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
  • 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
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
  • B32B7/04—Interconnection of layers
  • B32B7/06—Interconnection of layers permitting easy separation
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
  • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
  • G03F7/033—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/075—Silicon-containing compounds
• • 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
• • H—ELECTRICITY
  • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
  • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
  • H05K3/00—Apparatus or processes for manufacturing printed circuits
  • H05K3/10—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern
  • H05K3/18—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using precipitation techniques to apply the conductive material

Definitions

• the present disclosure relates to a transfer film, a method for manufacturing a laminate, a method for manufacturing a circuit wiring board, a circuit wiring board, and a semiconductor package.
• a photosensitive layer is placed on an arbitrary substrate using a transfer film, the photosensitive layer is exposed to light through a mask, and then developed. The method is widely used.
• a support (A) and a composition for forming a negative photosensitive layer having a thickness of 1 to 35 ⁇ m are applied to the metal-coated surface of a metal-coated insulating plate having a metal conductor layer on one or both surfaces.
• a photosensitive resin laminate having a material layer (B) and a protective layer (C) is laminated such that the negative photosensitive layer forming composition layer (B) is in close contact with the metal-coated surface of the metal-coated insulating plate.
• a method for exposing a photosensitive layer-forming composition layer to light which comprises peeling off the support before exposure and projecting the image of the photomask through a lens when exposing to ultraviolet light through a photomask. ' has been disclosed.
• Patent Document 1 Patent No. 4477077
• Patent Document 1 has high adhesion between the photosensitive layer-forming composition layer and the support, resulting in peeling of the photosensitive layer-forming composition layer and aggregation of the support. It was learned that there is a risk of damage. Further, the above-mentioned transfer film is usually required to have excellent resolution so that fine patterns can be formed.
• the problem to be solved by an embodiment of the present disclosure is to provide a transfer film with excellent releasability and resolution of a temporary support, a method for manufacturing a laminate, a method for manufacturing a circuit wiring board, a circuit wiring board, and a semiconductor package. It is to be.
• the specific means to solve the problem are as follows. ⁇ 1> It has a temporary support, an intermediate layer containing a surfactant, and a photosensitive layer, and when the temporary support is peeled off, the surface free energy of the exposed surface not including the temporary support is , 66.0 mJ/m 2 or less. ⁇ 2> The transfer film according to ⁇ 1> above, wherein the surfactant includes a silicone surfactant. ⁇ 3> The transfer film according to ⁇ 1> or ⁇ 2> above, wherein the photosensitive layer contains a surfactant including a silicone surfactant.
• the photosensitive layer contains an alkali-soluble resin, and the alkali-soluble resin contains at least one of a styrene-derived structural unit and a styrene derivative-derived structural unit, and a (meth)acrylic acid ester-derived structural unit. containing, when the content of the structural units derived from the styrene and the structural units derived from the styrene derivative is 1, the content of the structural units derived from the (meth)acrylic acid ester is from 0.3 to 2.5.
• the transfer film according to any one of the above items ⁇ 1> to ⁇ 3>.
• ⁇ 5> The transfer film according to any one of ⁇ 1> to ⁇ 4> above, wherein the intermediate layer contains polyvinyl alcohol.
• ⁇ 6> The transfer film according to ⁇ 5> above, wherein the content of polyvinyl alcohol based on the total mass of the intermediate layer is 15% by mass to 90% by mass.
• the intermediate layer contains one or more compounds X selected from the group consisting of a water-soluble cellulose compound, a polyether compound, a phenol compound, and a polyhydric alcohol compound.
• ⁇ 8> The transfer film according to ⁇ 7> above, wherein the sum of the content of compound X with respect to the total mass of the intermediate layer is 0.1% by mass to 36% by mass.
• ⁇ 9> The transfer film according to any one of ⁇ 1> to ⁇ 8> above, wherein the intermediate layer contains hydroxypropylmethylcellulose.
• ⁇ 10> The transfer film according to any one of ⁇ 1> to ⁇ 9> above, wherein the intermediate layer has a thickness of 5.0 ⁇ m or less.
• ⁇ 11> The transfer film according to any one of ⁇ 1> to ⁇ 10> above, wherein the photosensitive layer has a thickness of 2.0 ⁇ m to 20.0 ⁇ m.
• thermoplastic resin layer containing a surfactant including a silicone surfactant between the temporary support and the intermediate layer.
• the transfer film described in . ⁇ 13> The transfer film according to ⁇ 12> above, wherein the thermoplastic resin layer has a thickness of 2.0 ⁇ m to 15.0 ⁇ m.
• ⁇ 14> The transfer film and the substrate such that the surface of the photosensitive layer of the transfer film according to any one of ⁇ 1> to ⁇ 13> on the side opposite to the intermediate layer side is in contact with the substrate.
• ⁇ 18> The above ⁇ 14> to ⁇ 17>, wherein the transfer film has a thermoplastic resin layer containing a surfactant including a silicone surfactant between the temporary support and the intermediate layer.
• a method for producing a laminate according to any one of the above. ⁇ 19> The method for manufacturing a laminate according to any one of ⁇ 14> to ⁇ 18> above, wherein the substrate has a dielectric loss tangent of 0.05 or less at 25 GHz.
• ⁇ 20> The method for manufacturing a laminate according to any one of ⁇ 14> to ⁇ 19> above, wherein the substrate is a substrate incorporating an element that interconnects semiconductor elements.
• ⁇ 21> A step of manufacturing a laminate by the method according to any one of ⁇ 14> to ⁇ 20> above, and a step of performing a plating treatment on an area where the pattern is not formed to form a conductive pattern. and a step of removing the pattern, in this order.
• ⁇ 22> A circuit wiring board manufactured by the manufacturing method described in ⁇ 21> above.
• ⁇ 23> A semiconductor package including the circuit wiring board according to ⁇ 22> above.
• a transfer film a method for manufacturing a laminate, a method for manufacturing a circuit wiring board, a circuit wiring board, and a semiconductor package that have excellent removability and resolution of a temporary support.
• FIG. 1 is a schematic cross-sectional view for explaining one embodiment of a method for manufacturing a circuit wiring board, which is a semiconductor package.
• FIG. 2 is a schematic cross-sectional view for explaining one embodiment of a method for manufacturing a circuit wiring board, which is a semiconductor package.
• FIG. 3 is a schematic cross-sectional view for explaining one embodiment of a method for manufacturing a circuit wiring board, which is a semiconductor package.
• FIG. 4 is a schematic cross-sectional view for explaining one embodiment of a method for manufacturing a circuit wiring board, which is a semiconductor package.
• FIG. 5 is a schematic cross-sectional view for explaining one embodiment of a method for manufacturing a circuit wiring board, which is a semiconductor package.
• FIG. 1 is a schematic cross-sectional view for explaining one embodiment of a method for manufacturing a circuit wiring board, which is a semiconductor package.
• FIG. 2 is a schematic cross-sectional view for explaining one embodiment of a method for manufacturing a circuit wiring board, which is a
• FIG. 6 is a schematic cross-sectional view for explaining one embodiment of a method for manufacturing a circuit wiring board, which is a semiconductor package.
• FIG. 7 is a schematic cross-sectional view for explaining one embodiment of a method for manufacturing a circuit wiring board, which is a semiconductor package.
• FIG. 8 is a schematic cross-sectional view for explaining one embodiment of a method for manufacturing a circuit wiring board, which is a semiconductor package.
• FIG. 9 is a schematic cross-sectional view for explaining one embodiment of a method for manufacturing a circuit wiring board, which is a semiconductor package.
• FIG. 10 is a schematic cross-sectional view for explaining one embodiment of a method for manufacturing a circuit wiring board, which is a semiconductor package.
• FIG. 11 is a schematic cross-sectional view for explaining one embodiment of a method for manufacturing a circuit wiring board, which is a semiconductor package.
• FIG. 12 is a schematic cross-sectional view for explaining one embodiment of a method for manufacturing a circuit wiring board, which is a semiconductor package.
• FIG. 13 is a schematic cross-sectional view for explaining one embodiment of a method for manufacturing a circuit wiring board, which is a semiconductor package.
• FIG. 14 is a schematic cross-sectional view for explaining one embodiment of a method for manufacturing a circuit wiring board, which is a semiconductor package.
• a numerical range expressed using " ⁇ " means a range that includes the numerical values written before and after " ⁇ " as lower and upper limits.
• the upper limit or lower limit of a certain numerical range may be replaced with the upper or lower limit of another numerical range described in stages. .
• the upper limit or lower limit described in a certain numerical range may be replaced with the value shown in the Examples.
• process is used not only to refer to an independent process, but also to include it in the term even if the process cannot be clearly distinguished from other processes, as long as the intended purpose of the process is achieved. .
• transparent means that the average transmittance of visible light with a wavelength of 400 nm to 700 nm is 80% or more, preferably 90% or more.
• the average transmittance of visible light is a value measured using a spectrophotometer, and can be measured using, for example, a spectrophotometer U-3310 manufactured by Hitachi, Ltd.
• weight average molecular weight (Mw) and number average molecular weight (Mn) are expressed as columns such as TSKgel GMHxL, TSKgel G4000HxL, or TSKgel G2000HxL (all brand names manufactured by Tosoh Corporation). ), using THF (tetrahydrofuran) as the eluent, a differential refractometer as the detector, and polystyrene as the standard material, and the value calculated using polystyrene as the standard material measured with a gel permeation chromatography (GPC) analyzer.
• GPC gel permeation chromatography
• the molecular weight of a compound having a molecular weight distribution is a weight average molecular weight (Mw).
• (meth)acrylic is a concept that includes both acrylic and methacrylic
• (meth)acryloyloxy group is a concept that includes both acryloyloxy and methacryloyloxy groups
• (meth)acrylamide group is a concept that includes both an acrylamide group and a methacrylamide group
• (meth)acrylate is a concept that includes both acrylate and methacrylate.
• alkali-soluble means that the solubility in 100 g of a 1% by mass sodium carbonate aqueous solution at a liquid temperature of 22° C. is 0.1 g or more. Therefore, for example, an alkali-soluble resin is intended to be a resin that satisfies the above-mentioned solubility conditions.
• water-soluble means that the solubility in 100 g of water at pH 7.0 and a liquid temperature of 22° C. is 0.1 g or more. Therefore, for example, water-soluble resin is intended to be a resin that satisfies the above-mentioned solubility conditions.
• solid content of a composition refers to components that form a composition layer formed using the composition, and when the composition contains a solvent (organic solvent, water, etc.), the means all ingredients except.
• liquid components are also considered solid components as long as they form a composition layer.
• the thickness of the temporary support, etc. is calculated as the average value of five arbitrary points measured by cross-sectional observation using a SEM (Scanning Electron Microscope).
• the surface free energy is calculated using the actually measured contact angles ⁇ H2O and ⁇ CH2I2 of pure water H 2 O and methylene iodide CH 2 I 2 , and is calculated using the Owens equation (simultaneous equation ( A) and (B)).
• the contact angle of pure water ( ⁇ H2O ) is measured by the following method. Under an atmosphere with a room temperature of 25°C and a relative humidity of 50%, drop 12 ⁇ L of pure water onto the surface of the object whose surface free energy, such as an intermediate layer, is to be measured, and after 20 seconds, measure the contact angle using a contact angle meter. . The above measurement is performed a total of 5 times. Then, the arithmetic mean of three measured values excluding the maximum value and minimum value among the five measured values is defined as the contact angle of pure water ( ⁇ H2O ). As the contact angle meter, a contact angle meter CA-D type (manufactured by Kyowa Interface Science Co., Ltd.) or an equivalent device can be used.
• the contact angle ( ⁇ CH2I2 ) of methylene iodide (diiodomethane) is measured by the following method.
• drop 12 ⁇ L of diiodomethane manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.
• the contact angle is measured using a meter.
• the above measurement is performed a total of 5 times.
• the arithmetic mean of three measured values excluding the maximum value and minimum value among the five measured values is defined as the contact angle of methylene iodide ( ⁇ CH2I2 ).
• ⁇ s d + ⁇ s h value' is the surface free energy.
• ⁇ L d is represented by ⁇ H2O d .
• ⁇ L d is represented by ⁇ CH2I2 d .
• the dielectric loss tangent of the substrate at 24 GHz is measured by the resonator method.
• a 24 GHz split cylinder type resonator manufactured by Kanto Denshi Application Development Co., Ltd. or a device equivalent to this can be used.
• the transfer film of the present disclosure has a temporary support, an intermediate layer containing a surfactant, and a photosensitive layer, and when the temporary support is peeled off, the surface of the side that does not include the temporary support is exposed. Free energy is 66.0 mJ/m 2 or less.
• the transfer film of the present disclosure has excellent releasability and resolution of the temporary support. Although the mechanism by which the above effects are produced is not clear, it is presumed as follows.
• the transfer film of the present disclosure has an intermediate layer containing a surfactant, and when the temporary support is peeled off, the surface free energy of the exposed surface not including the temporary support is 66.0 mJ/m 2 or less. be. It is presumed that this makes it possible to reduce the interaction with the temporary support and improve the releasability of the temporary support. Furthermore, as a result of improving the releasability of the temporary support, it is possible to suppress roughening of the surface of the transfer film from which the temporary support has been removed, and it is possible to suppress excessive improvement in adhesion to the mask. It is presumed that this makes it possible to form fine patterns with suppressed residue in areas between patterns.
• the surface free energy of the surface on the side not containing the temporary support exposed by peeling can be adjusted, for example, by the composition of the layer on the side exposed by peeling and not containing the temporary support.
• the transfer film may have a thermoplastic resin layer containing a surfactant between the temporary support and the intermediate layer.
• the transfer film may have a protective film on the surface of the photosensitive layer opposite to the intermediate layer side.
• the temporary support is a member that supports the photosensitive layer and the like, and is finally removed by a peeling process.
• the temporary support may have a single layer structure or a multilayer structure.
• the temporary support is preferably a film, more preferably a resin film.
• the temporary support is preferably a film that is flexible and does not undergo significant deformation, shrinkage, or elongation under pressure or under pressure and heat.
• Examples of the above film include polyethylene terephthalate film, polymethyl methacrylate film, cellulose triacetate film, polystyrene film, polyimide film, and polycarbonate film.
• the resin film may be a stretched film or a non-stretched film, it is preferably a stretched film, and more preferably a biaxially stretched film.
• polyethylene terephthalate film is preferred as the temporary support.
• the film used as the temporary support is free from deformation such as wrinkles, scratches, etc.
• the thickness of the temporary support is not particularly limited, but is preferably 5.0 ⁇ m to 200.0 ⁇ m, more preferably 5.0 ⁇ m to 150.0 ⁇ m from the viewpoint of ease of handling and versatility.5. It is more preferably 0 ⁇ m to 50.0 ⁇ m, and most preferably 5.0 ⁇ m to 25.0 ⁇ m.
• a layer containing fine particles may be provided on the surface of the temporary support in order to impart handling properties.
• the lubricant layer may be provided on one side or both sides of the temporary support.
• the diameter of the particles contained in the lubricant layer is preferably 0.05 ⁇ m to 0.8 ⁇ m. Further, the thickness of the lubricant layer is preferably 0.05 ⁇ m to 1.0 ⁇ m.
• the surface free energy of the intermediate layer side surface of the temporary support is preferably 66.0 mJ/m 2 or less, and preferably 63.0 mJ/m 2 or less. More preferably, it is 60.0 mJ/m 2 or less.
• the lower limit of the surface free energy is preferably 35 mJ/m 2 or more, more preferably 40 mJ/m 2 or more, and even more preferably 45 mJ/m 2 or more. .
• the temporary support includes only a base material; a laminate comprising a base material and a particle-containing layer disposed on one side of the base material; A laminate including particle-containing layers disposed on both sides can be mentioned.
• the base material constituting the temporary support examples include the above-mentioned resin film, glass, paper, and the like.
• the base material constituting the temporary support is preferably a resin film from the viewpoints of strength, flexibility, and light transmittance.
• the resin film is preferably a polyethylene terephthalate film, more preferably a biaxially stretched polyethylene terephthalate film.
• the number of particle-containing layers may be one layer, or two or more layers.
• the particle-containing layer is formed, for example, by applying a particle-containing layer composition onto a base material and drying it. Moreover, the particle-containing layer can also be arranged by a coextrusion method when forming a resin film.
• the composition for a particle-containing layer preferably contains a binder polymer and particles.
• the type of binder polymer is not particularly limited, and can be appropriately selected depending on the purpose, for example.
• Examples of the binder polymer include acrylic resin, urethane resin, olefin resin, styrene-butadiene resin, ester resin, vinyl chloride resin, and vinylidene chloride resin.
• polyethylene terephthalate it is preferable to use as the binder polymer.
• the particle-containing layer may contain one type of binder polymer and particles, or may contain two or more types of particles.
• the particles contained in the particle-containing layer are not particularly limited and can be appropriately selected depending on the purpose.
• the content of particles in the particle-containing layer can be adjusted as appropriate by adjusting the amount of particles added to the composition for particle-containing layer.
• the particles contained in the particle-containing layer are referred to as "additional particles.”
• Additive particles are to be distinguished from impurities unexpectedly mixed in during the manufacturing process of the temporary support and particles formed during the manufacturing process of the temporary support.
• the additive particles are preferably particles that do not melt at 200°C.
• Whether or not the temporary support is an added particle can be determined, for example, by the following method. Since the additive particles usually have uniformity in shape and distribution, they can be identified by observing them with an optical microscope.
• additive particles examples include inorganic particles and organic particles.
• inorganic particles examples include particles of inorganic oxides such as silicon oxide (silica), titanium oxide (titania), zirconium oxide (zirconia), magnesium oxide (magnesia), and aluminum oxide (alumina).
• inorganic oxides such as silicon oxide (silica), titanium oxide (titania), zirconium oxide (zirconia), magnesium oxide (magnesia), and aluminum oxide (alumina).
• organic particles examples include particles of polymers such as acrylic resin, polyester, polyurethane, polycarbonate, polyolefin, and polystyrene.
• the additive particles contained in the particle-containing layer are preferably particles of an inorganic oxide.
• the average particle diameter of the additive particles is not particularly limited, but is, for example, 0.1 ⁇ m to 10 ⁇ m.
• the average particle size is measured by cutting a section with a thickness of 100 nm using an ultramicrotome and using a TEM (transmission electron microscope).
• the thermal deformation rate of the temporary support is preferably 1.0% or less, more preferably 0.5% or less.
• the lower limit of the thermal deformation rate is not particularly limited, and is preferably 0%.
• the thermal deformation rate of the temporary support is 1.0% or less, deformation of the substrate to be bonded to the transfer film is suppressed.
• the thermal deformation rate is measured by the following method.
• the direction parallel to one of the two opposing sides is the A direction
• the direction perpendicular to this direction is defined as the B direction.
• a test piece cut out to have a length of 30 mm in the A direction and 4 mm in the B direction, and a test piece cut out to have a length of 30 mm in the B direction and 4 mm in the A direction are prepared.
• the following measurements are performed using two test pieces.
• a thermal expansion coefficient measuring device for example, product name "TMA450EM", manufactured by TA Instruments
• the measurement conditions are as follows. Measurement mode: tensile mode, Distance between grips: 16mm
• Each test piece is heated from 25°C to 100°C at a heating rate of 20°C/min, the elongation rate of each test piece is measured five times, and the average value is calculated. Of the two test pieces, the one with the larger average elongation rate is adopted as the thermal deformation rate.
• Examples of methods for reducing the thermal deformation rate of the temporary support include a method of increasing the thickness of the temporary support, and a method of increasing the number of particles contained in the temporary support by making the temporary support contain particles. It will be done.
• the haze of the temporary support is preferably greater than 2.0% from the viewpoint of suppressing deformation of the substrate to be bonded to the transfer film.
• the haze of the temporary support is more preferably 2.5% or more.
• the upper limit of haze is not particularly limited, and is, for example, 10%.
• the temporary support When forming a pattern using the transfer film according to the present disclosure, it is preferable to peel off the temporary support after the transfer film and the substrate are bonded together and before exposure. If the temporary support is peeled off before exposure, there is no need to consider the influence of the high haze of the temporary support on exposure.
• haze is measured using a haze meter according to JIS K7136:2000.
• the haze meter for example, the product name "NDH-2000" manufactured by Nippon Denshoku Kogyo Co., Ltd. is used.
• the total number of particles with a diameter of 5 ⁇ m or more and aggregates with a diameter of 5 ⁇ m or more contained in the temporary support is 30. Preferably it is greater than /mm 2 .
• the total number of particles and aggregates is more preferably 40 particles/mm 2 or more.
• the upper limit of the total number is not particularly limited, and is, for example, 50 pieces/mm 2 .
• particles and aggregates as used herein means those having a region in which a difference in polarization from the surrounding region can be observed when the temporary support is observed with a polarizing microscope.
• Particles and aggregates include, for example, resin carbides formed during the manufacture of the base material and catalysts used in the manufacture of the base material. Further, when providing a particle-containing layer as described above, the additive particles contained in the particle-containing layer also correspond to the above-mentioned particles.
• the total number of particles and aggregates contained in the temporary support is measured by the following method.
• the temporary support was observed with a polarizing microscope (product name: "BX60” with "U-POT” filter and "U-AN360” filter inserted to make a simple polarizing microscope, 10x objective lens, manufactured by Olympus). Then, the part where the polarization disturbance occurs is identified as a foreign object (particle or aggregate). The identified foreign matter is observed with an epi-illumination laser microscope (product name: "Confocal Laser Microscope VL2000D", manufactured by Lasertec). Further, the diameter of the foreign object is measured using an optical microscope (product name "BX60", objective lens 100 times, manufactured by Olympus Corporation), and the number of foreign objects with a diameter of 5 ⁇ m or more included in the observation area of 1 mm 2 is counted. Note that if the foreign object contains voids, the diameter is measured including the voids. If the foreign object is not circular, measure the longest diameter.
• the temporary support When forming a pattern using the transfer film according to the present disclosure, it is preferable to peel off the temporary support after bonding the transfer film and the base material and before exposure. If the temporary support is peeled off before exposure, it is not necessary to consider the influence on exposure due to the large number of particles and aggregates contained in the temporary support.
• the temporary support has an optically abnormal area when observed with an epi-illumination laser microscope in an area of 13.5 mm 2 It is preferable to include a region in which the total area ratio of is larger than 300 ppm.
• the total area ratio of the optically abnormal region is 350 ppm or more.
• the upper limit of the total area ratio is not particularly limited, and is, for example, 500 ppm.
• the area of the optically abnormal region means the area of the optically abnormal region observed in a region up to 2 ⁇ m from the center position of the thickness of the temporary support in one or the other direction of the thickness.
• an optically abnormal region is a region having different optical properties from the main region of the temporary support (resin constituting the temporary support) (specifically, whether the reflectance or refractive index is different from the main region, or a region in which optical phenomena such as scattering and diffraction occur more strongly than in the main region).
• the optically abnormal region includes a light-shielding portion by the particles and an optically abnormal region other than the particles (for example, an abnormal refractive index region having a refractive index different from that of the particles and the main region of the temporary support).
• the optically abnormal region include a region having a different orientation and/or crystallinity from the main region of the temporary support, an air region, a region of a gas other than air, a cavity region where almost no gas exists, and the like.
• the total area of the optically abnormal region is measured by the following method.
• a polarizing filter (OLS4000-QWP) is inserted above the objective lens of an epi-reflection laser microscope (OLYMPUS OLS-4100).
• OLS4000-QWP epi-reflection laser microscope
• the temporary support cut into 30 mm x 30 mm is horizontally suctioned and fixed onto the stage of a laser microscope using a porous suction plate (65F-HG manufactured by Universal Giken) and a vacuum pump.
• the suction-fixed temporary support is observed under the conditions of a 50x objective lens and a laser light intensity of 60 nm (laser wavelength is 405 nm).
• the light amount difference between the pixel with the maximum light amount and the pixel with the minimum light amount in the measured image is divided into 4096 gradations (the value of the maximum light amount is 4095 and the value of the minimum light amount is 0).
• a histogram horizontal axis: gradation of light amount (minimum value 0, maximum value 4095), vertical axis: number of pixels) is created as a graph of the light amount distribution of pixels in the image.
• the measured image is binarized using the gradation that is 400 gradations plus 400 gradations from the larger of the two base values of the created histogram as the threshold, and the areas of pixels with a larger amount of light than the threshold are summed.
• the total area is the total area of the optically abnormal region.
• the ratio of the total area of the optical abnormality region to the measurement area is calculated.
• the surface of the temporary support in contact with the intermediate layer may be subjected to surface treatment such as ultraviolet irradiation, corona discharge, plasma treatment, etc., from the viewpoint of improving adhesion with the intermediate layer.
• surface treatment such as ultraviolet irradiation, corona discharge, plasma treatment, etc.
• the exposure amount is preferably 10 mJ/cm 2 to 2000 mJ/cm 2 , more preferably 50 mJ/cm 2 to 1000 mJ/cm 2 .
• Examples of light sources for ultraviolet irradiation include light sources that emit light in the wavelength range of 150 nm to 450 nm (for example, low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, carbon arc lamps, metal halide lamps, xenon lamps, chemical lamps, electrode discharge lamps, and light emitting diodes (LEDs).
• the output and illuminance are not particularly limited.
• the intermediate layer is in contact with the surface of the temporary support.
• the surface roughness Rmax of the intermediate layer side surface of the temporary support is preferably 0.5 ⁇ m or less, more preferably 0.01 ⁇ m to 0.5 ⁇ m. preferable.
• the surface roughness Rmax of the intermediate layer side surface of the temporary support is measured by the following method.
• the surface roughness Rmax is measured using a three-dimensional optical profiler (for example, New View 7300, manufactured by Zygo).
• the temporary support is peeled off from the transfer film. Obtain the surface profile of the intermediate layer side surface of the temporary support. Microscope Application of MetroPro ver. 8.3.2 is used as the measurement/analysis software. Next, a Surface Map screen is displayed using the measurement/analysis software, and histogram data is obtained on the Surface Map screen. The surface roughness Rmax is obtained from the obtained histogram data. Note that the surface roughness Rmax corresponds to the maximum height of the roughness curve at the reference length.
• the temporary support may be a recycled product.
• recycled products include those made by cleaning used films and the like, turning them into chips, and using the chips as raw materials to make films.
• a specific example of a recycled product is Toray's Ecouse series.
• the surface free energy is 66.0 mJ/m 2 or less, more preferably 63.0 mJ/m 2 or less, and 60. More preferably, it is 0 mJ/m 2 or less.
• the lower limit of the surface free energy is preferably 45 mJ/m 2 or more, more preferably 50 mJ/m 2 or more, and preferably 55 mJ/m 2 or more. More preferred.
• the surface free energy of the surface of the intermediate layer can be adjusted by adjusting the type and content of the surfactant contained in the intermediate layer, the type and content of the water-soluble resin contained in the intermediate layer, and the like.
• the intermediate layer has oxygen blocking ability. Since the intermediate layer has oxygen blocking ability, the sensitivity during exposure is improved, the time load on the exposure machine can be reduced, and productivity can be improved. Furthermore, when the photosensitive layer in the transfer film is a negative photosensitive layer containing a radically polymerizable compound, there is an advantage that oxygen inhibition is less likely to occur in the polymerization reaction during exposure.
• the intermediate layer can contain one or more water-soluble resins.
• water-soluble resins include polyvinyl alcohol, polyvinylpyrrolidone, water-soluble cellulose compounds, (meth)acrylamide, polyether compounds, gelatin, vinyl ether compounds, polyamides, phenol compounds, and copolymers thereof.
• the intermediate layer is made of at least polyvinyl alcohol and polyvinylpyrrolidone. It is preferable to contain one of them, more preferably to contain polyvinyl alcohol, and still more preferably to contain polyvinyl alcohol and polyvinylpyrrolidone.
• the content of polyvinyl alcohol based on the total mass of the intermediate layer is 5% by mass to 95% by mass from the viewpoint of removability, resolution, oxygen blocking ability, defect suppression property, etc. of the temporary support. It is preferably % by mass, more preferably 15% by mass to 90% by mass, even more preferably 25% to 80% by mass, particularly preferably 50% to 75% by mass, Most preferably it is between 55% and 70% by weight.
• the content of polyvinylpyrrolidone based on the total mass of the intermediate layer is 20% by mass to 98% from the viewpoint of releasability, resolution, oxygen blocking ability, defect suppression property, etc. of the temporary support.
• the intermediate layer contains polyvinyl alcohol and polyvinyl pyrrolidone
• the content of polyvinyl alcohol and polyvinyl pyrrolidone relative to the total mass of the intermediate layer is The sum is preferably 50% to 99% by weight, more preferably 70% to 99% by weight, and even more preferably 75% to 99% by weight.
• the intermediate layer is selected from the group consisting of a water-soluble cellulose compound, a polyether compound, a phenol compound, and a polyhydric alcohol compound. It is preferable that one or more types of compounds X are included.
• water-soluble cellulose compounds include hydroxyethylcellulose, hydroxypropylmethylcellulose, hydroxypropylcellulose, methylcellulose, and ethylcellulose.
• the polyether compound include polyethylene glycol, polypropylene glycol, and the like.
• the phenol compound include bisphenol A, bisphenol S, and the like.
• the polyhydric alcohol compound examples include glycerin, diglycerin, diethylene glycol, and the like.
• the intermediate layer is one selected from the group consisting of hydroxypropyl methylcellulose, polyethylene glycol, bisphenol A, and glycerin. It is preferable to contain the above compound X, more preferably to contain one or more compounds X selected from the group consisting of hydroxypropyl methylcellulose and polyethylene glycol, and even more preferably to contain hydroxypropyl methylcellulose.
• the sum of the content of compound X with respect to the total mass of the intermediate layer is 0.1 It is preferably from 1% to 36% by weight, more preferably from 0.5% to 20% by weight, even more preferably from 1% to 15% by weight.
• the intermediate layer preferably contains at least one of polyvinyl alcohol and polyvinylpyrrolidone, and compound X, and polyvinyl alcohol and the compound It is more preferable that the compound contains X, and even more preferably that it contains polyvinyl alcohol, polyvinylpyrrolidone, and compound X.
• the intermediate layer has the above-mentioned composition, compound can be suppressed. As a result, the surface free energy of the intermediate layer on the temporary support side is adjusted to an appropriate value, and the temporary support removability and resolution can be further improved.
• the weight average molecular weight (Mw) of the water-soluble resin is preferably 5,000 to 200,000, and preferably 7,000 to 100,000. is more preferable, and even more preferably 7,000 to 50,000.
• the degree of dispersion (Mw/Mn) of the water-soluble resin is preferably 1 to 10, more preferably 1 to 5.
• the content of the water-soluble resin with respect to the total mass of the intermediate layer is preferably 60% by mass or more, and 80% by mass. It is preferably at least 95% by mass, and may be at least 100% by mass.
• the intermediate layer contains a surfactant.
• the intermediate layer may contain two or more types of surfactants.
• the surfactant preferably includes one or more selected from the group consisting of nonionic surfactants, fluorine surfactants, and silicone surfactants.
• the surfactant preferably contains a silicone surfactant.
• silicone surfactants are preferred from the viewpoint of improving the adhesion between the intermediate layer and adjacent layers (photosensitive layer, thermoplastic resin, etc.) (hereinafter also referred to as "interlayer adhesion"). From the viewpoint of releasability, resolution, oxygen blocking ability, defect suppression ability, interlayer adhesion, etc.
• the content of silicone surfactant should be 60% by mass or more based on the total mass of surfactant. It is preferably 80% by mass or more, preferably 95% by mass or more, and may be 100% by mass.
• silicone surfactants include linear polymers consisting of siloxane bonds, modified siloxane polymers having an organic group introduced into at least one of the side chain and the f-terminus.
• the content of the surfactant is 0.1% by mass to 10% by mass with respect to the total mass of the intermediate layer. It is preferably 0.5% by mass to 7% by mass, and even more preferably 1% by mass to 5% by mass.
• the intermediate layer may include a water-insoluble resin.
• water-insoluble resins include polyester resins, (meth)acrylic resins, and the like.
• the content of the water-insoluble resin with respect to the total mass of the intermediate layer is preferably 10% by mass or less, preferably 5% by mass or less, and 1% by mass or less. It is preferable that
• the intermediate layer can contain additives such as colorants, flame retardants, antioxidants, anti-rust agents, and dispersants.
• the thickness of the intermediate layer is preferably 5.0 ⁇ m or less, and 0.01 ⁇ m to 4.0 ⁇ m. It is more preferably 0 ⁇ m, and even more preferably 0.1 ⁇ m to 3.0 ⁇ m.
• the photosensitive layer may be a positive photosensitive layer or a negative photosensitive layer, but in the transfer film of the present disclosure, it is preferably a negative photosensitive layer.
• a negative photosensitive layer is a photosensitive layer whose solubility in a developing solution in exposed areas decreases when exposed to light. When the photosensitive layer is a negative photosensitive layer, the pattern formed corresponds to a cured layer.
• the photosensitive layer can contain one or more kinds of polymers.
• the polymer is an alkali-soluble resin.
• the polymer may include structural units formed from monomers having acid groups. Examples of the acid group include a carboxy group, a sulfo group, a phosphoric acid group, and a phosphonic acid group. Monomers having acid groups include (meth)acrylic acid, fumaric acid, cinnamic acid, crotonic acid, itaconic acid, 4-vinylbenzoic acid, maleic anhydride, etc.
• the polymer does not have acid groups. It may also contain structural units formed from monomers.
• Examples of monomers without acid groups include (meth)acrylic acid esters, vinyl alcohol ester compounds, (meth)acrylonitrile, and aromatic vinyl compounds.
• (Meth)acrylic acid esters include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert -butyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, benzyl (meth)acrylate, and the like.
• vinyl alcohol ester compounds include vinyl acetate.
• aromatic vinyl compounds include styrene and styrene derivatives.
• the non-acidic monomer is one or more monomers selected from the group consisting of methyl (meth)acrylate, n-butyl (meth)acrylate, styrene, styrene derivatives, and benzyl (meth)acrylate.
• the alkali-soluble resin preferably contains at least one of a styrene-derived structural unit and a styrene derivative-derived structural unit.
• styrene derivatives include vinyltoluene, p-methylstyrene, and p-chlorostyrene.
• the copolymerization ratio of the structural units derived from styrene and the structural units derived from styrene derivatives in the alkali-soluble resin is preferably 5% by mass to 60% by mass, and 10% by mass to 50% by mass, based on the total mass of the alkali-soluble resin. is more preferable, and even more preferably 15% by mass to 40% by mass.
• the alkali-soluble resin preferably contains a structural unit derived from (meth)acrylic acid ester.
• the alkali-soluble resin contains at least one of a styrene-derived structural unit and a styrene derivative-derived structural unit, and a (meth)acrylic acid ester-derived structural unit, the styrene-derived structural unit and the styrene derivative-derived structural unit
• the content rate is 1, from the viewpoint of achieving both resolution and adhesion
• the content rate of the structural unit derived from (meth)acrylic ester is preferably 0.3 to 2.5, and 0.5 ⁇ 2.0 is more preferable, and 0.7 ⁇ 1.7 is even more preferable.
• the weight average molecular weight (Mw) of the polymer is preferably 5,000 to 500,000, more preferably 10,000 to 100,000, and even more preferably 30,000 to 60,000.
• the degree of dispersion (Mw/Mn) of the polymer is preferably 1.0 to 6.0, more preferably 1.0 to 5.0, even more preferably 1.0 to 4.0, and 1.0 to 3.0. 0 is particularly preferred.
• the acid value of the polymer is preferably 60 mgKOH/g to 220 mgKOH/g, more preferably 120 mgKOH/g to 200 mgKOH/g, and 150 mgKOH/g to 190 mgKOH /g is more preferable.
• the acid value (mgKOH/g) is the mass [mg] of potassium hydroxide required to neutralize 1 g of sample.
• the acid value can be determined, for example, according to the method described in JIS K0070:1992.
• the acid value of the polymer can be adjusted by changing the types of constituent units and the content of the constituent units containing acid groups.
• the content of the polymer is preferably 30% by mass to 70% by mass, and preferably 40% by mass to 60% by mass, based on the total mass of the photosensitive layer. More preferably, it is 45% by mass to 57% by mass.
• the photosensitive layer may contain one or more kinds of polymerizable compounds.
• the polymerizable compound is not limited, and any known polymerizable compound can be used.
• the polymerizable compound is an ethylenically unsaturated compound.
• Ethylenically unsaturated compounds are compounds that have one or more ethylenically unsaturated groups.
• the ethylenically unsaturated group is preferably a (meth)acryloyl group.
• the ethylenically unsaturated compound is a (meth)acrylate compound.
• an ethylenically unsaturated compound having a bisphenol structure is also suitably used.
• Examples of the ethylenically unsaturated compound having a bisphenol structure include alkylene oxide-modified bisphenol A di(meth)acrylate.
• the alkylene oxide-modified bisphenol A di(meth)acrylate includes ethylene glycol dimethacrylate, which has an average of 5 moles of ethylene oxide added to each end of bisphenol A, and bisphenol A with an average of 2 moles of ethylene oxide added to each end of the bisphenol A.
• Examples include dimethacrylate of glycol and dimethacrylate of alkylene glycol in which an average of 15 moles of ethylene oxide and an average of 2 moles of propylene oxide are added to both ends of bisphenol A.
• alkylene oxide-modified bisphenol A di(meth)acrylate include 2,2-bis(4-(methacryloxydiethoxy)phenyl)propane, 2,2-bis(4-(methacryloxyethoxypropoxy)phenyl) Examples include propane.
• the molecular weight of the polymerizable compound is preferably 200 to 3,000, more preferably 280 to 2,200, and even more preferably 300 to 2,200.
• the polymerizable compound is a compound having a molecular weight distribution (for example, a polymer)
• the weight average molecular weight of the polymerizable compound is preferably 200 to 3000, more preferably 280 to 2200, and 300 to 2200. It is more preferable that
• the content of the polymerizable compound is preferably 10% to 70% by mass, more preferably 20% to 60% by mass, and 20% to 50% by mass, based on the total mass of the photosensitive layer. % is more preferable.
• the photosensitive layer preferably contains one or more of the above surfactants.
• Preferred embodiments of the surfactant are as described in the intermediate layer, and description thereof will be omitted here.
• the content of the surfactant with respect to the total mass of the photosensitive layer is preferably 0.05% by mass to 5% by mass, and preferably 0.1% by mass to 3% by mass. %, and even more preferably 0.2% by mass to 1% by mass.
• the photosensitive layer can contain one or more types of polymerization initiators.
• polymerization initiator conventionally known radical polymerization initiators, cationic polymerization initiators, etc. can be used.
• the content of the polymerization initiator with respect to the total mass of the photosensitive layer is not particularly limited, and can be 1% by mass to 10% by mass.
• the photosensitive layer contains a colorant, a sensitizer, a chain transfer agent (N-phenylcarbamoylmethyl-N-carboxymethylaniline, N,N-tetraethyl-4,4-diaminobenzophenone, etc.), a polymerization inhibitor, a plasticizer, It can contain additives such as flame retardants, antioxidants, rust preventives, dispersants, thermally crosslinkable compounds (methylol compounds, blocked isocyanate compounds, etc.).
• the thickness of the photosensitive layer is preferably 0.6 ⁇ m to 30.0 ⁇ m, more preferably 1.5 ⁇ m to 20.0 ⁇ m, and 2. More preferably, the thickness is from .0 ⁇ m to 15.0 ⁇ m.
• the transfer film may have a thermoplastic resin layer containing a surfactant between the temporary support and the intermediate layer.
• the surface of the transfer film exposed by peeling off the temporary support is the surface of the thermoplastic resin layer.
• Its surface free energy is 66.0mJ/m 2 63.0 mJ/m 2 or less is more preferable, 60.0 mJ/m 2 or less is even more preferable, and 55.0 mJ/m 2 or less is particularly preferable.
• the lower limit of the surface free energy is preferably 35 mJ/m 2 or more, more preferably 40 mJ/m 2 or more, and even more preferably 45 mJ/m 2 or more.
• the surface free energy of the surface of the thermoplastic resin layer can be adjusted by adjusting the type and content of the surfactant contained in the thermoplastic resin layer, the type and content of the thermoplastic resin contained in the thermoplastic resin layer, etc. can do.
• the thermoplastic resin contains one or more of the above surfactants. Preferred embodiments of the surfactant are as described in the intermediate layer, and description thereof will be omitted here. From the viewpoint of temporary support removability, resolution, oxygen barrier ability, etc., the content of the surfactant is preferably 0.01% by mass to 3% by mass, based on the total mass of the thermoplastic resin layer. It is more preferably 0.02% by mass to 1% by mass, and even more preferably 0.03% by mass to 0.3% by mass.
• the thermoplastic resin layer can contain one or more thermoplastic resins.
• Thermoplastic resins are not particularly limited as long as they are plasticized by heat, but include acrylic resins, polystyrene resins, styrene-acrylic copolymers, polyurethane resins, polyvinyl alcohol, polyvinyl formal, polyamide resins, polyester resins, polyamide resins, Examples include epoxy resin, polyacetal resin, polyhydroxystyrene resin, polyimide resin, polybenzoxazole resin, polysiloxane resin, polyethyleneimine, polyallylamine, polyalkylene glycol, and the like.
• the thermoplastic resin is preferably an acrylic resin.
• the acrylic resin is selected from the group consisting of a structural unit formed by (meth)acrylic acid, a structural unit formed by (meth)acrylic acid ester, and a structural unit formed by (meth)acrylic acid amide.
• the content of the above-mentioned structural unit is preferably 50% by mass or more based on the total amount of the resin.
• thermoplastic resin has an acid group.
• the weight average molecular weight (Mw) of the thermoplastic resin is preferably from 5,000 to 500,000, more preferably from 10,000 to 100,000, and even more preferably from 30,000 to 60,000. preferable.
• the degree of dispersion (Mw/Mn) of the thermoplastic resin is preferably 1.0 to 6.0, more preferably 1.0 to 5.0, even more preferably 1.0 to 4.0, and 1.0 to 3. .0 is particularly preferred.
• the acid value of the thermoplastic resin is preferably 60 mgKOH/g to 220 mgKOH/g, more preferably 120 mgKOH/g to 200 mgKOH/g, and 150 mgKOH/g to More preferably, it is 190 mgKOH/g.
• the content of the thermoplastic resin relative to the total mass of the thermoplastic resin layer is preferably 10% by mass to 80% by mass, more preferably 30% by mass to 75% by mass. % to 65% by mass is more preferable.
• the thermoplastic resin layer may contain one or more types of plasticizer.
• the plasticizer is not particularly limited as long as it is a compound that is compatible with the thermoplastic resin and exhibits plasticity, but from the viewpoint of imparting plasticity, the plasticizer preferably has an alkyleneoxy group in the molecule, and polyalkylene glycol More preferably, it is a compound. It is more preferable that the alkyleneoxy group contained in the plasticizer has a polyethyleneoxy structure or a polypropyleneoxy structure.
• the plasticizer is a (meth)acrylate compound.
• the content of the plasticizer with respect to the total mass of the thermoplastic resin layer is preferably 15% by mass to 60% by mass, more preferably 25% by mass to 50% by mass, and 35% by mass. % to 40% by mass is more preferable.
• the thermoplastic resin layer can contain additives such as colorants, pigments, acid generators, flame retardants, antioxidants, rust preventives, and dispersants.
• the thickness of the thermoplastic resin layer is preferably 1.0 ⁇ m to 20.0 ⁇ m, and preferably 2.0 ⁇ m to 15.0 ⁇ m. It is more preferable.
• the transfer film may have a protective film on the surface of the photosensitive layer opposite to the intermediate layer side.
• a resin film can be used as the protective film.
• the resin film include polyolefin films such as polypropylene films and polyethylene films, polyester films such as polyethylene terephthalate films, polycarbonate films, and polystyrene films.
• the protective film is preferably a polyolefin film, more preferably a polypropylene film or a polyethylene film, and even more preferably a polyethylene film.
• the thickness of the protective film is not particularly limited, and from the viewpoint of mechanical strength etc., it is preferably 1.0 ⁇ m to 100.0 ⁇ m, more preferably 5.0 ⁇ m to 50.0 ⁇ m, More preferably, the thickness is 5.0 ⁇ m to 40.0 ⁇ m.
• the transfer film of the present disclosure is applicable to circuit wiring arranged on a supporting substrate such as a sheet, a metal substrate, a ceramic substrate, and glass in a manufacturing process film for semiconductor packages, printed circuit boards, flexible printed wiring boards, and interposer rewiring layers. Preferably, it is used in the formation of.
• the method for producing a transfer film of the present disclosure includes a step of applying an intermediate layer forming composition on the surface of a temporary support and drying it to form an intermediate layer (hereinafter referred to as an intermediate layer forming step). , a step of applying a photosensitive layer forming composition on the surface of the intermediate layer and drying it to form a photosensitive layer (hereinafter referred to as a photosensitive layer forming step).
• the method for producing a transfer film of the present disclosure includes a step of applying a thermoplastic resin forming composition to the surface of a temporary support, drying it, and forming a thermoplastic resin layer (hereinafter referred to as a thermoplastic resin layer).
• a step of applying a composition for forming an intermediate layer on the surface of the thermoplastic resin layer and drying it to form an intermediate layer and a step of applying a composition for forming a photosensitive layer on the surface of the intermediate layer and drying it. and forming a photosensitive layer.
• the above two methods of manufacturing a transfer film of the present disclosure may include a step of providing a protective film on the surface of the photosensitive layer (hereinafter referred to as a protective film placement step).
• drying means removing at least a portion of the solvent contained in the composition. Examples of the drying method include natural drying, heat drying, and reduced pressure drying. The above methods can be applied alone or in combination.
• the composition for forming an intermediate layer used in the intermediate layer forming step can be prepared by dissolving or dispersing the above-described materials to be contained in the intermediate layer (surfactant, etc.) in a solvent.
• the solvent include water, alcohol having 1 to 3 carbon atoms, acetone, ethylene glycol, glycerin, and the like.
• the method for applying the composition for forming an intermediate layer include a printing method, a spray method, a roll coating method, a bar coating method, a curtain coating method, a spin coating method, a die coating method (ie, a slit coating method), and the like.
• the drying temperature can be between 80°C and 130°C. Note that the drying temperature means the temperature of the environment in which the composition for forming an intermediate layer is dried. Drying time can be from 20 seconds to 600 seconds.
• the composition for forming a photosensitive layer used in the photosensitive layer forming step can be prepared by dissolving or dispersing the above-described material to be included in the photosensitive layer in a solvent.
• solvents include alkylene glycol ether, alkylene glycol ether acetate, alcohol (methanol, ethanol, etc.), ketone solvents (acetone, methyl ethyl ketone, etc.), aromatic hydrocarbon solvents (toluene, etc.), aprotic polar solvents (N, N- (dimethylformamide, etc.), cyclic ether solvents (tetrahydrofuran, etc.), ester solvents (n-propyl acetate, etc.), amide solvents, lactone solvents, etc.
• the coating method, drying temperature, and drying time of the composition for forming a photosensitive layer are the same as in the intermediate layer forming step, and their description is omitted here.
• the thermoplastic resin layer forming composition used in the thermoplastic resin layer forming step can be prepared by dissolving or dispersing the above-described material to be included in the thermoplastic resin layer in a solvent.
• solvents include alkylene glycol ether, alkylene glycol ether acetate, alcohol (methanol, ethanol, etc.), ketone solvents (acetone, methyl ethyl ketone, etc.), aromatic hydrocarbon solvents (toluene, etc.), aprotic polar solvents (N, N- (dimethylformamide, etc.), cyclic ether solvents (tetrahydrofuran, etc.), ester solvents (n-propyl acetate, etc.), amide solvents, lactone solvents, etc.
• the coating method, drying temperature, and drying time of the composition for forming a thermoplastic resin layer are the same as in the intermediate layer forming step, and their description is omitted here.
• the protective film placement step can include attaching a protective film to the surface of the photosensitive layer.
• the protective film can be laminated using a known laminator such as a vacuum laminator or an auto-cut laminator.
• the laminator is preferably equipped with any heatable rollers such as rubber rollers and is capable of applying pressure and heating.
• the method for manufacturing a laminate of the present disclosure includes: A step of laminating the transfer film and the substrate so that the surface of the photosensitive layer of the transfer film on the side opposite to the intermediate layer side is in contact with the substrate (hereinafter also referred to as “transfer film lamination step”); A step of peeling off the temporary support (hereinafter also referred to as “temporary support peeling step”), After peeling off the temporary support, the method includes the steps of performing an exposure treatment, and further performing a development treatment after the exposure to form a pattern (hereinafter also referred to as "pattern forming step").
• Preferred embodiments of the transfer film used in the method for producing a laminate of the present disclosure are as described above, and therefore will not be described here.
• the method for producing a laminate of the present disclosure has excellent releasability and resolution of the temporary support. Although the mechanism by which the above effects are produced is not clear, it is presumed as follows.
• the transfer film used in the method for producing a laminate of the present disclosure has an intermediate layer containing a surfactant, and when the temporary support is peeled off, the surface free energy of the exposed surface not including the temporary support is is 66.0 mJ/ m2 or less. It is presumed that this makes it possible to reduce the interaction with the temporary support and improve the releasability of the temporary support.
• the temporary support is peeled off before exposure treatment. It is presumed that this makes it possible to reduce the distance between the photosensitive layer and the exposure light source, making it possible to form fine patterns in which residues are suppressed in areas between patterns.
• the transfer film bonding step includes a temporary support, an intermediate layer containing a surfactant, and a photosensitive layer.
• the surface of the transfer film on the side opposite to the intermediate layer side of the photosensitive layer is in contact with the substrate.
• the transfer film and the substrate are laminated.
• the transfer film may have a thermoplastic resin layer containing a surfactant between the temporary support and the intermediate layer.
• the transfer film may have a protective film on the surface of the photosensitive layer opposite to the intermediate layer side.
• the method for bonding the transfer film and the substrate is not particularly limited, and known transfer methods and lamination methods can be used. Among these, it is preferable to bond the transfer film and the substrate by a method in which the surface of the photosensitive layer of the transfer film on the side opposite to the intermediate layer side is placed on the substrate, and the transfer film and the substrate are pressed and heated using a roll or the like.
• a known laminator such as a vacuum laminator or an auto-cut laminator can be used.
• the laminator is preferably equipped with any heatable rollers such as rubber rollers and is capable of applying pressure and heating.
• the bonding temperature is not particularly limited, and can be, for example, 70°C to 130°C.
• the substrate is preferably a conductive substrate (wiring board) having a support substrate and a conductive layer disposed on the support substrate.
• the support substrate examples include a resin substrate, a glass substrate, a semiconductor substrate, and the like.
• a preferred embodiment of the support substrate is described, for example, in paragraph [0140] of International Publication No. 2018/155193, the content of which is incorporated herein.
• the material of the resin substrate is preferably a substrate containing cycloolefin polymer, polyethylene terephthalate, or polyimide.
• the thickness of the support substrate is not particularly limited, and can be 5.0 ⁇ m to 200.0 ⁇ m.
• the conductive layer is at least one layer selected from the group consisting of a metal layer, a conductive metal oxide layer, a graphene layer, a carbon nanotube layer, and a conductive polymer layer in terms of conductivity and fine line formation. It is preferable to have one. Furthermore, only one conductive layer, or two or more conductive layers may be disposed on the support substrate. When two or more conductive layers are arranged, it is preferable to have conductive layers made of different materials. A preferred embodiment of the conductive layer is described, for example, in paragraph [0141] of International Publication No. 2018/155193, the content of which is incorporated herein.
• a substrate having at least one of a transparent electrode and a lead wiring is preferable.
• a conductive substrate having such a configuration 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, a metal thin wire such as metal nanowire, or the like.
• 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, manganese, and 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 substrate may be a substrate incorporating elements that connect semiconductor elements to each other.
• the element that interconnects semiconductor elements include an element in which a wiring pattern for interconnecting semiconductor elements is formed on a silicon substrate.
• the substrate may have a seed layer on its surface.
• materials constituting the seed layer include copper, chromium, lead, nickel, gold, silver, tin, and zinc.
• the thickness of the seed layer is not particularly limited, and can be 50 nm to 2 ⁇ m.
• the method for forming the seed layer is not particularly limited, and examples thereof include a method of applying a dispersion in which fine metal particles are dispersed and sintering a coating film, a sputtering method, a vapor deposition method, and the like.
• the dielectric loss tangent of the substrate at 24 GHz is preferably 0.05 or less, more preferably 0.03 or less.
• the method for peeling off the temporary support is not particularly limited, and can be carried out based on known methods.
• a mechanism similar to the cover film peeling mechanism described in paragraphs [0161] to [0162] of JP-A-2010-072589 can be used.
• the pattern forming step After the temporary support is peeled off, an exposure treatment is performed, and after the exposure, a development treatment is performed to form a pattern.
• the pattern is formed by bringing the exposed intermediate layer or thermoplastic resin into contact with a mask, performing an exposure process, and further performing a development process.
• the photosensitive layer of the laminate is exposed in a pattern.
• patterned exposure means exposure that causes exposed areas and non-exposed areas in the photosensitive layer.
• the exposure light source may be appropriately selected as long as it can irradiate light in a wavelength range that can at least harden the photosensitive layer (for example, 365 nm or 405 nm). Can be used.
• the main wavelength of exposure light for pattern exposure is preferably 365 nm.
• the dominant wavelength is the wavelength with the highest intensity.
• the light source include semiconductor light sources such as various lasers and light emitting diodes (LEDs); discharge lamps such as ultra-high-pressure mercury lamps, high-pressure mercury lamps, and metal halide lamps; and the like.
• the exposure amount is not particularly limited, and can be 5 mJ/cm 2 to 200 mJ/cm 2 .
• the development process is a process of developing a photosensitive layer exposed in a pattern obtained by the exposure process to form a pattern.
• the photosensitive layer can be developed using a developer. For example, if the photosensitive layer is a negative photosensitive layer, the non-exposed areas of the photosensitive layer are removed by development using an alkaline developer, and a pattern is formed by the photosensitive layer remaining in the exposed areas. .
• the developer is preferably an alkaline aqueous solution.
• alkaline compounds that can be contained in the alkaline aqueous solution include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, Examples include tetrabutylammonium hydroxide, choline (2-hydroxyethyltrimethylammonium hydroxide), and the like.
• Development methods include paddle development, shower development, spin development, dip development, and the like.
• the method for manufacturing a laminate of the present disclosure can include a step of peeling off the protective film before bonding to the substrate.
• the method for peeling off the protective film is not particularly limited, and any conventionally known method can be used.
• the method for manufacturing a laminate of the present disclosure includes a step of exposing the formed pattern (hereinafter also referred to as "post-exposure step”) and a step of heating the formed pattern (hereinafter also referred to as “post-bake step”). ) may have at least one of the following.
• post-exposure step a step of exposing the formed pattern
• post-bake step a step of heating the formed pattern
• the exposure amount for post-exposure is preferably 100 mJ/cm 2 to 5000 mJ/cm 2 , more preferably 200 mJ/cm 2 to 3000 mJ/cm 2 .
• the post-baking temperature is preferably 80°C to 250°C, more preferably 90°C to 160°C.
• the post-bake time is preferably 1 minute to 180 minutes, more preferably 10 minutes to 60 minutes.
• a method for manufacturing a circuit wiring board according to the present disclosure includes a step of manufacturing a laminate using the above-described method for manufacturing a laminate according to the present disclosure; A step of performing plating treatment on an area where no pattern is formed to form a conductive pattern (hereinafter also referred to as “conductive pattern forming step”); a process of removing the pattern (hereinafter also referred to as “pattern removal process”); in this order.
• the method for manufacturing a circuit wiring board of the present disclosure may include a step of forming a protective layer on the surface of the plating layer after the conductor pattern forming step and before the pattern removal step (hereinafter referred to as "protective layer forming step”). ).
• the method for manufacturing a circuit wiring board of the present disclosure may include a step of removing the seed layer (hereinafter also referred to as “seed layer removal step"). Note that the process of manufacturing a laminate using the method for manufacturing a laminate of the present disclosure described above has been described above, so the description thereof will be omitted here.
• the circuit wiring board may be a semiconductor package.
• the method for manufacturing the circuit wiring board includes a step of forming a solder resist layer having openings on the surface of the board using a solder resist after the seed layer removal step (hereinafter referred to as (hereinafter also referred to as “solder resist layer forming process”), a process of forming bump electrodes in the openings (hereinafter also referred to as “bump electrode forming process”), and a process of mounting a semiconductor element to be connected to the bump electrodes (hereinafter also referred to as a “semiconductor element mounting process").
• a method for manufacturing a circuit wiring board includes a step of performing a plating process on an area where a pattern of a laminate is not formed by the method for manufacturing a laminate of the present disclosure to form a conductor pattern.
• Examples of the plating method include electrolytic plating and electroless plating, with electrolytic plating being preferred from the viewpoint of productivity.
• the metal used in the plating process is not particularly limited, and any known metal can be used.
• metals that can be used include copper, chromium, lead, nickel, gold, silver, tin, zinc, and alloys of these metals. From the viewpoint of electrical conductivity, copper or an alloy thereof is preferable.
• the thickness of the plating layer formed by the plating process is not particularly limited, and can be from 0.1 ⁇ m to 20.0 ⁇ m.
• the method for removing the pattern is not particularly limited, but includes a method of removing it by chemical treatment, and a method of removing it using a removal liquid is preferable.
• the removal liquid include a removal liquid in which an inorganic alkali component or an organic alkali component is dissolved in water, dimethyl sulfoxide, N-methylpyrrolidone, a mixed solution thereof, or the like.
• the inorganic alkali component include sodium hydroxide, potassium hydroxide, and the like.
• Examples of the organic alkali component include primary amine compounds, secondary amine compounds, tertiary amine compounds, and quaternary ammonium salt compounds.
• the temperature of the removal liquid is preferably 30°C to 80°C, more preferably 50°C to 80°C.
• a preferred embodiment of the removal method includes a method in which a laminate having a pattern to be removed is immersed in a stirring removal solution having a liquid temperature of 50° C. to 80° C. for 1 minute to 30 minutes.
• the pattern may be removed using a removal liquid by a known method such as a spray method, a shower method, or a paddle method.
• the method for manufacturing a circuit wiring board according to the present disclosure may include a step of forming a protective layer on the surface of the plating layer after the conductor pattern forming step and before the pattern removal step.
• the material constituting the protective layer is preferably a material that does not dissolve in the removal solution or etching solution used in the pattern removal step or the seed layer removal step.
• Examples of the material constituting the protective layer include nickel, chromium, tin, zinc, magnesium, gold, silver, alloys thereof, resins, and the like.
• the material constituting the protective layer is preferably nickel or chromium.
• Methods for forming the protective layer include electroless plating, electroplating, and the like, with electroplating being preferred.
• the thickness of the protective layer is not particularly limited, and can be 0.3 ⁇ m to 3.0 ⁇ m.
• the method for manufacturing a circuit wiring board of the present disclosure may include a step of removing the seed layer.
• the seed layer removal step is a step of removing the exposed seed layer to obtain a conductive thin wire.
• the method for removing the seed layer is not particularly limited, and a method using a known etching solution may be used.
• the etching solution include a ferric chloride solution, a cupric chloride solution, an ammonia alkaline solution, a sulfuric acid-hydrogen peroxide mixture, a phosphoric acid-hydrogen peroxide mixture, and the like.
• solder resist layer formation process The method for manufacturing a circuit wiring board of the present disclosure can include the step of forming a solder resist layer having an opening on the surface of the substrate from which the seed layer has been removed, using a solder resist. Preferably, the opening exposes a conductor pattern formed on the surface of the substrate.
• solder resist conventionally known ones can be used. Examples of the solder resist include azide-cyclized polyisoprene resin, azide-phenol resin, and chloromethyl polystyrene resin.
• the thickness of the solder resist layer is not particularly limited, and can be 5 ⁇ m to 50 ⁇ m.
• the method for forming the solder resist layer is not particularly limited, and any conventionally known method can be used.
• the method for manufacturing a circuit wiring board according to the present disclosure can include a step of forming bump electrodes in openings of a solder resist layer.
• the bump electrode is connected to the conductor pattern exposed at the opening.
• the method for manufacturing a circuit wiring board according to the present disclosure can include a step of mounting a semiconductor element connected to a bump electrode. It is preferable that the semiconductor to be mounted has an electrode, and it is preferable that this is connected to a bump electrode. After mounting the semiconductor, it is preferable to seal the semiconductor using a conventionally known sealing material.
• a support substrate on which a conductive layer 11 is formed is prepared as a wiring board 10.
• a recess is formed in the wiring board 10 using a laser drill or the like.
• an element 12 for connecting semiconductor elements to each other is prepared in the recess, and then placed in the recess as shown in FIG.
• the dielectric material 13 is prepared as shown in FIG. 4, and the dielectric material 13 is bonded to the substrate as shown in FIG.
• the bonding method is not particularly limited, and can be performed by the method described above.
• via holes 14 are formed in the dielectric material 13 bonded to the wiring board 10.
• the via hole can be formed by using a CO 2 laser, a UV (ultraviolet) laser, or the like.
• a seed layer 15 is formed on the surface of the dielectric material 13 in which the via hole 14 is formed, as shown in FIG.
• the surface of the transfer film 20 on the side opposite to the intermediate layer side of the photosensitive layer is bonded to the seed layer 15 formed on the surface of the wiring board 10, as shown in FIG.
• an exposure process is performed, and furthermore, a development process is performed after the exposure to form a pattern 21 as shown in FIG.
• a plating process is performed on a region of the seed layer 15 where no pattern is formed to form a conductive pattern 22.
• a semiconductor package 100 can be obtained by connecting electrodes 40A and 41A of semiconductor elements 40 and 41 to bump electrodes 31 and sealing them.
• a circuit wiring board of the present disclosure is a circuit wiring board manufactured by the above method for manufacturing a circuit wiring board.
• a semiconductor package of the present disclosure includes the circuit wiring board described above.
• the transfer film of the present disclosure can be used for manufacturing printed wiring boards.
• the method for manufacturing a printed wiring board includes the step of subjecting the substrate having the pattern in the method for manufacturing the laminate described above to at least one type selected from the group consisting of etching treatment and plating treatment.
• the etching or plating of the substrate can be performed by using the developed pattern as a mask and etching or plating the surface of the substrate by a known method.
• a residual film removal process may be performed using resin etching using a chemical solution containing a permanganic acid component, resin ashing using plasma, or the like.
• etching solution used for etching for example, a cupric chloride solution, a ferric chloride solution, and an alkaline etching solution can be used.
• plating include copper plating, solder plating, nickel plating, and gold plating.
• the pattern can be removed, for example, with an aqueous solution that is more strongly alkaline than the alkaline aqueous solution used for development.
• an aqueous solution that is more strongly alkaline than the alkaline aqueous solution used for development.
• this strong alkaline aqueous solution for example, a 1% to 10% by mass aqueous sodium hydroxide solution and a 1% to 10% by mass potassium hydroxide aqueous solution are used.
• examples of the peeling method include a dipping method and a spray method.
• the printed wiring board on which the pattern is formed may be a multilayer printed wiring board, and may have small-diameter through holes.
• This removal method includes, for example, a method in which the pattern is peeled off and then lightly etched; after the above plating is followed by solder plating, the wiring part is masked with solder by peeling off the pattern, and then the wiring part is masked with solder.
• One example is a method of processing using an etching solution that can etch only the portions of the conductor layer that are not etched.
• the present disclosure will be described in further detail based on Examples below.
• the materials, amounts used, proportions, processing details, processing procedures, etc. shown in the following examples can be changed as appropriate without departing from the spirit of the present disclosure. Therefore, the scope of the present disclosure should not be construed as being limited by the examples shown below.
• “parts” and “%” are based on mass.
• the weight average molecular weight of the resin is the weight average molecular weight determined in terms of polystyrene by gel permeation chromatography (GPC).
• GPC gel permeation chromatography
• the theoretical acid value was used for the acid value.
• Table 2 shows the compositions of intermediate layers 1 to 19 shown in Tables 7 to 12.
• composition for forming intermediate layer After mixing each component according to the description in Table 2, mix the solvent (ion-exchanged water and methanol (manufactured by Mitsubishi Gas Chemical Co., Ltd.) so that the mixing ratio (ion-exchanged water/methanol [mass ratio]) is 40/60.
• a composition for forming an intermediate layer was prepared by adding the mixed solvent (mixed solvent). Note that the numerical values in Table 2 represent the content in parts by mass of each component relative to the total mass of the intermediate layer.
• Table 3 shows the compositions of photosensitive layers 1 to 15 shown in Tables 7 to 12.
• surface is a solid content amount.
• the solid content concentration of the solution containing Polymer A-1 was set to 30.0% by mass.
• the acid value of Polymer A-1 was 189 mgKOH/g.
• the solid content concentration of the solution containing Polymer A-4 was 30% by mass.
• the acid value of Polymer A-4 was 124 mgKOH/g.
• the solid content concentration of the solution containing Polymer A-5 was 30% by mass.
• the acid value of Polymer A-5 was 124 mgKOH/g.
• ⁇ N-phenylcarbamoylmethyl-N-carboxymethylaniline Fujifilm Wako Pure Chemical Industries, Ltd.
• Made (rust preventive agent) ⁇ CBT-1: Carboxybenzotriazole, manufactured by Johoku Kagaku Co., Ltd. (polymerization inhibitor) ⁇ TDP-G: Phenothiazine, manufactured by Kawaguchi Chemical Co., Ltd.
• ⁇ Irganox245 Hindered phenol antioxidant, manufactured by BASF (antioxidant) ⁇ 4-Hydroxymethyl-4-methyl-1-phenyl-3-pyrazolidone: manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.
• Surfactant Surfactant
• E Silicone surfactant, manufactured by DIC Corporation, EXP. S-315
• F Silicone surfactant, manufactured by DIC Corporation, EXP. S-503-2
• G Silicone surfactant, manufactured by Shin-Etsu Chemical Co., Ltd., KP-124
• H Fluorine surfactant, Megafac (registered trademark) F-552
• composition for forming photosensitive layer After mixing each component according to the description in Table 3, methyl ethyl ketone was added to prepare a composition for forming a photosensitive layer in which the solid content concentration was adjusted to 25% by mass.
• the numerical values in Table 3 represent the content in parts by mass of each component based on the total mass of the photosensitive layer.
• thermosetting resin layer Table 5 shows the compositions of thermosetting resin layers 1 to 5 shown in Tables 7 to 12.
• surface is a solid content amount.
• thermoplastic resin layer ⁇ Various components of thermoplastic resin layer>>
• Each component of the thermoplastic resin layer shown in Table 5 is as follows. Note that the description of the components that have already been explained will be omitted.
• the numerical values in Table 5 represent the content of each component in parts by mass based on the total mass of the thermoplastic resin layer.
• thermoplastic resin A A solution containing thermoplastic resin A was obtained by changing the types of monomers used as shown in Table 6 below and using the same method as for polymer A-1 for other conditions. Ta. The solid content concentration of the solution containing thermoplastic resin A was 30% by mass. The acid value of thermoplastic resin A was 155 mgKOH/g.
• thermoplastic resin A The type and mass ratio of each monomer used to synthesize thermoplastic resin A and the weight average molecular weight of thermoplastic resin A are shown below.
• unit of the amount of monomer in Table 6 is mass %.
• the abbreviations in Table 6 represent the following compounds, respectively.
• BzMA Benzyl methacrylate (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.)
• Photoacid generator C Compound with the structure shown below (Photoacid generator, compound described in paragraph 0227 of JP 2013-47765A, synthesized according to the method described in paragraph 0227.)
• thermoplastic resin layer ⁇ Preparation of composition for forming thermoplastic resin layer>> After mixing each component according to the description in Table 5, a solvent (methyl ethyl ketone, propylene glycol monomethyl ether acetate) was added to prepare a composition for forming a thermoplastic resin layer.
• the numerical values in Table 5 represent the content of each component in parts by mass based on the total mass of the thermoplastic resin layer.
• Transfer films each consisting of a temporary support, an intermediate layer, and a photosensitive layer were produced so as to have the configurations shown in Tables 7 to 9 or 11 to 12. Specifically, the details are as follows. First, an intermediate layer forming composition for forming an intermediate layer shown in Tables 7 to 9 or 11 to 12 was placed on a temporary support (thickness 16 ⁇ m, manufactured by Toray Industries, Inc., 16KS40) through a slit. After drying, the coating was applied using a shaped nozzle so that the coating width was 1.0 m and the film thickness after drying was the values listed in Tables 7 to 9 or 11 to 12.
• the middle layer was formed by passing through a drying zone for 40 seconds. Further, on the intermediate layer, a composition for forming a photosensitive layer for forming a photosensitive layer shown in Tables 7 to 9 or 11 to 12 was applied using a slit-shaped nozzle to a coating width of 1 after drying. 0 m and the film thickness after drying is the value listed in Tables 7 to 9 or 11 to 12, and passed through a drying zone at 80 ° C. for 40 seconds, A negative photosensitive layer was formed.
• a polypropylene film (Alphan E200C3, manufactured by Oji F-Tex Co., Ltd.) having a thickness of 18 ⁇ m was pressure-bonded thereon as a protective film to prepare a transfer film, and the film was wound into a roll.
• a copper layer with a thickness of 200 nm was provided on a (glass epoxy resin) substrate with a thickness of 300 ⁇ m by a vapor deposition method to prepare a PET substrate with a copper layer.
• the dielectric loss tangent of the substrate at 24 GHz was measured using a 24 GHz split cylinder resonator manufactured by Kanto Denshi Application Development Co., Ltd., and found to be 0.029.
• the copper layer was laminated under the following lamination conditions: roll temperature 100°C, linear pressure 1.0 MPa, linear speed 4.0 m/min so that the copper layer and photosensitive layer were in contact with each other. It was bonded to a PET substrate (transfer film bonding process).
• the temporary support was peeled off at an angle of 180° (temporary support peeling step).
• the intermediate layer was peeled off and brought into contact with the mask for exposure.
• a high-pressure mercury lamp with i-line (365 nm) as the main exposure wavelength was used for exposure.
• the exposure amount was arbitrarily set so that the top shape of each pattern coincided with the mask opening.
• shower development was performed with a 1% by mass aqueous sodium carbonate solution at a liquid temperature of 25° C., followed by water washing to form a predetermined pattern on the copper to obtain a laminate (pattern forming step).
• the temporary support was peeled off, and the surface free energy of the exposed transfer film surface (intermediate layer surface) was calculated using the Owens equation described above, and the results were expressed as the surface free energy of the peeled surface of the temporary support in Tables 7 to 9. Or summarized in Tables 11 and 12.
• thermoplastic resin layer forming composition for forming a thermoplastic resin layer shown in Table 10 or Table 12 was applied onto the temporary support using a slit-shaped nozzle, and after drying, the coating width was 1.0 m. And the coating was applied so that the film thickness after drying became the values listed in Table 10 or Table 12, and passed through a drying zone at 80° C. for 40 seconds to form a thermoplastic resin layer.
• an intermediate layer forming composition for forming an intermediate layer shown in Table 10 or Table 12 was applied using a slit-shaped nozzle, and after drying, the coating width was 1.0 m. Further, the coating was applied so that the film thickness after drying became the values listed in Table 10 or Table 12, and passed through a drying zone at 80° C. for 40 seconds to form an intermediate layer.
• a composition for forming a photosensitive layer for forming a photosensitive layer shown in Table 10 or Table 12 was applied using a slit-shaped nozzle, and after drying, the coating width was 1.0 m, and The coating was applied so that the film thickness after drying would be the numerical values listed in Table 10 or Table 12, and passed through a drying zone at 80° C. for 40 seconds to form a negative photosensitive layer.
• a polyethylene terephthalate film manufactured by Toray Industries, Inc., 16KS40
• 16KS40 having a thickness of 16 ⁇ m was pressure-bonded thereon as a protective film to prepare a transfer film, and the film was wound into a roll.
• the temporary support was peeled off, and the surface free energy of the exposed surface of the transfer film (thermoplastic resin layer surface) was calculated using the Owens equation described above, and the results are summarized in Table 10 or Table 12.
• a laminate was produced in the same manner as in Example 1, except that the above transfer film was used.
• C Residues or patterns were generated when forming a pattern with an aspect ratio of 1.8 or more and less than 2.0, but a pattern with an aspect ratio of 1.5 or more and less than 1.8 was formed without any residue or pattern collapse. did it.
• D Residues or patterns were generated during pattern formation with an aspect ratio of 1.5.
• the surface free energy of the surface that has a temporary support, an intermediate layer containing a surfactant, and a photosensitive layer and from which the temporary support has been peeled off is 66.0 mJ/m. It can be seen that transfer films with a value of 2 or less are excellent in releasability of the temporary support, resolution, defect suppression, and interlayer adhesion.
• Example 100 Manufacturing of circuit wiring board (semiconductor package)
• a support substrate on which a conductive layer 11 was formed was prepared as a wiring board 10.
• a recess was formed in the wiring board 10 using a laser drill.
• an element 12 for connecting semiconductor elements to each other was prepared in the recess, and was placed in the recess as shown in FIG.
• the dielectric material 13 was prepared as shown in FIG. 4, and the dielectric material 13 was bonded to the substrate as shown in FIG.
• via holes 14 were formed in the dielectric material 13 bonded to the wiring board 10 using a CO 2 laser and a UV laser.
• a seed layer 15 having a thickness of 0.2 ⁇ m was formed by Cu/Ti sputtering, as shown in FIG.
• the dielectric loss tangent at 24 GHz of the substrate on which the seed layer was formed was measured using a 24 GHz split cylinder resonator manufactured by Kanto Applied Development Co., Ltd., and found to be 0.029.
• the surface of the transfer film 20 on the side opposite to the intermediate layer side of the photosensitive layer was bonded to the seed layer 15 formed on the surface of the wiring board 10 (transfer film bonding step).
• a development process was performed after the exposure to form a pattern 21 as shown in FIG. 8 (pattern formation process).
• the photosensitive layer was exposed to light using an ultra-high pressure mercury lamp, and developed for 30 seconds using a 1% by mass aqueous solution of sodium carbonate (30°C) as a developer. .
• rinsing was performed for 30 seconds, and air was further blown to remove moisture and form a pattern.
• a plating process was performed on the region of the seed layer 15 where no pattern was formed to form a conductive pattern 22 (conductive pattern forming step).
• electrolytic plating treatment was performed using a copper sulfate aqueous solution.
• the pattern 21 was removed using a removal solution (3.0% by mass aqueous sodium hydroxide solution, 50° C.) (pattern removal step).
• the seed layer was removed using an etching solution (aqueous solution containing 0.1% by mass sulfuric acid and 0.1% by mass hydrogen peroxide, 28° C.) (seed layer removal step).
• etching solution aqueous solution containing 0.1% by mass sulfuric acid and 0.1% by mass hydrogen peroxide, 28° C.
• seed layer removal step After removing the seed layer, as shown in FIG. 12, a solder resist was laminated on the entire surface of the wiring board 10, exposed to light using an ultra-high pressure mercury lamp, and then developed with a 1% by mass aqueous solution of sodium carbonate (30° C.).
• solder resist layer forming step After development, the solder resist layer was thermally cured by heating at 180° C. for 30 minutes to form a solder resist layer 30 having openings (solder resist layer forming step). Note that the conductive pattern 22 was exposed in the opening. Then, bump electrodes 31 were formed in the openings of the solder resist layer 30 as shown in FIG. 13 (bump electrode forming step). Note that the bump electrode was connected to the exposed conductive pattern 22. As shown in FIG. 14, a semiconductor package 100 was obtained by connecting electrodes 40A and 41A of semiconductor elements 40 and 41 to bump electrodes 31 and sealing them (semiconductor element mounting process). The manufactured semiconductor package was confirmed to operate normally.
• Example 101 Production of flexible printed wiring board> A copper layer with a thickness of 300 nm was provided on both sides of a polyimide base material (Kapton 100H, manufactured by Toray Industries, Inc.) with a thickness of 25 ⁇ m by a vapor deposition method to prepare a polyimide base material with a copper layer.
• a polyimide base material Kerpton 100H, manufactured by Toray Industries, Inc.
• Example 49 The transfer film of Example 49 was laminated on the above-mentioned copper layer-coated polyimide base material under the laminating conditions of a roll temperature of 100° C., a linear pressure of 1.0 MPa, and a linear speed of 1.0 m/min, so that the copper layer and the photosensitive layer were in contact with each other. Both sides were laminated to produce a laminate for evaluation. Next, the temporary supports on both sides were peeled off at an angle of 180°.
• the intermediate layer was brought into contact with the mask to simultaneously expose both sides.
• a high-pressure mercury lamp with i-line (365 nm) as the main exposure wavelength was used for exposure.
• the exposure amount was arbitrarily set so that the top shape of each pattern coincided with the mask opening.
• shower development was performed on both sides with a 1% by mass aqueous sodium carbonate solution at a liquid temperature of 30° C., followed by washing with water to obtain a laminate in which a predetermined pattern was formed on the copper on both sides.
• the above laminate was sequentially subjected to acid degreasing, water washing, and sulfuric acid dipping, and copper plating was performed using a copper sulfate plating solution at 1 A/dm 2 until the plating thickness reached 15 ⁇ m.
• the resist was removed using a 3.0 mass% sodium hydroxide aqueous solution at 50°C, and the seed layer was removed using an etching solution (containing 0.1 mass% sulfuric acid and 0.1 mass% hydrogen peroxide). It was removed with an aqueous solution (28° C.) and washed with water to produce a flexible printed wiring board. It was confirmed that the manufactured flexible printed wiring board operated normally.
• Example 51 The transfer film of Example 51 was laminated on both sides of a polyimide substrate with a copper layer so that the copper layer and the photosensitive layer were in contact with each other under the laminating conditions of a roll temperature of 100°C, a linear pressure of 1.0 MPa, and a linear speed of 1.0 m/min. A laminate for evaluation was produced. Next, one side of the temporary support was peeled off at an angle of 180°, and the peeled side was exposed to light. Exposure was carried out using a projection exposure machine equipped with a high-pressure mercury lamp, and reduced projection exposure was performed using an i-line (365 nm) through a mask. The mask used had a pattern with a predetermined line width ( ⁇ m)/space width ( ⁇ m). Further, the exposure amount was arbitrarily set so that the top shape of each pattern coincided with the mask opening.
• the temporary support of the transfer film on the side opposite to the exposed side was peeled off at an angle of 180°, and the peeled side was exposed under the same conditions as the first exposed side.
• shower development was performed on both sides with a 1% by mass aqueous sodium carbonate solution at a liquid temperature of 30° C., followed by washing with water to obtain a laminate in which a predetermined pattern was formed on the copper on both sides.
• the above laminate was sequentially subjected to acid degreasing, water washing, and sulfuric acid dipping, and copper plating was performed using a copper sulfate plating solution at 1 A/dm 2 until the plating thickness reached 15 ⁇ m.
• the resist was removed using a 3.0 mass% sodium hydroxide aqueous solution at 50°C, and the seed layer was removed using an etching solution (containing 0.1 mass% sulfuric acid and 0.1 mass% hydrogen peroxide). It was removed with an aqueous solution (28° C.) and washed with water to produce a flexible printed wiring board. It was confirmed that the manufactured flexible printed wiring board operated normally.
• Example 102 to 114 Flexible printed wiring boards were produced in the same manner as in Example 101 using the transfer films of Examples 50 to 62. It was confirmed that the flexible printed wiring boards manufactured by either exposure method 1 or exposure method 2 operated normally.

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