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
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
  • G03F7/11—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having cover layers or intermediate layers, e.g. subbing layers
• • 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

Definitions

• the present disclosure relates to a photosensitive transfer material and a method for manufacturing the same, a method for manufacturing a resin pattern, and a method for manufacturing circuit wiring.
• a display device equipped with a touch panel such as a capacitive input device (organic electroluminescence (EL) display device, liquid crystal display device, etc.)
• the electrode pattern corresponding to the sensor in the viewing section the wiring of the peripheral wiring part and the lead-out wiring part
• a conductive layer pattern such as the above is provided inside the touch panel.
• forming a patterned layer requires a small number of steps to obtain the required pattern shape, so a composition for forming a photosensitive layer is provided on an arbitrary substrate using a photosensitive transfer material.
• a widely used method is to expose the layer to light through a mask having a desired pattern and then develop it.
• JP 2019-128445A discloses that a cover film has a photosensitive layer, an adhesive layer, and a temporary support in this order, the photosensitive layer contains particles, and the photosensitive layer and the temporary support have a photosensitive layer, an adhesive layer, and a temporary support in this order.
• the photosensitive layer and the adhesive layer are in contact with each other, and the photosensitive layer and the adhesive layer are peelable, and the surface of the photosensitive layer after peeling off the photosensitive layer and the adhesive layer is the particle.
• a photosensitive transfer material having unevenness formed by the method is described.
• International Publication No. 2019/146380 has a photosensitive layer, an intermediate layer, an adhesive layer, and a temporary support in this order on a cover film, the intermediate layer contains particles, and the intermediate layer has a photosensitive layer, an intermediate layer, an adhesive layer, and a temporary support in this order.
• the intermediate layer and the adhesive layer are in contact with each other, the intermediate layer and the adhesive layer are peelable, and the surface of the intermediate layer after peeling off the intermediate layer and the adhesive layer is the particle.
• a photosensitive transfer material having unevenness formed by the method is described.
• the problem to be solved by one embodiment of the present invention is to provide a photosensitive transfer material with excellent slip properties and a method for producing the same.
• Another problem to be solved by another embodiment of the present invention is to provide a method for manufacturing a resin pattern and a method for manufacturing circuit wiring using the photosensitive transfer material.
• a cover film has a transfer layer and a temporary support in this order, the transfer layer has a photosensitive layer and a particle layer containing particles in this order, and the particle layer and The particle layer and the temporary support are in contact with each other, the particle layer and the temporary support are removable, the surface of the particle layer on the temporary support side has a convex structure containing the particles, and the particle layer has a convex structure containing the particles.
• a photosensitive transfer material wherein the average layer thickness of the portion of the layer where the convex structure does not exist is smaller than the arithmetic mean particle size of the particles contained in the particle layer.
• a transfer layer and a temporary support are provided in this order on the cover film, and the transfer layer has a photosensitive layer, an intermediate layer, and a particle layer containing particles in this order, The particle layer and the temporary support are in contact with each other, the particle layer and the temporary support are removable, and the surface of the particle layer on the temporary support side has a convex structure containing the particles.
• Photosensitive transfer material ⁇ 3> The photosensitive transfer material according to ⁇ 1> or ⁇ 2>, wherein the temporary support has an adhesive layer on a surface in contact with the particle layer.
• the adhesive layer contains a polyester resin.
• ⁇ 5> The photosensitive transfer material according to any one of ⁇ 1> to ⁇ 4>, wherein the photosensitive layer is a negative photosensitive layer.
• ⁇ 6> The photosensitive transfer material according to any one of ⁇ 1> to ⁇ 5>, wherein the transfer layer has an oxygen permeability of 25,000 cc/m 2 ⁇ day ⁇ atm or less.
• ⁇ 7> The photosensitive transfer material according to ⁇ 2>, wherein the intermediate layer contains polyvinyl alcohol.
• ⁇ 8> The photosensitive transfer material according to any one of ⁇ 1> to ⁇ 7>, wherein the particle layer contains an alkali-soluble resin.
• ⁇ 9> The photosensitive transfer material according to any one of ⁇ 1> to ⁇ 8>, wherein the particles have an arithmetic mean particle diameter of 10 nm to 200 nm.
• a method for producing a photosensitive transfer material wherein the average layer thickness of the portion where the convex structure does not exist is smaller than the arithmetic mean particle diameter of the particles included in the particle layer.
• a method for producing a photosensitive transfer material comprising: ⁇ 13> A step of peeling off the cover film in the photosensitive transfer material according to any one of ⁇ 1> to ⁇ 10>, and the photosensitive layer in the photosensitive transfer material from which the cover film has been peeled off.
• a method for producing a resin pattern comprising, in this order, exposing the photosensitive layer to pattern light through a photosensitive layer, and developing the photosensitive layer to form a resin pattern.
• a step of pattern-exposing the photosensitive layer through a photosensitive layer a step of developing the photosensitive layer to form a resin pattern, and a step of etching the conductive layer using the formed resin pattern as a mask.
• Methods for manufacturing circuit wiring included in this order ⁇ 15>
• a method for manufacturing circuit wiring comprising, in this order, the steps of peeling off the formed resin pattern and etching the conductive layer.
• a photosensitive transfer material with excellent slip properties and a method for producing the same. Further, according to other embodiments of the present invention, it is possible to provide a method for manufacturing a resin pattern and a method for manufacturing circuit wiring using the photosensitive transfer material.
• FIG. 1 is a schematic diagram showing an example of the configuration of a photosensitive transfer material.
• 3 is a schematic plan view showing pattern A.
• FIG. 3 is a schematic plan view showing pattern B.
• FIG. 1 is a schematic diagram showing an example of the configuration of a photosensitive transfer material.
• 3 is a schematic plan view showing pattern A.
• FIG. 3 is a schematic plan view showing pattern B.
• FIG. 1 is a schematic diagram showing an example of the configuration of a photosensitive transfer material.
• 3 is a schematic plan view showing pattern A.
• FIG. 3 is a schematic plan view showing pattern B.
• the amount of each component in the composition is the total amount of the corresponding substances present in the composition, unless otherwise specified. means quantity.
• the term "step” is used not only to refer to an independent step but also to include a step in which the intended purpose of the step is achieved even if the step cannot be clearly distinguished from other steps.
• groups (atomic groups) in this specification descriptions that do not indicate substituted or unsubstituted include those with no substituents as well as those with substituents.
• alkyl group includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
• exposure includes not only exposure using light but also drawing using particle beams such as electron beams and ion beams, unless otherwise specified.
• the light used for exposure generally includes active rays (active energy rays) such as the bright line spectrum of mercury lamps, far ultraviolet rays typified by excimer lasers, extreme ultraviolet rays (EUV light), X-rays, and electron beams. Can be mentioned.
• the chemical structural formulas in this specification may be written as simplified structural formulas in which hydrogen atoms are omitted.
• “mass %” and “weight %” have the same meaning
• “mass parts” and “weight parts” have the same meaning.
• a combination of two or more preferred embodiments is a more preferred embodiment.
• the weight average molecular weight (Mw) and number average molecular weight (Mn) in this disclosure are determined using columns of TSKgel GMHxL, TSKgel G4000HxL, and TSKgel G2000HxL (all product names manufactured by Tosoh Corporation).
• total solid content refers to the total mass of the components excluding the solvent from the entire composition of the composition. Further, as described above, the “solid content” refers to components excluding the solvent, and may be solid or liquid at 25° C., for example.
• a first embodiment of the photosensitive transfer material according to the present disclosure has a transfer layer and a temporary support in this order on a cover film, and the transfer layer includes a photosensitive layer and particles containing particles.
• layer in this order, the particle layer and the temporary support are in contact, the particle layer and the temporary support are removable, and the surface of the particle layer on the temporary support side is , has a convex structure containing the particles, and the average layer thickness of a portion of the particle layer where the convex structure does not exist is smaller than the arithmetic mean particle size of the particles included in the particle layer.
• a second embodiment of the photosensitive transfer material according to the present disclosure has a transfer layer and a temporary support in this order on a cover film, and the transfer layer includes a photosensitive layer, an intermediate layer, a particle layer containing particles in this order, the particle layer and the temporary support are in contact with each other, the particle layer and the temporary support are removable, and the temporary support of the particle layer is in contact with the temporary support.
• the body side surface has a convex structure containing the particles.
• the term "photosensitive transfer material according to the present disclosure” refers to both the first embodiment and the second embodiment.
• the term “cover film” or the like refers to the cover film, etc. of both or either of the first embodiment and the second embodiment.
• Dry film resist is widely used because resist patterns can be easily formed on various base materials by using thermal lamination. Furthermore, due to the recent trend toward higher integration of semiconductors and invisible fine wiring, high resolution is increasingly required, such as when DFR is used to form patterns of 5 ⁇ m or less.
• foreign matter that is difficult to remove may be mixed into a temporary support (such as a PET base material) used in a dry film resist even when the foreign matter is removed by filtering treatment.
• a temporary support such as a PET base material
• a mask contact exposure also referred to as mask contact exposure.
• the outermost layer for example, a photosensitive layer or an intermediate layer exposed after peeling off the temporary support retains the flat surface shape of the temporary support. Because it is copied, it has a flat shape.
• the average layer thickness of the part of the particle layer where no convex structure exists is smaller than the arithmetic mean particle size of the particles included in the particle layer, so that the convex structure of the required height is formed by the particles. is formed, improving the slipperiness between the resist outermost layer and the mask surface.
• the second embodiment by having both the intermediate layer and the particle layer, although the details are unknown, a convex structure formed by particles is favorably formed, and the slipperiness is improved.
• slipperiness is sometimes used to include the slipperiness between the outermost resist layer and the roll surface in addition to the slipperiness between the outermost resist layer and the mask surface.
• the photosensitive transfer material according to the present disclosure can be arranged between a temporary support and a photosensitive layer or an intermediate layer, between an intermediate layer and a photosensitive layer, between a photosensitive layer and a particle layer, and between a particle layer and a cover film. There may be other layers in between.
• the photosensitive transfer material according to the present disclosure is preferably a roll-shaped photosensitive transfer material from the viewpoint of exhibiting the effects of the present disclosure more.
• the oxygen transmittance of the transfer layer in the photosensitive transfer material according to the present disclosure is 25,000 cc/( m2 ⁇ day ⁇ atm) from the viewpoint of defect suppression, sensitivity, and resolution in the resulting resist pattern. It is preferably at most 1,000 cc/(m 2 ⁇ day atm), more preferably at most 100 cc/(m 2 ⁇ day atm), even more preferably at most 50 cc/(m 2 ⁇ day atm). ⁇ day ⁇ atm) or less is particularly preferable. Within the above range, polymerization inhibition of the photosensitive layer due to oxygen is suppressed, and durability after curing is excellent, exposure unevenness is suppressed, shape stability and resolution are excellent, and wiring such as circuit wiring is prevented.
• the method for measuring the oxygen permeability of the transfer layer in the present disclosure is as follows.
• a photosensitive transfer material was laminated onto a cellulose triacetate (TAC) base material (40 ⁇ m thick) from the photosensitive resin layer side under lamination conditions of a roll temperature of 100°C, a linear pressure of 1.0 MPa, and a linear speed of 4.0 m/min, and temporarily supported.
• the sample is peeled off and the transfer layer is transferred onto the TAC base material to prepare a measurement sample.
• the measurement sample was attached to the electrode part of the measurement device (oxygen concentration meter MODEL 3600 manufactured by Huck Ultra Analytical) via silicone grease, and the measurement environment was adjusted to 23° C. and 50% RH.
• the oxygen permeability coefficient is estimated from the amount of oxygen that reaches the electrode in steady state.
• the method for adjusting the oxygen permeability of the transfer layer to the above range there are no particular restrictions on the method for adjusting the oxygen permeability of the transfer layer to the above range, but there are methods such as having an intermediate layer or other layer as an oxygen barrier layer in addition to the photosensitive resin layer, or using an inorganic compound in the intermediate layer. , a method of adding an inorganic layered compound to the intermediate layer, and a method of including a water-soluble compound with low oxygen permeability, preferably a water-soluble resin, in the intermediate layer.
• the photosensitive layer is preferably a negative photosensitive layer.
• the photosensitive layer is a colored resin layer.
• the photosensitive transfer material according to the present disclosure is preferably used as a photosensitive transfer material for etching resist.
• the structure of the photosensitive transfer material is preferably one of the above-mentioned structures (1) to (3), for example.
• the total thickness of the other layers arranged on the side opposite to the temporary support side of the photosensitive layer is The amount is preferably 0.1% to 30%, more preferably 0.1% to 20%, based on the layer thickness of the photosensitive layer.
• the photosensitive transfer material will be explained below by giving an example.
• the photosensitive transfer material 20 shown in FIG. Have them in this order.
• the particle layer 18 has a convex structure 18a, and the convex structure 18a contains particles (not shown).
• the photosensitive transfer material 20 shown in FIG. 1 has a particle layer 18, a thermoplastic resin layer 13, and an intermediate layer 15, but the thermoplastic resin layer 13 and intermediate layer 15 may be arbitrary layers. , may not be placed.
• the layers included in the transfer layer include a photosensitive layer, an intermediate layer, a particle layer, a thermoplastic resin layer, and the like. Further, the temporary support and the cover film are not included in the transfer layer.
• Each element constituting the photosensitive transfer material will be explained below.
• the photosensitive transfer material according to the present disclosure has a particle layer containing particles, the particle layer and the temporary support are in contact with each other, the particle layer and the temporary support are releasable, and the particle layer and the temporary support are removable, and The surface of the particle layer on the temporary support side has a convex structure containing the particles.
• the fact that the particle layer and the temporary support are releasable means that the cover film of the photosensitive transfer material is peeled off, the surface of the base material exposed after the thermal lamination is applied to the base material and the temporary support is further peeled off. This can be confirmed by observing a layer containing particles, that is, a particle layer, using a scanning electron microscope (SEM).
• SEM scanning electron microscope
• the convex structure refers to a structure in which the layer thickness is locally large. It is preferable that the convex structure protrudes toward the temporary support.
• the convex structure is obtained by taking out the photosensitive transfer material as a section (thin section) with a film thickness of about 100 nm using a focused ion beam (FIB) processing method, and then cutting the photosensitive transfer material into a cross section using a transmission electron microscope (TEM). can be observed and confirmed as a structure where the layer thickness is locally larger than the surrounding area.
• TEM transmission electron microscope
• the convex structure can be seen when the cover film of the photosensitive transfer material is peeled off and laminated onto the base material, and then the temporary support is peeled off and the exposed surface of the base material is observed from the surface using SEM. , which can be confirmed as a structure that locally protrudes from the surrounding area.
• the average layer thickness of the portion of the particle layer where the convex structure does not exist is smaller than the arithmetic mean particle size of the particles included in the particle layer.
• the second embodiment of the photosensitive transfer material according to the present disclosure is characterized by smoothness, line width uniformity of the obtained resin pattern (hereinafter also simply referred to as "line width uniformity"), and the obtained resin. From the perspective of the linearity of the pattern and etching pattern (hereinafter also simply referred to as "linearity”), the average layer thickness of the part of the particle layer where the convex structure does not exist is determined by the arithmetic of the particles included in the particle layer.
• the particle size is smaller than the average particle size.
• an arithmetic mean particle diameter R of the particles included in the particle layer, an average layer thickness L of a portion of the particle layer where the convex structure is not present and From the viewpoint of slipperiness, line width uniformity, and linearity, the value of the ratio R/L is preferably greater than 1 and less than or equal to 5, more preferably greater than or equal to 1.1 and less than or equal to 4, and 1. .2 or more and 3 or less is particularly preferable.
• an arithmetic average particle diameter R of the particles included in the particle layer and an average layer thickness L of a portion of the particle layer where the convex structure is not present is preferably 0.5 or more and 5 or less, more preferably 1 or more and 4 or less, and 1 It is particularly preferable that the value exceeds 3 or less.
• the average layer thickness of the part of the particle layer where the convex structure does not exist was obtained by observing a cross section perpendicular to the main surface of the photosensitive transfer material using a scanning electron microscope (SEM). It is measured by measuring the thickness of the part of the particle layer where no convex structure exists at 10 or more points based on the observed image and calculating the arithmetic average value.
• SEM scanning electron microscope
• the average layer thickness of the part of the particle layer where the convex structure does not exist is preferably 5 nm to 250 nm, more preferably 10 nm to 200 nm, from the viewpoint of slipperiness, line width uniformity, and linearity.
• the thickness is preferably 10 nm to 100 nm, more preferably 15 nm to 70 nm.
• the above particles may be spherical, flat, or fibrous, and may be inorganic particles or organic particles.
• the particles are preferably inorganic particles from the viewpoint of slipperiness.
• the inorganic particles known inorganic particles can be used.
• the material of the inorganic particles include BN, Al 2 O 3 , AlN, TiO 2 , SiO 2 , barium titanate, strontium titanate, aluminum hydroxide, calcium carbonate, and materials containing two or more of these. It will be done.
• metal oxide particles are preferred, silica particles or titania particles are more preferred, and silica particles are particularly preferred, from the viewpoints of slipperiness, line width uniformity, and linearity.
• organic particles known organic particles can be used.
• the material of the organic particles include polyethylene, polystyrene, urea-formalin filler, polyester, cellulose, acrylic resin, fluororesin, hardened epoxy resin, crosslinked benzoguanamine resin, crosslinked acrylic resin, liquid crystal polymer, and two or more of these.
• materials include: Further, the organic particles may be fibrous such as nanofibers, or may be hollow resin particles. Among these, as the organic particles, crosslinked resin particles are preferred, and crosslinked acrylic resin particles are more preferred, from the viewpoints of slipperiness, line width uniformity, and linearity.
• the arithmetic mean particle diameter of the particles contained in the particle layer is preferably 5 nm to 300 nm, more preferably 10 nm to 200 nm, from the viewpoint of slipperiness, line width uniformity, and linearity. It is more preferably 20 nm to 150 nm, particularly preferably 20 nm to 65 nm.
• the arithmetic mean particle size of particles in the present disclosure shall be measured by the following method.
• the photosensitive transfer material is taken out as a 100 nm thick section (thin section) using a focused ion beam (FIB) processing method, and the cross section is observed using a transmission electron microscope (TEM).
• TEM transmission electron microscope
• the major axis of any 100 observed particles is measured, and the arithmetic average value thereof is used as the arithmetic mean particle diameter.
• the particle layer further includes a resin.
• the resin preferably includes a water-soluble resin from the viewpoints of layer-forming properties and convex structure-forming properties.
• the resin preferably contains an alkali-soluble resin or a water-soluble resin from the viewpoint of layer-forming properties and convex structure-forming properties, More preferably, it contains an alkali-soluble resin.
• the particle layer when the intermediate layer and the particle layer are in direct contact with each other, it is preferable that the particle layer contains an alkali-soluble resin.
• the particle layer when the thermoplastic resin layer described below and the particle layer are in direct contact with each other, the particle layer preferably contains a water-soluble resin.
• water-soluble resin in the particle layer examples include water-soluble resins in the intermediate layer described below.
• the alkali-soluble resin in the particle layer the alkali-soluble resin in the photosensitive layer described below is preferably mentioned.
• the above-mentioned particle layer may contain only one type of particle, or may contain two or more types of particles.
• the content of particles in the particle layer is preferably 5% by mass to 80% by mass, and 10% by mass, based on the total mass of the particle layer, from the viewpoint of slipperiness, line width uniformity, and linearity. It is more preferably from 15% to 65% by weight, and particularly preferably from 20% to 60% by weight.
• the particle layer may contain only one type of resin, or may contain two or more types of resin.
• the content of the resin in the particle layer is preferably 20% to 95% by mass, and 30% by mass, based on the total mass of the particle layer, from the viewpoint of slipperiness, line width uniformity, and linearity. It is more preferably from 90% by weight, even more preferably from 35% to 85% by weight, and particularly preferably from 40% to 80% by weight.
• the particle layer may contain other known components such as surfactants.
• the surfactant include anionic surfactants, cationic surfactants, nonionic (nonionic) surfactants, and amphoteric surfactants, with nonionic surfactants being preferred.
• anionic surfactants cationic surfactants
• nonionic surfactants nonionic surfactants
• amphoteric surfactants with nonionic surfactants being preferred.
• fluorine-based surfactants or silicone-based surfactants are preferred, and fluorine-based surfactants are more preferred.
• Preferred specific examples of the surfactant include the surfactants described in the section of the photosensitive layer described below.
• the photosensitive transfer material according to the present disclosure has a temporary support.
• the temporary support is a support that supports the photosensitive layer or the laminate including the photosensitive layer and is removable.
• the temporary support has a concave structure corresponding to the convex structure of the particle layer.
• the peeling force between the temporary support and the particle layer is preferably 0.5 N/25 mm or less.
• the peeling force between the temporary support and the particle layer is preferably 0.001 N/25 mm or more. The above-mentioned peeling force is measured by the method described below.
• the temporary support preferably has light transmittance from the viewpoint of enabling exposure of the photosensitive layer through the temporary support during pattern exposure of the photosensitive layer.
• “having light transmittance” means that the transmittance of light at the wavelength used for pattern exposure is 50% or more.
• the temporary support preferably has a transmittance of light at a wavelength used for pattern exposure (more preferably a wavelength of 365 nm) of 60% or more, and preferably 70% or more. is more preferable.
• the transmittance of a layer provided in a photosensitive transfer material refers to the amount of light emitted through the layer relative to the intensity of the incident light when the light is incident in the direction perpendicular to the main surface of the layer (thickness direction). It is a ratio of the intensity of emitted light, and is measured using MCPD Series manufactured by Otsuka Electronics Co., Ltd.
• Examples of the material constituting the temporary support include a glass substrate, a resin film, and paper, and resin films are preferred from the viewpoints of strength, flexibility, and light transmittance.
• Examples of the resin film include polyethylene terephthalate (PET) film, cellulose triacetate film, polystyrene film, and polycarbonate film. Among these, PET film is preferred, and biaxially stretched PET film is more preferred.
• the thickness (layer thickness) of the temporary support is not particularly limited, and is determined by the strength as a support, the flexibility required for bonding with the circuit wiring forming substrate, and the light transmission required during the first exposure. From the viewpoint of performance, the material may be selected depending on the material.
• the thickness of the temporary support is preferably in the range of 5 ⁇ m to 100 ⁇ m, more preferably in the range of 10 ⁇ m to 50 ⁇ m, even more preferably in the range of 10 ⁇ m to 20 ⁇ m, and even more preferably in the range of 10 ⁇ m to 16 ⁇ m from the viewpoint of ease of handling and versatility. Particularly preferred. Further, from the viewpoint of defect suppression, resolution, and linearity of the resin pattern, the thickness of the temporary support is preferably 50 ⁇ m or less, more preferably 25 ⁇ m or less, and preferably 20 ⁇ m or less. Particularly preferred.
• the film used as the temporary support has no deformation such as wrinkles, scratches, defects, etc.
• the number of fine particles, foreign matter, defects, precipitates, etc. contained in the temporary support is small.
• the number of fine particles, foreign objects, and defects with a diameter of 1 ⁇ m or more is preferably 50 pieces/10 mm 2 or less, more preferably 10 pieces/10 mm 2 or less, and even more preferably 3 pieces/10 mm 2 or less. , 0 pieces/10 mm 2 is particularly preferable.
• the haze of the temporary support is small.
• the haze value of the temporary support is preferably 2% or less, more preferably 1.5% or less, even more preferably less than 1.0%, and particularly preferably 0.5% or less.
• the haze value in the present disclosure is measured by a method according to JIS K 7105:1981 using a haze meter (NDH-2000, manufactured by Nippon Denshoku Industries Co., Ltd.).
• a layer containing fine particles may be provided on the surface of the temporary support from the viewpoint of imparting 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 can be, for example, 0.05 ⁇ m to 0.8 ⁇ m. Further, the thickness of the lubricant layer can be, for example, 0.05 ⁇ m to 1.0 ⁇ m.
• the arithmetic mean roughness Ra of the surface of the temporary support opposite to the photosensitive layer side is determined from the viewpoints of transportability, defect suppression of the resin pattern, and resolution. It is preferable that the arithmetic mean roughness of the side surface is equal to or greater than Ra.
• the arithmetic mean roughness Ra of the surface of the temporary support opposite to the photosensitive layer side is preferably 100 nm or less from the viewpoints of transportability, defect suppression of the resin pattern, and resolution,
• the thickness is more preferably 50 nm or less, even more preferably 20 nm or less, and particularly preferably 10 nm or less.
• the arithmetic mean roughness Ra of the surface of the photosensitive layer side of the temporary support is preferably 100 nm or less from the viewpoint of removability of the temporary support, defect suppression of the resin pattern, and resolution,
• the thickness is more preferably 50 nm or less, even more preferably 20 nm or less, and particularly preferably 10 nm or less.
• the value of the difference obtained by dividing the arithmetic mean roughness Ra of the surface of the temporary support on the photosensitive layer side from the arithmetic mean roughness Ra of the surface of the temporary support opposite to the photosensitive layer side is: From the viewpoints of transportability, resin pattern defect suppression, and resolution, the thickness is preferably 0 nm to 10 nm, more preferably 0 nm to 5 nm. That is, the arithmetic mean roughness Ra of the surface of the temporary support opposite to the photosensitive layer side is preferably the same as or larger than the arithmetic mean roughness Ra of the surface of the photosensitive layer side. .
• the arithmetic mean roughness Ra of the surface of the temporary support or cover film in the present disclosure shall be measured by the following method. Using a three-dimensional optical profiler (New View 7300, manufactured by Zygo), the surface of the temporary support or cover film is measured under the following conditions to obtain the surface profile of the film. Microscope Application of MetroPro ver. 8.3.2 is used as the measurement/analysis software. Next, a Surface Map screen is displayed using the analysis software, and histogram data is obtained on the Surface Map screen. From the obtained histogram data, the arithmetic mean roughness is calculated to obtain the Ra value of the surface of the temporary support or cover film. When the temporary support or cover film is bonded to a photosensitive layer or the like, the temporary support or cover film may be peeled off from the photosensitive layer and the Ra value of the surface of the peeled side may be measured.
• the peeling force of the temporary support is determined by From the viewpoint of suppressing peeling of the temporary support due to adhesion between the stacked laminates, the laminate is preferably 0.5 mN/mm or more, and 0.5 mN/mm to 2.0 mN/mm. It is more preferable that there be.
• the peeling force of the temporary support in the present disclosure shall be measured as follows.
• a copper layer with a thickness of 200 nm is formed on a polyethylene terephthalate (PET) film with a thickness of 100 ⁇ m by a sputtering method, thereby producing a PET substrate with a copper layer.
• PET polyethylene terephthalate
• the cover film is peeled off from the produced photosensitive transfer material, and laminated onto the above copper layer-coated PET substrate under laminating conditions of a laminating roll temperature of 100° C., a linear pressure of 0.6 MPa, and a linear speed (laminate speed) of 1.0 m/min.
• the laminate having at least the temporary support and the photosensitive layer is placed on the PET substrate with a copper layer to a size of 70 mm x 10 mm. Cut and prepare a sample.
• the PET substrate side of the sample was fixed on a document table.
• a tensile compression tester manufactured by Imada Seisakusho Co., Ltd., SV-55
• the tape was pulled at 5.5 mm/sec in a 180 degree direction to test the photosensitive layer or thermoplastic resin layer and the temporary support.
• the force required for peeling (peel force) and adhesion force are measured.
• Preferred embodiments of the temporary support include, for example, paragraphs 0017 to 0018 of JP 2014-85643, paragraphs 0019 to 0026 of JP 2016-27363, and paragraphs 0041 to 0057 of WO 2012/081680. , paragraphs 0029 to 0040 of International Publication No. 2018/179370, and paragraphs 0012 to 0032 of JP 2019-101405, and the contents of these publications are incorporated herein.
• the temporary support preferably has an adhesive layer on the surface in contact with the particle layer from the viewpoints of slipperiness, releasability, and convex structure formation properties.
• the material for the adhesive layer is not particularly limited and can be appropriately selected depending on the purpose, and examples include known adhesives or layers containing adhesives.
• adhesives examples include acrylic adhesives, urethane adhesives, rubber adhesives, silicone adhesives, and the like.
• adhesives include acrylic adhesives, ultraviolet (UV) curing adhesives, and ultraviolet (UV) curing adhesives, as described in "Characteristic Evaluation and Control Technology of Release Papers, Release Films, and Adhesive Tapes", Information Technology Organization, 2004, Chapter 2. and silicone adhesives.
• the acrylic adhesive refers to an adhesive containing a polymer containing a (meth)acrylic monomer ((meth)acrylic polymer).
• a tackifier may be further included.
• the adhesive examples include urethane resin adhesive, polyester resin adhesive, acrylic resin adhesive, ethylene vinyl acetate resin adhesive, polyvinyl alcohol adhesive, polyamide adhesive, silicone adhesive, and the like.
• the pressure-sensitive adhesive layer contains a polyester resin from the viewpoints of slipperiness, releasability, and ability to form a convex structure.
• the method of forming the adhesive layer is not particularly limited, and methods include laminating the temporary support on which the adhesive layer is formed so that the adhesive layer and the intermediate layer are in contact with each other, and forming the adhesive layer alone as the intermediate layer. Examples include a method of laminating the layers so that they are in contact with each other, and a method of applying a composition containing the pressure-sensitive adhesive or adhesive onto the intermediate layer.
• the temporary support on which the adhesive layer is formed commercially available ones may be used, such as E-MASK AW303D, E-MASK RP207 (both manufactured by Nitto Denko Corporation), PanaProtect HP25, and PanaProtect. Examples include MK38S (both manufactured by Panac Corporation).
• the thickness of the adhesive layer is preferably 5 ⁇ m to 100 ⁇ m from the viewpoint of achieving both adhesive strength and handling properties.
• the thickness of the adhesive layer is preferably 0.01 ⁇ m or more and 50 ⁇ m or less, more preferably 0.1 ⁇ m or more and 20 ⁇ m or less, particularly preferably 0.2 ⁇ m or more and 10 ⁇ m or less.
• the thickness of the adhesive layer is 0.01 ⁇ m or more, particles are prevented from being buried in the photosensitive layer during lamination, and good slipperiness during mask contact may be easily exhibited.
• it is 50 micrometers or less, the releasability of a temporary support body and a particle layer may become favorable.
• the photosensitive transfer material used in this disclosure has a photosensitive layer.
• the photosensitive layer may be a positive photosensitive layer or a negative photosensitive layer, and is preferably a negative photosensitive layer.
• the negative photosensitive layer preferably contains an alkali-soluble resin, a polymerizable compound, and a photopolymerization initiator, and based on the total mass of the photosensitive layer, the alkali-soluble resin: 10% by mass to 90% by mass; ethylene It is more preferable to contain a sexually unsaturated compound: 5% by mass to 70% by mass; and a photopolymerization initiator: 0.01% by mass to 20% by mass.
• the positive type photosensitive layer is not limited, and any known positive type photosensitive layer can be used.
• the positive photosensitive layer preferably contains an acid-decomposable resin, that is, a polymer having a structural unit having an acid group protected with an acid-decomposable group, and a photoacid generator. Moreover, it is preferable that the positive photosensitive layer contains a resin having a structural unit having a phenolic hydroxyl group and a quinonediazide compound. Further, the positive-working photosensitive layer is more preferably a chemically amplified positive-working photosensitive layer containing a photoacid generator and a polymer having a structural unit having an acid group protected with an acid-decomposable group. Each component will be explained in order below. Note that the term "photosensitive layer” refers to both a positive-type photosensitive layer and a negative-type photosensitive layer.
• the negative photosensitive layer contains a polymerizable compound.
• the term “polymerizable compound” refers to a compound that polymerizes under the action of a photopolymerization initiator, which will be described later, and is different from the “alkali-soluble resin", which will be described later.
• the polymerizable group possessed by the polymerizable compound is not particularly limited as long as it is a group that participates in a polymerization reaction, and includes, for example, an ethylenically unsaturated group such as a vinyl group, an acryloyl group, a methacryloyl group, a styryl group, and a maleimide group. group; and a group having a cationic polymerizable group such as an epoxy group and an oxetane group.
• a group having an ethylenically unsaturated group is preferable, and an acryloyl group or a methacryloyl group is more preferable.
• a polymeric compound it is preferable that an ethylenically unsaturated compound is included, and it is more preferable that a (meth)acrylate compound is included.
• the negative photosensitive layer preferably contains a bifunctional or more functional polymerizable compound (polyfunctional polymerizable compound), and preferably contains a trifunctional or more functional polymerizable compound. is more preferable.
• the term "bifunctional or higher functional polymerizable compound” means a compound having two or more polymerizable groups in one molecule.
• the number of polymerizable groups in one molecule of the polymerizable compound is preferably 6 or less.
• the negative photosensitive layer preferably contains a difunctional or trifunctional ethylenically unsaturated compound, from the viewpoint of achieving a better balance between the photosensitivity, resolution, and releasability of the photosensitive layer. It is more preferable to include a saturated compound.
• the content of bifunctional or trifunctional ethylenically unsaturated compounds relative to the total content of ethylenically unsaturated compounds in the negative photosensitive layer is preferably 60% by mass or more, and more than 70% by mass from the viewpoint of excellent peelability. is more preferable, and still more preferably 90% by mass or more.
• the upper limit is not particularly limited and may be 100% by mass. That is, all the ethylenically unsaturated compounds contained in the negative photosensitive layer may be difunctional ethylenically unsaturated compounds.
• the negative photosensitive layer preferably contains a polymerizable compound having a polyalkylene oxide structure, and more preferably contains a polymerizable compound having a polyethylene oxide structure.
• Preferred examples of the polymerizable compound having a polyalkylene oxide structure include polyalkylene glycol di(meth)acrylate, which will be described later.
• the negative photosensitive layer preferably contains an ethylenically unsaturated compound B1 having an aromatic ring and two ethylenically unsaturated groups.
• the ethylenically unsaturated compound B1 is a bifunctional ethylenically unsaturated compound having one or more aromatic rings in one molecule among the ethylenically unsaturated compounds mentioned above.
• the mass ratio of the content of ethylenically unsaturated compound B1 to the total content of ethylenically unsaturated compounds is preferably 40% by mass or more from the viewpoint of better resolution, It is more preferably 50% by mass or more, even more preferably 55% by mass or more, and particularly preferably 60% by mass or more.
• the upper limit is not particularly limited, but from the viewpoint of releasability, it is preferably 99% by mass or less, more preferably 95% by mass or less, even more preferably 90% by mass or less, and particularly preferably 85% by mass or less.
• Examples of the aromatic ring possessed by the ethylenically unsaturated compound B1 include aromatic hydrocarbon rings such as a benzene ring, a naphthalene ring and an anthracene ring, a thiophene ring, a furan ring, a pyrrole ring, an imidazole ring, a triazole ring and a pyridine ring.
• aromatic hydrocarbon rings such as a benzene ring, a naphthalene ring and an anthracene ring, a thiophene ring, a furan ring, a pyrrole ring, an imidazole ring, a triazole ring and a pyridine ring.
• Examples include aromatic heterocycles and condensed rings thereof, with aromatic hydrocarbon rings being preferred and benzene rings being more preferred. Note that the aromatic ring may have a substituent.
• the ethylenically unsaturated compound B1 preferably has a bisphenol structure, since resolution is improved by suppressing swelling of the negative photosensitive 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).
• Examples include the F structure and the bisphenol B structure derived from bisphenol B (2,2-bis(4-hydroxyphenyl)butane), with the bisphenol A structure being preferred.
• Examples of the ethylenically unsaturated compound B1 having a bisphenol structure include a compound having a bisphenol structure and two ethylenically unsaturated groups (preferably (meth)acryloyl groups) bonded to both ends of the bisphenol structure. . Both ends of the bisphenol structure and the two ethylenically unsaturated groups may be bonded directly or 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.
• the ethylenically unsaturated compound B1 having a bisphenol structure is described in paragraphs 0072 to 0080 of JP 2016-224162A, and the content described in this publication is incorporated herein.
• ethylenically unsaturated 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 examples include 2,2-bis(4-(methacryloxydiethoxy)phenyl)propane (FA-324M, Hitachi Chemical ( Co., Ltd.), 2,2-bis(4-(methacryloxyethoxypropoxy)phenyl)propane, 2,2-bis(4-(methacryloxypentaethoxy)phenyl)propane (BPE-500, Shin Nakamura Chemical Co., Ltd.) (manufactured by Hitachi Chemical Co., Ltd.), 2,2-bis(4-(methacryloxydecaethoxytetrapropoxy)phenyl)propane (FA-3200MY, manufactured by Hitachi Chemical Co., Ltd.), 2,2-bis(4-(methacryloxypentadeca) ethoxy)phenyl)propane (BPE-1300, manufactured by Shin Nakamura Chemical Co., Ltd.), 2,2-bis(4-(me
• ethylenically unsaturated compound B1 a compound represented by the following formula (Bis) can be used.
• R 1 and R 2 each independently represent a hydrogen atom or a methyl group
• A is C 2 H 4
• B is C 3 H 6
• n 1 and n 3 are each independently is an integer from 1 to 39
• n 1 + n 3 is an integer from 2 to 40
• n 2 and n 4 are each independently an integer from 0 to 29, and n 2 + n 4 is from 0 to It is an integer of 30, and the arrangement of repeating units of -(AO)- and -(BO)- may be random or block. In the case of a block, either -(AO)- or -(BO)- may be on the bisphenol structure side.
• n 1 +n 2 +n 3 +n 4 is preferably an integer of 2 to 20, more preferably 2 to 16, and even more preferably 4 to 12. Further, n 2 + n 4 is preferably an integer of 0 to 10, more preferably an integer of 0 to 4, even more preferably an integer of 0 to 2, and particularly preferably 0.
• the ethylenically unsaturated compounds B1 may be used alone or in combination of two or more.
• the content of the ethylenically unsaturated compound B1 in the negative photosensitive layer is preferably 10% by mass or more, and 20% by mass or more based on the total mass of the negative photosensitive layer, from the viewpoint of better resolution. is more preferable.
• the upper limit is not particularly limited, but from the viewpoint of transferability and edge fusion suppression, it is preferably 70% by mass or less, more preferably 60% by mass or less.
• the edge fusion described above refers to a phenomenon in which components in the negative photosensitive layer ooze out from the edges of the photosensitive transfer material.
• the negative photosensitive layer may contain an ethylenically unsaturated compound other than the above-mentioned ethylenically unsaturated compound B1.
• the ethylenically unsaturated compounds other than the ethylenically unsaturated 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 more ethylenically unsaturated compounds. Examples include compounds.
• 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 compound having no aromatic ring examples include alkylene glycol di(meth)acrylate, polyalkylene glycol di(meth)acrylate, urethane di(meth)acrylate, and trimethylolpropane diacrylate. It will be done.
• 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, Shin Nakamura Chemical Co., Ltd.), 1,6-hexanediol diacrylate (A-HD-N, Shin Nakamura Chemical Co., Ltd.) ), ethylene glycol dimethacrylate, 1,10-decanediol diacrylate, and neopentyl glycol di(meth)acrylate.
• A-DCP tricyclodecane dimethanol diacrylate
• DCP tricyclodecane dimethanol dimethacrylate
• 1,9-nonanediol diacrylate A-NOD-N, Shin Nakamura Chemical Co.
• 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.
• trifunctional or more ethylenically unsaturated compounds include dipentaerythritol (tri/tetra/penta/hexa)(meth)acrylate, pentaerythritol (tri/tetra)(meth)acrylate, and trimethylolpropane tri(meth)acrylate.
• 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 layer preferably contains the above-mentioned ethylenically unsaturated compound B1 and a trifunctional or more trifunctional ethylenically unsaturated compound, and the above-mentioned ethylenically unsaturated compound B1 and two or more trifunctional It is more preferable that the above ethylenically unsaturated compounds are included.
• a negative photosensitive layer contains the ethylenically unsaturated 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 manufactured by Shin Nakamura Chemical Co., Ltd.
• alkylene oxide-modified (meth)acrylate compounds (KAYARAD RP-1040 manufactured by Nippon Kayaku Co., Ltd., ATM-35E and A-9300 manufactured by Shin-Nakamura Chemical Co., Ltd., EBECRYL manufactured by Daicel Allnex Co., Ltd.) (registered trademark) 135, etc.), ethoxylated glycerin triacrylate (A-GLY-9E, etc.
• ethylenically unsaturated compound other than the ethylenically unsaturated compound B1 ethylenically unsaturated compounds having acid groups described in paragraphs 0025 to 0030 of JP-A No. 2004-239942 may be used.
• the value of the ratio Mm/Mb between the content Mm of ethylenically unsaturated compounds and the content Mb of alkali-soluble resin in the negative photosensitive layer should be 1.0 or less from the viewpoint of resolution and linearity. is preferably 0.9 or less, more preferably 0.5 or more and 0.9 or less. Moreover, it is preferable that the ethylenically unsaturated compound in the negative photosensitive layer contains a (meth)acrylic compound from the viewpoint of curability and resolution.
• the ethylenically unsaturated compound in the negative photosensitive layer contains a (meth)acrylic compound, and the above (meth)acrylic compound contained in the negative photosensitive layer It is more preferable that the content of the acrylic compound is 60% by mass or less based on the total mass of the compound.
• the molecular weight of the ethylenically unsaturated compound containing the ethylenically unsaturated compound B1 (if it has a distribution, the weight average molecular weight (Mw)) is preferably 200 to 3,000, more preferably 280 to 2,200, and 300 to 3,000. ⁇ 2,200 is more preferable.
• the ethylenically unsaturated compounds may be used alone or in combination of two or more.
• the content of the ethylenically unsaturated compound in the negative photosensitive layer is preferably 10% by mass to 70% by mass, more preferably 20% by mass to 60% by mass, and 20% by mass based on the total mass of the negative photosensitive layer. % to 50% by mass is more preferred.
• the negative photosensitive layer preferably contains a photopolymerization initiator.
• a photopolymerization initiator is a compound that initiates polymerization of an ethylenically unsaturated 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. Among these, a radical photopolymerization initiator is preferable for the photosensitive layer from the viewpoints of resolution and pattern formation.
• 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, a photopolymerization initiator having an N-phenylglycine structure, and a biimidazole compound.
• the photoradical polymerization initiator for example, 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 be used.
• photoradical polymerization initiators examples include ethyl dimethylaminobenzoate (DBE, CAS No. 10287-53-3), benzoin methyl ether, anisyl (p,p'-dimethoxybenzyl), and TAZ-110 (trade name: Midori Kagaku Co., Ltd.), benzophenone, TAZ-111 (product name: Midori Kagaku Co., Ltd.), Irgacure OXE01, OXE02, OXE03, OXE04 (manufactured by BASF), Omnirad 651 and 369 (product name: IGM Resins B.V.
• DBE ethyl dimethylaminobenzoate
• anisyl p,p'-dimethoxybenzyl
• TAZ-110 trade name: Midori Kagaku Co., Ltd.
• benzophenone TAZ-111 (product name: Midori Kagaku Co., Ltd.)
• photoradical polymerization initiators include, for example, 1-[4-(phenylthio)phenyl]-1,2-octanedione-2-(O-benzoyloxime) (trade name: IRGACURE (registered trademark) OXE01, BASF), 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone-1-(O-acetyloxime) (product name: IRGACURE OXE02, manufactured by BASF) , IRGACURE OXE03 (manufactured by BASF), 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone (product name: Omnirad 379EG) , manufactured by IGM Resins B.V.), 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one (product name: Omnirad 90
• 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.
• photocationic polymerization initiator 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, and a photocationic polymerization initiator that generates an acid with a pKa of 2 or less is preferable.
• 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 2014-85643A 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 No. 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 layer may contain one type of photopolymerization initiator alone, or may contain two or more types of photopolymerization initiators.
• the content of the photopolymerization initiator in the negative photosensitive layer is not particularly limited, but is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, based on the total mass of the photosensitive layer. More preferably, it is 0% by mass or more.
• the upper limit is not particularly limited, but is preferably 10% by mass or less, more preferably 5% by mass or less, based on the total mass of the negative photosensitive layer.
• the negative photosensitive layer contains an alkali-soluble resin.
• alkali-soluble means that the solubility in 100 g of a 1% by mass aqueous solution of sodium carbonate at a liquid temperature of 22° C. is 0.1 g or more.
• the alkali-soluble resin is not particularly limited, and suitable examples include known alkali-soluble resins used in etching resists.
• the alkali-soluble resin is a binder polymer.
• the alkali-soluble resin is preferably an alkali-soluble resin having an acid group. Among these, as the alkali-soluble resin, Polymer A, which will be described later, is preferable.
• the alkali-soluble resin contains Polymer A.
• the acid value of the polymer A is preferably 220 mgKOH/g or less, more preferably less than 200 mgKOH/g, and less than 190 mgKOH/g, from the viewpoint of better resolution by suppressing swelling of the photosensitive layer by the developer. is even more preferable.
• the lower limit of the acid value of the polymer A is not particularly limited, but from the viewpoint of better developability, it is preferably 60 mgKOH/g or more, more preferably 120 mgKOH/g or more, even more preferably 150 mgKOH/g or more, and 170 mgKOH/g or more. Particularly preferred.
• the acid value is the mass [mg] of potassium hydroxide required to neutralize 1 g of sample, and in this specification, the unit is expressed as mgKOH/g.
• the acid value can be calculated, for example, from the average content of acid groups in the compound.
• the acid value of the polymer A may be adjusted by the types of structural units constituting the polymer A and the content of the structural units containing acid groups.
• the weight average molecular weight of Polymer A is preferably 5,000 to 500,000. It is preferable to adjust the weight average molecular weight to 500,000 or less from the viewpoint of improving resolution and developability.
• the weight average molecular weight is more preferably 100,000 or less, even more preferably 60,000 or less, and particularly preferably 50,000 or less.
• 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 to which the photosensitive layer easily protrudes from the end surface of the roll when the photosensitive transfer material is wound up 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 photosensitive layer, it will be transferred to a mask in a later exposure step, etc., resulting in defective products.
• the degree of dispersion of the polymer A is preferably 1.0 to 6.0, more preferably 1.0 to 5.0, even more preferably 1.0 to 4.0, and 1. It is more preferably from .0 to 3.0.
• molecular weight is a value measured using gel permeation chromatography. Further, the degree of dispersion is the ratio of the weight average molecular weight to the number average molecular weight (weight average molecular weight/number average molecular weight).
• the negative photosensitive layer must contain a monomer component having an aromatic hydrocarbon group as the polymer A, from the viewpoint of suppressing thickening of line width and deterioration of resolution when the focal position shifts during exposure. is preferred.
• aromatic hydrocarbon groups include, for example, substituted or unsubstituted phenyl groups and substituted or unsubstituted aralkyl groups.
• the content of the monomer component having an aromatic hydrocarbon group in the polymer A is preferably 20% by mass or more, and preferably 30% by mass or more, based on the total mass of all monomer components. The content is more preferably 40% by mass or more, even more preferably 45% by mass or more, and most preferably 50% by mass or more.
• the upper limit is not particularly limited, but is preferably 95% by mass or less, more preferably 85% by mass or less.
• the content of the monomer component having an aromatic hydrocarbon group was determined as a weight average value.
• Examples of the monomer having an aromatic hydrocarbon group include monomers having an aralkyl group, styrene, and polymerizable styrene derivatives (for example, methylstyrene, vinyltoluene, tert-butoxystyrene, acetoxystyrene, 4-vinyl benzoic acid, styrene dimer, styrene trimer, etc.).
• monomers having an aralkyl group or styrene are preferred.
• the content of the styrene monomer component is 20% by mass based on the total mass of all monomer components. It is preferably ⁇ 50% by mass, more preferably from 25% to 45% by mass, even more preferably from 30% to 40% by mass, particularly preferably from 30% to 35% by mass. preferable.
• aralkyl group examples include substituted or unsubstituted phenylalkyl groups (excluding benzyl groups), substituted or unsubstituted benzyl groups, and substituted or unsubstituted benzyl groups are preferred.
• Examples of the monomer having a phenylalkyl group include phenylethyl (meth)acrylate and the like.
• Monomers having a benzyl group include (meth)acrylates having a benzyl group, such as benzyl (meth)acrylate, chlorobenzyl (meth)acrylate, etc.; vinyl monomers having a benzyl group, such as vinylbenzyl chloride, vinylbenzyl Examples include alcohol. Among them, benzyl (meth)acrylate is preferred.
• the content of the benzyl (meth)acrylate monomer component is the sum of all monomer components. Based on the mass, it is preferably 50% to 95% by mass, more preferably 60% to 90% by mass, even more preferably 70% to 90% by mass, and even more preferably 75% to 90% by mass. Particularly preferred is 90% by mass.
• Polymer A containing a monomer component having an aromatic hydrocarbon group includes a monomer having an aromatic hydrocarbon group and at least one of the first monomers described below and/or the second monomer described below. It is preferable that it is obtained by polymerizing at least one monomer of
• the polymer A containing no monomer component having an aromatic hydrocarbon group is preferably obtained by polymerizing at least one of the first monomers described below, and at least one of the first monomers is preferably obtained by polymerizing at least one of the first monomers described below. It is more preferable to obtain the monomer by copolymerizing one type with at least one of the second monomers described below.
• the first monomer is a monomer having a carboxy group in its molecule.
• the first monomer include (meth)acrylic acid, fumaric acid, cinnamic acid, crotonic acid, itaconic acid, 4-vinylbenzoic acid, maleic anhydride, maleic acid half ester, and the like. Among these, (meth)acrylic acid is preferred.
• the content of the first monomer in Polymer A is preferably 5% by mass to 50% by mass, and preferably 10% by mass to 40% by mass, based on the total mass of all monomer components. is more preferable, and even more preferably 15% by mass to 30% by mass.
• the copolymerization ratio of the first monomer is preferably 10% by mass to 50% by mass based on the total mass of all monomer components.
• the copolymerization ratio is preferably 10% by mass or more from the viewpoint of expressing good developability and controlling edge fusing properties, more preferably 15% by mass or more, and even more preferably 20% by mass or more.
• the second monomer is a monomer that is non-acidic and has at least one polymerizable unsaturated group in its molecule.
• Examples of the second monomer include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, and isobutyl (meth)acrylate.
• (meth)acrylates such as , tert-butyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate; vinyl acetate and (meth)acrylonitrile.
• methyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, and n-butyl (meth)acrylate are preferred, and methyl (meth)acrylate is particularly preferred.
• the content of the second monomer in polymer A is preferably 5% to 60% by mass, and preferably 15% to 50% by mass, based on the total mass of all monomer components. is more preferable, and even more preferably 20% by mass to 45% by mass.
• a monomer having an aralkyl group and/or styrene as a monomer from the viewpoint of suppressing thickening of line width and deterioration of resolution when the focal position during exposure is shifted.
• a copolymer containing methacrylic acid, benzyl methacrylate, and styrene, a copolymer containing methacrylic acid, methyl methacrylate, benzyl methacrylate, and styrene, etc. are preferred.
• the polymer A contains 25% to 40% by mass of a monomer component having an aromatic hydrocarbon group, 20% to 35% by mass of a first monomer component, and 20% to 35% by mass of a first monomer component.
• the polymer preferably contains 30% to 45% by mass of body components.
• the polymer preferably contains 70% to 90% by mass of a monomer component having an aromatic hydrocarbon group and 10% to 25% by mass of the first monomer component. .
• Polymer A may have any one of a linear structure, a branched structure, and an alicyclic structure in its side chain. Introducing a branched structure or alicyclic structure into the side chain of the polymer A by using a monomer containing a group having a branched structure in the side chain or a monomer containing a group having an alicyclic structure in the side chain. Can be done.
• the group having an alicyclic structure may be monocyclic or polycyclic. Specific examples of monomers containing a group having a branched structure in the side chain include i-propyl (meth)acrylate, i-butyl (meth)acrylate, s-butyl (meth)acrylate, and (meth)acrylate.
• t-butyl acid i-amyl (meth)acrylate, t-amyl (meth)acrylate, iso-amyl (meth)acrylate, 2-octyl (meth)acrylate, 3-octyl (meth)acrylate
• examples include t-octyl (meth)acrylate.
• i-propyl (meth)acrylate, i-butyl (meth)acrylate, or t-butyl methacrylate is preferred, and i-propyl methacrylate or t-butyl methacrylate is more preferred.
• Examples of 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, and the number of carbon atoms (number of carbon atoms)
• Examples include (meth)acrylates having 5 to 20 alicyclic hydrocarbon groups. More specific examples include (meth)acrylic acid (bicyclo[2.2.1]heptyl-2), (meth)acrylic acid-1-adamantyl, (meth)acrylic acid-2-adamantyl, and (meth)acrylic acid-2-adamantyl.
• cyclohexyl (meth)acrylate, (nor)bornyl (meth)acrylate, isobornyl (meth)acrylate, 1-adamantyl (meth)acrylate, and (meth)acrylic acid- 2-adamantyl, fentyl (meth)acrylate, 1-menthyl (meth)acrylate, or tricyclodecane (meth)acrylate is preferred, and cyclohexyl (meth)acrylate, (nor)bornyl (meth)acrylate, Particularly preferred are isobornyl (meth)acrylate, 2-adamantyl (meth)acrylate, or tricyclodecane (meth)acrylate.
• Polymer A can be used alone or in combination of two or more.
• a mixture of two or more types use a mixture of two types of polymer A containing a monomer component having an aromatic hydrocarbon group, or use a mixture of two types of polymer A containing a monomer component having an aromatic hydrocarbon group.
• the proportion of polymer A containing a monomer component having an aromatic hydrocarbon group is preferably 50% by mass or more, and preferably 70% by mass or more, based on the total amount of polymer A.
• the content is more preferably 80% by mass or more, and even more preferably 90% by mass or more.
• Synthesis of Polymer A is carried out by adding a radical polymerization initiator such as benzoyl peroxide or azoisobutyronitrile to a solution of one or more of the monomers described above diluted with a solvent such as acetone, methyl ethyl ketone, or isopropanol. It is preferable to add an appropriate amount of and heat and stir. In some cases, synthesis may be carried out while dropping a portion of the mixture into the reaction solution. After the reaction is completed, a solvent may be further added to adjust the concentration to a desired level. As a synthesis means, in addition to solution polymerization, bulk polymerization, suspension polymerization, or emulsion polymerization may be used.
• a radical polymerization initiator such as benzoyl peroxide or azoisobutyronitrile
• the glass transition temperature Tg of polymer A is preferably 30°C or more and 135°C or less.
• Polymer A having a Tg of 135° C. or lower in the photosensitive layer it is possible to suppress thickening of line width and deterioration of resolution when the focal position during exposure shifts.
• the Tg of the polymer A is more preferably 130°C or lower, even more preferably 120°C or lower, and particularly preferably 110°C or lower.
• Polymer A having a Tg of 30° C. or higher from the viewpoint of improving edge fuse resistance. From this point of view, the Tg of polymer A is more preferably 40°C or higher, even more preferably 50°C or higher, particularly preferably 60°C or higher, and most preferably 70°C or higher. .
• the negative photosensitive layer may contain resins other than alkali-soluble resins.
• resins other than alkali-soluble resins include acrylic resins, styrene-acrylic copolymers (with a styrene content of 40% by mass or less), polyurethane resins, polyvinyl alcohol, polyvinyl formal, polyamide resins, polyester resins, and epoxy resins.
• the alkali-soluble resins can be used alone or in combination of two or more.
• the ratio of the alkali-soluble resin to the total mass of the negative photosensitive layer is preferably in the range of 10% by mass to 90% by mass, more preferably 30% by mass to 70% by mass, and even more preferably 40% by mass. ⁇ 60% by mass. It is preferable from the viewpoint of controlling the development time that the ratio of the alkali-soluble resin to the negative photosensitive layer is 90% by mass or less. On the other hand, it is preferable that the proportion of the alkali-soluble resin in the negative photosensitive layer be 10% by mass or more from the viewpoint of improving edge fuse resistance.
• the photosensitive layer preferably contains a compound having a lone pair of electrons from the viewpoint of adhesion to the conductive layer.
• the compound having a lone pair of electrons is preferably a compound having at least a nitrogen atom, an oxygen atom, or a sulfur atom from the viewpoint of adhesion with the conductive layer, such as a heterocyclic compound, a thiol compound, or a disulfide. It is more preferably a compound, even more preferably a heterocyclic compound, and particularly preferably a nitrogen-containing heterocyclic compound.
• the nitrogen-containing heterocyclic compound preferably has a heterocycle having two or more nitrogen atoms, from the viewpoint of coordination and dimensional stability of the conductive pattern after electricity is applied, and preferably has three or more nitrogen atoms. It is more preferable to have a heterocycle having atoms, and it is particularly preferable to have a heterocycle having 3 or 4 nitrogen atoms.
• the heterocycle possessed by the heterocyclic compound may be either a monocyclic or polycyclic heterocycle.
• the heteroatom contained in the heterocyclic compound include a nitrogen atom, an oxygen atom, and a sulfur atom.
• the heterocyclic compound preferably contains at least one atom selected from the group consisting of a nitrogen atom, an oxygen atom, and a sulfur atom, and more preferably a nitrogen atom.
• heterocyclic compound examples include a triazole compound, a benzotriazole compound, a tetrazole compound, a thiadiazole compound, a triazine compound, a rhodanine compound, a thiazole compound, a benzothiazole compound, a benzimidazole compound, a benzoxazole compound, or a pyrimidine compound. It will be done.
• heterocyclic compounds include triazole compounds, benzotriazole compounds, tetrazole compounds, thiadiazole compounds, triazine compounds, rhodanine compounds, thiazole compounds, benzimidazole compounds, and It is preferably at least one compound selected from the group consisting of benzoxazole compounds, including triazole compounds, benzotriazole compounds, tetrazole compounds, thiadiazole compounds, thiazole compounds, benzothiazole compounds, benzimidazole compounds, and benzoxazole compounds. It is more preferably at least one compound selected from the group consisting of triazole compounds and tetrazole compounds, and triazole compounds are particularly preferable. .
• heterocyclic compound Preferred specific examples of the heterocyclic compound are shown below.
• examples of the triazole compound and benzotriazole compound include the following compounds.
• Examples of the tetrazole compound include the following compounds.
• thiadiazole compounds include the following compounds.
• triazine compounds include the following compounds.
• rhodanine compounds include the following compounds.
• thiazole compounds include the following compounds.
• benzothiazole compounds include the following compounds.
• benzimidazole compounds include the following compounds.
• benzoxazole compounds include the following compounds.
• thiol compounds and disulfide compounds are preferably mentioned.
• aliphatic thiol compounds are preferably mentioned.
• a monofunctional aliphatic thiol compound or a polyfunctional aliphatic thiol compound that is, an aliphatic thiol compound having two or more functionalities is suitably used.
• polyfunctional aliphatic thiol compounds include trimethylolpropane tris(3-mercaptobutyrate), 1,4-bis(3-mercaptobutyryloxy)butane, pentaerythritol tetrakis(3-mercaptobutyrate), 1,3,5-tris(3-mercaptobutyryloxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, trimethylolethane tris(3-mercaptobutyrate) ), tris[(3-mercaptopropionyloxy)ethyl]isocyanurate, trimethylolpropane tris(3-mercaptopropionate), pentaerythritol tetrakis(3-mercaptopropionate), tetraethylene glycol bis(3-mercaptopropionate) pionate), dipentaerythritol hexakis (3-mercap
• Examples of monofunctional aliphatic thiol compounds include 1-octanethiol, 1-dodecanethiol, ⁇ -mercaptopropionic acid, methyl-3-mercaptopropionate, 2-ethylhexyl-3-mercaptopropionate, n- Included are octyl-3-mercaptopropionate, methoxybutyl-3-mercaptopropionate, and stearyl-3-mercaptopropionate.
• disulfide compounds include 2-(4'-morpholinodithio)benzthiazole, 2,2'-benzthiazoyl disulfide, bis(2-benzamidophenyl) disulfide, 1,1-thiobis(2-naphthol), bis( 2,4,5-trichlorophenyl) disulfide, 4,4'-dithiomorpholine, tetraethylthiuram disulfide, dibenzyl disulfide, bis(2,4-dinitrophenyl) disulfide, 4,4'-diaminodiphenyl disulfide, diallyl disulfide , di-tert-butyl disulfide, bis(6-hydroxy-2-naphthyl) disulfide, dicyclohexyl disulfide, o-isobutyroylthiamine disulfide, and diphenyl disulfide.
• the molecular weight of the compound having a lone pair of electrons is preferably less than 1,000, more preferably 50 to 500, and 50 to 200 from the viewpoint of adhesion with the conductive layer. is more preferable, and 50 to 150 is particularly preferable.
• the photosensitive layer may contain one type of compound having a lone pair of electrons, or may contain two or more types of compounds having lone pairs of electrons.
• the content of the compound having a lone pair of electrons is preferably 0.01% by mass to 20% by mass, and 0.1% by mass based on the total mass of the photosensitive layer. It is more preferably from 0.3% to 8% by weight, and particularly preferably from 0.5% to 5% by weight.
• the photosensitive layer preferably contains a dye from the viewpoint of visibility of exposed areas and non-exposed areas, pattern visibility after development, and resolution, and has a maximum absorption in the wavelength range of 400 nm to 780 nm during color development. It is more preferable to contain a dye having a wavelength of 450 nm or more and whose maximum absorption wavelength changes depending on an acid, a base, or a radical (also simply referred to as "dye N").
• dye N although the detailed mechanism is unknown, the adhesion between the photosensitive layer and an adjacent layer (for example, a temporary support and a base material) 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 an aspect in which a dye in a colored state is decolored by an acid, a base, or a radical, and a dye in a decolored state is changed by an acid, a base, or a radical. It may mean either an aspect in which color is developed by 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 whose coloring or decoloring state is changed by the generation and action of acids, bases, or radicals in the photosensitive layer upon exposure to light; It may also be a dye whose coloring or decoloring state changes as the pH changes. 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 layer preferably contains both a dye whose maximum absorption wavelength changes with radicals as the dye N 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 the dye N in the present disclosure, a photoradical polymerization initiator, a photocationic polymerization initiator (photoacid generator), or a photobase generator is added to the photosensitive layer to initiate photoradical polymerization after exposure.
• examples include embodiments in which radical-reactive dyes, acid-reactive dyes, or base-reactive dyes (for example, leuco dyes) develop color due to radicals, acids, or bases generated from agents, photocationic polymerization initiators, or photobase generators.
• the dye N preferably has a maximum absorption wavelength of 550 nm or more in the wavelength range of 400 nm to 780 nm during color development, more preferably 550 nm to 700 nm, and 550 nm or more. More preferably, the wavelength is 650 nm.
• the maximum absorption wavelength of dye N was measured in the range of 400 nm to 780 nm under atmospheric conditions using a spectrophotometer: UV3100 (manufactured by Shimadzu Corporation). It is obtained by measuring the spectrum and detecting the wavelength at which the light intensity is minimum (maximum absorption wavelength) in the above wavelength range.
• 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
• 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, thereby changing the leuco compound into a ring-closed state.
• the color can be decolored, or the leuco compound can be changed to an open ring state to develop color.
• 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 acid. More preferred are compounds that develop color when the lactone ring opens.
• Examples of the dye N include the following dyes and leuco compounds. Specific examples of dyes among 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 BASF), 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-diethylamino)-6-
• 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 a dye that develops color due to radicals. It is more preferable that As the dye N, leuco crystal violet, crystal violet lactone, brilliant green, or Victoria Pure Blue-naphthalene sulfonate is preferable.
• the dyes may be used alone or in combination of two or more.
• the content of the dye is preferably 0.1% by mass or more based on the total mass of the photosensitive layer, from the viewpoint of visibility of exposed areas and non-exposed areas, pattern visibility after development, and resolution.
• the content is more preferably 0.1% by mass to 10% by mass, even more preferably 0.1% by mass to 5% by mass, and particularly preferably 0.1% by mass to 1% by mass.
• the content of dye N is 0.1% by mass or more based on the total mass of the photosensitive layer, from the viewpoint of visibility of exposed areas and non-exposed areas, pattern visibility after development, and resolution. It is preferably 0.1% by mass to 10% by mass, even more preferably 0.1% to 5% by mass, and particularly preferably 0.1% to 1% by mass.
• the content of the dye N means the content of the dye when all the dye N contained in the photosensitive 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.
• Two types of solutions are prepared by dissolving 0.001 g or 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.
• 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 layer is dissolved in methyl ethyl ketone instead of the dye. From the absorbance of the solution containing the obtained photosensitive layer, the content of the dye contained in the photosensitive layer is calculated based on a calibration curve.
• the photosensitive layer preferably contains a thermally crosslinkable compound from the viewpoint of the strength of the cured film obtained and the adhesiveness of the uncured film obtained.
• 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 resulting cured film and the tackiness of the resulting uncured film.
• 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. There is a tendency for the function to be enhanced when a film obtained by hardening the photosensitive layer is used as a protective film.
• the blocked isocyanate compound refers to "a compound having a structure in which the isocyanate group of isocyanate is protected (so-called masked) with a blocking agent.”
• the dissociation temperature of the blocked isocyanate compound is not particularly limited, but is preferably 100°C to 160°C, more preferably 130°C to 150°C.
• the dissociation temperature of the blocked isocyanate means "the temperature of the endothermic peak associated with the deprotection reaction of the blocked isocyanate when measured by DSC (differential scanning calorimetry) analysis using a differential scanning calorimeter.”
• DSC differential scanning calorimeter
• 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 blocking agent having a dissociation temperature of 100° C. to 160° C. preferably includes, for example, an oxime compound from the viewpoint of storage stability.
• the blocked isocyanate compound preferably has an isocyanurate structure, for example, from the viewpoint of improving the brittleness of the film and 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 not having 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 K.K.), Block Examples include the Duranate series of molds (eg, Duranate (registered trademark) TPA-B80E, Duranate (registered trademark) WT32-B75P, etc., manufactured by Asahi Kasei Chemicals Co., Ltd.). Moreover, 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% by mass to 50% by mass, more preferably 5% by mass to 30% by mass, based on the total mass of the photosensitive layer. preferable.
• the positive photosensitive layer is made of a polymer (hereinafter sometimes referred to as "polymer ) is preferably included.
• the positive photosensitive layer may contain one type of polymer X alone, or may contain two or more types of polymers X.
• the acid groups protected by the acid-decomposable groups are converted into acid groups through a deprotection reaction by the action of a catalytic amount of an acidic substance (for example, an acid) generated by exposure to light.
• the generation of acid groups in the polymer X increases the solubility of the positive photosensitive layer in the developer.
• the polymer X is preferably an addition polymerization type polymer, and more preferably a polymer having a structural unit derived from (meth)acrylic acid or an ester thereof.
• the polymer X has a structural unit (structural unit A) having an acid group protected with an acid-decomposable group.
• structural unit A structural unit having an acid group protected with an acid-decomposable group.
• the acid group is not limited and any known acid group can be used.
• the acid group is preferably a carboxy group or a phenolic hydroxyl group.
• Examples of acid-decomposable groups include groups that are relatively easily decomposed by acids and groups that are relatively difficult to decompose by acids.
• groups that are relatively easily decomposed by acids include acetal-type protecting groups (eg, 1-alkoxyalkyl group, tetrahydropyranyl group, and tetrahydrofuranyl group).
• groups that are relatively difficult to decompose with acids include tertiary alkyl groups (eg, tert-butyl group) and tertiary alkyloxycarbonyl groups (eg, tert-butyloxycarbonyl group).
• the acid-decomposable group is preferably an acetal-type protecting group.
• the molecular weight of the acid-decomposable group is preferably 300 or less from the viewpoint of suppressing variations in line width of the resin pattern.
• the structural unit A is preferably a structural unit represented by the following formula A1, a structural unit represented by formula A2, or a structural unit represented by formula A3, and is preferably a structural unit represented by formula A3. More preferably, it is a structural unit represented by the following.
• the structural unit represented by formula A3 is a structural unit having a carboxy group protected with an acetal type acid-decomposable group.
• R 11 and R 12 each independently represent a hydrogen atom, an alkyl group, or an aryl group, at least one of R 11 and R 12 is an alkyl group or an aryl group, and R 13 is It represents an alkyl group or an aryl group, R 11 or R 12 and R 13 may be linked to form a cyclic ether, R 14 represents a hydrogen atom or a methyl group, and X 1 represents a single represents a bond or a divalent linking group, R 15 represents a substituent, and n represents an integer of 0 to 4.
• R 21 and R 22 each independently represent a hydrogen atom, an alkyl group, or an aryl group, at least one of R 21 and R 22 is an alkyl group or an aryl group, and R 23 is It represents an alkyl group or an aryl group, R 21 or R 22 and R 23 may be linked to form a cyclic ether, and R 24 each independently represents a hydroxy group, a halogen atom, an alkyl group, an alkoxy group, alkenyl group, aryl group, aralkyl group, alkoxycarbonyl group, hydroxyalkyl group, arylcarbonyl group, aryloxycarbonyl group, or cycloalkyl group, and m represents an integer of 0 to 3.
• R 31 and R 32 each independently represent a hydrogen atom, an alkyl group, or an aryl group, at least one of R 31 and R 32 is an alkyl group or an aryl group, and R 33 is an alkyl group. , or represents an aryl group, R 31 or R 32 and R 33 may be linked to form a cyclic ether, R 34 represents a hydrogen atom or a methyl group, X 0 represents a single bond, Or represents an arylene group.
• R 31 or R 32 when R 31 or R 32 is an alkyl group, the alkyl group preferably has 1 to 10 carbon atoms. In formula A3, when R 31 or R 32 is an aryl group, a phenyl group is preferred.
• R 31 and R 32 are each independently preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
• R 33 is preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms.
• the alkyl group and aryl group represented by R 31 to R 33 may have a substituent.
• R 31 or R 32 and R 33 are preferably linked to form a cyclic ether.
• the number of ring members in the cyclic ether is preferably 5 or 6, more preferably 5.
• X 0 is preferably a single bond.
• the arylene group may have a substituent.
• R 34 is preferably a hydrogen atom from the viewpoint of lowering the glass transition temperature (Tg) of the polymer X.
• the content of the structural unit in which R 34 in formula A3 is a hydrogen atom is preferably 20% by mass or more based on the total mass of the structural unit A contained in the polymer X.
• the content of the structural unit in which R 34 in formula A3 is a hydrogen atom in the structural unit A should be confirmed by the intensity ratio of the peak intensities calculated by a conventional method from 13 C-nuclear magnetic resonance spectrum (NMR) measurement. Can be done.
• the acid-decomposable group is preferably a group having a cyclic structure from the viewpoint of sensitivity, more preferably a group having a tetrahydrofuran ring structure or a tetrahydropyran ring structure; It is more preferable that it is a group having the following, and particularly preferable is a tetrahydrofuranyl group.
• the polymer X may have only one type of structural unit A, or may have two or more types of structural units A.
• the content of structural unit A is preferably 10% to 70% by mass, more preferably 15% to 50% by mass, and 20% to 40% by mass, based on the total mass of polymer X. Particularly preferred is mass %. When the content of the structural unit A is within the above range, the resolution is further improved. When the polymer X contains two or more types of structural units A, the content of the structural units A mentioned above shall represent the total content of the two or more types of structural units A.
• the content of structural unit A can be confirmed by the intensity ratio of peak intensities calculated by a conventional method from 13 C-NMR measurement.
• the polymer X may have a structural unit having an acid group (hereinafter sometimes referred to as "structural unit B").
• Structural unit B is a structural unit having an acid group that is not protected with an acid-decomposable group, that is, an acid group that does not have a protecting group. Since the polymer X has the structural unit B, the sensitivity during pattern formation is improved. Moreover, since it becomes easily soluble in an alkaline developer in the development step after exposure, the development time can be shortened.
• the acid group in structural unit B means a proton dissociative group with pKa of 12 or less.
• the pKa of the acid group is preferably 10 or less, more preferably 6 or less. Further, the pKa of the acid group is preferably ⁇ 5 or more.
• the acid group examples include a carboxy group, a sulfonamide group, a phosphonic acid group, a sulfo group, a phenolic hydroxyl group, and a sulfonylimide group.
• the acid group is preferably a carboxy group or a phenolic hydroxyl group, and more preferably a carboxy group.
• the polymer X may have only one type of structural unit B, or may have two or more types of structural units B.
• the content of the structural unit B is preferably 0.01% by mass to 20% by mass, more preferably 0.01% by mass to 10% by mass, based on the total mass of the polymer .1% to 5% by weight is particularly preferred. When the content of the structural unit B is within the above range, resolution becomes better.
• the polymer X has two or more types of structural units B, the content of the structural units B mentioned above shall represent the total content of the two or more types of structural units B.
• the content of structural unit B can be confirmed by the intensity ratio of peak intensities calculated by a conventional method from 13 C-NMR measurement.
• the polymer X has other structural units (hereinafter sometimes referred to as "structural unit C") other than the above-mentioned structural units A and B.
• structural unit C other structural units
• Various properties of the polymer X can be adjusted by adjusting at least one of the type and content of the structural unit C.
• Examples of monomers forming the structural unit C include styrenes, (meth)acrylic acid alkyl esters, (meth)acrylic acid cyclic alkyl esters, (meth)acrylic acid aryl esters, unsaturated dicarboxylic acid diesters, and bicyclounsaturated compounds. , maleimide compounds, unsaturated aromatic compounds, conjugated diene compounds, unsaturated monocarboxylic acids, unsaturated dicarboxylic acids, and unsaturated dicarboxylic acid anhydrides.
• the monomer forming the structural unit C is preferably an alkyl (meth)acrylate ester, and is an alkyl (meth)acrylate having an alkyl group having 4 to 12 carbon atoms. It is more preferable.
• (meth)acrylic acid alkyl esters include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, n-butyl (meth)acrylate, and 2-(meth)acrylate. Ethylhexyl is mentioned.
• Structural unit C includes styrene, ⁇ -methylstyrene, acetoxystyrene, methoxystyrene, ethoxystyrene, chlorostyrene, methyl vinylbenzoate, ethyl vinylbenzoate, methyl (meth)acrylate, ethyl (meth)acrylate, ( n-propyl meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-(meth)acrylate A structural unit derived from hydroxypropyl, benzyl (meth)acrylate, cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, acrylonitrile, or ethylene glycol monoacetoacetate mono(meth)
• the structural unit C includes a structural unit having a basic group from the viewpoint of resolution.
• the basic group include a group having a nitrogen atom.
• the group having a nitrogen atom include an aliphatic amino group, an aromatic amino group, and a nitrogen-containing heteroaromatic ring group.
• the basic group is preferably an aliphatic amino group.
• the aliphatic amino group may be any of a primary amino group, a secondary amino group, and a tertiary amino group, but from the viewpoint of resolution, a secondary amino group or a tertiary amino group may be used. It is preferably a grade amino group.
• Examples of monomers forming structural units having a basic group include 1,2,2,6,6-pentamethyl-4-piperidyl methacrylate, 2-(dimethylamino)ethyl methacrylate, 2,2, acrylic acid, 6,6-tetramethyl-4-piperidyl, 2,2,6,6-tetramethyl-4-piperidyl methacrylate, 2,2,6,6-tetramethyl-4-piperidyl acrylate, 2-(methacrylate) diethylamino)ethyl, 2-(dimethylamino)ethyl acrylate, 2-(diethylamino)ethyl acrylate, N-(3-dimethylamino)propyl methacrylate, N-(3-dimethylamino)propyl acrylate, N-methacrylate -(3-diethylamino)propyl, N-(3-diethylamino)propyl acrylate, 2-(diisopropylamin
• the structural unit C is preferably a structural unit having an aromatic ring or a structural unit having an aliphatic cyclic skeleton.
• monomers forming these structural units include styrene, ⁇ -methylstyrene, dicyclopentanyl (meth)acrylate, cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, and benzyl ( Examples include meth)acrylates. Among the above, cyclohexyl (meth)acrylate is preferred.
• the polymer X may have only one type of structural unit C, or may have two or more types of structural units C.
• the content of the structural unit C is preferably 90% by mass or less, more preferably 85% by mass or less, and particularly preferably 80% by mass or less, based on the total mass of the polymer X.
• the content of the structural unit C is preferably 10% by mass or more, more preferably 20% by mass or more, based on the total mass of the polymer X.
• the content of the structural unit C is within the above range, resolution and adhesion to the substrate are further improved.
• the polymer X has two or more types of structural units C
• the content of the structural units C mentioned above shall represent the total content of the two or more types of structural units C.
• the content of the structural unit C can be confirmed by the intensity ratio of peak intensities calculated by a conventional method from 13 C-NMR measurement.
• polymer X Preferable examples of polymer X are shown below. However, the polymer X is not limited to the following examples. In addition, the ratio of each structural unit and the weight average molecular weight in the polymer X shown below are each suitably selected in order to obtain preferable physical properties.
• the glass transition temperature (Tg) of the polymer X is preferably 90°C or lower, more preferably 20°C to 60°C, particularly preferably 30°C to 50°C.
• Tg glass transition temperature
• the transferability of the positive photosensitive layer can be improved by having the glass transition temperature of the polymer X within the above range.
• An example of a method for adjusting the Tg of the polymer X within the above range is a method using the FOX formula.
• the Tg of the desired polymer X can be adjusted, for example, based on the homopolymer Tg of each structural unit in the desired polymer X and the mass fraction of each structural unit.
• the glass transition temperature of the homopolymer of the first structural unit is Tg1
• the mass fraction of the first structural unit in the copolymer is W1
• the glass transition temperature of the homopolymer of the second structural unit is Tg2
• the copolymer When the mass fraction of the second structural unit in the coalescence is W2, the glass transition temperature Tg0 (unit: K) of the copolymer having the first structural unit and the second structural unit is expressed by the following formula: Therefore, it can be estimated.
• FOX formula: 1/Tg0 (W1/Tg1)+(W2/Tg2)
• the Tg of the polymer can also be adjusted by adjusting the weight average molecular weight of the polymer.
• the acid value of the polymer It is particularly preferable that there be.
• the acid value of a polymer represents the mass of potassium hydroxide required to neutralize acidic components per gram of polymer.
• A 56.11 ⁇ Vs ⁇ 0.1 ⁇ f/w
• w Mass (g) of measurement sample (solid content equivalent)
• the weight average molecular weight (Mw) of the polymer X is preferably 60,000 or less in polystyrene equivalent weight average molecular weight.
• the weight average molecular weight of the polymer can.
• the weight average molecular weight of the polymer X is preferably 2,000 to 60,000, more preferably 3,000 to 50,000.
• the ratio of the number average molecular weight to the weight average molecular weight (dispersity) of the polymer X is preferably 1.0 to 5.0, more preferably 1.05 to 3.5.
• the weight average molecular weight of the polymer X is measured by GPC (gel permeation chromatography).
• GPC gel permeation chromatography
• Various commercially available devices can be used as the measuring device.
• HLC registered trademark
• 8220GPC manufactured by Tosoh Corporation
• TSKgel registered trademark
• Super HZM-M 4.6 mm ID x 15 cm, manufactured by Tosoh Corporation
• Super HZ4000 4.6 mm ID x 15 cm, manufactured by Tosoh Corporation
• Super HZ3000 4.6 mm ID x 15 cm
• Super HZ2000 4.6 mm ID x 15 cm, manufactured by Tosoh Corporation
• THF tetrahydrofuran
• the measurement conditions are a sample concentration of 0.2% by mass, a flow rate of 0.35 mL/min, a sample injection amount of 10 ⁇ L, and a measurement temperature of 40° C.
• a differential refractive index (RI) detector is used as the detector.
• the calibration curve is based on "standard sample TSK standard, polystyrene” manufactured by Tosoh Corporation: “F-40", “F-20”, “F-4”, “F-1”, “A-5000”, “A -2500” and "A-1000".
• the content of the polymer It is more preferable that
• the method for producing the polymer X is not limited, and any known method can be used. For example, in an organic solvent, using a polymerization initiator, a monomer for forming structural unit A, and further, if necessary, a monomer for forming structural unit B and a monomer for forming structural unit C are polymerized. Polymer X can be produced by doing so. Moreover, the polymer X can also be manufactured by a so-called polymer reaction.
• the positive photosensitive layer contains a polymer having a constitutional unit having an acid group protected with an acid-decomposable group
• a polymer (hereinafter sometimes referred to as "other polymer") that does not have a structural unit having an acid group protected with an acid-decomposable group may be included.
• Examples of other polymers include polyhydroxystyrene.
• Commercial products of polyhydroxystyrene include SMA 1000P, SMA 2000P, SMA 3000P, SMA 1440F, SMA 17352P, SMA 2625P, and SMA 3840F manufactured by Sartomer, and ARUFON UC- manufactured by Toagosei Co., Ltd. 3000, ARUFON UC-3510 , ARUFON UC-3900, ARUFON UC-3910, ARUFON UC-3920, and ARUFON UC-3080, and BASF's Joncryl 690, Joncryl 678, Joncryl 67, and Jo ncryl 586 is mentioned.
• the positive photosensitive layer may contain only one kind of other polymer, or may contain two or more kinds of other polymers.
• the content of the other polymers is preferably 50% by mass or less, and 30% by mass or less based on the total mass of the polymer components. is more preferable, and particularly preferably 20% by mass or less.
• polymer component is a general term for all polymers contained in the positive photosensitive layer.
• polymer component when the positive photosensitive layer contains polymer X and other polymers, polymer X and other polymers are collectively referred to as a "polymer component.” Note that compounds corresponding to crosslinking agents, dispersants, and surfactants, which will be described later, are not included in the polymer component even if they are polymeric compounds.
• the content of the polymer component is preferably 50% by mass to 99.9% by mass, more preferably 70% by mass to 98% by mass, based on the total mass of the positive photosensitive layer.
• the positive photosensitive layer preferably contains an alkali-soluble resin, more preferably contains an alkali-soluble resin and a quinonediazide compound, and particularly preferably contains a resin having a structural unit having a phenolic hydroxyl group and a quinonediazide compound.
• alkali-soluble resin examples include resins having a hydroxyl group, a carboxy group, or a sulfo group in the main chain or side chain.
• alkali-soluble resin examples include polyamide resin, polyhydroxystyrene, derivatives of polyhydroxystyrene, styrene-maleic anhydride copolymer, polyvinylhydroxybenzoate, carboxy group-containing (meth)acrylic resin, and novolak resin.
• Preferred alkali-soluble resins include, for example, a condensation polymer of m-/p-mixed cresol and formaldehyde, and a condensation polymer of phenol, cresol, and formaldehyde.
• the alkali-soluble resin has a phenolic hydroxyl group (-Ar-OH), a carboxy group (-CO 2 H), a sulfo group (-SO 3 H), a phosphoric acid group (-OPO 3 H), a sulfonamide group (-SO 2 NH-R) or substituted sulfonamide acid groups (eg, active imide groups, -SO 2 NHCOR, -SO 2 NHSO 2 R and -CONHSO 2 R).
• Ar represents a divalent aryl group which may have a substituent
• R represents a hydrocarbon group which may have a substituent.
• a novolac resin can be obtained, for example, by condensing a phenolic compound and an aldehyde compound in the presence of an acid catalyst.
• phenolic compounds include o-, m- or p-cresol, 2,5-, 3,5- or 3,4-xylenol, 2,3,5-trimethylphenol, 2-t-butyl-5 -Methylphenol and t-butylhydroquinone.
• aldehyde compounds include aliphatic aldehydes (eg, formaldehyde, acetaldehyde, and glyoxal) and aromatic aldehydes (eg, benzaldehyde and salicylaldehyde).
• Acid catalysts include, for example, inorganic acids (e.g., hydrochloric acid, sulfuric acid, and phosphoric acid), organic acids (e.g., oxalic acid, acetic acid, and p-toluenesulfonic acid), and divalent metal salts (e.g., zinc acetate).
• the condensation reaction can be carried out according to conventional methods. The condensation reaction is carried out, for example, at a temperature in the range of 60° C. to 120° C. for 2 hours to 30 hours. The condensation reaction may be carried out in a suitable solvent.
• the alkali-soluble resin a resin having a structural unit having a phenolic hydroxyl group such as a novolak resin is preferable.
• the weight average molecular weight of the alkali-soluble resin is preferably 5.0 ⁇ 10 2 to 2.0 ⁇ 10 5 from the viewpoint of pattern formation.
• the number average molecular weight of the alkali-soluble resin is preferably 2.0 ⁇ 10 2 to 1.0 ⁇ 10 5 from the viewpoint of pattern formation.
• an alkyl group having 3 to 8 carbon atoms is substituted with a substituent, such as a condensation polymer of t-butylphenol and formaldehyde and a condensation polymer of octylphenol and formaldehyde, which are described in US Pat. No. 4,123,279.
• a condensation polymer of phenol and formaldehyde may be used in combination.
• a condensate of formaldehyde and phenol having an alkyl group having 3 to 8 carbon atoms such as t-butylphenol formaldehyde resin and octylphenol formaldehyde resin described in U.S. Pat. No. 4,123,279, It's okay.
• the positive photosensitive layer may contain one or more alkali-soluble resins.
• the content of the alkali-soluble resin is preferably 30% by mass to 99.9% by mass, more preferably 40% by mass to 99.5% by mass, based on the total mass of the positive photosensitive layer. , 70% to 99% by weight is particularly preferred.
• the positive photosensitive layer preferably contains a photoacid generator as a photosensitive compound.
• a photoacid generator is a compound that can generate acid upon irradiation with actinic light (eg, ultraviolet rays, deep ultraviolet rays, X-rays, and electron beams).
• the photoacid generator is preferably a compound that generates an acid by being sensitive to actinic light having a wavelength of 300 nm or more, preferably from 300 nm to 450 nm.
• photoacid generators that are not directly sensitive to actinic rays with a wavelength of 300 nm or more, if they are compounds that generate acid when sensitized to actinic rays with a wavelength of 300 nm or more when used in combination with a sensitizer, they can be used as sensitizers. It can be preferably used in combination with.
• the photoacid generator is preferably a photoacid generator that generates an acid with a pKa of 4 or less, more preferably a photoacid generator that generates an acid with a pKa of 3 or less, and a photoacid generator that generates an acid with a pKa of 2 or less.
• a photoacid generator that generates an acid is particularly preferred.
• the lower limit of the pKa of the acid derived from the photoacid generator is not limited.
• the pKa of the acid derived from the photoacid generator is preferably -10.0 or higher, for example.
• photoacid generators examples include ionic photoacid generators and nonionic photoacid generators.
• Examples of ionic photoacid generators include onium salt compounds.
• Examples of onium salt compounds include diaryliodonium salt compounds, triarylsulfonium salt compounds, and quaternary ammonium salt compounds.
• the ionic photoacid generator is preferably an onium salt compound, particularly preferably at least one of a triarylsulfonium salt compound and a diaryliodonium salt compound.
• the ionic photoacid generators described in paragraphs 0114 to 0133 of JP-A No. 2014-85643 can also be preferably used.
• nonionic photoacid generators examples include trichloromethyl-s-triazine compounds, diazomethane compounds, imidosulfonate compounds, and oxime sulfonate compounds.
• the nonionic photoacid generator is preferably an oxime sulfonate compound from the viewpoints of sensitivity, resolution, and adhesion to the substrate.
• oxime sulfonate compound those described in paragraphs 0084 to 0088 of International Publication No. 2018/179640 can be suitably used.
• the photoacid generator is preferably at least one compound selected from the group consisting of onium salt compounds and oxime sulfonate compounds, and more preferably oxime sulfonate compounds.
• photoacid generators having the following structure.
• Examples of the photoacid generator having absorption at a wavelength of 405 nm include ADEKA Arkles (registered trademark) SP-601 (manufactured by ADEKA Corporation).
• the positive photosensitive layer preferably contains a quinonediazide compound as an acid generator (preferably a photoacid generator).
• a quinonediazide compound can be synthesized, for example, by subjecting a compound having a phenolic hydroxyl group and a quinonediazide sulfonic acid halide to a condensation reaction in the presence of a dehydrohalogenating agent.
• Examples of the quinonediazide compound include 1,2-benzoquinonediazide-4-sulfonic acid ester, 1,2-naphthoquinonediazide-4-sulfonic acid ester, 1,2-naphthoquinonediazide-5-sulfonic acid ester, 1,2- Naphthoquinonediazide-6-sulfonic acid ester, 2,1-naphthoquinonediazide-4-sulfonic acid ester, 2,1-naphthoquinonediazide-5-sulfonic acid ester, 2,1-naphthoquinonediazide-6-sulfonic acid ester, etc.
• the positive photosensitive layer may contain one type of photoacid generator alone, or may contain two or more types of photoacid generators. From the viewpoint of sensitivity and resolution, the content of the photoacid generator is preferably 0.1% by mass to 10% by mass, and 0.5% by mass to 10% by mass, based on the total mass of the positive photosensitive layer. More preferably, it is 5% by mass.
• the photosensitive layer may contain components other than those mentioned above.
• the photosensitive layer preferably contains a surfactant from the viewpoint of thickness uniformity.
• the surfactant include anionic surfactants, cationic surfactants, nonionic (nonionic) surfactants, and amphoteric surfactants, with nonionic surfactants being preferred.
• the surfactant include the surfactants described in paragraph 0017 of Japanese Patent No. 4502784 and paragraphs 0060 to 0071 of JP-A-2009-237362.
• fluorine-based surfactants or silicone-based surfactants are preferred.
• fluorosurfactants include, for example, Megafac (registered trademark: hereinafter the same) F-171, F-172, F-173, F-176, F-177, F-141, F-142, F-143, F-144, F-437, F-444, F-475, F-477, F-479, F-482, F-551-A, F-552, F-554, F-555- A, F-556, F-557, F-558, F-559, F-560, F-561, F-565, F-563, F-568, F-575, F-780, EXP, MFS- 330, MFS-578, MFS-579, MFS-586, MFS-587, R-41, R-41-LM, R-01, R-40, R-40-LM, RS-43, TF-1956, RS-90, R-94, RS-72-K, DS
• fluorine-based surfactants are acrylic compounds that have a molecular structure with a functional group containing a fluorine atom, and when heated, the functional group containing a fluorine atom is severed and the fluorine atom volatizes. It can be used suitably.
• fluorine-based surfactants include Megafac (trade name) DS series manufactured by DIC Corporation (Kagaku Kogyo Nippo (February 22, 2016), Nikkei Sangyo Shimbun (February 23, 2016)).
• Megafac (trade name) DS-21 can be mentioned.
• 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 as the fluorinated surfactant.
• a block polymer can also be used as the fluorosurfactant.
• the fluorine-based surfactant has a structural unit derived from a (meth)acrylate compound having a fluorine atom and two or more (preferably five or more) alkyleneoxy groups (preferably ethyleneoxy group, propyleneoxy group) (meth).
• a fluorine-containing polymer compound containing a structural unit derived from an acrylate compound can also be preferably used.
• a fluorine-based surfactant a fluorine-containing polymer having an ethylenically unsaturated group in its side chain can also be used.
• examples include Megafac (trade name) RS-101, RS-102, RS-718K, RS-72-K (manufactured by DIC Corporation).
• nonionic surfactants include glycerol, trimethylolpropane, trimethylolethane, and their ethoxylates and propoxylates (e.g., glycerol propoxylate, glycerol ethoxylate, etc.), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, Polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester, Pluronic (registered trademark) L10, L31, L61, L62, 10R5, 17R2 , 25R2 (manufactured by BASF), Tetronic (trade name) 304, 701, 704, 901, 904, 150R1 (manufactured by BASF), Solsperse (trade name) 20000 (manufactured by Japan Lubrizol Co., Ltd
• silicone surfactants include linear polymers consisting of siloxane bonds and modified siloxane polymers in which organic groups are introduced into side chains or terminals.
• Specific examples of silicone surfactants include DOWSIL (trade name) 8032 ADDITIVE, Tore Silicone DC3PA, Tore Silicone SH7PA, Tore Silicone DC11PA, Tore Silicone SH21PA, Tore Silicone SH28PA, Tore Silicone SH29PA, Tore Silicone SH30PA, Tore Silicone SH8400 (all manufactured by Dow Corning Toray Co., Ltd.), and X-22-4952, X-22-4272, KF-642, KF-643, X-22-6191, X-22-4515, KF-6004, KP-341, KF-6001, KF-6002 (all manufactured by Shin-Etsu Chemical Co., Ltd.), F-4440 , TSF-4300, TSF-4445, TSF-4460, TSF-4452 (manufactured by Momentive Performance Materials), BY
• the photosensitive layer may contain one type of surfactant alone, or may contain two or more types of surfactants.
• the content of the surfactant is preferably 0.001% by mass to 10% by mass, more preferably 0.01% by mass to 3% by mass, based on the total mass of the photosensitive layer.
• the photosensitive layer may contain known additives as necessary.
• additives include polymerization inhibitors, sensitizers, plasticizers, alkoxysilane compounds, and solvents.
• the photosensitive layer may contain one type of each additive, or may contain two or more types of each additive.
• additives include metal oxide particles, antioxidants, dispersants, acid multiplying agents, development accelerators, conductive fibers, thermal radical polymerization initiators, thermal acid generators, ultraviolet absorbers, thickeners, and organic or inorganic suspending agents. Preferred embodiments of these additives are described in paragraphs 0165 to 0184 of JP-A No. 2014-85643, the contents of which are incorporated herein by reference.
• the photosensitive layer may contain a polymerization inhibitor.
• a radical polymerization inhibitor is preferable.
• the polymerization inhibitor include thermal polymerization inhibitors described in paragraph 0018 of Japanese Patent No. 4502784. Among these, phenothiazine, phenoxazine or 4-methoxyphenol are preferred.
• Other polymerization inhibitors include naphthylamine, cuprous chloride, nitrosophenylhydroxyamine aluminum salt, diphenylnitrosamine, and the like. In order not to impair the sensitivity of the composition for forming a photosensitive layer, it is preferable to use a nitrosophenylhydroxyamine aluminum salt as a polymerization inhibitor.
• the content of the polymerization inhibitor is preferably 0.01% by mass to 3% by mass, more preferably 0.05% by mass to 1% by mass, based on the total mass of the photosensitive layer. It is preferable that the content be 0.01% by mass or more from the viewpoint of imparting storage stability to the composition for forming a photosensitive layer. On the other hand, it is preferable for the content to be 3% by mass or less from the viewpoint of maintaining sensitivity.
• the photosensitive layer may contain a sensitizer.
• the sensitizer is not particularly limited, and known sensitizers, dyes, and pigments can be used.
• Examples of the sensitizer include dialkylaminobenzophenone compounds, pyrazoline compounds, anthracene compounds, coumarin compounds, xanthone compounds, thioxanthone compounds, acridone compounds, oxazole compounds, benzoxazole compounds, thiazole compounds, benzothiazole compounds, triazole compounds (for example, 1,2,4-triazole), stilbene compounds, triazine compounds, thiophene compounds, naphthalimide compounds, triarylamine compounds, and aminoacridine compounds.
• the photosensitive layer may contain one type of sensitizer alone, or may contain two or more types of sensitizers.
• 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% by mass to 5% by mass, and more preferably 0.05% by mass to 1% by mass, based on the total mass of the photosensitive layer.
• the photosensitive layer may contain at least one selected from the group consisting of a plasticizer and a heterocyclic compound.
• a plasticizer and a heterocyclic compound include compounds described in paragraphs 0097 to 0103 and 0111 to 0118 of International Publication No. 2018/179640.
• the photosensitive layer may contain an alkoxysilane compound.
• alkoxysilane compounds include ⁇ -aminopropyltrimethoxysilane, ⁇ -aminopropyltriethoxysilane, ⁇ -glycidoxypropyltriakoxysilane, ⁇ -glycidoxypropylalkyldialkoxysilane, and ⁇ -methacryloxysilane.
• Propyltrialkoxysilane, ⁇ -methacryloxypropylalkyldialkoxysilane, ⁇ -chloropropyltrialkoxysilane, ⁇ -mercaptopropyltrialkoxysilane, ⁇ -(3,4-epoxycyclohexyl)ethyltrialkoxysilane, and vinyltrialkoxy Examples include silane.
• the alkoxysilane compound is preferably a trialkoxysilane compound, more preferably ⁇ -glycidoxypropyltrialkoxysilane or ⁇ -methacryloxypropyltrialkoxysilane, and ⁇ -glycidoxypropyltrialkoxysilane.
• Propyltrialkoxysilane is more preferred, and 3-glycidoxypropyltrimethoxysilane is particularly preferred.
• the photosensitive layer may contain one type of alkoxysilane compound alone, or may contain two or more types of alkoxysilane compounds.
• the content of the alkoxysilane compound is preferably 0.1% by mass to 50% by mass, and 0.5% by mass based on the total mass of the photosensitive layer. It is more preferably from 1.0% to 30% by weight, and particularly preferably from 1.0% to 30% by weight.
• the photosensitive layer may contain a solvent.
• the solvent may remain in the photosensitive layer.
• the photosensitive layer may contain a predetermined amount of impurities.
• impurities include sodium, potassium, magnesium, calcium, iron, manganese, copper, aluminum, titanium, chromium, cobalt, nickel, zinc, tin, halogen, and ions thereof.
• halide ions, sodium ions, and potassium ions are likely to be mixed in as impurities, so it is preferable to have the following content.
• the content of impurities in the photosensitive 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 can be 1 ppb or more, and may be 0.1 ppm or more, based on mass.
• Methods for keeping impurities within the above range include selecting materials with a low content of impurities as raw materials for the composition, preventing contamination of impurities during the preparation of the photosensitive layer, and removing them by washing. . By such a method, the amount of impurities can be kept within the above range.
• Impurities can be quantified by known methods such as ICP (Inductively Coupled Plasma) emission spectroscopy, atomic absorption spectroscopy, and ion chromatography.
• ICP Inductively Coupled Plasma
• the content of compounds such as benzene, formaldehyde, trichloroethylene, 1,3-butadiene, carbon tetrachloride, chloroform, N,N-dimethylformamide, N,N-dimethylacetamide, and hexane in the photosensitive layer may be small. preferable.
• the content of these compounds relative to the total mass of the photosensitive layer is preferably 100 ppm or less, more preferably 20 ppm or less, and even more preferably 4 ppm or less, based on mass.
• the lower limit can be 10 ppb or more, and can be 100 ppb or more based on the total mass of the photosensitive layer.
• 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 layer is preferably 0.01% by mass to 1.0% by mass, more preferably 0.05% by mass to 0.5% by mass, from the viewpoint of improving reliability and lamination properties.
• the photosensitive layer may contain residual monomers corresponding to the constituent units of the alkali-soluble resin described above.
• the content of the residual monomer is preferably 5,000 mass ppm or less, more preferably 2,000 mass ppm or less, and 500 mass ppm or less based on the total mass of the alkali-soluble resin. is even more preferable.
• the lower limit is not particularly limited, but is preferably at least 1 ppm by mass, more preferably at least 10 ppm by mass.
• the residual monomer of each structural unit of the alkali-soluble resin is preferably 3,000 mass ppm or less, more preferably 600 mass ppm or less, based on the total mass of the photosensitive layer, from the viewpoint of patterning properties and reliability. More preferably, it is 100 mass ppm or less. Although the lower limit is not particularly limited, it is preferably 0.1 mass ppm or more, and more preferably 1 mass ppm or more.
• the amount of residual monomers in the synthesis of the alkali-soluble resin by polymer reaction is within the above range.
• the content of glycidyl acrylate is preferably within the above range.
• the amount of residual monomer can be measured by known methods such as liquid chromatography and gas chromatography.
• the thickness of the photosensitive layer is preferably 0.1 ⁇ m to 300 ⁇ m, more preferably 0.2 ⁇ m to 100 ⁇ m, even more preferably 0.5 ⁇ m to 50 ⁇ m, even more preferably 0.5 ⁇ m to 15 ⁇ m, and even more preferably 0.5 ⁇ m to 10 ⁇ m. Particularly preferred, and most preferably 0.5 ⁇ m to 8 ⁇ m. This improves the developability of the photosensitive layer and improves the resolution.
• the layer thickness (thickness) of the photosensitive layer is preferably 10 ⁇ m or less, more preferably 5.0 ⁇ m or less, from the viewpoint of resolution and further exerting the effects of the present disclosure.
• the layer thickness of each layer of the photosensitive transfer material is determined based on the observed image obtained by observing a cross section perpendicular to the main surface of the photosensitive transfer material using a scanning electron microscope (SEM). It is measured by measuring the thickness of each layer at 10 or more points and calculating the average value.
• SEM scanning electron microscope
• the transmittance of the photosensitive layer for light at a wavelength of 365 nm is preferably 10% or more, preferably 30% or more, and more preferably 50% or more.
• the upper limit is not particularly limited, but is preferably 99.9% or less.
• the method for forming the photosensitive layer is not particularly limited as long as it is capable of forming a layer containing the above components.
• a method for forming a photosensitive layer for example, in the case of a negative photosensitive layer, a composition for forming a photosensitive layer containing an alkali-soluble resin, a polymerizable compound, a photopolymerization initiator, a solvent, etc. is prepared, and a temporary layer is formed. Examples include a method of forming a photosensitive layer-forming composition by applying a photosensitive layer-forming composition to the surface of a support or the like and drying a coating film of the photosensitive layer-forming composition.
• Examples of the photosensitive layer forming composition used to form the photosensitive layer include a composition containing an alkali-soluble resin, a polymerizable compound, a photopolymerization initiator, the above-mentioned optional components, and a solvent.
• the composition for forming a photosensitive layer preferably contains a solvent in order to adjust the viscosity of the composition for forming a photosensitive layer and facilitate formation of the photosensitive layer.
• the solvent contained in the composition for forming a photosensitive layer is not particularly limited as long as it can dissolve or disperse the alkali-soluble resin, polymerizable compound, photopolymerization initiator, and any of the above optional components, and any known solvent may be used. can.
• solvents include alkylene glycol ether solvents, alkylene glycol ether acetate solvents, alcohol solvents (methanol and ethanol, etc.), ketone solvents (acetone and methyl ethyl ketone, etc.), aromatic hydrocarbon solvents (toluene, etc.), and aprotic polar solvents.
• the composition for forming the photosensitive layer consists of an alkylene glycol ether solvent and an alkylene glycol ether acetate solvent. It is preferable to contain at least one selected from the group.
• 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 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 dialkyl ether, diethylene glycol dialkyl ether, dipropylene glycol monoalkyl ether, and dipropylene glycol dialkyl ether.
• alkylene glycol ether acetate solvent examples include ethylene glycol monoalkyl ether acetate, propylene glycol monoalkyl ether acetate, diethylene glycol monoalkyl ether acetate, and dipropylene glycol monoalkyl ether acetate.
• the solvents described in paragraphs 0092 to 0094 of International Publication No. 2018/179640 and the solvents described in paragraph 0014 of JP 2018-177889 may be used, and the contents of these are disclosed herein. incorporated into the book.
• the composition for forming a photosensitive layer may contain one type of solvent alone, or may contain two or more types of solvents.
• the content of the solvent when applying the composition for forming a photosensitive layer is preferably 50 parts by mass to 1,900 parts by mass, based on 100 parts by mass of the total solid content in the composition for forming a photosensitive layer, and 100 parts by mass. Parts to 900 parts by mass are more preferred.
• the method for preparing the composition for forming a photosensitive layer is not particularly limited, and for example, by preparing a solution in which each component is dissolved in the above-mentioned solvent in advance and mixing the obtained solutions in a predetermined ratio, the composition for forming a photosensitive layer can be prepared. Methods of preparing forming compositions are included. From the viewpoint of particle removability, the photosensitive layer forming composition is preferably filtered using a filter before forming the photosensitive layer, and preferably filtered using a filter with a pore size of 0.2 ⁇ m to 10 ⁇ m.
• a filter with a pore size of 0.2 ⁇ m to 7 ⁇ m is more preferable, it is even more preferable to use a filter with a pore size of 0.2 ⁇ m to 7 ⁇ m, and it is particularly preferable to use a filter with a pore size of 0.2 ⁇ m to 5 ⁇ m.
• the method for applying the composition for forming a photosensitive layer is not particularly limited, and any known method may be used. Examples of the coating method include slit coating, spin coating, curtain coating, and inkjet coating.
• the photosensitive layer may be formed by applying a composition for forming a photosensitive layer onto a cover film, which will be described later, and drying it.
• the photosensitive transfer material in the present disclosure preferably has another layer between the particle layer and the photosensitive layer from the viewpoint of resolution and releasability of the temporary support.
• Preferred examples of other layers include an intermediate layer and a thermoplastic resin layer.
• the transfer layer preferably includes an intermediate layer, and more preferably includes a thermoplastic resin layer and an intermediate layer.
• the second embodiment of the photosensitive transfer material according to the present disclosure is provided between the particle layer and the photosensitive layer, and when it has a thermoplastic resin layer described below, between the thermoplastic resin layer and the photosensitive layer.
• An embodiment with an intermediate layer By having the intermediate layer, mixing of components contained in each layer can be suppressed when forming a plurality of layers and during storage.
• the intermediate layer is preferably a water-soluble layer from the viewpoint of developability and suppressing mixing of components when coating multiple layers and during storage after coating.
• water-soluble means that the solubility in 100 g of water with a pH of 7.0 and a liquid temperature of 22° C. is 0.1 g or more.
• the intermediate layer examples include an oxygen barrier layer having an oxygen barrier function, which is described as a "separation layer" in JP-A-5-72724. Since the intermediate layer is an oxygen barrier layer, the sensitivity during exposure is improved and the time load on the exposure machine is reduced, resulting in improved productivity.
• the oxygen barrier layer used as the intermediate layer may be appropriately selected from known layers.
• the oxygen barrier layer used as the intermediate layer is preferably an oxygen barrier layer that exhibits low oxygen permeability and is dispersed or dissolved in water or an alkaline aqueous solution (1% by mass aqueous solution of sodium carbonate at 22° C.).
• the intermediate layer contains an inorganic layered compound from the viewpoints of oxygen barrier properties, resolution, and pattern formability.
• inorganic layered compounds include particles having a thin tabular shape, such as mica compounds such as natural mica and synthetic mica, talc represented by the formula: 3MgO.4SiO.H 2 O, taeniolite, montmorillonite, saponite, Examples include hectorite and zirconium phosphate.
• a mica compound for example, the formula: A(B,C) 2-5 D 4 O 10 (OH, F, O) 2 [wherein A is K, Na, or Ca, and B and C are It is any one of Fe(II), Fe(III), Mn, Al, Mg, and V, and D is Si or Al.
• mica groups such as natural mica and synthetic mica represented by ].
• natural micas include muscovite, soda mica, phlogopite, biotite, and lepidolite.
• synthetic micas include non-swellable micas such as fluorophlogopite KMg 3 (AlSi 3 O 10 )F 2 , potassium tetrasilicon mica KMg 2.5 Si 4 O 10 )F 2 , and Na tetrasilylic mica NaMg 2.
• the aspect ratio is preferably 20 or more, more preferably 100 or more, particularly preferably 200 or more.
• the aspect ratio is the ratio of the major axis to the thickness of a particle, and can be measured, for example, from a projection of a microscopic photograph of the particle. The larger the aspect ratio, the greater the effect obtained.
• the particle diameter of the inorganic layered compound is preferably 0.3 ⁇ m to 20 ⁇ m, more preferably 0.5 ⁇ m to 10 ⁇ m, and particularly preferably 1 ⁇ m to 5 ⁇ m.
• the average thickness of the particles is preferably 0.1 ⁇ m or less, more preferably 0.05 ⁇ m or less, particularly preferably 0.01 ⁇ m or less.
• preferred embodiments include a thickness of about 1 nm to 50 nm and a surface size (longer axis) of about 1 ⁇ m to 20 ⁇ m.
• the content of the inorganic layered compound is preferably 0.1% by mass to 50% by mass, and 1% by mass to 50% by mass, based on the total mass of the intermediate layer, from the viewpoints of oxygen barrier properties, resolution, and pattern forming properties. 20% by mass is more preferred.
• the intermediate layer contains a resin.
• resins included in the intermediate layer include polyvinyl alcohol resins, polyvinylpyrrolidone resins, cellulose resins, acrylamide resins, polyethylene oxide resins, gelatin, vinyl ether resins, polyamide resins, and copolymers thereof. Can be mentioned.
• the resin contained in the intermediate layer is preferably a water-soluble resin.
• the resin contained in the intermediate layer is composed of polymer A contained in the negative photosensitive layer and thermoplastic resin (alkali-soluble resin) contained in the thermoplastic resin layer, from the viewpoint of suppressing mixing of components between multiple layers. It is preferable that the resin is different from both.
• the intermediate layer preferably contains a water-soluble compound, and more preferably contains a water-soluble resin.
• Water-soluble compounds are not particularly limited, but from the viewpoint of oxygen barrier properties, developability, resolution, and pattern forming properties, water-soluble cellulose derivatives, polyhydric alcohols, and oxide adducts of polyhydric alcohols are preferred. , polyethers, phenol derivatives, and amide compounds, and at least one compound selected from the group consisting of polyvinyl alcohol, polyvinylpyrrolidone, hydroxypropylcellulose, and hydroxypropylmethylcellulose. More preferably, it is a type of water-soluble resin.
• water-soluble resins examples include water-soluble cellulose derivatives, polyvinyl alcohol, polyvinylpyrrolidone, acrylamide resins, (meth)acrylate resins, polyethylene oxide resins, gelatin, vinyl ether resins, polyamide resins, and copolymers thereof.
• the water-soluble compound preferably water-soluble resin
• the water-soluble compound preferably water-soluble resin
• the water-soluble compound preferably contains polyvinyl alcohol, and more preferably polyvinyl alcohol, from the viewpoints of oxygen barrier properties, developability, resolution, and pattern formation properties.
• the degree of hydrolysis of polyvinyl alcohol is not particularly limited, but is preferably 73 mol% to 99 mol% from the viewpoints of oxygen barrier properties, developability, resolution, and pattern formation properties.
• polyvinyl alcohol contains ethylene as a monomer unit from the viewpoints of oxygen barrier properties, developability, resolution, and pattern formation properties.
• the intermediate layer preferably contains polyvinyl alcohol, and preferably contains polyvinyl alcohol and polyvinylpyrrolidone, from the viewpoint of oxygen barrier properties and suppressing mixing of components when applying multiple layers and during storage after application. is more preferable.
• the intermediate layer may contain one type of resin alone or two or more types of resin.
• the content of the water-soluble compound in the intermediate layer is 50% relative to the total mass of the intermediate layer, from the viewpoint of oxygen barrier properties and suppressing mixing of components during coating of multiple layers and storage after coating. It is preferably from 70% to 100% by mass, even more preferably from 80% to 100% by mass, and even more preferably from 90% to 100% by mass. is particularly preferred.
• the intermediate layer may contain additives as necessary.
• additives include surfactants.
• the thickness of the intermediate layer is not limited.
• the average thickness of the intermediate layer is preferably 0.1 ⁇ m to 5 ⁇ m, more preferably 0.5 ⁇ m to 3 ⁇ m.
• the method for forming the intermediate layer is not limited as long as it can form a layer containing the above components.
• Examples of the method for forming the intermediate layer include a method in which the composition for forming an intermediate layer is applied to the surface of the thermoplastic resin layer or the photosensitive layer, and then the coating film of the composition for forming the intermediate layer is dried. .
• the intermediate layer forming composition examples include a composition containing a resin and optional additives.
• the composition for forming an intermediate layer preferably contains a solvent in order to adjust the viscosity of the composition for forming an intermediate layer and facilitate formation of the intermediate layer.
• the solvent is not limited as long as it can dissolve or disperse the resin.
• the solvent is preferably at least one selected from the group consisting of water and a water-miscible organic solvent, and more preferably water or a mixed solvent of water and a water-miscible organic solvent.
• water-miscible organic solvents examples include alcohols having 1 to 3 carbon atoms, acetone, ethylene glycol, and glycerin.
• the water-miscible organic solvent is preferably an alcohol having 1 to 3 carbon atoms, more preferably methanol or ethanol.
• thermoplastic resin layer A second embodiment of the photosensitive transfer material used in the present disclosure may have a thermoplastic resin layer.
• the thermoplastic resin layer preferably contains an alkali-soluble resin as the thermoplastic resin.
• alkali-soluble resin examples include acrylic resin, polystyrene resin, styrene-acrylic copolymer, polyurethane resin, polyvinyl alcohol, polyvinyl formal, polyamide resin, polyester resin, epoxy resin, polyacetal resin, polyhydroxystyrene resin, polyimide resin, Examples include polybenzoxazole resin, polysiloxane resin, polyethyleneimine, polyallylamine, and polyalkylene glycol.
• the alkali-soluble resin is preferably an acrylic resin from the viewpoint of developability and adhesion with the layer adjacent to the thermoplastic resin layer.
• acrylic resin is selected from the group consisting of structural units derived from (meth)acrylic acid, structural units derived from (meth)acrylic acid esters, and structural units derived from (meth)acrylic acid amide. It means a resin having at least one type.
• the ratio of the total content of structural units derived from (meth)acrylic acid, structural units derived from (meth)acrylic acid ester, and structural units derived from (meth)acrylic acid amide is It is preferable that the amount is 50% by mass or more based on the total mass.
• the ratio of the total content of structural units derived from (meth)acrylic acid and structural units derived from (meth)acrylic acid ester is 30% by mass to 100% by mass with respect to the total mass of the acrylic resin. %, more preferably 50% to 100% by weight.
• the alkali-soluble resin is preferably a polymer having acid groups.
• 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 preferably an alkali-soluble resin with an acid value of 60 mgKOH/g or more, and more preferably a carboxyl group-containing acrylic resin with an acid value of 60 mgKOH/g or more.
• the upper limit of the acid value is not limited.
• the acid value of the alkali-soluble resin is preferably 200 mgKOH/g or less, more preferably 150 mgKOH/g or less.
• the carboxy group-containing acrylic resin having an acid value of 60 mgKOH/g or more is not limited, and can be appropriately selected from known resins.
• Examples of the carboxyl group-containing acrylic resin having an acid value of 60 mgKOH/g or more include carboxy group-containing acrylic resins having an acid value of 60 mgKOH/g or more among the polymers described in paragraph 0025 of JP-A No.
• the content of the structural unit having a carboxyl group in the carboxy group-containing acrylic resin is preferably 5% to 50% by mass, and 10% to 40% by mass, based on the total mass of the acrylic resin containing a carboxylic group. It is more preferable that the amount is 12% by mass to 30% by mass.
• the alkali-soluble resin is particularly preferably an acrylic resin having a structural unit derived from (meth)acrylic acid from the viewpoint of developability and adhesion with a layer adjacent to the thermoplastic resin layer.
• the alkali-soluble resin may have a reactive group.
• the reactive group may be, for example, a group capable of addition polymerization.
• Examples of reactive groups include ethylenically unsaturated groups, polycondensable groups (e.g., hydroxy groups and carboxy groups), and polyaddition-reactive groups (e.g., epoxy groups and (block) isocyanate groups). It will be done.
• 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 particularly preferably 20,000 to 50,000.
• the thermoplastic resin layer may contain one or more alkali-soluble resins.
• the content of the alkali-soluble resin is preferably 10% by mass to 99% by mass based on the total mass of the thermoplastic resin layer, from the viewpoint of developability and adhesion with the layer adjacent to the thermoplastic resin layer. It is preferably 20% by mass to 90% by mass, even more preferably 40% to 80% by mass, and particularly preferably 50% to 70% by mass.
• the thermoplastic resin layer contains a dye (hereinafter referred to as "dye B") that has a maximum absorption wavelength of 450 nm or more in the wavelength range of 400 nm to 780 nm during color development, and whose maximum absorption wavelength changes with acid, base, or radical. ) is preferable.
• dye B a dye that has a maximum absorption wavelength of 450 nm or more in the wavelength range of 400 nm to 780 nm during color development, and whose maximum absorption wavelength changes with acid, base, or radical.
• dye B is preferably a dye whose maximum absorption wavelength changes with acid or radicals, and whose maximum absorption wavelength changes with acid. More preferably, it is a dye that
• thermoplastic resin layer should include a dye B whose maximum absorption wavelength changes with acid, and a compound C described below. is preferred.
• the thermoplastic resin layer may contain one type of dye B or two or more types of dye B.
• the content of dye B is preferably 0.2% by mass or more, and 0.2% by mass based on the total mass of the thermoplastic resin layer, from the viewpoint of visibility of exposed areas and visibility of non-exposed areas. % to 6% by weight, even more preferably 0.2% to 5% by weight, particularly preferably 0.25% to 3.0% by weight.
• the content of 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.
• Two solutions are prepared by dissolving the dye (0.001 g) and the dye (0.01 g) in methyl ethyl ketone (100 mL). After adding IRGACURE OXE01 (manufactured by BASF) as a photoradical polymerization initiator to each of the obtained solutions, irradiation with 365 nm light generates radicals and brings all the dyes into a colored state.
• IRGACURE OXE01 manufactured by BASF
• 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 the thermoplastic resin layer (0.1 g) 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.
• the thermoplastic resin layer may contain a compound (hereinafter sometimes 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 (for example, ultraviolet rays and visible rays).
• actinic rays for example, ultraviolet rays and visible rays.
• Examples of the compound C include known photoacid generators, photobase generators, and photoradical polymerization initiators (photoradical generators).
• Compound C is preferably a photoacid generator.
• the thermoplastic resin layer preferably contains a photoacid generator from the viewpoint of resolution.
• the photoacid generator include the photocationic polymerization initiators that may be included in the photosensitive layer described above, and preferred embodiments are the same except for the points described below.
• the photoacid generator preferably contains at least one selected from the group consisting of onium salt compounds and oxime sulfonate compounds. From this point of view, it is more preferable to include an oxime sulfonate compound.
• the photoacid generator has the following structure.
• the thermoplastic resin layer may contain a photobase generator.
• photobase generators 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-dimethylamino Propane, N-(2-nitrobenzyloxycarbonyl)pyrrolidine, hexaamminecobalt(III) tris(triphenylmethylborate), 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butanone, 2,6 -dimethyl-3,5-diacetyl-4
• the thermoplastic resin layer may contain a photoradical polymerization initiator.
• the radical photopolymerization initiator include the radical photopolymerization initiator that may be included in the photosensitive layer described above, and the preferred embodiments are also the same.
• the thermoplastic resin layer may contain one type of compound C or two or more types of compound C.
• the content of compound C is 0.1% by mass to 10% by mass based on the total mass of the thermoplastic resin layer, from the viewpoint of visibility of exposed areas, visibility of non-exposed areas, and resolution. It is preferably 0.5% by mass to 5% by mass.
• the thermoplastic resin layer preferably contains a plasticizer from the viewpoints of resolution, adhesion with a layer adjacent to the thermoplastic resin layer, and developability.
• the molecular weight of the plasticizer (the molecular weight of an oligomer or polymer refers to weight average molecular weight (Mw); hereinafter the same applies in this paragraph) is preferably smaller than the molecular weight of the alkali-soluble resin.
• the molecular weight of the plasticizer is preferably 200 to 2,000.
• the plasticizer is not limited as long as it is a compound that is compatible with the alkali-soluble resin and exhibits plasticity. From the viewpoint of imparting plasticity, the plasticizer is preferably a compound having an alkyleneoxy group in its molecule, and more preferably a polyalkylene glycol compound.
• the alkyleneoxy group contained in the plasticizer preferably has at least one type of structure selected from a polyethyleneoxy structure and a polypropyleneoxy structure.
• the plasticizer preferably contains a (meth)acrylate compound from the viewpoint of resolution and storage stability. From the viewpoint of compatibility, resolution, and adhesion with a layer adjacent to the thermoplastic resin layer, it is more preferable that the alkali-soluble resin is an acrylic resin and that the plasticizer contains a (meth)acrylate compound.
• thermoplastic resin layer and the photosensitive layer examples include the (meth)acrylate compounds described in the ethylenically unsaturated compound above.
• thermoplastic resin layer and the photosensitive layer when the thermoplastic resin layer and the photosensitive layer are placed in direct contact with each other, it is preferable that the thermoplastic resin layer and the photosensitive layer each contain the same (meth)acrylate compound. This is because the thermoplastic resin layer and the photosensitive layer each contain the same (meth)acrylate compound, thereby suppressing component diffusion between the layers and improving storage stability.
• the thermoplastic resin layer contains a (meth)acrylate compound as a plasticizer
• the (meth)acrylate compound may not polymerize even in the exposed area after exposure. preferable.
• the (meth)acrylate compound used as a plasticizer has two or more ( A (meth)acrylate compound having a meth)acryloyl group is preferred.
• the (meth)acrylate compound used as a plasticizer is preferably a (meth)acrylate compound having an acid group or a urethane (meth)acrylate compound.
• the thermoplastic resin layer may contain one type of plasticizer or two or more types of plasticizer.
• the content of the plasticizer is 1% by mass to 70% by mass based on the total mass of the thermoplastic resin layer from the viewpoint of resolution, adhesion with the layer adjacent to the thermoplastic resin layer, and developability. It is preferably from 10% by mass to 60% by mass, and particularly preferably from 20% by mass to 50% by mass.
• the thermoplastic resin layer preferably contains a surfactant from the viewpoint of thickness uniformity.
• the surfactant include the surfactants that may be included in the photosensitive layer described above, and preferred embodiments are also the same.
• the thermoplastic resin layer may contain one type of surfactant or two or more types of surfactants.
• the content of the surfactant is preferably 0.001% by mass to 10% by mass, more preferably 0.01% by mass to 3% by mass, based on the total mass of the thermoplastic resin layer.
• the thermoplastic resin layer may contain a sensitizer.
• the sensitizer include the sensitizers that may be included in the above-mentioned negative photosensitive layer.
• the thermoplastic resin layer may contain one type of sensitizer or two or more types of sensitizers.
• the content of the sensitizer is 0.01% by mass to 5% by mass based on the total mass of the thermoplastic resin layer, from the viewpoint of improving sensitivity to light sources, visibility of exposed areas, and visibility of non-exposed areas. %, more preferably 0.05% by mass to 1% by mass.
• thermoplastic resin layer may contain known additives as necessary.
• thermoplastic resin layer is described in paragraphs 0189 to 0193 of JP-A No. 2014-85643. The contents of the above publications are incorporated herein by reference.
• the thickness of the thermoplastic resin layer is not limited.
• the average thickness of the thermoplastic resin layer is preferably 1 ⁇ m or more, more preferably 2 ⁇ m or more, from the viewpoint of adhesion to a layer adjacent to the thermoplastic resin layer.
• the average thickness of the thermoplastic resin layer is preferably 20 ⁇ m or less, more preferably 10 ⁇ m or less, and particularly preferably 5 ⁇ m or less.
• the method for forming the thermoplastic resin layer is not limited as long as it can form a layer containing the above components.
• Examples of the method for forming the thermoplastic resin layer include a method of applying a thermoplastic resin composition to the surface of a temporary support and drying the coated film of the thermoplastic resin composition.
• thermoplastic resin composition examples include compositions containing the above components.
• the thermoplastic resin composition preferably contains a solvent in order to adjust the viscosity of the thermoplastic resin composition and facilitate formation of the thermoplastic resin layer.
• the solvent contained in the thermoplastic resin composition is not limited as long as it can dissolve or disperse the components contained in the thermoplastic resin layer.
• examples of the solvent include solvents that may be included in the photosensitive layer forming composition described above, and preferred embodiments are also the same.
• thermoplastic resin composition may contain one type of solvent or two or more types of solvents.
• the content of the solvent in the thermoplastic resin composition is preferably 50 parts by mass to 1,900 parts by mass, and 100 parts by mass to 900 parts by mass, based on 100 parts by mass of the total solid content in the thermoplastic resin composition. It is more preferable that it is part.
• thermoplastic resin composition and formation of the thermoplastic resin layer may be performed according to the method for preparing the composition for forming a photosensitive layer and the method for forming the negative photosensitive layer described above.
• a thermoplastic resin composition is prepared by preparing a solution in which each component contained in the thermoplastic resin layer is dissolved in a solvent, and mixing the obtained solutions at a predetermined ratio.
• a thermoplastic resin layer can be formed by applying a thermoplastic resin composition to the surface of a temporary support and drying the coating film of the thermoplastic resin composition.
• a thermoplastic resin layer may be formed on the surface of the photosensitive layer.
• the photosensitive transfer material has a cover film.
• the cover film is not included in the transfer layer. It is preferable that the photosensitive layer and the cover film are in direct contact with each other.
• cover film Materials constituting the cover film include resin films and paper, and resin films are preferred from the viewpoints of strength and flexibility.
• resin films include polyethylene film, polypropylene film, polyethylene terephthalate film, cellulose triacetate film, polystyrene film, and polycarbonate film. Among these, polyethylene film, polypropylene film, or polyethylene terephthalate film is preferred.
• the thickness (layer thickness) of the cover film is not particularly limited, but is preferably from 5 ⁇ m to 100 ⁇ m, more preferably from 10 ⁇ m to 50 ⁇ m.
• the arithmetic mean roughness Ra of the surface of the cover film opposite to the photosensitive layer side is determined from the viewpoints of transportability, defect suppression of the resin pattern, and resolution.
• the arithmetic mean roughness of the surface is preferably equal to or less than Ra, and more preferably smaller than the arithmetic mean roughness Ra of the surface of the cover film on the photosensitive layer side.
• the arithmetic mean roughness Ra of the surface of the cover film opposite to the photosensitive layer side is preferably 300 nm or less, more preferably 100 nm or less, even more preferably 70 nm or less, and 50 nm or less, from the viewpoint of transportability and winding property. The following is particularly preferred. Further, the arithmetic mean roughness Ra of the surface of the photosensitive layer side of the cover film is preferably 300 nm or less, more preferably 100 nm or less, still more preferably 70 nm or less, and 50 nm or less, from the viewpoint of better resolution. is particularly preferred.
• the lower limit of the Ra value on the surface of the cover film is not particularly limited, but is preferably 1 nm or more, more preferably 10 nm or more, particularly preferably 20 nm or more on both surfaces. Moreover, it is preferable that the peeling force of the cover film is smaller than that of the temporary support.
• the photosensitive transfer material may include layers other than the above-mentioned layers (hereinafter also referred to as "other layers”).
• other layers include a contrast enhancement layer.
• the contrast enhancement layer is described in paragraph 0134 of International Publication No. 2018/179640.
• JP2014-85643 It is described in paragraphs 0194 to 0196 of the publication. The contents of these publications are incorporated herein.
• the total thickness of the photosensitive transfer material is preferably 5 ⁇ m to 55 ⁇ m, more preferably 10 ⁇ m to 50 ⁇ m, particularly preferably 20 ⁇ m to 40 ⁇ m.
• the total thickness of the photosensitive transfer material is measured by a method similar to the method for measuring the thickness of each layer described above.
• the total thickness of each layer excluding the temporary support and the cover film in the photosensitive transfer material is preferably 20 ⁇ m or less, more preferably 10 ⁇ m or less, and 8 ⁇ m or less, from the viewpoint of exhibiting the effects of the present disclosure. It is more preferable that the particle size is 2 ⁇ m or more and 8 ⁇ m or less.
• the total thickness of the photosensitive layer, intermediate layer, and thermoplastic resin layer in the photosensitive transfer material is preferably 20 ⁇ m or less, more preferably 10 ⁇ m or less, from the viewpoint of more exerting the effects of the present disclosure. , more preferably 8 ⁇ m or less, particularly preferably 2 ⁇ m or more and 8 ⁇ m or less.
• the photosensitive 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 can 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 ⁇ m to 0.1 ⁇ m, more preferably 0.01 ⁇ m 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 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. From the viewpoint of reducing the thickness of the photosensitive layer after heating, at least one of alumina treatment and zirconia treatment is preferable as the surface treatment on the surface of titanium oxide, and surface treatment including both alumina treatment and zirconia treatment is particularly preferable. .
• the photosensitive layer when the photosensitive layer is a colored resin layer, from the viewpoint of transferability, it is also preferable that the photosensitive 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, more preferably more than 3% by mass and not more than 35% by mass, based on the total mass of the photosensitive layer. It is more preferably more than 35% by mass, and particularly preferably 10% by mass or more and 35% by mass or less.
• the content of pigments other than black pigments is preferably 30% by mass or less, and 1% by mass to 20% by mass based on the black pigment. It is more preferably 3% by mass to 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).
• 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).
• a first embodiment of the method for producing a photosensitive transfer material according to the present disclosure includes a step of forming a photosensitive layer by applying a composition for forming a photosensitive layer on a cover film, and a step of forming a photosensitive layer on the photosensitive layer. , applying a particle layer forming composition to form a particle layer having a convex structure on the surface; and applying a temporary support to the surface of the particle layer having the convex structure so as to be in contact with the particle layer. bonding step, the average layer thickness of the portion of the particle layer where the convex structure does not exist is smaller than the arithmetic mean particle diameter of the particles included in the particle layer.
• a second embodiment of the method for producing a photosensitive transfer material according to the present disclosure includes a step of forming a photosensitive layer by applying a composition for forming a photosensitive layer on a cover film, and a step of forming a photosensitive layer on the photosensitive layer. , a step of applying a composition for forming an intermediate layer to form an intermediate layer; a step of applying a composition for forming a particle layer on the intermediate layer to form a particle layer; and a step of forming a particle layer on the particle layer.
• the method includes a step of laminating a support so as to be in contact with the particle layer.
• FIG. 1 is a schematic cross-sectional view showing an example of the layer structure in a second embodiment of the photosensitive transfer material according to the present disclosure.
• the photosensitive transfer material 20 shown in FIG. 1 has a temporary support 11, a particle layer 18, a thermoplastic resin layer 13, an intermediate layer 15, a photosensitive layer 17, and a cover film 19 laminated in this order. It has a configuration.
• the photosensitive layer forming composition is coated on the cover film 19, and then the coating film of the photosensitive layer forming composition is dried to form the photosensitive layer 17.
• a step of forming an intermediate layer 15 by coating the intermediate layer forming composition on the surface of the photosensitive layer 17 and drying the coating film of the intermediate layer forming composition; After applying the thermoplastic resin composition to the surface, a step of drying the coating film of the thermoplastic resin composition to form the thermoplastic resin layer 13, and a step of applying the particle layer forming layer composition to the surface of the thermoplastic resin layer 13.
• a method including a step of drying the coating film of the particle layer forming layer composition to form the particle layer 18, and a step of press-bonding the temporary support 11 to the particle layer 18 can be mentioned.
• a particle layer forming composition containing at least one selected from the group consisting of water and a water-miscible organic solvent, and an alkylene glycol ether solvent and an alkylene glycol ether acetate solvent selected from the group consisting of a thermoplastic resin composition containing at least one kind selected from the group consisting of water and a water-miscible organic solvent; a polymerizable compound; It is preferable to use a composition for forming a photosensitive layer containing at least one selected from the group consisting of an alkylene glycol ether solvent and an alkylene glycol ether acetate solvent. This makes it possible to suppress mixing of the components of each layer during formation of each layer.
• the photosensitive transfer material 20 is manufactured by pressing the temporary support 11 onto the particle layer 18 of the laminate manufactured by the above manufacturing method. After producing the photosensitive transfer material 20 by the above production method, the photosensitive transfer material 20 may be wound up to produce and store the photosensitive transfer material in the form of a roll.
• the photosensitive transfer material in the form of a roll can be provided as it is for the process of bonding it to a substrate using a roll-to-roll method, which will be described later.
• the coating film of the photosensitive layer forming composition is dried. After applying the particle layer forming layer composition to the surface of the photosensitive layer, drying the coating film of the particle layer forming layer composition to form a particle layer having a convex structure on the surface.
• a method including a step of forming a temporary support and a step of press-bonding a temporary support to the surface having a convex structure of a particle layer can be mentioned.
• the photosensitive transfer material according to the present disclosure can be suitably used in various applications requiring precise microfabrication by photolithography. After patterning the photosensitive layer, etching may be performed using the photosensitive layer as a film, or electroforming, mainly electroplating, may be performed. Further, the cured film obtained by patterning may be used as a permanent film, for example, as an interlayer insulating film, a wiring protective film, a wiring protective film having an index matching layer, or the like.
• the photosensitive transfer material according to the present disclosure is applicable to semiconductor packages, printed circuit boards, various wiring formation applications for sensor boards, touch panels, electromagnetic shielding materials, conductive films such as film heaters, liquid crystal sealing materials, and micromachine or microelectronics fields. It can be suitably used for applications such as forming structures in.
• the photosensitive layer is a colored resin layer containing a pigment
• the colored resin layer can be used, for example, as a color used in liquid crystal display devices (LCDs) and solid-state image sensors (e.g., CCDs (charge-coupled devices) and CMOSs (complementary metal oxide semiconductors)). It is suitable for use in forming colored pixels or black matrices in filters and the like.
• Embodiments other than the pigment in the colored resin layer are the same as those described above.
• a method for manufacturing a resin pattern according to the present disclosure is a method for manufacturing a resin pattern in which a resin pattern is formed on a substrate using a photosensitive transfer material according to the present disclosure.
• the method for manufacturing a resin pattern according to the present disclosure includes a step of peeling off the cover film of the photosensitive transfer material according to the present disclosure (hereinafter also referred to as a "cover film peeling step"), and a step in which the cover film is peeled off.
• a step of bringing the outermost layer on the photosensitive layer side of the photosensitive transfer material into contact with a support having a conductive layer hereinafter also referred to as "bonding step", and moving the particle layer from the temporary support.
• a step of peeling off the body hereinafter also referred to as "temporary support peeling step”
• a step of bringing an exposure mask into contact with the particle layer and exposing the photosensitive layer in a pattern through the exposure mask hereinafter referred to as "exposure step”
• exposure step a step of developing the photosensitive layer to form a resin pattern
• pattern forming step a step of developing the photosensitive layer to form a resin pattern
• the method for manufacturing a resin pattern, the method for manufacturing a laminate, the method for manufacturing circuit wiring, or the method for manufacturing an electronic device requires the cover film to be added before the lamination process. including the step of peeling off.
• the method for manufacturing circuit wiring according to the present disclosure is not particularly limited as long as it is a method using the photosensitive transfer material according to the present disclosure.
• the method for manufacturing circuit wiring according to the present disclosure includes a step of peeling off the cover film in the photosensitive transfer material according to the present disclosure, and a step of peeling off the cover film on the photosensitive layer side of the photosensitive transfer material from which the cover film has been peeled off.
• a step of exposing the photosensitive layer in a pattern, a step of developing the photosensitive layer to form a resin pattern, and a step of etching the conductive layer using the formed resin pattern as a mask (hereinafter referred to as "etching step"). '') in this order, or a step of peeling off the cover film in the photosensitive transfer material according to the present disclosure, and the photosensitive transfer from which the cover film has been peeled off.
• a method for manufacturing circuit wiring comprising, in this order, a step of applying electrolytic plating (hereinafter also referred to as a "plating step"), a step of peeling off the formed resin pattern, and a step of etching the conductive layer. It is preferable that Each process included in the method for manufacturing a resin pattern and the method for manufacturing circuit wiring will be explained below. However, unless otherwise specified, the explanation for each process included in the method for manufacturing a resin pattern will be explained below. This shall also apply to each process included in the above.
• the method for manufacturing a resin pattern preferably includes a step of peeling the cover film from the photosensitive transfer material according to the present disclosure.
• the method for peeling off the cover film is not limited, and any known method can be applied.
• the resin pattern manufacturing method includes a bonding step.
• the substrate or the conductive layer if a conductive layer is provided on the surface of the substrate
• the substrate is brought into contact with the outermost layer of the photosensitive transfer material on the side that has the photosensitive layer with respect to the temporary support. It is preferable to press the photosensitive transfer material and the substrate together.
• the patterned photosensitive layer after exposure and development can be suitably used as an etching resist when etching a conductive layer.
• the photosensitive transfer material further includes a layer other than the cover film (for example, a high refractive index layer and/or a low refractive index layer) on the surface of the photosensitive layer on the side that does not face the temporary support.
• a layer other than the cover film for example, a high refractive index layer and/or a low refractive index layer
• the surface of the photosensitive layer that does not have the temporary support and the substrate are bonded together via that layer.
• the method of press-bonding the substrate and the photosensitive transfer material is not particularly limited, and known transfer methods and lamination methods can be used.
• the photosensitive transfer material is attached to the substrate by overlapping the outermost layer of the photosensitive transfer material on the side that has the photosensitive layer on the temporary support and applying pressure and heat using a means such as a roll. Preferably, this is done by applying.
• known laminators such as a laminator, a vacuum laminator, and an auto-cut laminator that can further improve productivity can be used.
• the lamination temperature is not particularly limited, but is preferably, for example, 70°C to 130°C.
• the resin pattern manufacturing method and the laminate manufacturing method including the bonding process are preferably performed by a roll-to-roll method.
• the roll-to-roll method will be explained below.
• the roll-to-roll method uses a substrate that can be rolled up and unrolled as a substrate, and the substrate or a structure including the substrate is rolled before any of the steps included in the resin pattern manufacturing method or the etching method.
• a method in which the steps (preferably all steps or all steps other than the heating step) are carried out while transporting the substrate or a structure including the substrate.
• the unwinding method in the unwinding step and the winding method in the winding step are not particularly limited, and any known method may be used in a manufacturing method that applies a roll-to-roll method.
• any known support having a conductive layer may be used, but it is preferable to have a conductive layer on the surface of the support. .
• the support may have any layer other than the conductive layer, if necessary. Examples of the support include a resin substrate, a glass substrate, and a semiconductor substrate.
• a preferred embodiment of the support includes, for example, the description in paragraph 0140 of International Publication No. 2018/155193, the contents of which are incorporated herein.
• the base material constituting the support examples include glass, silicon, and film.
• the base material constituting the support is preferably transparent.
• transparent means that the transmittance of light with a wavelength of 400 nm to 700 nm is 80% or more.
• the refractive index of the substrate constituting the substrate is preferably 1.50 to 1.52.
• the transparent glass substrate examples include tempered glass such as Corning's Gorilla Glass. Further, as the transparent glass substrate, materials used in JP-A-2010-86684, JP-A-2010-152809, and JP-A-2010-257492 can be used.
• film substrate When using a film substrate as a support, it is preferable to use a film substrate with low optical distortion and/or high transparency.
• film substrates include, for example, polyethylene terephthalate (PET), polyethylene naphthalate, polycarbonate, triacetylcellulose, and cycloolefin polymers.
• a film substrate is preferable when manufacturing by roll-to-roll method. Moreover, when manufacturing circuit wiring for a touch panel by a roll-to-roll method, it is preferable that the substrate is a sheet-like resin composition.
• the conductive layer examples include conductive layers used for general circuit wiring or touch panel wiring.
• the conductive layer is preferably at least one layer selected from the group consisting of a metal layer, a conductive metal oxide layer, a graphene layer, a carbon nanotube layer, and a conductive polymer layer, from the viewpoint of conductivity and fine wire formation. , a metal layer is more preferred, and a copper layer or a silver layer is even more preferred.
• the substrate may have only one conductive layer, or may have two or more conductive layers. When having two or more conductive layers, it is preferable to have conductive layers made of different materials.
• Materials for the conductive layer include metals and conductive metal oxides.
• Metals include Al, Zn, Cu, Fe, Ni, Cr, Mo, Ag and Au.
• conductive metal oxides include ITO (Indium Tin Oxide), IZO (Indium Zinc Oxide), and SiO2 .
• conductivity means that the volume resistivity is less than 1 ⁇ 10 6 ⁇ cm.
• the volume resistivity of the conductive metal oxide is preferably less than 1 ⁇ 10 4 ⁇ cm.
• the conductive layer is preferably an electrode pattern corresponding to a sensor in a visual recognition part used in a capacitive touch panel or wiring in a peripheral extraction part.
• a preferred embodiment of the conductive layer includes, for example, the description in paragraph 0141 of International Publication No. 2018/155193, the content of which is incorporated herein.
• a substrate having at least one of a transparent electrode and a lead-out wiring is preferable.
• the above substrate can be suitably used as a touch panel substrate.
• the transparent electrode can suitably function as an electrode for a touch panel.
• the transparent electrode is preferably composed of a metal oxide film such as ITO (indium tin oxide) and IZO (indium zinc oxide), a metal mesh, and a metal thin wire such as silver nanowire.
• 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.
• Metal is preferable as the material for the lead-out wiring.
• the metal that is the material of the routing wiring include gold, silver, copper, molybdenum, aluminum, titanium, chromium, zinc, and manganese, as well as alloys made of two or more of these metal elements.
• the material for the lead-out wiring is preferably copper, molybdenum, aluminum, or titanium, with copper being particularly preferred.
• the touch panel electrode protective film formed using the photosensitive transfer material according to the present disclosure is intended to protect the electrode, etc. (i.e., at least one of the touch panel electrode and the touch panel wiring), by directly or by other means. It is preferable that it be provided so as to be covered with a layer.
• the method for producing a resin pattern preferably includes a temporary support peeling process of peeling off the temporary support between the bonding process and the exposure process.
• the method for peeling off the temporary support is not particularly limited, and a mechanism similar to the cover film peeling mechanism described in paragraphs 0161 to 0162 of JP-A-2010-072589 can be used.
• the method for producing a resin pattern preferably includes a step (exposure step) of bringing an exposure mask into contact with the particle layer and exposing the photosensitive layer to pattern light through the exposure mask.
• the above exposure process is a patterned exposure process (also referred to as "pattern exposure"), that is, an exposure process in which an exposed area and a non-exposed area exist.
• pattern exposure also referred to as "pattern exposure”
• 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 detailed arrangement and specific size of the pattern in pattern exposure are not particularly limited.
• at least part of the pattern preferably includes a thin line with a width of 20 ⁇ m or less, and more preferably includes a thin line with a width of 10 ⁇ m or less.
• the light source used for exposure can be appropriately selected and used as long as it irradiates light with a wavelength (for example, 365 nm or 405 nm) that can expose the photosensitive layer.
• a wavelength for example, 365 nm or 405 nm
• Specific examples include ultra-high pressure mercury lamps, high-pressure mercury lamps, metal halide lamps, and LEDs (Light Emitting Diodes).
• the exposure amount is preferably 5 mJ/cm 2 to 200 mJ/cm 2 , more preferably 10 mJ/cm 2 to 100 mJ/cm 2 .
• Preferred embodiments of the light source, exposure amount, and exposure method used for exposure include, for example, those described in paragraphs 0146 to 0147 of International Publication No. 2018/155193, the contents of which are incorporated herein.
• a preferable exposure method is a contact exposure method.
• an exposure machine having an appropriate lens numerical aperture (NA) can be used depending on the required resolving power and depth of focus.
• NA numerical aperture
• the exposure may be performed not only in the atmosphere but also under reduced pressure or vacuum, or may be performed with a liquid such as water interposed between the light source and the photosensitive layer.
• the exposed photosensitive layer is developed to form a resin pattern.
• the exposed photosensitive layer in the pattern forming step can be developed using a developer.
• the developer is not particularly limited as long as it can remove the non-image area of the photosensitive layer, and for example, known developers such as the developer described in JP-A-5-72724 can be used.
• the developer may contain a water-soluble organic solvent and/or a surfactant.
• the developer the developer described in paragraph 0194 of International Publication No. 2015/093271 is also preferably mentioned.
• the development method described in paragraph 0195 of International Publication No. 2015/093271 can be mentioned.
• the developing method is not particularly limited and may be any of paddle development, shower development, shower and spin development, and dip development.
• shower development is a development process in which non-image areas are removed by spraying a developer onto the exposed photosensitive layer using a shower. After the pattern forming step, it is preferable to spray a cleaning agent with a shower and remove development residues while rubbing with a brush.
• the temperature of the developer is not particularly limited, but is preferably 20°C to 40°C.
• the method for manufacturing a resin pattern or the method for manufacturing a laminate includes a step of exposing the resin pattern obtained by the pattern forming step (post-exposure step) and/or a step of heating (post-bake step). It's okay. When both a post-exposure step and a post-bake step are included, it is preferable to perform the post-bake after the post-exposure.
• the method for manufacturing circuit wiring preferably includes a step of etching the conductive layer (etching step), and more preferably includes a step of etching the conductive layer using the formed resin pattern as a mask. .
• the resin pattern formed from the photosensitive layer is used as an etching resist and the conductive layer is etched, or the resin pattern is removed after the electrolytic plating process described below and the plating pattern is used as a resist.
• the etching process of the conductive layer is performed using the following method.
• known methods can be applied, such as the method described in paragraphs 0209 to 0210 of JP2017-120435A, and the method described in paragraphs 0048 to 0054 of JP2010-152155A. Examples include 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 circuit wiring includes a step of performing electrolytic plating on the conductive layer using the formed resin pattern as a mask.
• plating method a known method can be applied, and for example, electrolytic plating (electroplating) is preferable, and electrolytic copper plating is more preferable.
• Components of the plating solution used in electrolytic plating include, for example, water-soluble copper salts.
• water-soluble copper salt water-soluble copper salts commonly used as components of plating solutions can be used.
• the water-soluble copper salt is preferably at least one selected from the group consisting of, for example, an inorganic copper salt, an alkanesulfonic acid copper salt, an alkanolsulfonic acid copper salt, and an organic acid copper salt.
• inorganic copper salts include copper sulfate, copper oxide, copper chloride, and copper carbonate.
• copper alkanesulfonate include copper methanesulfonate and copper propanesulfonate.
• Examples of copper alkanolsulfonate salts include copper isethionate and copper propanolsulfonate.
• Examples of organic acid copper salts include copper acetate, copper citrate, and copper tartrate.
• a corresponding salt of another metal may be used instead of the above-mentioned copper.
• the plating solution may contain sulfuric acid. By including sulfuric acid in the plating solution, the pH and sulfate ion concentration of the plating solution can be adjusted.
• the method and conditions of electrolytic plating are not limited. For example, by supplying the conductive base material after the development process to a plating tank to which a plating solution is added, a conductive pattern is formed on the conductive layer in an area where the resin pattern is not arranged. be able to.
• a conductive pattern can be formed by controlling the current density and the transport speed of the conductive base material.
• the temperature of the plating solution used in electrolytic plating is preferably 70°C or lower, more preferably 10°C to 40°C.
• the current density in electrolytic plating is preferably 0.1 A/dm 2 to 100 A/dm 2 , more preferably 0.5 A/dm 2 to 20 A/dm 2 .
• the productivity of conductor patterns can be improved by increasing the current density. By lowering the current density, the uniformity of the thickness of the conductive pattern can be improved.
• the method for manufacturing circuit wiring includes a peeling step of peeling off the resin pattern.
• the method of peeling off the remaining resin pattern is not particularly limited, but includes a method of peeling using chemical treatment, and a method of peeling using a removal liquid is preferable.
• the conductive substrate having the remaining resin pattern is placed in a stirring removal solution whose temperature is preferably 30°C to 80°C, more preferably 50°C to 80°C, for 1 minute.
• An example is a method of soaking for ⁇ 30 minutes.
• 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 resin pattern manufacturing method, the laminate manufacturing method, and the circuit wiring manufacturing method may include any steps (other steps) other than the steps described above. Examples include, but are not limited to, the following steps. Furthermore, examples of the pattern forming process and other processes applicable to the method for manufacturing circuit wiring include the processes described in paragraphs 0035 to 0051 of JP-A No. 2006-23696. Furthermore, other steps include, for example, the step of reducing visible light reflectance described in paragraph 0172 of International Publication No. 2019/022089, and the step of reducing the visible light reflectance described in paragraph 0172 of International Publication No. 2019/022089, Examples include a process of forming a conductive layer, but are not limited to these processes.
• the method for manufacturing circuit wiring may include a step of performing a process of reducing the visible light reflectance of some or all of the plurality of conductive layers included in the substrate.
• 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 treatment for reducing visible light reflectance is described in paragraphs 0017 to 0025 of JP 2014-150118, and paragraphs 0041, 0042, 0048, and 0058 of JP 2013-206315. , the contents of these publications are incorporated herein.
• the method for manufacturing circuit wiring includes the steps of forming an insulating film on the surface of the circuit wiring, 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. good.
• circuit wiring it is also preferable to use a substrate having a plurality of conductive layers on both surfaces of the substrate, and to form circuits on the conductive layers formed on both surfaces of the substrate sequentially or simultaneously.
• circuit wiring for a touch panel in which the first conductive pattern is formed on one surface of the substrate and the second conductive pattern is formed on the other surface.
• the resin pattern manufactured by the resin pattern manufacturing method according to the present disclosure and the circuit wiring manufactured by the circuit wiring manufacturing method according to the present disclosure can be applied to various devices.
• Examples of the above device include an input device, etc., preferably a touch panel, and more preferably a capacitive touch panel.
• the input device can be applied to display devices such as organic electroluminescent display devices and liquid crystal display devices.
• the formed resin pattern is preferably used as a protective film for touch panel electrodes or touch panel wiring. That is, the photosensitive transfer material according to the present disclosure is preferably used for forming an electrode protective film for a touch panel or wiring for a touch panel.
• the method for manufacturing an electronic device according to the present disclosure is not particularly limited as long as it uses the photosensitive transfer material according to the present disclosure.
• the method for manufacturing an electronic device according to the present disclosure includes a step of peeling off the cover film of the photosensitive transfer material according to the present disclosure, and a step of peeling off the cover film on the photosensitive layer side of the photosensitive transfer material from which the cover film has been peeled off.
• the steps of pattern-exposing the photosensitive layer, developing the photosensitive layer to form a resin pattern, and etching the conductive layer using the formed resin pattern as a mask are performed in this order. or the step of peeling off the cover film in the photosensitive transfer material according to the present disclosure, and the outermost layer on the photosensitive layer side of the photosensitive transfer material from which the cover film has been peeled off, a step of bringing the layer into contact with a support and bonding it; a step of peeling off the temporary support from the particle layer; and a step of bringing an exposure mask into contact with the particle layer and patterning the photosensitive layer through the exposure mask.
• the method includes a step of peeling and a step of etching the conductive layer in this order.
• the method for manufacturing an electronic device according to the present disclosure preferably includes a step of peeling off the cover film before the bonding step.
• each step and the order in which each step is performed in the method for manufacturing an electronic device are as described above, and the preferred embodiments are also the same.
• the method of manufacturing an electronic device reference may be made to a known method of manufacturing an electronic device, except for forming the wiring for an electronic device by the method described above.
• the method for manufacturing an electronic device may include any steps (other steps) other than those described above.
• Electronic devices are not particularly limited, but include semiconductor packages, printed circuit boards, various wiring formation applications for sensor boards, touch panels, electromagnetic shielding materials, conductive films such as film heaters, liquid crystal sealing materials, micromachines, and microelectronics fields. Suitable examples include structures.
• the resin pattern is preferably used as a permanent film, such as an interlayer insulating film, a wiring protective film, a wiring protective film having an index matching layer, etc. in the electronic device.
• a touch panel is particularly suitable as an electronic device.
• FIGS. 2 and 3 An example of a mask pattern used for manufacturing a touch panel is shown in FIGS. 2 and 3.
• pattern A shown in FIG. 2 and pattern B shown in FIG. 3 GR is a non-image area (light-shielding area), EX is an image area (exposed area), and DL is a virtual alignment frame. This is what is shown.
• a method for manufacturing a touch panel for example, by exposing the photosensitive layer to light through a mask having a pattern A shown in FIG. 2, a touch panel in which circuit wiring having a pattern A corresponding to EX is formed can be manufactured. Specifically, it can be produced by the method described in FIG. 1 of International Publication No. 2016/190405.
• the central part of the exposed part EX is the part where the transparent electrode (touch panel electrode) is formed
• the peripheral part (thin line part) of the exposed part EX is the part where the transparent electrode (touch panel electrode) is formed. This is the part where the wiring of the peripheral extraction part is formed.
• an electronic device having at least wiring for an electronic device is manufactured, and preferably, for example, a touch panel having at least wiring for a touch panel is manufactured. It is preferable that the touch panel has a transparent substrate, an electrode, and an insulating layer or a protective layer.
• Detection methods for touch panels include known methods such as a resistive film method, a capacitance method, an ultrasonic method, an electromagnetic induction method, and an optical method. Among these, the capacitive method is preferable.
• Examples of the touch panel type include the so-called in-cell type (for example, those shown in FIGS. 5, 6, 7, and 8 of Japanese Patent Publication No. 2012-517051), and the so-called on-cell type (for example, those shown in Japanese Patent Application Laid-Open No. 2013-168125). 19, and those shown in FIGS. 1 and 5 of JP-A-2012-89102), OGS (One Glass Solution) type, TOL (Touch-on-Lens) type (for example, JP-A-2012-89102) 2 of JP-A No.
• composition 1 for forming a photosensitive layer was obtained by mixing the following components and filtering through a polytetrafluoroethylene filter with a pore size of 0.2 ⁇ m.
• Surfactant E-1 0.1 part by mass
• F-1 0.5 part by mass Additive G-1: 0.17 part by mass
• ATHF Tetrahydrofuran-2-yl acrylate (synthetic product)
• MAA Methacrylic acid (manufactured by Tokyo Chemical Industry Co., Ltd.)
• CHMA cyclohexyl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.)
• CHA cyclohexyl acrylate (manufactured by Tokyo Chemical Industry Co., Ltd.)
• V-601 Dimethyl 2,2'-azobis(2-methylpropionate) (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.)
• Photoacid generator B-1 Compound with the structure shown below (a compound described in paragraph 0227 of JP-A No. 2013-047765, synthesized according to the method described in paragraph 0204)
• Surfactant E-1 Compound with the structure shown below
• Basic compound F-1 Compound with the structure shown below
• composition 1 for forming a particle layer was obtained by mixing the components listed in Table 1 and filtering the mixture through a polytetrafluoroethylene filter with a pore size of 5.0 ⁇ m.
• particle layer forming compositions 2 to 9 were obtained in the same manner.
• Kuraray Poval 4-88LA (polyvinyl alcohol, manufactured by Kuraray Co., Ltd.) Metrose 60SH-03: (Hydroxypropyl methylcellulose, manufactured by Shin-Etsu Chemical Co., Ltd.) Metrose 60SH-06: (Hydroxypropyl methylcellulose, manufactured by Shin-Etsu Chemical Co., Ltd.) Polyvinylpyrrolidone K-30: (Polyvinylpyrrolidone, manufactured by Nippon Shokubai Co., Ltd.) Polymer A-1: Polymer shown below Polymer A-2: Polymer shown below Snowtex OZL-35: (Silica particles, arithmetic mean particle size 80 nm, solid content 35% by mass, Nissan Chemical Industries, Ltd.) made) Snowtex OYL: (Silica particles, arithmetic mean particle size 60 nm, solid content 20% by mass, manufactured by Nissan Chemical Industries, Ltd.) Eposter M
• Polymer A-1 was synthesized according to the following method. In the method for synthesizing polymer A-1, the following abbreviations represent the following compounds, respectively.
• St Styrene (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.)
• MAA Methacrylic acid (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.)
• MMA Methyl methacrylate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.)
• AA Acrylic acid (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.)
• BzMA Benzyl methacrylate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.)
• V-601 2,2'-azobis(isobutyric acid) dimethyl (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., polymerization initiator)
• PGMEA Propylene glycol monomethyl ether acetate
• PGME Propylene
• PGMEA (58.25 parts) and PGME (58.25 parts) were placed in a three-necked flask, and the temperature was raised to 90°C under a nitrogen atmosphere. While maintaining the liquid temperature in the three-necked flask at 90°C ⁇ 2°C, St (52.0 parts), MMA (19.0 parts), MAA (29.0 parts), and V-601 (4.0 parts) were added. A mixture of PGMEA (58.25 parts) and PGME (58.25 parts) was dropped into the three-necked flask over 2 hours.
• Polymer A had an acid value of 189 mgKOH/g, a weight average molecular weight of 60,000, and a glass transition temperature of 131°C.
• Polymer A-2 Polymer A-2 was synthesized in the same manner as Polymer A-1.
• Polymer A-2 is a copolymer of benzyl methacrylate, methacrylic acid, and acrylic acid (content of each monomer: 78% by mass/14.5% by mass/7.5% by mass, Mw: 30000, Tg 75°C, acid
• This is a 1:1 mixed solution of propylene glycol monomethyl ether acetate with a value of 153 mg KOH/g) and propylene glycol monomethyl ether (solid content concentration: 30.0% by mass).
• Photosensitive layer forming composition 1 was applied onto the cover film (16KS40, manufactured by Toray Industries, Inc., biaxially stretched polyethylene terephthalate (PET) film with a film thickness of 16 ⁇ m) listed in Table 2, and the dry film thickness was adjusted using a slit-shaped nozzle. It was coated to a thickness of 3.0 ⁇ m. After the above coating, it was dried in a convection oven at 100° C. for 1 minute to form a photosensitive layer. After forming the photosensitive layer, Intermediate layer forming composition 1 was applied onto the photosensitive layer so that the dry film thickness was 1.0 ⁇ m. Thereafter, it was dried in a convection oven at 100° C.
• cover film (16KS40, manufactured by Toray Industries, Inc., biaxially stretched polyethylene terephthalate (PET) film with a film thickness of 16 ⁇ m) listed in Table 2, and the dry film thickness was adjusted using a slit-shaped nozzle. It was coated to a thickness of 3.0 ⁇ m. After the
• the produced photosensitive transfer materials of each example were taken out as a section (thin section) with a film thickness of 100 nm using a focused ion beam (FIB) processing method, and were taken out using a transmission electron microscope (TEM). The cross section was observed. The major axis of any 100 observed particles was measured, and the arithmetic average value was used as the arithmetic mean particle diameter. Furthermore, regarding the particle layer, it was confirmed that there was a structure that contained particles and was locally thicker than the surrounding area. Structures with locally large layer thickness protruded toward the temporary support.
• FIB focused ion beam
• layer thickness of the particle layer in Table 2 represents the average layer thickness of the portion of the particle layer where no convex structure exists.
• PET substrate with copper layer Copper layers each having a thickness of 200 nm were formed on both sides of a polyethylene terephthalate (PET) film having a thickness of 100 ⁇ m by a sputtering method to produce a PET base material with a copper layer (base material 1).
• PET polyethylene terephthalate
• the surface of the slipperiness evaluation samples of each example was observed using a scanning electron microscope (SEM), and it was confirmed that there was a particle layer having a convex structure containing particles. That is, it was confirmed that the particle layer and the temporary support could be separated. Furthermore, even after peeling off the cover film of the photosensitive transfer material, thermally laminating it to the base material, and further peeling off the temporary support, the surface of the particle layer on the temporary support side has a convex structure containing particles. This was confirmed.
• SEM scanning electron microscope
• Standard deviation less than 0.10 um 4 Standard deviation 0.10 ⁇ m or more and less than 0.20 ⁇ m 3: Standard deviation 0.20 ⁇ m or more and less than 0.30 ⁇ m 2: Standard deviation 0.30 ⁇ m or more and less than 0.50 ⁇ m 1: Standard deviation 0. 50 or more or no resolved part
• ⁇ Preparation of circuit wiring pattern subtract method>
• the patterned sample was etched for 80 seconds at 25°C using a copper etching solution (MEC Bright SF-5404, manufactured by MEC Co., Ltd.), and the resist was removed using a 4% by mass sodium hydroxide solution to create a circuit wiring pattern. Created.
• MEC Bright SF-5404 manufactured by MEC Co., Ltd.
• NK ester BPE-500 (2,2-bis(4-(methacryloxypentaethoxy)phenyl)propane, manufactured by Shin Nakamura Chemical Co., Ltd.
• ⁇ B-2 Aronix M-270 (polypropylene glycol diacrylate, manufactured by Toagosei Co., Ltd.)
• [Coloring agent] ⁇ N-1 LCV (leuco crystal violet, manufactured by Tokyo Kasei Kogyo Co., Ltd., a pigment that develops color due to radicals)
• ⁇ anti-rust ⁇ ⁇ CBT-1 (carboxybenzotriazole, manufactured by Johoku Kagaku Kogyo Co., Ltd.)
• Composition 2 for forming a photosensitive layer was prepared by mixing the following components.
• - Polymer A-1 solid content concentration 30.0%
• B-1 solid content concentration 30.0%
• B-2 5.00 parts
• Photoinitiator 7.00 parts
• Increase Sensitizer 0.50 parts
• N-1 0.40 parts
• chain transfer agent 0.20 parts
• rust preventive 0.10 parts
• polymerization inhibitor 0.30 parts
• antioxidant 0. 01 parts ⁇ Surfactant: 0.29 parts ⁇ Methyl ethyl ketone (manufactured by Sankyo Chemical Co., Ltd.): 396.00 parts ⁇ PGMEA (manufactured by Showa Denko Co., Ltd.): 170.00 parts
• Intermediate layer forming composition 1 was obtained by preparing the following composition and filtering it through a polytetrafluoroethylene filter with a pore size of 3.0 ⁇ m.
• composition 1 for forming an adhesive layer was obtained by preparing the following composition and filtering it through a polytetrafluoroethylene filter with a pore size of 3.0 ⁇ m.
• 89.2 parts by mass ⁇ Megafac F-552 manufactured by DIC Corporation
• 0.39 parts by mass ⁇ Methyl ethyl ketone manufactured by Sankyo Chemical Co., Ltd.
• 765.0 parts ⁇ PGMEA manufactured by Showa Denko Co., Ltd.
• composition 1 for forming a photosensitive layer was applied onto the cover film (16KS40, manufactured by Toray Industries, Inc.) shown in Table 4 using a slit-shaped nozzle so that the dry film thickness was 3.0 ⁇ m. After the above coating, it was dried in a convection oven at 100° C. for 1 minute to form a photosensitive layer. After forming the photosensitive layer, Intermediate layer forming composition 1 was applied onto the photosensitive layer so that the dry film thickness was 1.0 ⁇ m. Thereafter, it was dried in a convection oven at 100° C. for 1 minute to form an intermediate layer on the photosensitive layer.
• the particle layer forming composition 10 was applied onto the intermediate layer so that the dry film thickness was 0.1 ⁇ m. Thereafter, it was dried in a convection oven at 100° C. for 1 minute to produce a film A having a photosensitive layer, an intermediate layer, and a particle layer in this order on the cover film.
• Composition 1 for forming an adhesive layer was applied onto a PET support (16KS40, manufactured by Toray Industries, Inc.) using a slit-shaped nozzle so that the dry film thickness was 3.0 ⁇ m. After the above coating, it was dried in a convection oven at 100° C. for 1 minute to produce a film B (temporary support) having an adhesive layer on a PET support.
• Photosensitive transfer material 7 of Example 7 was prepared by thermally laminating at 70° C. at a speed of 14 m/min so that the particle layer of Film A and the adhesive layer of Film B were in contact with each other.
• photosensitive transfer materials of Examples 7 to 18, 20 and 21, and Comparative Examples 3 to 5 were prepared as shown in Table 4, Table 5, or Table 6. These photosensitive transfer materials were measured and evaluated in the same manner as in Example 1. As a result, it was confirmed that the particle layer of the photosensitive transfer material of each of the produced examples contained particles and had a structure in which the layer thickness was locally larger than the surrounding area. Structures with locally large layer thickness protruded toward the temporary support. Furthermore, it was confirmed that the particle layer and the temporary support were removable for the photosensitive transfer materials of each example.
• the layer thickness of the particle layer in Tables 4 to 6 represents the average layer thickness of the part where no convex structure exists in the particle layer, and the unit of oxygen permeability is cc/m 2 day atm. .
• the photosensitive transfer materials of Examples 1 to 21 have excellent slipperiness compared to the photosensitive transfer materials of Comparative Examples 1 to 5. Furthermore, as shown in Table 2 and Tables 4 to 6 above, the photosensitive transfer materials of Examples 1 to 21 are also excellent in line width uniformity and linearity.

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• 2023
  • 2023-07-26 WO PCT/JP2023/027464 patent/WO2024024864A1/ja not_active Ceased
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