zeolite.
• Mizuga Sieves Y-500 synthetic zeolite manufactured by Mizusawa Chemical Industry Co., Ltd. was added to an aqueous solution obtained by dissolving 300 g of ammonium sulfate in 1500 g of ion-exchanged water. The mixture was treated at 100° C. for 30 minutes with stirring.
• the recovered zeolite was further treated in the same manner as above using an aqueous solution obtained by dissolving 300 g of ammonium sulfate in 1500 g of ion-exchanged water.
• the synthesized zeolite was collected again and washed with water until no sulfate ions were detected in the washing solution.
• the water-washed synthetic zeolite was further heat-treated at 550°C for 3 hours.
• heat-treated synthetic zeolite was added to an aqueous solution in which 300 g of ammonium sulfate was dissolved in 6000 g of ion-exchanged water, and the mixture was stirred at 100° C. for 30 minutes, and the zeolite was collected by filtration.
• the recovered synthetic zeolite was washed with water and subjected to heat treatment (550°C) twice. After repeating the treatment twice, it was thoroughly washed with water and further heat-treated at 850° C. for 3 hours. Through the above treatment, the sodium ions contained in the synthetic zeolite were replaced with ammonium ions, and a metal ion adsorbent made of ultra-stable zeolite was obtained.
• Composition B was also obtained by subjecting pre-treatment composition B1 to the same treatment as above.
• the composition of the pre-treatment composition B1 used for the treatment is as follows. Note that the alkali-soluble resin, polymerizable compound, and photopolymerization initiator used in the preparation of pre-treatment composition B1 were those that had been subjected to the treatment described in the ion removal treatment of the raw materials.
• composition for forming photosensitive composition layer (Preparation of composition for forming photosensitive composition layer)
• the above compounds I1 to I4 are added to the composition A or B obtained in the above procedure to adjust the ion content so that the ion content in the photosensitive composition layer becomes the content shown in the latter part, respectively.
• photosensitive composition layer forming compositions A1 to A7 and B1 to B7 used in Examples were obtained. Note that for the photosensitive composition layer forming composition A1 having an ion content of 0.00 mass ppm, the corresponding above-mentioned compound was not added.
• the photosensitive composition layer forming composition AC1 used in Comparative Example 1 had the above-mentioned compounds I1 to I4 added so that the ion content in the photosensitive composition layer was the content shown in the latter part.
• compositions were obtained in the same manner as the photosensitive composition layer-forming compositions A1 to A7.
• the composition BC1 for forming a photosensitive composition layer used in Comparative Example 2 had the following compounds except that the above compounds I1 to I4 were added so that the content of ions in the photosensitive composition layer was as shown in the latter part. , were obtained in the same manner as the photosensitive composition layer-forming compositions B1 to B7.
• a substrate having a conductive layer on the surface (conductive substrate) was obtained using the following procedure, and the adhesion of the photosensitive composition layer formed using the transfer film of each example and comparative example and the generation of residue were evaluated. We conducted an evaluation.
• a silver nitrate solution prepared by dissolving 0.85 parts by mass (5.0 mmol) of silver nitrate in 7.65 parts by mass of ethylene glycol was added in a separate container.
• the stirring speed was changed to 100 rpm and the temperature was maintained at 135° C. for 3.0 hours, then heating was terminated and the mixture was naturally cooled to room temperature (25° C.).
• the solution temperature in the container reached room temperature (25° C.)
• the slurry after the reaction was collected into a centrifuge tube, washed by adding distilled water, and centrifuged at 3,000 rpm for 5 minutes.
• methanol was added to the remaining precipitate to form a slurry, and the slurry was centrifuged at 2500 rpm for 5 minutes. After removing the supernatant after centrifugation, methanol was again added to the remaining precipitate to form a slurry, which was then centrifuged at 1500 rpm for 10 minutes. After removing the supernatant after centrifugation, the remaining precipitate was added to water and stirred at 500 rpm for 10 minutes to obtain a silver nanowire dispersion.
• the average long axis length and average short axis length of the obtained silver nanowires were measured using the following method, the average long axis length was 10 ⁇ m, the average short axis length (average diameter) was 70 nm, and the average aspect ratio was It was 140.
• a transmission electron microscope (TEM; manufactured by JEOL Ltd., JEM-2000FX) was used to measure the average long axis length and average short axis length of the silver nanowires.
• 300 metal nanowires were randomly selected, the long axis length and short axis length (diameter) of the selected metal nanowires were measured, and the arithmetic mean value of each was calculated as the average of the metal nanowires.
• the long axis length and the average short axis length (average diameter) were defined as the long axis length and the average short axis length (average diameter).
• the silver nanowire dispersion obtained in the above procedure was applied to one side of a polyethylene terephthalate substrate (thickness: 40 ⁇ m) and dried at 80°C for 2 minutes to form a 200 nm-thick transparent conductor containing silver nanowires on the base material.
• a substrate (conductive substrate) having a layer containing silver nanowires was prepared by forming a layer.
• Adhesion evaluation was performed using the following procedure. First, the protective film was peeled off from the transfer film to expose the photosensitive composition layer of the transfer film. Next, the transparent conductive layer of the conductive substrate and the photosensitive composition layer of the transfer film were laminated to face each other under lamination conditions of a roll temperature of 90° C., a linear pressure of 0.8 MPa, and a linear speed of 3.0 m/min. A laminate was obtained. The laminate had a substrate, a transparent conductive layer, a photosensitive composition layer, and a temporary support in this order. The temporary support was peeled off from the obtained laminate, and cross-cuts were made in 100 squares of 1 mm x 1 mm on the photosensitive composition layer of the laminate.
• Nichiban's plant-based sellotape (registered trademark) No. 1 was applied to the cross-cut laminate.
• a tape peel test was conducted using No. 405, and the adhesion was evaluated based on the following criteria.
• a to C are preferable, B is more preferable, and A is particularly preferable.
• D The number of peeled squares is 11. That's all
• a resin pattern (resist pattern) was formed by development.
• Development was performed using a 1.0% potassium carbonate aqueous solution (developer) at 30° C. for 30 seconds by shower development.
• the space portion of the obtained resist pattern was examined using an ultra-high resolution scanning electron microscope (manufactured by Hitachi High-Technologies Corporation) at an acceleration voltage of 2.0 kV and an observation magnification of 5,000 times to remove development residues (residues of the photosensitive composition layer). ), and the occurrence of development residue was evaluated according to the following criteria.
• a to C are preferable, B is more preferable, and A is particularly preferable.
• composition of the photosensitive composition layer-forming composition used in each Example and Comparative Example, as well as the results of adhesion evaluation and development residue generation evaluation are shown in the table.
• the "composition for forming a photosensitive composition layer” column indicates which of the photosensitive composition layer forming compositions A and B obtained by performing the above ion removal treatment was used.
• the amount of each ion in the column "Amount of ions in photosensitive composition layer” was measured by the method described above, and is the content of each ion with respect to the total mass of the photosensitive composition layer.
• the "phosphate ion” column shows the content of phosphate ions
• the "iodide ion” column shows the content of iodide ions
• the "bromide ion” column shows the content of bromide ions
• the "nitric acid ion” column shows the content of bromide ions.
• the “ion” column means the content of nitrate ions.
• a 30% by mass aqueous solution of ferric nitrate (pH: 0.6) at 40° C. was supplied for 120 seconds using a shower method to the line-and-space portions of the substrates after evaluation of development residue generation in each example. Thereafter, the resist was peeled off by immersion in a 3% by mass aqueous sodium hydroxide solution at 50°C. Note that the transparent conductive layer (layer containing silver nanowires) can be etched using a 30% by mass aqueous solution of ferric nitrate at 40°C.
• the transparent conductive layer had a good pattern with no peeling or chipping.

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