WO2022065049A1 - 転写フィルム、積層体の製造方法、回路配線の製造方法 - Google Patents

転写フィルム、積層体の製造方法、回路配線の製造方法 Download PDF

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Publication number
WO2022065049A1
WO2022065049A1 PCT/JP2021/033130 JP2021033130W WO2022065049A1 WO 2022065049 A1 WO2022065049 A1 WO 2022065049A1 JP 2021033130 W JP2021033130 W JP 2021033130W WO 2022065049 A1 WO2022065049 A1 WO 2022065049A1
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Prior art keywords
layer
preferable
photosensitive composition
mass
group
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English (en)
French (fr)
Japanese (ja)
Inventor
陽平 有年
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Fujifilm Corp
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Fujifilm Corp
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Priority to CN202180063024.XA priority Critical patent/CN116157264B/zh
Priority to JP2022551863A priority patent/JP7416969B2/ja
Publication of WO2022065049A1 publication Critical patent/WO2022065049A1/ja
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    • 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
    • B32B7/02—Physical, chemical or physicochemical properties
    • B32B7/023—Optical properties
    • 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
    • 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
    • G—PHYSICS
    • G06—COMPUTING OR CALCULATING; COUNTING
    • G06F—ELECTRIC DIGITAL DATA PROCESSING
    • G06F3/00—Input arrangements for transferring data to be processed into a form capable of being handled by the computer; Output arrangements for transferring data from processing unit to output unit, e.g. interface arrangements
    • G06F3/01—Input arrangements or combined input and output arrangements for interaction between user and computer
    • G06F3/03—Arrangements for converting the position or the displacement of a member into a coded form
    • G06F3/041—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means

Definitions

  • the present invention relates to a method for manufacturing a transfer film, a laminate, and a method for manufacturing a circuit wiring.
  • a photosensitive composition layer is arranged on a transfer target such as a substrate using a transfer film, and the photosensitive composition layer is subjected to a mask. A method of developing after exposure is widely used.
  • Patent Document 1 discloses a polyester film for ultrafine wire photoresist containing predetermined particles on the surface of the laminated polyester film opposite to the resist layer side.
  • the transfer film has excellent peelability. Specifically, first, when using the transfer film, the protective film is peeled off. When the protective film is peeled off, it is required that the photosensitive composition layer does not easily remain on the surface of the protective film. Further, after the photosensitive composition layer of the transfer film is attached to the transferred object, the temporary support is peeled off. It is also required that the photosensitive composition layer does not easily remain on the surface of the temporary support when the temporary support is peeled off. That is, it is required that the photosensitive composition layer does not easily remain on the surface of the temporary support and on the surface of the protective film when the protective film is peeled off and when the temporary support is peeled off. ..
  • the photosensitive composition layer when the photosensitive composition layer is peeled off, it is difficult for the photosensitive composition layer to remain on the surfaces of the temporary support and the protective film, and the fact that the photosensitive composition layer can be peeled off is also referred to as excellent peelability.
  • the present inventor examined the characteristics of the transfer film having the conventional temporary support such as Patent Document 1, and found that the patterning property and the peelability of the transfer film could not be compatible with each other.
  • Another object of the present invention is to provide a transfer film having excellent patterning property and excellent peelability. Another object of the present invention is to provide a method for manufacturing a laminated body and a method for manufacturing a circuit wiring using a transfer film.
  • a transfer film having a temporary support, a photosensitive composition layer arranged on the temporary support, and a protective film in this order.
  • the temporary support has a temporary support body, a first layer arranged on one surface of the temporary support body, and a second layer arranged on the other surface of the temporary support body. Of the first layer and the second layer, the first layer is arranged on the photosensitive composition layer side.
  • the first layer contains first organic particles having an average particle diameter of 100 to 1000 nm and first inorganic particles having an average particle diameter of 70 nm or less. .0-100, A transfer film in which the second layer contains or does not contain second inorganic particles having an average particle diameter of 70 nm or less.
  • the thickness of the temporary support body is 6.0 to 30.0 ⁇ m.
  • the average particle size of the first organic particles is 350 to 800 nm.
  • the first inorganic particles contain aluminum oxide and The transfer film according to any one of [1] to [7], wherein the average particle diameter of the first inorganic particles is 10 to 50 nm.
  • the second layer contains second organic particles having an average particle diameter of 350 to 800 nm.
  • the second inorganic particle contains aluminum oxide and contains The transfer film according to any one of [1] to [8], wherein the average particle diameter of the second inorganic particles is 10 to 50 nm.
  • One of [1] to [10] wherein the Kurtosis Rku on the surface of the first layer is 3.0 to 5.0, and the first inorganic particles and the second inorganic particles contain aluminum oxide.
  • An exposure process for pattern exposure of the photosensitive composition layer and It comprises a developing step of developing an exposed photosensitive composition layer to form a pattern.
  • a method for producing a laminated body comprising a peeling step of peeling a temporary support from a substrate with a photosensitive composition layer between a bonding step and an exposure step, or between an exposure step and a developing step. .. [16]
  • the protective film is peeled off from the transfer film according to any one of [1] to [14], and the surface opposite to the temporary support is attached to a substrate having a conductive layer to form a conductive layer.
  • a method for manufacturing a circuit wiring comprising a peeling step of peeling a temporary support from a substrate with a photosensitive composition layer between a bonding step and an exposure step, or between an exposure step and a developing step. ..
  • the present invention it is possible to provide a transfer film having excellent patterning property and excellent peelability. Further, according to the present invention, it is also possible to provide a method for manufacturing a laminate and a method for manufacturing a circuit wiring using a transfer film.
  • the numerical range represented by using “-" means a range including the numerical values before and after "-" as the lower limit value and the upper limit value.
  • the upper limit value or the lower limit value described in one numerical range may be replaced with the upper limit value or the lower limit value in another numerical range described in stages. ..
  • the upper limit value or the lower limit value described in a certain numerical range may be replaced with the values shown in the examples.
  • process is included in this term not only as an independent process but also as long as the intended purpose of the process is achieved even if it cannot be clearly distinguished from other processes. ..
  • transparent means that the average transmittance of visible light having a wavelength of 400 to 700 nm is 80% or more, and is preferably 90% or more.
  • the average transmittance of visible light is a value measured by using a spectrophotometer, and can be measured by, for example, a spectrophotometer U-3310 manufactured by Hitachi, Ltd.
  • the weight average molecular weight (Mw) and the number average molecular weight (Mn) are three series of TSK gel Super HZM-N (manufactured by Toso Co., Ltd.) as a column and THF as an eluent. It is a value converted using (tetrahexyl), a differential refraction meter as a detector, and polystyrene as a standard material, and polystyrene as a standard material measured by a gel permeation chromatography (GPC) analyzer.
  • the molecular weight of a compound having a molecular weight distribution is a weight average molecular weight.
  • the ratio of the constituent units of the polymer is the mass ratio.
  • the refractive index is a value measured by an ellipsometer at a wavelength of 550 nm unless otherwise specified.
  • (meth) acrylic is a concept that includes both acrylic and methacrylic
  • (meth) acrylate is a concept that includes both acrylate and methacrylate
  • (meth) acrylic acid is a concept that includes both an acrylic group and a methacrylic acid group.
  • organic group means a group containing at least one carbon atom.
  • the type of substituent, the position of the substituent, and the number of substituents in the case of “may have a substituent” are not particularly limited.
  • the number of substituents may be, for example, one, two, three, or more.
  • the substituent include a monovalent non-metal atomic group excluding a hydrogen atom, and for example, it can be selected from the following substituent group T.
  • substituent T examples include a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom; an alkoxy group such as a methoxy group, an ethoxy group and a tert-butoxy group; a phenoxy group and a p-tolyloxy group.
  • alkoxycarbonyl groups such as methoxycarbonyl group, butoxycarbonyl group and phenoxycarbonyl group
  • acyloxy groups such as acetoxy group, propionyloxy group and benzoyloxy group
  • Acryl groups such as acryloyl group, methacryloyl group, and metoxalyl group
  • alkylsulfanyl groups such as methylsulfanyl group and tert-butylsulfanyl group
  • arylsulfanyl groups such as phenylsulfanyl group and p-tolylsulfonyl group
  • alkyl groups such as cyclo Alkyl group; aryl group; heteroaryl group; hydroxyl group; carboxy group; formyl group; sulfo group; cyano group; nitro group; ether group; alkylaminocarbonyl group; aryla
  • the transfer film has a temporary support, a photosensitive composition layer arranged on the temporary support, and a protective film in this order.
  • the temporary support has a temporary support body, a first layer arranged on one surface of the temporary support body, and a second layer arranged on the other surface of the temporary support body. Of the first layer and the second layer, the first layer is arranged on the photosensitive composition layer side. That is, the transfer film has a second layer, a temporary support body, a first layer, a photosensitive composition layer, and a protective film in this order.
  • the feature of the transfer film of the present invention is that the temporary support of the transfer film has a first layer and a second layer.
  • the present inventors have studied conventional transfer films and found that both patterning property and peelability have not been achieved.
  • the desired effect was obtained when the temporary support having the first layer and the second layer was provided.
  • the present inventions speculate about the mechanism as follows. By controlling the first inorganic particles that can be contained in each layer to a predetermined average particle diameter, scattering of light during exposure is suppressed, uniform exposure is achieved, and variation in the line width of the resin pattern is reduced.
  • the Kurtosis Rku is adjusted to a predetermined range, and the photosensitive composition layer and the temporary support are used, and the photosensitive composition is formed. It is presumed that the desired peelability between the layer and the protective film could be imparted.
  • the effect of the present invention is further excellent in that at least one of the effect of the excellent patterning property of the transfer film and the effect of the excellent peelability of the transfer film can be obtained.
  • the photosensitive composition layer is preferably a negative photosensitive composition layer. It is also preferable that the photosensitive composition layer is a colored resin layer.
  • the transfer film of the present invention may be used as a transfer film for a wiring protective film or as a transfer film for an etching resist, as will be described later.
  • the composition of the transfer film is preferably the above-mentioned configurations (1) and (2).
  • the composition of the transfer film is preferably the above-mentioned configurations (2) to (4).
  • the first embodiment and the second embodiment described later can be mentioned.
  • the transfer film 10 shown in FIG. 1 has a temporary support 1, a composition layer 2 including a photosensitive composition layer 3 and a refractive index adjusting layer 5, and a protective film 7 in this order. Further, the transfer film 10 shown in FIG. 1 has a form in which the refractive index adjusting layer 5 is arranged, but the refractive index adjusting layer 5 may not be arranged.
  • the transfer film 20 shown in FIG. 2 has a temporary support 11, a composition layer 12 including a thermoplastic resin layer 13, an intermediate layer 15, and a photosensitive composition layer 17, and a protective film 19 in this order. .. Further, the transfer film 20 shown in FIG. 2 has a form in which the thermoplastic resin layer 13 and the intermediate layer 15 are arranged, but the thermoplastic resin layer 13 and the intermediate layer 15 may not be arranged.
  • examples of the temporary support 11 and the protective film 17 are the same as those of the temporary support 1 and the protective film 9 of the first embodiment described above.
  • each configuration of the transfer film will be described in detail.
  • the transfer film has a temporary support.
  • the temporary support has a temporary support main body, a first layer described later, and a second layer described later.
  • the temporary support is a member that supports the photosensitive composition layer, and is finally removed by a peeling treatment.
  • each member constituting the temporary support will be described in detail.
  • the temporary support has a temporary support body.
  • the temporary support body is a member arranged between the first layer and the second layer.
  • Examples of the temporary support main body include a glass substrate and a film, and a resin film is preferable. Further, as the temporary support main body, a film that does not cause significant deformation, shrinkage, or elongation under pressure, pressure, and heating, and has flexibility is preferable.
  • the resin film examples include polyester films such as polyethylene terephthalate (PET) films, cellulose triacetate films, polystyrene films, polyimide films, and polycarbonate films.
  • PET polyethylene terephthalate
  • cellulose triacetate films examples of the resin film
  • polystyrene films examples of the resin film
  • polycarbonate films examples of the resin film.
  • a polyester film is preferable, a biaxially stretched polyester film is more preferable, and a biaxially stretched PET film is further preferable. Further, it is also preferable that the temporary support main body is not deformed or scratched such as wrinkles.
  • a biaxially stretched polyester film is preferable.
  • Biaxial stretching means that biaxial stretching treatment is performed and the molecule has molecular orientation in the biaxial direction.
  • the molecular orientation is measured using a microwave transmission type molecular orientation meter (for example, MOA-6004, manufactured by Oji Measuring Instruments Co., Ltd.).
  • the angle formed in the biaxial direction is preferably 90 ° ⁇ 5 °, more preferably 90 ° ⁇ 3 °, and even more preferably 90 ° ⁇ 1 °.
  • the biaxially stretched polyester film preferably has molecular orientation in the longitudinal direction and the width direction.
  • the width direction means a direction orthogonal to the longitudinal direction.
  • the width direction is the direction with the strongest orientation among the orientations measured using a microwave transmission type molecular orientation meter (for example, MOA-6004, manufactured by Oji Measuring Instruments Co., Ltd.).
  • a microwave transmission type molecular orientation meter for example, MOA-6004, manufactured by Oji Measuring Instruments Co., Ltd.
  • the orthogonality is not limited to a strict orthogonality, but includes a substantially orthogonality. Approximately orthogonal means intersecting at 90 ° ⁇ 5 °, preferably at 90 ° ⁇ 3 °, and more preferably at 90 ° ⁇ 1 °.
  • the biaxially stretched polyester film is a biaxially stretched polyester film containing polyester as a main polymer component.
  • the main polymer component means a polymer having the largest content ratio (% by mass) among all the polymers contained in the film, and polyester means a polymer having an ester bond in the main chain.
  • polyesters examples include known polyesters.
  • examples of the polyester include polyethylene terephthalate (PET) and polyethylene-2,6-naphthalate (PEN). Among them, PET is preferable as the polyester.
  • the intrinsic viscosity of polyester is preferably 0.50 dl / g or more and less than 0.80 dl / g, and more preferably 0.55 dl / g or more and less than 0.70 dl / g.
  • the biaxially stretched polyester film may contain only one type of polyester, or may contain two or more types of polyester.
  • the polyester content is preferably 85% by mass or more, more preferably 90% by mass or more, further preferably 95% by mass or more, still more preferably 98% by mass or more, based on the total mass of the polymer in the biaxially stretched polyester film.
  • the upper limit is not particularly limited, and is preferably 100% by mass or less with respect to the total mass of the polymer in the biaxially stretched polyester film.
  • the polyester content is preferably 85% by mass or more, more preferably 90% by mass or more, further preferably 95% by mass or more, and particularly preferably 98% by mass or more, based on the total mass of the biaxially stretched polyester film.
  • the upper limit is not particularly limited, and is preferably 100% by mass or less with respect to the total mass of the biaxially stretched polyester film.
  • the content of PET is preferably 90 to 100% by mass, more preferably 95 to 100% by mass, and 98 by mass, based on the total mass of the polyester in the biaxially stretched polyester film. ⁇ 100% by mass is more preferable, and 100% by mass is particularly preferable.
  • polyester can be produced by polycondensing at least one dicarboxylic acid compound and at least one diol compound in the presence of a catalyst.
  • dicarboxylic acid compound include an aliphatic dicarboxylic acid compound, an alicyclic dicarboxylic acid compound, and an aromatic dicarboxylic acid compound.
  • diol compound include an aliphatic diol compound, an alicyclic diol compound, and an aromatic diol compound.
  • Examples of the catalyst include alkali metal compounds, alkaline earth metal compounds, zinc compounds, lead compounds, manganese compounds, cobalt compounds, aluminum compounds, antimony compounds, titanium compounds, germanium compounds, and phosphorus compounds.
  • a known end-capping agent can be used in the production of polyester, if necessary.
  • Examples of the terminal encapsulant include an oxazoline-based compound, a carbodiimide compound, and an epoxy compound.
  • the haze of the temporary support body is preferably small. Specifically, the haze of the temporary support is preferably less than 0.5%, more preferably 0.4% or less.
  • the lower limit is not particularly limited, and is preferably 0% or more.
  • the haze can be measured using a haze meter by a method according to JIS K 7105: 1981, and the haze described in the present specification is measured using a haze meter (NDH-2000, manufactured by Nippon Denshoku Kogyo Co., Ltd.). It is the value that was set.
  • the B * value in the L * a * b * color system is preferably 0 to 1, more preferably 0 to 0.8, further preferably 0 to 0.6, and 0 to 0. 4 is particularly preferable.
  • the b * value in the L * a * b * color system is 0 to 1, the yellowness of the film can be reduced, so that the hue of the film can be made almost colorless. As a result, it can be preferably applied, for example, in applications where high visibility is required (for example, a display device).
  • the L * a * b * value in the color system of the temporary support body is measured by the transmission method using a spectrocolorimeter (for example, SE-2000, manufactured by Nippon Denshoku Kogyo Co., Ltd.).
  • the thickness of the temporary support body is preferably 1.0 to 100.0 ⁇ m, more preferably 6.0 to 30.0 ⁇ m, and 10. It is more preferably 0 to 30.0 ⁇ m.
  • the thickness of the temporary support body is 10.0 ⁇ m or more, good strength is obtained and handling in the processing step becomes easy, and when it is 50.0 ⁇ m or less, a better haze value can be obtained.
  • the dimensional change rate of the temporary support body is within the following range because distortion and wrinkles due to heat shrinkage in the DFR processing process can be suppressed.
  • the dimensional change rate can be adjusted by appropriately adjusting conditions such as relaxation and heat treatment under the film forming conditions by a known method.
  • the dimensional change rate at 150 ° C. is preferably less than 3% in the longitudinal direction and less than 2.5% in the width direction, 0.5% or more and less than 2% in the longitudinal direction, and 1% or more and 2% in the width direction. Less than is more preferred.
  • the dimensional change rate in the longitudinal direction and the width direction at 100 ° C. is preferably less than 1%, more preferably less than 0.8%. When the dimensional change rate is within the above range, the flatness when the photosensitive composition is applied tends to be better.
  • the strength when the film in the longitudinal direction is stretched by 5% is preferably 70 MPa or more and less than 150 MPa. If the F-5 in the longitudinal direction is less than 70 MPa, the processing characteristics may deteriorate due to scratches or the like due to insufficient strength. On the other hand, if the F-5 in the longitudinal direction is 150 MPa or more, it may be difficult to achieve compatibility with the F-5 in the width direction.
  • the F-5 in the longitudinal direction is more preferably 80 MPa or more and less than 140 MPa, and further preferably 90 MPa or more and less than 130 MPa.
  • the F-5 in the width direction is preferably 80 MPa or more and less than 160 MPa.
  • F-5 in the width direction is within the above range, deterioration of processing characteristics due to generation of scratches due to insufficient strength is suppressed, and compatibility with F-5 in the longitudinal direction is also good. It is more preferably 90 MPa or more and less than 150 MPa, and further preferably 100 MPa or more and less than 140 MPa.
  • the breaking strength of the temporary support body in the longitudinal direction is preferably 200 MPa or more and less than 360 MPa, more preferably 220 MPa or more and less than 340 MPa.
  • the breaking strength in the width direction is preferably 260 MPa or more and less than 420 MPa, more preferably 280 MPa or more and less than 400 MPa.
  • F-5 and breaking strength can be achieved by appropriately adjusting the stretching temperature and stretching ratio in the vertical and horizontal directions.
  • the temporary support has a first layer arranged on the side of the photosensitive composition layer.
  • the first layer contains first organic particles having an average particle diameter of 100 to 1000 nm and first inorganic particles having an average particle diameter of 70 nm or less. ⁇ 100.
  • the surface of the surface of the first layer in contact with the photosensitive composition layer is preferably 2.5 to 80, more preferably 2.5 to 10, and 2.5 to 10. 6.0 is more preferable, and 3.0 to 5.0 is particularly preferable.
  • 10 randomly selected surfaces (the surface opposite the temporary support body) in contact with the photosensitive composition layer of the first layer were selected using New View 6000 manufactured by Zygo. It shall be the average value obtained by measuring and excluding the minimum and maximum values from the obtained measured values.
  • Examples of the method for adjusting Kurtosis Rku include a method for adjusting the type and content of the first organic particles and the first inorganic particles, which will be described later.
  • the average particle size of the first organic particles is 100 to 1000 nm, preferably 350 to 800 nm, more preferably 350 to 700 nm, and even more preferably 400 to 600 nm in that the effect of the present invention is more excellent.
  • the average particle size of the first organic particles is determined by arithmetically averaging the particle sizes of 50 first organic particles randomly selected from images of a transmission electron microscope (TEM). Specifically, after cutting out the cross section of the temporary support, the cross section of the temporary support is observed by TEM, and 50 particles are randomly selected from the observation image of TEM.
  • TEM transmission electron microscope
  • EDX Energy dispersive X-ray analysis
  • Resin particles are preferable as the first organic particles.
  • the resin particles include polystyrene resin particles, acrylic resin particles, polyester resin particles, silicone organic particles, and styrene-acrylic organic particles, and polystyrene resin particles are preferable.
  • the first organic particles preferably have a crosslinked structure.
  • the first layer may contain only one kind of first organic particles, or may contain two or more kinds of first organic particles.
  • the content of the first organic particles is preferably 0.01 to 10.0% by mass, more preferably 0.05 to 1.0% by mass, and 0.1 to 1. 0% by mass is more preferable, and 0.1 to 0.3% by mass is particularly preferable.
  • the average particle size of the first inorganic particles is 70 nm or less, and is preferably 65 nm or less, more preferably 50 nm or less, in that the effect of the present invention is more excellent.
  • the lower limit is not particularly limited, and is preferably 1 nm or more, more preferably 5 nm or more, further preferably 8 nm or more, and particularly preferably 10 nm or more.
  • the average particle size of the first inorganic particles can be measured by using the above-mentioned method for measuring the average particle size of organic particles.
  • the first inorganic particle preferably contains at least one selected from the group consisting of a silicon atom and an aluminum atom, and more preferably contains an aluminum atom.
  • the first inorganic particles include silicon dioxide particles (silica particles), titania particles (titanium oxide particles), calcium carbonate, barium sulfate, and aluminum oxide particles (alumina particles).
  • silicon dioxide particles silicon dioxide particles
  • titania particles titanium oxide particles
  • calcium carbonate calcium carbonate
  • barium sulfate calcium carbonate
  • aluminum oxide particles alumina particles
  • aluminum oxide particles or silicon dioxide particles are preferable, and aluminum oxide particles are more preferable, in terms of haze and durability.
  • the silicon dioxide particles are not particularly limited, and examples thereof include known silica particles.
  • Examples of the silicon dioxide particles include fumed silica particles and colloidal silica particles.
  • the fumed silica particles can be obtained, for example, by reacting a compound containing a silicon atom with oxygen and hydrogen in a gas phase.
  • Examples of the silicon compound as a raw material include silicon halide (for example, silicon chloride).
  • the colloidal silica particles can be synthesized, for example, by a sol-gel method in which a raw material compound is hydrolyzed and condensed.
  • Examples of the raw material compound of colloidal silica include alkoxysilicon (for example, tetraethoxysilane) and halogenated silane compound (for example, diphenyldichlorosilane).
  • the form of the silicon dioxide particles may be primary particles or aggregates of primary particles (aggregated silica particles).
  • the first layer may contain only one kind of the first inorganic particles, or may contain two or more kinds.
  • the content of the first inorganic particles is preferably 0.01 to 10.0% by mass, more preferably 0.05 to 1.0% by mass, and 0.1 to 1. 0% by mass is more preferable, and 0.2 to 0.5% by mass is particularly preferable.
  • the content of the first inorganic particles is preferably higher than the content of the first organic particles.
  • the mass ratio of the content of the first inorganic particles to the content of the first organic particles is preferably 1.0 or more, 2 .0 or more is more preferable.
  • the upper limit is not particularly limited, and is preferably 10.0 or less, more preferably 5.0 or less, and even more preferably 3.0 or less.
  • the first layer may contain other components in addition to the above-mentioned components.
  • examples of other components include resins, surfactants, cross-linking agents, and film-forming aids, with resins being preferred.
  • the first layer may contain only one kind of other components, or may contain two or more kinds.
  • the resin means a polymer having a weight average molecular weight of 3000 or more.
  • the weight average molecular weight of the resin can be measured using gel permeation chromatography (GPC).
  • GPC gel permeation chromatography
  • the resin include an olefin resin, the resin constituting the temporary support body described above, and a binder polymer contained in the photosensitive composition layer described later, and the resin constituting the temporary support body or the binder polymer may be used.
  • a polyester resin is more preferable, and a PET resin is further preferable.
  • the olefin resin include known olefin resins.
  • the olefin resin include polyethylene and polypropylene.
  • the content of the resin is preferably 50% by mass or more, more preferably 80% by mass or more, and more preferably 90% by mass or more, based on the total mass of the first layer in terms of durability of the first layer and dispersibility of particles. Is more preferable.
  • the upper limit is not particularly limited, and is preferably 99.99% by mass or less, more preferably 99.9% by mass or less.
  • the surfactant examples include anionic surfactants, cationic surfactants, nonionic surfactants, and amphoteric surfactants, and anionic surfactants or nonionic surfactants are preferable.
  • anionic surfactant examples include Lapizol (registered trademark) A-90 (manufactured by NOF Corporation), Sanded BL (manufactured by Sanyo Chemical Industries, Ltd.), and Nikkor SCS (manufactured by Nikko Chemicals Co., Ltd.).
  • the nonionic surfactant examples include Naroacty (registered trademark) CL95 (manufactured by Sanyo Chemical Industries, Ltd.).
  • examples of the surfactant include the surfactants described in the Handbook of Physical Properties and Performance of Surfactants (Technical Information Association).
  • the content of the surfactant is preferably 10% by mass or less, more preferably 0.001 to 10% by mass, still more preferably 0.01 to 3% by mass, based on the total mass of the first layer.
  • cross-linking agent examples include known cross-linking agents for carbodiimide compounds, oxazoline compounds, epoxy compounds, melamine compounds, and isocyanate compounds.
  • examples of the cross-linking agent include Carbodilite (registered trademark) V-02-L2 (manufactured by Nisshinbo Chemical Co., Ltd.), Epocross (registered trademark) WS-700 (manufactured by Nippon Shokubai Co., Ltd.), and Denacol (registered trademark) EX614B (manufactured by Nagase ChemteX Corporation).
  • WM44 manufactured by Asahi Kasei Chemicals Co., Ltd.
  • Duranate registered trademark
  • the content of the cross-linking agent is preferably 1 to 50% by mass, more preferably 2 to 20% by mass, based on the total mass of the first layer.
  • the thickness of the first layer is preferably 0.01 ⁇ m or more, more preferably 0.1 ⁇ m or more, further preferably 0.5 ⁇ m or more, and particularly preferably 0.8 ⁇ m or more.
  • the upper limit is not particularly limited, and is preferably 10.0 ⁇ m or less, more preferably 5.0 ⁇ m or less, further preferably 3.0 ⁇ m or less, particularly preferably 2.0 ⁇ m or less, and most preferably 1.0 ⁇ m or less.
  • the second layer is a layer containing the second inorganic particles having an average particle diameter of 70 nm or less, or a layer containing no inorganic particles.
  • the second layer contains the second inorganic particles or does not contain the inorganic particles regardless of the average particle size.
  • the second layer contains the second inorganic particles.
  • the average particle diameter of the second inorganic particles contained in the second layer is preferably 65 nm or less, preferably 50 nm, because the effect of the present invention is more excellent. The following are more preferable.
  • the lower limit is not particularly limited, and is preferably 1 nm or more, more preferably 5 nm or more, further preferably 8 nm or more, and particularly preferably 10 nm or more.
  • the average particle size of the second inorganic particles can be measured by using the above-mentioned method for measuring the average particle size of the first organic particles.
  • the second inorganic particle preferably contains at least one selected from the group consisting of a silicon atom and an aluminum atom, and more preferably contains an aluminum atom.
  • the second inorganic particles include silicon dioxide particles (silica particles), titania particles (titanium oxide particles), calcium carbonate, barium sulfate, and aluminum oxide particles (alumina particles).
  • silicon dioxide particles silicon dioxide particles
  • titania particles titanium oxide particles
  • calcium carbonate calcium carbonate
  • barium sulfate calcium carbonate
  • aluminum oxide particles alumina particles
  • aluminum oxide particles aluminum oxide particles or silicon dioxide particles are preferable, and aluminum oxide particles are more preferable, in terms of haze and durability.
  • the embodiment of the silicon dioxide particles is as described above.
  • the second layer may contain only one kind of second inorganic particles, or may contain two or more kinds.
  • the content of the second inorganic particles is preferably 0.01 to 10.0% by mass, more preferably 0.05 to 1.0% by mass, and 0.1 to 1. 0% by mass is more preferable, and 0.2 to 0.5% by mass is particularly preferable.
  • the second layer does not contain inorganic particles
  • the second layer does not contain inorganic particles regardless of the average particle size.
  • the second layer may contain second organic particles having an average particle diameter of 100 to 1000 nm.
  • the definition of the second organic particle is synonymous with the first organic particle contained in the first layer described above, and the preferred embodiment is also the same.
  • the second layer may contain only one kind of second organic particles, or may contain two or more kinds.
  • the content of the second organic particles is preferably 0.01 to 10.0% by mass, more preferably 0.05 to 1.0% by mass, and 0.1 to 1. 0% by mass is more preferable, and 0.1 to 0.3% by mass is particularly preferable.
  • the second layer may contain other components in addition to the above-mentioned components.
  • the other component has the same meaning as the other component contained in the first layer described above, and the preferred embodiment is also the same.
  • the thickness of the second layer is preferably 0.01 ⁇ m or more, more preferably 0.1 ⁇ m or more, further preferably 0.5 ⁇ m or more, and particularly preferably 0.8 ⁇ m or more.
  • the upper limit is not particularly limited, and is preferably 10.0 ⁇ m or less, more preferably 5.0 ⁇ m or less, further preferably 3.0 ⁇ m or less, particularly preferably 2.0 ⁇ m or less, and most preferably 1.0 ⁇ m or less.
  • the aspect of the first layer and the aspect of the second layer may be the same layer or different layers. Among them, the same layer is preferable because the effect of the present invention is more excellent.
  • the same layer means a layer having the same component and layer thickness contained in the layer.
  • the first organic particles contained in the first layer and the second organic particles contained in the second layer may be the same organic particles or different organic particles. Among them, the same organic particles are preferable because the effect of the present invention is more excellent.
  • the content of the first organic particles contained in the first layer and the content of the second organic particles contained in the second layer may be the same content or different contents. Among them, the same content is preferable in that the effect of the present invention is more excellent.
  • the first inorganic particles contained in the first layer and the second inorganic particles contained in the second layer may be the same inorganic particles or different inorganic particles. Among them, the same inorganic particles are preferable because the effect of the present invention is more excellent. Further, the content of the first inorganic particles contained in the first layer and the content of the second inorganic particles contained in the second layer may be the same content or different contents. Among them, the same content is preferable in that the effect of the present invention is more excellent.
  • the thickness of the first layer and the thickness of the second layer may be the same or different. Among them, the same thickness is preferable in that the effect of the present invention is more excellent.
  • the temporary support preferably has light transmission.
  • having light transmittance means that the transmittance of light having a wavelength used for pattern exposure is 50% or more.
  • the transmittance of light having a wavelength of 365 nm is preferably 60% or more, and more preferably 70% or more, from the viewpoint that pattern exposure can be performed via a temporary support.
  • the upper limit is not particularly limited, and is preferably 100% or less.
  • the transmittance is the emission light emitted through the layer to be measured with respect to the intensity of the incident light when the light is incident in the direction perpendicular to the main surface of the layer to be measured (thickness direction). Means the ratio of strength of.
  • the transmittance can be measured using MCPD Series manufactured by Otsuka Electronics Co., Ltd.
  • the haze of the temporary support is preferably small. Specifically, the haze of the temporary support is preferably less than 0.5%, more preferably 0.4% or less.
  • the lower limit is not particularly limited, and is preferably 0% or more.
  • the haze can be measured using a haze meter by a method according to JIS K 7105: 1981, and the haze described in the present specification is measured using a haze meter (NDH-2000, manufactured by Nippon Denshoku Kogyo Co., Ltd.). It is the value that was set.
  • the thickness of the temporary support can be determined, for example, according to the strength of the temporary support, the light transmittance, the material, and the flexibility required for bonding the transfer film and the substrate.
  • the thickness of the temporary support is not particularly limited, but is often 200.0 ⁇ m or less, and is preferably 100.0 ⁇ m or less, more preferably 40.0 ⁇ m or less, and 35.0 ⁇ m or less in that the effect of the present invention is more excellent. Is more preferable.
  • the lower limit is not particularly limited, and is preferably 1.0 ⁇ m or more, more preferably 5.0 ⁇ m or more, still more preferably 10.0 ⁇ m or more.
  • the thickness of the temporary support can be calculated as an average value of any five points measured by cross-sectional observation with a scanning electron microscope (SEM).
  • Preferred forms of the temporary support include, for example, paragraphs [0017] to [0018] of JP-A-2014-085643, paragraphs [0019]-[0026] of JP-A-2016-0273363, and WO2012 / 08168A1.
  • Paragraphs [0041] to [0057] and paragraphs [0029] to [0040] of WO2018 / 179370A1 can be incorporated, and the contents of these publications are incorporated herein.
  • the transfer film has a protective film.
  • the protective film By having the protective film, the surface of the layer in contact with the protective film (for example, the photosensitive composition layer) can be protected.
  • the protective film examples include a resin film and paper, and a resin film is preferable from the viewpoint of strength and flexibility.
  • the resin film include a polyethylene film, a polypropylene film, a polyethylene terephthalate film, a cellulose triacetate film, a polystyrene film, and a polycarbonate film.
  • a polyethylene film, a polypropylene film, or a polyethylene terephthalate film is preferable, and a polyethylene terephthalate film is more preferable.
  • the thickness of the protective film is preferably 5 to 100 ⁇ m, more preferably 10 to 50 ⁇ m, and even more preferably 10 to 20 ⁇ m.
  • the arithmetic average roughness Ra of the surface on the side where the photosensitive composition layer of the protective film is arranged is preferably 0.3 ⁇ m or less, more preferably 0.1 ⁇ m or less, and more preferably 0.05 ⁇ m or less from the viewpoint of excellent resolution. Is more preferable.
  • the lower limit of the arithmetic mean roughness Ra is not particularly limited, and is preferably 0.001 ⁇ m or more.
  • the arithmetic mean roughness Ra of the surface on the side where the photosensitive composition layer of the protective film is arranged is absent among the surfaces in contact with the photosensitive composition layer of the first layer (the surface opposite to the temporary support body).
  • the 10 points selected at random are measured using New View 6000 manufactured by Zygo, and the average value of the obtained measured values excluding the minimum and maximum values is used.
  • the transfer film has a photosensitive composition layer disposed on the temporary support.
  • the photosensitive composition layer preferably contains a binder polymer, a polymerizable compound, and a polymerization initiator, which will be described later.
  • a pattern can be formed on the transferred object by transferring the photosensitive composition layer onto the transferred object and then exposing and developing the photosensitive composition layer.
  • the photosensitive composition layer may be a positive type photosensitive composition layer or a negative type photosensitive composition layer.
  • the positive photosensitive composition layer is a photosensitive composition layer in which the exposed portion is improved in solubility in a developing solution by exposure.
  • the negative photosensitive composition layer is a photosensitive composition layer in which the exposed portion is less soluble in a developing solution due to exposure. Above all, it is preferable to use a negative photosensitive composition layer.
  • the photosensitive composition layer is a negative photosensitive composition layer, the formed pattern corresponds to a protective film.
  • the thickness of the photosensitive composition layer is preferably 20.0 ⁇ m or less, more preferably 15.0 ⁇ m or less, still more preferably 10.0 ⁇ m or less, from the viewpoint of coatability.
  • the above lower limit is not particularly limited, and is preferably 0.05 ⁇ m or more, more preferably 3.0 ⁇ m or more, further preferably 4.0 ⁇ m or more, and particularly preferably 5.0 ⁇ m or more.
  • the thickness of the photosensitive composition layer is calculated as an average value of any five points measured by cross-sectional observation with a scanning electron microscope (SEM).
  • the refractive index of the photosensitive composition layer is preferably 1.47 to 1.56, more preferably 1.49 to 1.54.
  • the photosensitive composition layer is preferably achromatic.
  • the a * value of the photosensitive composition layer is preferably ⁇ 1.0 to 1.0, and the b * value of the photosensitive composition layer is preferably ⁇ 1.0 to 1.0.
  • the hue of the photosensitive composition layer can be measured using a colorimeter (CR-221, manufactured by Minolta).
  • the photosensitive composition layer may contain a binder polymer.
  • the binder polymer include (meth) acrylic resin, styrene resin, epoxy resin, amide resin, amide epoxy resin, alkyd resin, phenol resin, ester resin, urethane resin, and the reaction of epoxy resin with (meth) acrylic acid.
  • examples thereof include the obtained epoxy acrylate resin and the acid-modified epoxy acrylate resin obtained by reacting the epoxy acrylate resin with the acid anhydride.
  • the binder polymer is a (meth) acrylic resin in that it is excellent in alkali developability and film forming property.
  • the (meth) acrylic resin means a resin having a structural unit derived from the (meth) acrylic compound.
  • the content of the structural unit derived from the (meth) acrylic compound is preferably 50% by mass or more, more preferably 70% by mass or more, based on all the structural units of the (meth) acrylic resin.
  • the (meth) acrylic resin may be composed of only a structural unit derived from the (meth) acrylic compound, or may have a structural unit derived from a polymerizable monomer other than the (meth) acrylic compound. .. That is, the upper limit of the content of the structural unit derived from the (meth) acrylic compound is preferably 100% by mass or less with respect to all the structural units of the (meth) acrylic resin.
  • Examples of the (meth) acrylic compound include (meth) acrylic acid, (meth) acrylic acid ester, (meth) acrylamide, and (meth) acrylonitrile.
  • Examples of the (meth) acrylic acid ester include (meth) acrylic acid alkyl ester, (meth) acrylic acid tetrahydrofurfuryl ester, (meth) acrylic acid dimethylaminoethyl ester, (meth) acrylic acid diethylaminoethyl ester, and (meth) acrylic acid ester.
  • Acrylic acid glycidyl ester (meth) acrylic acid benzyl ester, 2,2,2-trifluoroethyl (meth) acrylate, and 2,2,3,3-tetrafluoropropyl (meth) acrylate.
  • Meta) Acrylic acid alkyl esters are preferred.
  • the (meth) acrylamide include acrylamide such as diacetone acrylamide.
  • the alkyl group of the (meth) acrylic acid alkyl ester may be linear or branched. Specific examples include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, ( Heptyl acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, undecyl (meth) acrylate, and (meth) acrylate.
  • Examples thereof include (meth) acrylic acid alkyl esters having an alkyl group having 1 to 12 carbon atoms such as dodecyl.
  • As the (meth) acrylic acid ester a (meth) acrylic acid alkyl ester having an alkyl group having 1 to 4 carbon atoms is preferable, and methyl (meth) acrylate or ethyl (meth) acrylate is more preferable.
  • the (meth) acrylic resin may have a structural unit other than the structural unit derived from the (meth) acrylic compound.
  • the polymerizable monomer forming the structural unit is not particularly limited as long as it is a compound other than the (meth) acrylic compound that can be copolymerized with the (meth) acrylic compound, and is, for example, styrene, vinyltoluene and ⁇ -methyl.
  • Styrene compounds such as styrene which may have a substituent at the ⁇ -position or an aromatic ring, vinyl alcohol esters such as acrylonitrile and vinyl-n-butyl ether, cinnamic acid, cinnamic acid anhydride, monomethyl maleate, monoethyl maleate and Examples thereof include maleic acid monoesters such as maleic acid monoisopropyl, fumaric acid, cinnamic acid, ⁇ -cyanocinnamic acid, itaconic acid, and crotonic acid. These polymerizable monomers may be used alone or in combination of two or more.
  • the (meth) acrylic resin preferably has a structural unit having an acid group from the viewpoint of improving the alkali developability.
  • the acid group include a carboxy group, a sulfo group, a phosphoric acid group, and a phosphonic acid group.
  • the (meth) acrylic resin more preferably has a structural unit having a carboxy group, and further preferably has a structural unit derived from the above-mentioned (meth) acrylic acid.
  • the content of the structural unit having an acid group (preferably the structural unit derived from (meth) acrylic acid) in the (meth) acrylic resin is excellent in developability, and is based on the total mass of the (meth) acrylic resin. 10% by mass or more is preferable.
  • the upper limit is not particularly limited, but is preferably 50% by mass or less, more preferably 40% by mass or less, in terms of excellent alkali resistance.
  • the (meth) acrylic resin has a structural unit derived from the above-mentioned (meth) acrylic acid alkyl ester.
  • the content of the structural unit derived from the (meth) acrylic acid alkyl ester in the (meth) acrylic resin is preferably 1 to 90% by mass, preferably 1 to 80% by mass, based on all the structural units of the (meth) acrylic resin. More preferably, 5 to 60% by mass is further preferable.
  • the (meth) acrylic resin a resin having both a structural unit derived from (meth) acrylic acid and a structural unit derived from (meth) acrylic acid alkyl ester is preferable, and the structural unit derived from (meth) acrylic acid and the structural unit derived from (meth) acrylic acid are preferable.
  • a resin composed only of structural units derived from the (meth) acrylic acid alkyl ester is more preferable.
  • an acrylic resin having a structural unit derived from methacrylic acid, a structural unit derived from methyl methacrylate, and a structural unit derived from ethyl acrylate is also preferable.
  • the (meth) acrylic resin may have at least one selected from the group consisting of a structural unit derived from methacrylic acid and a structural unit derived from methacrylic acid alkyl ester from the viewpoint that the effect of the present invention is more excellent. It is preferable to have both a structural unit derived from methacrylic acid and a structural unit derived from an alkyl methacrylate ester.
  • the total content of the constituent units derived from methacrylic acid and the constituent units derived from methacrylic acid alkyl ester in the (meth) acrylic resin is higher than that of all the constituent units of the (meth) acrylic resin because the effect of the present invention is more excellent.
  • 40% by mass or more is preferable, and 60% by mass or more is more preferable.
  • the upper limit is not particularly limited, and is preferably 100% by mass or less, more preferably 80% by mass or less.
  • the (meth) acrylic resin is at least one selected from the group consisting of a structural unit derived from methacrylic acid and a structural unit derived from methacrylic acid, and acrylic acid, because the effect of the present invention is more excellent. It is also preferable to have at least one selected from the group consisting of the structural unit derived from the acrylic acid alkyl ester and the structural unit derived from the acrylic acid alkyl ester. From the viewpoint that the effect of the present invention is more excellent, the total content of the structural unit derived from methacrylic acid and the structural unit derived from methacrylic acid alkyl ester is the structural unit derived from acrylic acid and the structural unit derived from acrylic acid alkyl ester. The mass ratio is preferably 60/40 to 80/20 with respect to the total content of the ester.
  • the (meth) acrylic resin preferably has an ester group at the terminal in that the photosensitive composition layer after transfer is excellent in developability.
  • the terminal portion of the (meth) acrylic resin is composed of a site derived from the polymerization initiator used in the synthesis.
  • a (meth) acrylic resin having an ester group at the terminal can be synthesized by using a polymerization initiator that generates a radical having an ester group.
  • the binder polymer is an acrylic soluble resin.
  • alkali-soluble means that the solubility of sodium carbonate in 100 g of a 1% by mass aqueous solution at 22 ° C. is 0.1 g or more.
  • the binder polymer is preferably, for example, a binder polymer having an acid value of 60 mgKOH / g or more from the viewpoint of developability.
  • the binder polymer is, for example, a resin having a carboxy group having an acid value of 60 mgKOH / g or more (so-called carboxy group-containing resin) from the viewpoint that it is easily crosslinked with the crosslinked component by heating to form a strong film.
  • the binder polymer is a resin having a carboxy group
  • the three-dimensional crosslink density can be increased by, for example, adding a thermally crosslinkable compound such as a blocked isocyanate compound to thermally crosslink the binder polymer.
  • a thermally crosslinkable compound such as a blocked isocyanate compound
  • the carboxy group-containing (meth) acrylic resin having an acid value of 60 mgKOH / g or more is not particularly limited as long as the above acid value conditions are satisfied, and can be appropriately selected from known (meth) acrylic resins.
  • carboxy group-containing acrylic resins having an acid value of 60 mgKOH / g or more paragraphs [0033] to [0052] of JP-A-2010-237589.
  • a carboxy group-containing acrylic resin having an acid value of 60 mgKOH / g or more can be preferably used.
  • the binder polymer is a styrene-acrylic copolymer.
  • the styrene-acrylic copolymer refers to a resin having a structural unit derived from a styrene compound and a structural unit derived from a (meth) acrylic compound, and the structural unit derived from the styrene compound.
  • the total content of the structural units derived from the (meth) acrylic compound is preferably 30% by mass or more, more preferably 50% by mass or more, based on all the structural units of the copolymer.
  • the lower limit is not particularly limited, but is preferably 100% by mass or less.
  • the content of the structural unit derived from the styrene compound is preferably 1% by mass or more, more preferably 5% by mass or more, still more preferably 5 to 80% by mass, based on all the structural units of the copolymer.
  • the content of the structural unit derived from the (meth) acrylic compound is preferably 5% by mass or more, more preferably 10% by mass or more, and 20 to 95% by mass, based on all the structural units of the copolymer. Is more preferable.
  • the binder polymer preferably has an aromatic ring structure, and more preferably has a structural unit having an aromatic ring structure, from the viewpoint that the effect of the present invention is more excellent.
  • the monomers forming the structural unit having an aromatic ring structure include a monomer having an aralkyl group, styrene, and a polymerizable styrene derivative (for example, methylstyrene, vinyltoluene, tert-butoxystyrene, acetoxystyrene, 4-vinylbenzoic acid). , Styrene dimer, styrene trimmer, etc.). Of these, a monomer having an aralkyl group or styrene is preferable.
  • aralkyl group examples include a substituted or unsubstituted phenylalkyl group (excluding a benzyl group), a substituted or unsubstituted benzyl group and the like, and a substituted or unsubstituted benzyl group is preferable.
  • Examples of the monomer having a phenylalkyl group include phenylethyl (meth) acrylate and the like.
  • Examples of the monomer having a benzyl group include (meth) acrylate having a benzyl group, for example, benzyl (meth) acrylate, and chlorobenzyl (meth) acrylate; a vinyl monomer having a benzyl group, for example, vinylbenzyl chloride, and the like. Examples include vinylbenzyl alcohol. Of these, benzyl (meth) acrylate is preferable. Further, it is more preferable that the binder polymer has a structural unit (constituent unit derived from styrene) represented by the following formula (S) from the viewpoint that the effect of the present invention is more excellent.
  • S structural unit represented by the following formula (S) from the viewpoint that the effect of the present invention is more excellent.
  • the content of the structural unit having an aromatic ring structure is 5 to 90 mass with respect to all the structural units of the binder polymer because the effect of the present invention is more excellent. % Is preferable, 10 to 70% by mass is more preferable, and 20 to 60% by mass is further preferable. Further, the content of the structural unit having an aromatic ring structure in the binder polymer is preferably 5 to 70 mol%, preferably 10 to 60 mol%, based on all the structural units of the binder polymer, from the viewpoint of further excellent effect of the present invention. Is more preferable, and 20 to 60 mol% is further preferable.
  • the content of the structural unit represented by the above formula (S) in the binder polymer is preferably 5 to 70 mol% with respect to all the structural units of the binder polymer from the viewpoint of further excellent effect of the present invention. -60 mol% is more preferred, and 20-60 mol% is even more preferred.
  • the above “constituent unit” shall be synonymous with the "monomer unit”.
  • the above-mentioned "monomer unit” may be modified after polymerization by a polymer reaction or the like. The same applies to the following.
  • the binder polymer preferably has a monocyclic aliphatic hydrocarbon ring structure or a polycyclic aliphatic hydrocarbon ring structure from the viewpoint that the effect of the present invention is more excellent. That is, the binder polymer preferably has a structural unit having a monocyclic or polycyclic aliphatic hydrocarbon ring structure. Among them, the binder polymer more preferably has a polycyclic aliphatic hydrocarbon ring structure, and further preferably has a ring structure in which two or more aliphatic hydrocarbon rings are fused.
  • Examples of the ring constituting the aliphatic hydrocarbon ring structure in the structural unit having the aliphatic hydrocarbon ring structure include a tricyclodecane ring, a cyclohexane ring, a cyclopentane ring, a norbornane ring, and an isoborone ring.
  • a ring in which two or more aliphatic hydrocarbon rings are condensed is preferable because the effect of the present invention is more excellent, and a tetrahydrodicyclopentadiene ring (tricyclo [5.2.1.0 2,6 ] decane) is preferable. Ring) is more preferred.
  • the monomer forming a structural unit having an aliphatic hydrocarbon ring structure examples include dicyclopentanyl (meth) acrylate, cyclohexyl (meth) acrylate, and isobornyl (meth) acrylate.
  • the binder polymer more preferably has a structural unit represented by the following formula (Cy), and the structural unit represented by the above formula (S) and the following formula. It is more preferable to have a structural unit represented by (Cy).
  • RM represents a hydrogen atom or a methyl group
  • RCy represents a monovalent group having an aliphatic hydrocarbon ring structure.
  • the aliphatic hydrocarbon ring structure in RCy of the formula ( Cy ) may be a monocyclic aliphatic hydrocarbon ring structure or a polycyclic aliphatic hydrocarbon ring structure.
  • the RM in the formula ( Cy ) is preferably a methyl group.
  • the RCy in the formula ( Cy ) is preferably a monovalent group having an aliphatic hydrocarbon ring structure having 5 to 20 carbon atoms, and a fat having 6 to 16 carbon atoms, because the effect of the present invention is more excellent. It is more preferably a monovalent group having a group hydrocarbon ring structure, and even more preferably a monovalent group having an aliphatic hydrocarbon ring structure having 8 to 14 carbon atoms.
  • aliphatic hydrocarbon ring structure in RCy of the formula ( Cy ) a monocyclic aliphatic ring structure such as a cyclopentane ring structure, a cyclohexane ring structure, or an isoborone ring structure is obtained because the effect of the present invention is more excellent. It is preferably a polycyclic aliphatic hydrocarbon ring structure such as a hydrocarbon ring structure, a tetrahydrodicyclopentadiene ring structure, or a norbornane ring structure, and is a cyclohexane ring structure or a tetrahydrodicyclopentadiene ring structure.
  • the aliphatic hydrocarbon ring structure in RCy of the formula ( Cy ) is preferably a polycyclic aliphatic hydrocarbon ring because the effect of the present invention is more excellent, and is preferably a polycyclic aliphatic hydrocarbon ring.
  • a ring structure in which the ring is condensed is more preferable, and a ring in which 2 to 4 aliphatic hydrocarbon rings are fused is further preferable.
  • the binder polymer may have one type of structural unit having an aliphatic hydrocarbon ring structure alone, or may have two or more types.
  • the content of the structural unit having an aliphatic hydrocarbon ring structure is higher than that of all the structural units of the binder polymer because the effect of the present invention is more excellent. 5 to 90% by mass is preferable, 10 to 80% by mass is more preferable, and 20 to 70% by mass is further preferable.
  • the content of the constituent unit having an aliphatic hydrocarbon ring structure in the binder polymer is preferably 5 to 70 mol% with respect to all the constituent units of the binder polymer from the viewpoint of further excellent effect of the present invention, and is preferably 10 to 70 mol%. 60 mol% is more preferable, and 20 to 60 mol% is further preferable. Further, the content of the structural unit represented by the above formula (Cy) in the binder polymer is preferably 5 to 70 mol% with respect to all the structural units of the binder polymer from the viewpoint of further excellent effect of the present invention. -60 mol% is more preferred, and 20-60 mol% is even more preferred.
  • the binder polymer has a structural unit having an aromatic ring structure and a structural unit having an aliphatic hydrocarbon ring structure
  • the total content of the structural unit having an aromatic ring structure and the structural unit having an aliphatic hydrocarbon ring structure is the present.
  • 10 to 90% by mass is preferable, 20 to 80% by mass is more preferable, and 30 to 75% by mass is further preferable, based on all the structural units of the binder polymer.
  • the total content of the structural unit having an aromatic ring structure and the structural unit having an aliphatic hydrocarbon ring structure in the binder polymer is 10 with respect to all the structural units of the binder polymer because the effect of the present invention is more excellent.
  • the total content of the structural unit represented by the above formula (S) and the structural unit represented by the above formula (Cy) in the binder polymer is the total structural unit of the binder polymer from the viewpoint that the effect of the present invention is more excellent.
  • 10 to 80 mol% is preferable, 20 to 70 mol% is more preferable, and 30 to 60 mol% is further preferable.
  • the molar amount nS of the structural unit represented by the above formula (S) and the molar amount nCy of the structural unit represented by the above formula (Cy) in the binder polymer are given by the following formulas because the effects of the present invention are more excellent. It is preferable to satisfy the relationship shown in (SCy), more preferably to satisfy the following formula (SCy-1), and further preferably to satisfy the following formula (SCy-2).
  • the binder polymer preferably has a structural unit having an acid group because the effect of the present invention is more excellent.
  • the acid group include a carboxy group, a sulfo group, a phosphonic acid group, and a phosphoric acid group, and a carboxy group is preferable.
  • the structural unit having the acid group the structural unit derived from (meth) acrylic acid shown below is preferable, and the structural unit derived from methacrylic acid is more preferable.
  • the binder polymer may have one type of structural unit having an acid group alone or two or more types.
  • the content of the structural unit having an acid group is 5 to 50% by mass with respect to all the structural units of the binder polymer because the effect of the present invention is more excellent. It is preferable, 5 to 40% by mass is more preferable, and 10 to 30% by mass is further preferable.
  • the content of the constituent unit having an acid group in the binder polymer is preferably 5 to 70 mol%, preferably 10 to 50 mol%, based on all the constituent units of the binder polymer, from the viewpoint of further excellent effect of the present invention. More preferably, 15-40 mol% is even more preferable.
  • the content of the structural unit derived from (meth) acrylic acid in the binder polymer is preferably 5 to 70 mol% with respect to all the structural units of the binder polymer from the viewpoint of further excellent effect of the present invention, and is preferably 10 to 50. More preferably, mol%, more preferably 15-40 mol%.
  • the binder polymer preferably has a reactive group, and more preferably has a structural unit having a reactive group, from the viewpoint that the effect of the present invention is more excellent.
  • a reactive group a radically polymerizable group is preferable, and an ethylenically unsaturated group is more preferable.
  • the binder polymer preferably has a structural unit having an ethylenically unsaturated group in the side chain.
  • the "main chain” represents a relatively longest bound chain among the molecules of the polymer compound constituting the resin
  • the "side chain” represents an atomic group branched from the main chain. ..
  • a (meth) acrylic group is preferable, and a (meth) acryloyl group is more preferable.
  • structural units having a reactive group include, but are not limited to, those shown below.
  • the binder polymer may have one type of structural unit having a reactive group alone or two or more types.
  • the content of the structural unit having a reactive group is 5 to 70 mass by mass with respect to all the structural units of the binder polymer because the effect of the present invention is more excellent. % Is preferable, 10 to 50% by mass is more preferable, and 20 to 40% by mass is further preferable.
  • the content of the structural unit having a reactive group in the binder polymer is preferably 5 to 70 mol%, preferably 10 to 60 mol%, based on all the structural units of the binder polymer, from the viewpoint of further excellent effect of the present invention. Is more preferable, and 20 to 50 mol% is further preferable.
  • a functional group such as a hydroxy group, a carboxy group, a primary amino group, a secondary amino group, an acetoacetyl group, and a sulfo group, an epoxy compound, and a blocked isocyanate are used.
  • a functional group such as a hydroxy group, a carboxy group, a primary amino group, a secondary amino group, an acetoacetyl group, and a sulfo group, an epoxy compound, and a blocked isocyanate.
  • examples thereof include a method of reacting a compound such as a compound, an isocyanate compound, a vinyl sulfone compound, an aldehyde compound, a methylol compound, and a carboxylic acid anhydride.
  • a preferred example of a means for introducing a reactive group into a binder polymer is that a polymer having a carboxy group is synthesized by a polymerization reaction and then glycidyl (meth) acrylate is added to a part of the carboxy group of the obtained polymer by the polymer reaction.
  • a means for introducing a (meth) acryloxy group into a polymer by reacting with the polymer By this means, a binder polymer having a (meth) acryloxy group in the side chain can be obtained.
  • the polymerization reaction is preferably carried out under a temperature condition of 70 to 100 ° C., and more preferably carried out under a temperature condition of 80 to 90 ° C.
  • an azo-based initiator is preferable, and for example, V-601 (trade name) or V-65 (trade name) manufactured by Wako Pure Chemical Industries, Ltd. is more preferable.
  • the polymer reaction is preferably carried out under temperature conditions of 80 to 110 ° C. In the above polymer reaction, it is preferable to use a catalyst such as an ammonium salt.
  • the binder polymer As the binder polymer, the polymers shown below are preferable because the effects of the present invention are more excellent.
  • the content ratios (a to d) and the weight average molecular weight Mw of each structural unit shown below can be appropriately changed according to the purpose.
  • the content ratio a of each structural unit shown below is preferably 20 to 60% by mass with respect to all the structural units of the following binder polymer.
  • b is preferably 10 to 50% by mass with respect to all the constituent units of the following binder polymers.
  • c is preferably 5.0 to 25% by mass with respect to all the constituent units of the following binder polymers.
  • d is preferably 10 to 50% by mass with respect to all the constituent units of the following binder polymers.
  • the content ratio a of each structural unit shown below is preferably 20 to 60% by mass with respect to all the structural units of the following binder polymer.
  • b is preferably 10 to 50% by mass with respect to all the constituent units of the following binder polymers.
  • c is preferably 5.0 to 25% by mass with respect to all the constituent units of the following binder polymers.
  • d is preferably 10 to 50% by mass with respect to all the constituent units of the following binder polymers.
  • the content ratio a of each structural unit shown below is preferably 30 to 65% by mass with respect to all the structural units of the following binder polymer.
  • b is preferably 1.0 to 20% by mass with respect to all the constituent units of the following binder polymers.
  • c is preferably 5.0 to 25% by mass with respect to all the constituent units of the following binder polymers.
  • d is preferably 10 to 50% by mass with respect to all the constituent units of the following binder polymers.
  • the content ratio a of each structural unit shown below is preferably 1.0 to 20% by mass with respect to all the structural units of the following binder polymer.
  • b is preferably 20 to 60% by mass with respect to all the constituent units of the following binder polymers.
  • c is preferably 5.0 to 25% by mass with respect to all the constituent units of the following binder polymers.
  • d is preferably 10 to 50% by mass with respect to all the constituent units of the following binder polymers.
  • the binder polymer may contain a polymer having a structural unit having a carboxylic acid anhydride structure (hereinafter, also referred to as “polymer X”).
  • the carboxylic acid anhydride structure may be either a chain carboxylic acid anhydride structure or a cyclic carboxylic acid anhydride structure, but a cyclic carboxylic acid anhydride structure is preferable.
  • a cyclic carboxylic acid anhydride structure As the ring having a cyclic carboxylic acid anhydride structure, a 5- to 7-membered ring is preferable, a 5-membered ring or a 6-membered ring is more preferable, and a 5-membered ring is further preferable.
  • the structural unit having a carboxylic acid anhydride structure is a structural unit containing a divalent group obtained by removing two hydrogen atoms from the compound represented by the following formula P-1 in the main chain, or the following formula P-1. It is preferable that the monovalent group obtained by removing one hydrogen atom from the represented compound is a structural unit bonded to the main chain directly or via a divalent linking group.
  • RA1a represents a substituent
  • n1a RA1a may be the same or different
  • Examples of the substituent represented by RA1a include an alkyl group.
  • Z 1a an alkylene group having 2 to 4 carbon atoms is preferable, an alkylene group having 2 or 3 carbon atoms is more preferable, and an alkylene group having 2 carbon atoms is further preferable.
  • n 1a represents an integer of 0 or more.
  • Z 1a represents an alkylene group having 2 to 4 carbon atoms
  • n 1a is preferably an integer of 0 to 4, more preferably an integer of 0 to 2, and even more preferably 0.
  • a plurality of RA1a may be the same or different. Further, although a plurality of RA1a may be bonded to each other to form a ring, it is preferable that the RA1a are not bonded to each other to form a ring.
  • a structural unit derived from an unsaturated carboxylic acid anhydride is preferable, a structural unit derived from an unsaturated cyclic carboxylic acid anhydride is more preferable, and an unsaturated aliphatic cyclic carboxylic acid is preferable.
  • a structural unit derived from an acid anhydride is more preferable, a structural unit derived from maleic anhydride or an itaconic acid anhydride is particularly preferable, and a structural unit derived from maleic anhydride is most preferable.
  • Rx represents a hydrogen atom, a methyl group, a CH 2 OH group, or CF 3 groups
  • Me represents a methyl group.
  • the structural unit having a carboxylic acid anhydride structure in the polymer X may be one kind alone or two or more kinds.
  • the total content of the structural units having a carboxylic acid anhydride structure is preferably 0 to 60 mol%, more preferably 5 to 40 mol%, and further preferably 10 to 35 mol% with respect to all the structural units of the polymer X. preferable.
  • the photosensitive composition layer may contain only one kind of polymer X, or may contain two or more kinds of polymer X.
  • the content of the polymer X is 0.10 to 30.00 with respect to the total mass of the photosensitive composition layer because the effect of the present invention is more excellent.
  • the mass% is preferable, 0.20 to 20.00 mass% is more preferable, 0.20 to 5.00 mass% is further preferable, and 0.50 to 1.50 mass% is particularly preferable.
  • the binder polymer polymer A is also preferable.
  • the photosensitive composition layer is preferably a negative photosensitive composition layer.
  • the polymer A is preferably an alkali-soluble resin.
  • the acid value of the polymer A is preferably 220 mgKOH / g or less, more preferably less than 200 mgKOH / g, and 190 mgKOH / g from the viewpoint of better resolution by suppressing the swelling of the photosensitive composition layer by the developing solution. Less than g is more preferable.
  • the lower limit of the acid value of the polymer A is not particularly limited, but from the viewpoint of better developability, 60 mgKOH / g or more is preferable, 120 mgKOH / g or more is more preferable, 150 mgKOH / g or more is further preferable, and 170 mgKOH / g or more is more preferable. Especially preferable.
  • the acid value (mgKOH / g) is the mass [mg] of potassium hydroxide required to neutralize 1 g of the sample.
  • the acid value can be calculated, for example, from the average content of acid groups in the compound.
  • the acid value of the polymer A may be adjusted according to the type of the structural unit constituting the polymer A and the content of the structural unit containing the acid group.
  • the weight average molecular weight of the polymer A is preferably 5,000 to 500,000. When the weight average molecular weight is 500,000 or less, it is preferable from the viewpoint of improving resolution and developability.
  • the weight average molecular weight is more preferably 100,000 or less, further preferably 60,000 or less.
  • the weight average molecular weight is more preferably 10,000 or more, further preferably 20,000 or more, and particularly preferably 30,000 or more.
  • the edge fuse property refers to the degree of ease with which the photosensitive composition layer protrudes from the end face of the roll when it is wound into a roll as a negative photosensitive resin laminate.
  • the cut chip property refers to the degree of ease of chip flying when the unexposed film is cut with a cutter. When this chip adheres to the upper surface of the negative photosensitive resin laminate or the like, it is transferred to the mask in a later exposure step or the like, which causes a defective product.
  • the dispersity of the polymer A is preferably 1.0 to 6.0, more preferably 1.0 to 5.0, still more preferably 1.0 to 4.0, and particularly preferably 1.0 to 3.0. ..
  • the polymer A is a structural unit based on a monomer having an aromatic hydrocarbon group. It is preferable to include it.
  • aromatic hydrocarbon groups include substituted or unsubstituted phenyl groups and substituted or unsubstituted aralkyl groups.
  • the content of the structural unit based on the monomer having an aromatic hydrocarbon group in the polymer A is preferably 20% by mass or more, more preferably 30% by mass or more, based on the total mass of the polymer A.
  • the upper limit is not particularly limited, but is preferably 95% by mass or less, more preferably 85% by mass or less, based on the total mass of the polymer A.
  • the average value of the content of the structural unit based on the monomer having an aromatic hydrocarbon group is within the above range.
  • the monomer having an aromatic hydrocarbon group examples include a monomer having an aralkyl group, styrene, and a polymerizable styrene derivative (for example, methylstyrene, vinyltoluene, tert-butoxystyrene, acetoxystyrene, 4-vinyl benzoic acid). Acids, styrene dimers, styrene trimers, etc.). Of these, a monomer having an aralkyl group or styrene is preferable.
  • the content of the structural unit based on styrene is 20 to 70% by mass with respect to the total mass of the polymer A. Is preferable, 25 to 65% by mass is more preferable, 30 to 60% by mass is further preferable, and 30 to 55% by mass is particularly preferable.
  • aralkyl group examples include a substituted or unsubstituted phenylalkyl group (excluding a benzyl group), a substituted or unsubstituted benzyl group and the like, and a substituted or unsubstituted benzyl group is preferable.
  • Examples of the monomer having a phenylalkyl group include phenylethyl (meth) acrylate.
  • the polymer A containing a structural unit based on a monomer having an aromatic hydrocarbon group includes a monomer having an aromatic hydrocarbon group, at least one of the first monomers described later, and / or described below. It is preferably obtained by polymerizing with at least one of the second monomers.
  • the polymer A containing no structural unit based on a monomer having an aromatic hydrocarbon group is preferably obtained by polymerizing at least one of the first monomers described later, and is preferably the first single amount. It is more preferable to obtain it by copolymerizing at least one kind of the body and at least one kind of the second monomer described later.
  • the first monomer is a monomer having a carboxyl group in the molecule.
  • the first monomer include (meth) acrylic acid, fumaric acid, cinnamic acid, crotonic acid, itaconic acid, 4-vinylbenzoic acid, maleic acid anhydride, and maleic acid semi-ester.
  • (meth) acrylic acid is preferable.
  • the content of the structural unit based on the first monomer in the polymer A is preferably 5 to 50% by mass, more preferably 10 to 40% by mass, and 10 to 30% by mass with respect to the total mass of the polymer A. % Is more preferable.
  • the content is 5% by mass or more from the viewpoint of exhibiting good developability, controlling edge fuseability, and the like. It is preferable that the content is 50% by mass or less from the viewpoint of high resolution of the resist pattern and the shape of the resist pattern, and further from the viewpoint of chemical resistance of the resist pattern.
  • the second monomer is a monomer that is non-acidic and has at least one polymerizable unsaturated group in the molecule.
  • Examples of the second monomer include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, and isobutyl (meth) acrylate.
  • Esters of vinyl alcohols such as vinyl; (meth) acrylonitrile can be mentioned.
  • methyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, or n-butyl (meth) acrylate is preferable, and methyl (meth) acrylate is more preferable.
  • the content of the structural unit based on the second monomer in the polymer A is preferably 5 to 90% by mass, more preferably 15 to 60% by mass, and 20 to 45% by mass with respect to the total mass of the polymer A. % Is more preferable.
  • the polymer A contains a monomer-based structural unit having an aralkyl group and / or a styrene-based monomer-based structural unit, it suppresses line width thickening and deterioration of resolution when the focal position shifts during exposure. It is preferable from the viewpoint of For example, a copolymer containing a methacrylic acid-based constituent unit, a benzyl methacrylate-based constituent unit, and a styrene-based constituent unit, a methacrylic acid-based constituent unit, a methyl methacrylate-based constituent unit, a benzyl methacrylate-based constituent unit, and a styrene.
  • the polymer A has 25 to 55% by mass of a structural unit based on a monomer having an aromatic hydrocarbon group, 20 to 35% by mass of a structural unit based on the first monomer, and a second. It is preferably a polymer containing 15 to 45% by mass of a constituent unit based on a monomer. In another embodiment, the polymer contains 70 to 90% by mass of a structural unit based on a monomer having an aromatic hydrocarbon group and 10 to 25% by mass of a structural unit based on the first monomer. Is preferable.
  • the polymer A may have a branched structure and / or an alicyclic structure in the side chain.
  • a monomer having a group having a branched structure in the side chain or a monomer having a group having an alicyclic structure in the side chain can be introduced into the side chain of the polymer A. ..
  • Specific examples of the monomer containing a group having a branched structure in the side chain include (meth) acrylate i-propyl, (meth) acrylate i-butyl, (meth) acrylate s-butyl, and (meth) acrylate t.
  • the monomer having a group having an alicyclic structure in the side chain include a monomer having a monocyclic aliphatic hydrocarbon group and a monomer having a polycyclic aliphatic hydrocarbon group.
  • (meth) acrylate having an alicyclic hydrocarbon group having 5 to 20 carbon atoms can be mentioned. More specific examples include (meth) acrylic acid (bicyclo [2.2.1] heptyl-2), (meth) acrylic acid-1-adamantyl, (meth) acrylic acid-2-adamantyl, (meth).
  • the polymer A may be used alone or in combination of two or more.
  • two kinds of polymers A containing a structural unit based on a monomer having an aromatic hydrocarbon group are mixed and used, or based on a monomer having an aromatic hydrocarbon group.
  • the ratio of the polymer A containing the structural unit based on the monomer having an aromatic hydrocarbon group is preferably 50% by mass or more, preferably 70% by mass or more, based on the total mass of the polymer A. More preferably, 80% by mass or more is further preferable, and 90% by mass or more is particularly preferable.
  • the upper limit is not particularly limited, and is preferably 100% by mass or less.
  • a radical polymerization initiator such as benzoyl peroxide and azoisobutyronitrile is prepared by diluting the above-mentioned one or more monomers with a solvent such as acetone, methyl ethyl ketone, and isopropanol. Is preferably added in an appropriate amount and heated and stirred. In some cases, a part of the mixture is added dropwise to the reaction solution for synthesis. After completion of the reaction, a solvent may be further added to adjust the concentration to a desired level.
  • a solvent may be further added to adjust the concentration to a desired level.
  • the synthesis means bulk polymerization, suspension polymerization, or emulsion polymerization may be used in addition to solution polymerization.
  • the glass transition temperature Tg of the polymer A is preferably 30 to 135 ° C.
  • the Tg of the polymer A is more preferably 130 ° C. or lower, further preferably 120 ° C. or lower, and particularly preferably 110 ° C. or lower.
  • the polymer A having a Tg of 30 ° C. or higher from the viewpoint of improving the edge fuse resistance.
  • the Tg of the polymer A is more preferably 40 ° C. or higher, further preferably 50 ° C. or higher, particularly preferably 60 ° C. or higher, and most preferably 70 ° C. or higher.
  • the photosensitive composition layer may contain a resin other than the above as the polymer A.
  • resins include acrylic resin, styrene-acrylic copolymer, polyurethane resin, polyvinyl alcohol, polyvinyl formal, polyamide resin, polyester resin, polyamide resin, epoxy resin, polyacetal resin, polyhydroxystyrene resin, polyimide resin, and poly. Examples thereof include benzoxazole resin, polysiloxane resin, polyethyleneimine, polyallylamine, and polyalkylene glycol.
  • the photosensitive composition layer may contain only one kind of binder polymer, or may contain two or more kinds of binder polymers.
  • the content of the binder polymer is preferably 10.00 to 90.00% by mass, and 30.00 to 80.00% by mass, based on the total mass of the photosensitive composition layer, because the effect of the present invention is more excellent. Is more preferable, 40.00 to 70.00% by mass is further preferable, and 45.00 to 60.00% by mass is particularly preferable.
  • the photosensitive composition layer may contain a polymerization initiator.
  • the polymerization initiator is not particularly limited, and a known polymerization initiator can be used.
  • a photopolymerization initiator or a thermal polymerization initiator is preferable.
  • the polymerization initiator may be a radical polymerization initiator or a cationic polymerization initiator.
  • Examples of the polymerization initiator include a photopolymerization initiator having an oxime ester structure (hereinafter, also referred to as “oxym-based photopolymerization initiator”) and a photopolymerization initiator having an ⁇ -aminoalkylphenone structure (hereinafter, “ ⁇ -amino”).
  • alkylphenone-based photopolymerization initiator a photopolymerization initiator having an ⁇ -hydroxyalkylphenone structure (hereinafter also referred to as “ ⁇ -hydroxyalkylphenone-based polymerization initiator”), and an acylphosphine oxide structure.
  • Photopolymerization initiator hereinafter, also referred to as “acylphosphine oxide-based photopolymerization initiator”
  • photopolymerization initiator having an N-phenylglycine structure hereinafter, also referred to as "N-phenylglycine-based photopolymerization initiator”
  • the photosensitive composition layer contains a 2,4,5-triarylimidazole dimer as a photoradical polymerization initiator from the viewpoints of photosensitive, visibility of exposed and unexposed areas, and resolution. It is preferable to contain at least one selected from the group consisting of the derivatives.
  • the two 2,4,5-triarylimidazole structures in the 2,4,5-triarylimidazole dimer and its derivatives may be the same or different. Examples of the derivative of 2,4,5-triarylimidazole dimer include 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer and 2- (o-chlorophenyl) -4,5-di.
  • the polymerization initiator is selected from the group consisting of an oxime-based photopolymerization initiator, an ⁇ -aminoalkylphenone-based photopolymerization initiator, an ⁇ -hydroxyalkylphenone-based polymerization initiator, and an N-phenylglycine-based photopolymerization initiator. It preferably contains at least one, and preferably contains at least one selected from the group consisting of an oxime-based photopolymerization initiator, an ⁇ -aminoalkylphenone-based photopolymerization initiator, and an N-phenylglycine-based photopolymerization initiator. Is more preferable, and it is further preferable to contain at least one selected from the group consisting of an oxime-based photopolymerization initiator and an ⁇ -aminoalkylphenone-based photopolymerization initiator.
  • polymerization initiator examples include the polymerization initiators described in paragraphs [0031] to [0042] of JP-A-2011-95716 and paragraphs [0064] to [0081] of JP-A-2015-014783. Can be mentioned.
  • polymerization initiator examples include 1- [4- (phenylthio)] phenyl-1,2-octanedione-2- (O-benzoyloxime) [trade name: IRGACURE (registered trademark) OXE-01, manufactured by BASF).
  • the photocationic polymerization initiator is a compound that generates an acid by receiving active light rays.
  • a compound that is sensitive to active light having a wavelength of 300 nm or more, preferably a wavelength of 300 to 450 nm and generates an acid is preferable, but its chemical structure is not limited.
  • a photocationic polymerization initiator that is not directly sensitive to active light with a wavelength of 300 nm or more is also a sensitizer if it is a compound that is sensitive to active light with a wavelength of 300 nm or more and generates an acid when used in combination with a sensitizer. Can be preferably used in combination with.
  • a photocationic polymerization initiator that generates an acid having a pKa of 4 or less is preferable, a photocationic polymerization initiator that generates an acid having a pKa of 3 or less is more preferable, and an acid having a pKa of 2 or less is used.
  • the generated photocationic polymerization initiator is particularly preferred.
  • the lower limit of pKa is not particularly defined, but is preferably -10.0 or higher, for example.
  • Examples of the photocationic polymerization initiator include an ionic photocationic polymerization initiator and a nonionic photocationic polymerization initiator.
  • Examples of the ionic photocationic polymerization initiator include onium salt compounds such as diaryliodonium salts and triarylsulfonium salts, and quaternary ammonium salts.
  • the ionic photocationic polymerization initiator described in paragraphs 0114 to 0133 of JP-A-2014-085643 may be used.
  • nonionic photocationic polymerization initiator examples include trichloromethyl-s-triazines, diazomethane compounds, imide sulfonate compounds, and oxime sulfonate compounds.
  • trichloromethyl-s-triazines the diazomethane compound and the imide sulfonate compound
  • the compounds described in paragraphs 0083 to 886 of JP-A-2011-22149 may be used.
  • the oxime sulfonate compound the compound described in paragraphs 0083 to 0088 of International Publication No. 2018/179640 may be used.
  • the photosensitive composition layer preferably contains a photoradical polymerization initiator, and more preferably contains at least one selected from the group consisting of 2,4,5-triarylimidazole dimers and derivatives thereof.
  • the polymerization initiator may be used alone or in combination of two or more.
  • the content of the polymerization initiator in the photosensitive composition layer is not particularly limited, but is preferably 0.10% by mass or more, more preferably 0.50% by mass or more, based on the total mass of the photosensitive composition layer.
  • the upper limit is not particularly limited, and is preferably 10.00% by mass or less, more preferably 5.00% by mass or less, based on the total mass of the photosensitive composition layer.
  • the photosensitive composition layer may contain a polymerizable compound.
  • the polymerizable compound is a compound having a polymerizable group. Examples of the polymerizable group include a radically polymerizable group and a cationically polymerizable group, and a radically polymerizable group is preferable.
  • the polymerizable compound preferably contains a radically polymerizable compound having an ethylenically unsaturated group (hereinafter, also simply referred to as “ethylenically unsaturated compound”).
  • ethylenically unsaturated compound a (meth) acryloxy group is preferable.
  • the ethylenically unsaturated compound is a compound other than the above binder polymer, and preferably has a molecular weight of less than 5,000.
  • a compound represented by the following formula (M) (simply also referred to as “Compound M”) is preferable.
  • Q2 -R 1a -Q 1 set (M) Q 1 and Q 2 each independently represent a (meth) acryloyloxy group, and R 1 represents a divalent linking group having a chain structure.
  • Q 1 and Q 2 in the formula (M) have the same group as Q 1 and Q 2 from the viewpoint of ease of synthesis. Further, Q 1 and Q 2 in the formula (M) are preferably acryloyloxy groups from the viewpoint of reactivity.
  • R 1a in the formula (M) an alkylene group, an alkyleneoxyalkylene group (-L 1 -OL 1- ), or a polyalkylene oxyalkylene group (-(L)" is used because the effect of the present invention is more excellent.
  • a hydrocarbon group having 2 to 20 carbon atoms or a polyalkyleneoxyalkylene group is more preferable, an alkylene group having 4 to 20 carbon atoms is further preferable, and an alkylene group having 6 to 20 carbon atoms is more preferable. Eighteen linear alkylene groups are particularly preferred.
  • the hydrocarbon group may have a chain structure at least partially, and the portion other than the chain structure is not particularly limited, and is, for example, a branched chain, cyclic, or having 1 to 1 to carbon atoms.
  • It may be any of 5 linear alkylene groups, arylene groups, ether bonds, and combinations thereof, and the alkylene group or the group in which two or more alkylene groups and one or more arylene groups are combined is used.
  • an alkylene group is more preferred, and a linear alkylene group is even more preferred.
  • the above L 1 independently represents an alkylene group, and an ethylene group, a propylene group, or a butylene group is preferable, and an ethylene group or a 1,2-propylene group is more preferable.
  • p represents an integer of 2 or more, and an integer of 2 to 10 is preferable.
  • the number of atoms of the shortest connecting chain for connecting Q1 and Q2 in compound M is preferably 3 to 50, more preferably 4 to 40, from the viewpoint of further excellent effect of the present invention. 6 to 20 are more preferable, and 8 to 12 are particularly preferable.
  • “the number of atoms in the shortest connecting chain connecting between Q1 and Q2" is the shortest linking from the atom in R1 connected to Q1 to the atom in R1 connected to Q2 . The number of atoms in.
  • Examples of the compound M include 1,3-butanediol di (meth) acrylate, tetramethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, and 1,6-hexanediol di (meth) acrylate.
  • the compound M includes 1,6-hexanediol di (meth) acrylate, 1,9-nonane diol di (meth) acrylate, and 1,10-decane di (meth) acrylate. It is preferably at least one compound selected from the group consisting of meta) acrylate and neopentyl glycol di (meth) acrylate, preferably 1,6-hexanediol di (meth) acrylate and 1,9-nonane diol di.
  • it is at least one compound selected from the group consisting of (meth) acrylate and 1,10-decanediol di (meth) acrylate, with 1,9-nonanediol di (meth) acrylate, and More preferably, it is at least one compound selected from the group consisting of 1,10-decanediol di (meth) acrylate.
  • a bifunctional or higher functional ethylenically unsaturated compound is preferable.
  • the term "bifunctional or higher functional ethylenically unsaturated compound” means a compound having two or more ethylenically unsaturated groups in one molecule.
  • a (meth) acryloyl group is preferable.
  • a (meth) acrylate compound is preferable.
  • the bifunctional ethylenically unsaturated compound is not particularly limited and may be appropriately selected from known compounds.
  • Examples of the bifunctional ethylenically unsaturated compound other than the compound M include tricyclodecanedimethanol di (meth) acrylate and tricyclodecanedimenanol di (meth) acrylate.
  • bifunctional ethylenically unsaturated compounds include, for example, tricyclodecanedimethanol diacrylate (trade name: NK ester A-DCP, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.) and tricyclodecanedimenanoldi.
  • Methacrylate (trade name: NK ester DCP, manufactured by Shin Nakamura Chemical Industry Co., Ltd.), 1,9-nonanediol diacrylate (trade name: NK ester A-NOD-N, manufactured by Shin Nakamura Chemical Industry Co., Ltd.), and Examples thereof include 1,6-hexanediol diacrylate (trade name: NK ester A-HD-N, manufactured by Shin Nakamura Chemical Industry Co., Ltd.).
  • the trifunctional or higher functional ethylenically unsaturated compound is not particularly limited and may be appropriately selected from known compounds.
  • Examples of the trifunctional or higher functional ethylenically unsaturated compound include dipentaerythritol (tri / tetra / penta / hexa) (meth) acrylate, pentaerythritol (tri / tetra) (meth) acrylate, and trimethylolpropane tri (meth) acrylate.
  • Examples thereof include ditrimethylolpropane tetra (meth) acrylate, isocyanuric acid (meth) acrylate, and (meth) acrylate compound having a glycerintri (meth) acrylate skeleton.
  • (tri / tetra / penta / hexa) (meth) acrylate) is a concept including tri (meth) acrylate, tetra (meth) acrylate, penta (meth) acrylate, and hexa (meth) acrylate.
  • (Tri / tetra) (meth) acrylate” is a concept that includes tri (meth) acrylate and tetra (meth) acrylate.
  • Examples of the polymerizable compound include a caprolactone-modified compound of a (meth) acrylate compound (KAYARAD® DPCA-20 manufactured by Nippon Kayaku Co., Ltd., A-9300-1CL manufactured by Shin-Nakamura Chemical Industry Co., Ltd., etc.).
  • KAYARAD® DPCA-20 manufactured by Nippon Kayaku Co., Ltd.
  • A-9300-1CL manufactured by Shin-Nakamura Chemical Industry Co., Ltd., etc.
  • (Meta) acrylate compound alkylene oxide-modified compound (KAYARAD (registered trademark) R-604 manufactured by Nippon Kayaku Co., Ltd., ATM-35E, A-9300 manufactured by Shin-Nakamura Chemical Industry Co., Ltd., and Dycel Ornex EBECRYL (registered trademark) 135, etc.) and ethoxylated glycerin triacrylate (NK ester A-GLY-9E, etc. manufactured by Shin-Nakamura Chemical Industry Co., Ltd.) can also be mentioned.
  • KAYARAD registered trademark
  • ATM-35E A-9300 manufactured by Shin-Nakamura Chemical Industry Co., Ltd.
  • Dycel Ornex EBECRYL registered trademark 135, etc.
  • ethoxylated glycerin triacrylate ethoxylated glycerin triacrylate
  • Examples of the polymerizable compound include urethane (meth) acrylate compounds [preferably trifunctional or higher functional urethane (meth) acrylate compounds].
  • Examples of the trifunctional or higher functional urethane (meth) acrylate compound include Acryt 8UX-015A (manufactured by Taisei Fine Chemicals Co., Ltd.), NK Ester UA-32P (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), and NK Ester UA-1100H (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.). (Manufactured by the company).
  • urethane (meth) acrylate a urethane (meth) acrylate having trifunctionality or higher can also be mentioned.
  • the lower limit of the number of functional groups 6-functionality or more is more preferable, and 8-functionality or more is further preferable.
  • the upper limit of the number of functional groups is preferably 20 or less.
  • trifunctional or higher functional urethane (meth) acrylates include 8UX-015A (manufactured by Taisei Fine Chemical Industry Co., Ltd.), UA-32P (manufactured by Shin Nakamura Chemical Industry Co., Ltd.), and U-15HA (manufactured by Shin Nakamura Chemical Industry Co., Ltd.).
  • UA-1100H manufactured by Shin Nakamura Chemical Industry Co., Ltd.
  • AH-600 trade name manufactured by Kyoeisha Chemical Co., Ltd.
  • UX-5000 both manufactured by Nippon Kayaku Co., Ltd.
  • an ethylenically unsaturated compound having an acid group is preferable.
  • the acid group include a phosphoric acid group, a sulfo group, and a carboxy group. Of these, the carboxy group is preferable as the acid group.
  • the ethylenically unsaturated compound having an acid group a 3- to 4-functional ethylenically unsaturated compound having an acid group [pentaerythritol tri and a tetraacrylate (PETA) skeleton introduced with a carboxy group (acid value: 80 to 80).
  • the ethylenically unsaturated compound having an acid group at least one selected from the group consisting of a bifunctional or higher functional ethylenically unsaturated compound having a carboxy group and a carboxylic acid anhydride thereof is preferable.
  • the ethylenically unsaturated compound having an acid group is at least one selected from the group consisting of a bifunctional or higher functional ethylenically unsaturated compound having a carboxy group and a carboxylic acid anhydride thereof, the developability and film strength are improved. It will be higher.
  • the bifunctional or higher functional unsaturated compound having a carboxy group is not particularly limited and can be appropriately selected from known compounds.
  • Examples of the bifunctional or higher functional unsaturated compound having a carboxy group include Aronix (registered trademark) TO-2349 (manufactured by Toagosei Co., Ltd.) and Aronix (registered trademark) M-520 (manufactured by Toagosei Co., Ltd.). ), Aronix (registered trademark) M-510 (manufactured by Toagosei Co., Ltd.).
  • the polymerizable compound having an acid group described in paragraphs [0025] to [0030] of JP-A-2004-239942 is preferable, and the content described in this publication is described in this publication. Incorporated in the specification.
  • Examples of the polymerizable compound include a compound obtained by reacting a polyhydric alcohol with an ⁇ , ⁇ -unsaturated carboxylic acid, a compound obtained by reacting a glycidyl group-containing compound with an ⁇ , ⁇ -unsaturated carboxylic acid, and a urethane.
  • Urethane monomers such as (meth) acrylate compounds having a bond, ⁇ -chloro- ⁇ -hydroxypropyl- ⁇ '-(meth) acryloyloxyethyl-o-phthalate, ⁇ -hydroxyethyl- ⁇ '-(meth) acryloyloxyethyl Examples thereof include phthalic acid compounds such as -o-phthalate and ⁇ -hydroxypropyl- ⁇ '-(meth) acryloyloxyethyl-o-phthalate, and (meth) acrylic acid alkyl esters. These may be used alone or in combination of two or more.
  • Examples of the compound obtained by reacting a polyvalent alcohol with an ⁇ , ⁇ -unsaturated carboxylic acid include 2,2-bis (4-((meth) acrylamide polyethoxy) phenyl) propane and 2,2-bis.
  • Bisphenol A-based (meth) acrylate compounds such as (4-((meth) acrylamide polypropoxy) phenyl) propane and 2,2-bis (4-((meth) acrylamide polyethoxypolypropoxy) phenyl) propane , Polyethylene glycol di (meth) acrylate having 2 to 14 ethylene oxide groups, polypropylene glycol di (meth) acrylate having 2 to 14 propylene oxide groups, and 2 to 14 ethylene oxide groups.
  • an ethylene unsaturated compound having a tetramethylolmethane structure or a trimethylolpropane structure is preferable, and tetramethylolmethanetri (meth) acrylate, tetramethylolmethanetetra (meth) acrylate, and trimethylolpropanetri (meth) are preferable.
  • Acrylate or di (trimethylolpropane) tetraacrylate is more preferable.
  • a compound containing an ester bond is preferable in that the photosensitive composition layer after transfer is excellent in developability.
  • the ethylenically unsaturated compound containing an ester bond is not particularly limited as long as it contains an ester bond in the molecule, but is not ethylene-free having a tetramethylolmethane structure or a trimethylolpropane structure in that the effect of the present invention is excellent.
  • the ethylenically unsaturated compound includes an ethylenically unsaturated compound having an aliphatic group having 6 to 20 carbon atoms and the above-mentioned ethylene unsaturated compound having a tetramethylol methane structure or a trimethylol propane structure from the viewpoint of imparting reliability. And, preferably.
  • Examples of the ethylenically unsaturated compound having an aliphatic structure having 6 or more carbon atoms include 1,9-nonanediol di (meth) acrylate, 1,10-decanediol di (meth) acrylate, and tricyclodecanedimethanol.
  • Di (meth) acrylate can be mentioned.
  • the polymerizable compound examples include a polymerizable compound having an aliphatic hydrocarbon ring structure (preferably a bifunctional ethylenically unsaturated compound).
  • a polymerizable compound having a ring structure in which two or more aliphatic hydrocarbon rings are condensed preferably a structure selected from the group consisting of a tricyclodecane structure and a tricyclodecene structure
  • a bifunctional ethylenically unsaturated compound having a ring structure in which two or more aliphatic hydrocarbon rings are fused is more preferable, and tricyclodecanedimethanol di (meth) acrylate is further preferable.
  • a cyclopentane structure, a cyclohexane structure, a tricyclodecane structure, a tricyclodecene structure, a norbornane structure, or an isoborone structure is preferable from the viewpoint that the effect of the present invention is more excellent.
  • the molecular weight of the polymerizable compound is preferably 200 to 3,000, more preferably 250 to 2,600, still more preferably 280 to 2,200, and particularly preferably 300 to 2,200.
  • the ratio of the content of the polymerizable compound having a molecular weight of 300 or less to the content of all the polymerizable compounds contained in the photosensitive composition layer is 30% by mass with respect to the content of all the polymerizable compounds contained in the photosensitive composition layer. % Or less is preferable, 25% by mass or less is more preferable, and 20% by mass or less is further preferable.
  • the lower limit of the content ratio of the polymerizable compound having a molecular weight of 300 or less is not particularly limited, but is preferably 1.0% by mass or more.
  • the photosensitive composition layer preferably contains a bifunctional or higher functional ethylenically unsaturated compound, more preferably a trifunctional or higher functional ethylenically unsaturated compound, and a trifunctional or tetrafunctional ethylenically unsaturated compound. It is more preferable to include it.
  • the photosensitive composition layer preferably contains a bifunctional ethylenically unsaturated compound having an aliphatic hydrocarbon ring structure and a binder polymer having a structural unit having an aliphatic hydrocarbon ring.
  • the photosensitive composition layer preferably contains a compound represented by the formula (M) and an ethylenically unsaturated compound having an acid group, and is preferably 1,9-nonanediol diacrylate, tricyclodecanedimethanol diacrylate, and the like. And more preferably containing a polyfunctional ethylenically unsaturated compound having a carboxylic acid group, succinic acid variants of 1,9-nonanediol diacrylate, tricyclodecanedimethanol diacrylate, and dipentaerythritol pentaacrylate. It is more preferable to include it.
  • the photosensitive composition layer preferably contains a compound represented by the formula (M), an ethylenically unsaturated compound having an acid group, and a thermally crosslinkable compound described later, and the compound represented by the formula (M). It is more preferable to contain an ethylenically unsaturated compound having an acid group and a blocked isocyanate compound described later.
  • the photosensitive composition layer comprises a bifunctional ethylenically unsaturated compound (preferably a bifunctional (meth) acrylate compound) and a trifunctional or higher functional ethylenically unsaturated compound (preferably a trifunctional or higher (meth) acrylate compound). ) It is preferable to contain an acrylate compound).
  • the photosensitive composition layer preferably contains compound M and a bifunctional ethylenically unsaturated compound having an aliphatic hydrocarbon ring structure.
  • the photosensitive composition layer preferably contains compound M and an ethylenically unsaturated compound having an acid group from the viewpoints of adhesion, development residue inhibitory property, and rust resistance, and the compound M and the aliphatic hydrocarbon are preferable. It is more preferable to contain a bifunctional ethylenically unsaturated compound having a ring structure and an ethylenically unsaturated compound having an acid group, and compound M, a bifunctional ethylenically unsaturated compound having an aliphatic hydrocarbon ring structure, and a trifunctional compound.
  • the photosensitive composition layer contains 1,9-nonanediol diacrylate and a polyfunctional ethylenically unsaturated compound having a carboxylic acid group from the viewpoints of adhesion, development residue inhibitory property, and rust resistance.
  • 1,9-nonanediol diacrylate, tricyclodecanedimethanol diacrylate, and a polyfunctional ethylenically unsaturated compound having a carboxylic acid group, 1,9-nonanediol diacrylate It is more preferable to contain tricyclodecanedimethanol diacrylate, dipentaerythritol hexaacrylate (A-DPH), and an ethylenically unsaturated compound having a carboxylic acid group, preferably 1,9-nonanediol diacrylate and tricyclode. It is particularly preferable to contain candimethane diacrylate, an ethylenically unsaturated compound having a carboxylic acid group, and a urethane acrylate compound.
  • the photosensitive composition layer may contain a monofunctional ethylenically unsaturated compound as the ethylenically unsaturated compound.
  • the content of the bifunctional or higher functional ethylenically unsaturated compound in the ethylenically unsaturated compound is 60 to 100% by mass with respect to the total content of all the ethylenically unsaturated compounds contained in the photosensitive composition layer. It is preferable, 80 to 100% by mass is more preferable, and 90 to 100% by mass is further preferable.
  • the photosensitive composition layer preferably contains a polymerizable compound B1 having an aromatic ring and two ethylenically unsaturated groups.
  • the polymerizable compound B1 is a bifunctional ethylenically unsaturated compound having one or more aromatic rings in one molecule among the above-mentioned polymerizable compounds B.
  • the ratio of the mass ratio of the content of the polymerizable compound B1 to the total mass of the polymerizable compound in the photosensitive composition layer is preferably 40% by mass or more, more preferably 50% by mass or more, from the viewpoint of better resolution. It is preferable, 55% by mass or more is more preferable, and 60% by mass or more is particularly preferable.
  • the upper limit is not particularly limited, but from the viewpoint of peelability, 100% by mass or less is preferable, 99% by mass or less is more preferable, 95% by mass or less is further preferable, 90% by mass or less is particularly preferable, and 85% by mass or less is the most. preferable.
  • aromatic ring contained in the polymerizable compound B1 examples include aromatic hydrocarbon rings such as benzene ring, naphthalene ring and anthracene ring, thiophene ring, furan ring, pyrrole ring, imidazole ring, triazole ring and pyridine ring. Heterocycles and fused rings thereof are mentioned, and aromatic hydrocarbon rings are preferable, and benzene rings are more preferable.
  • the aromatic ring may have a substituent.
  • the polymerizable compound B1 may have only one aromatic ring or may have two or more aromatic rings.
  • the polymerizable compound B1 preferably has a bisphenol structure from the viewpoint of improving the resolution by suppressing the swelling of the photosensitive composition layer due to the developing solution.
  • the bisphenol structure include a bisphenol A structure derived from bisphenol A (2,2-bis (4-hydroxyphenyl) propane) and a bisphenol derived from bisphenol F (2,2-bis (4-hydroxyphenyl) methane).
  • examples thereof include an F structure and a bisphenol B structure derived from bisphenol B (2,2-bis (4-hydroxyphenyl) butane), and a bisphenol A structure is preferable.
  • Examples of the polymerizable compound B1 having a bisphenol structure include a compound having a bisphenol structure and two polymerizable groups (preferably (meth) acryloyl groups) bonded to both ends of the bisphenol structure. Both ends of the bisphenol structure and the two polymerizable groups may be directly bonded or may be bonded via one or more alkyleneoxy groups. As the alkyleneoxy group added to both ends of the bisphenol structure, an ethyleneoxy group or a propyleneoxy group is preferable, and an ethyleneoxy group is more preferable.
  • the number of alkyleneoxy groups added to the bisphenol structure is not particularly limited, but is preferably 4 to 16 per molecule, more preferably 6 to 14.
  • the polymerizable compound B1 having a bisphenol structure is described in paragraphs [0072] to [0080] of JP-A-2016-224162, and the contents described in this publication are incorporated in the present specification.
  • the polymerizable compound B1 a bifunctional ethylenically unsaturated compound having a bisphenol A structure is preferable, and 2,2-bis (4-((meth) acryloxypolyalkoxy) phenyl) propane is more preferable.
  • 2,2-bis (4-((meth) acryloxypolyalkoxy) phenyl) propane examples include 2,2-bis (4- (methacryloxydiethoxy) phenyl) propane (FA-324M, Hitachi Kasei Co., Ltd.).
  • polymerizable compound B1 a compound represented by the following general formula (B1) is also preferable.
  • R 1 and R 2 independently represent a hydrogen atom or a methyl group, respectively.
  • A represents C 2 H 4 .
  • B represents C 3 H 6 .
  • n1 and n3 are independently integers of 1 to 39, and n1 + n3 are integers of 2 to 40.
  • n2 and n4 are independently integers of 0 to 29, and n2 + n4 are integers of 0 to 30.
  • the sequence of constituent units of-(AO)-and-(BO)- may be random or block. In the case of a block, either ⁇ (A—O) ⁇ or ⁇ (BO) ⁇ may be on the bisphenyl group side.
  • n1 + n2 + n3 + n4 is preferably 2 to 20, more preferably 2 to 16, and even more preferably 4 to 12. Further, n2 + n4 is preferably 0 to 10, more preferably 0 to 4, further preferably 0 to 2, and particularly preferably 0.
  • the polymerizable compound B1 may be used alone or in combination of two or more.
  • the content of the polymerizable compound B1 is preferably 10% by mass or more, more preferably 20% by mass or more, based on the total mass of the photosensitive composition layer, from the viewpoint of better resolution.
  • the upper limit is not particularly limited, but from the viewpoint of transferability and edge fusion (a phenomenon in which the photosensitive resin exudes from the end of the transfer member), 70% by mass or less is preferable, and 60% by mass or less is more preferable.
  • the polymerizable compound (particularly, the ethylenically unsaturated compound) may be used alone or in combination of two or more.
  • the content of the polymerizable compound (particularly, the ethylenically unsaturated compound) in the photosensitive composition layer is preferably 1.00 to 70.00% by mass with respect to the total mass of the photosensitive composition layer, and is 10.00. It is more preferably from 70.00% by mass, further preferably from 15.0 to 50.0% by mass, and particularly preferably from 20.0 to 40.0% by mass.
  • the photosensitive composition layer may contain a heterocyclic compound.
  • the heterocycle contained in the heterocyclic compound may be either a monocyclic or polycyclic complex.
  • Examples of the hetero atom contained in the heterocyclic compound include a nitrogen atom, an oxygen atom, and a sulfur atom.
  • the heterocyclic compound preferably has at least one atom selected from the group consisting of a nitrogen atom, an oxygen atom, and a sulfur atom, and more preferably has a nitrogen atom.
  • heterocyclic compound examples include triazole compounds, benzotriazole compounds, tetrazole compounds, thiadiazol compounds, triazine compounds, rodonin compounds, thiazole compounds, benzothiazole compounds, benzoimidazole compounds, benzoxazole compounds, pyrimidine compounds, and pyridine compounds.
  • the heterocyclic compound is selected from the group consisting of a triazole compound, a benzotriazole compound, a tetrazole compound, a thiadiazol compound, a triazine compound, a rhonin compound, a thiazole compound, a benzoimidazole compound, a benzoxazole compound, and a pyridine compound.
  • At least one compound is preferable, and at least one compound selected from the group consisting of a triazole compound, a benzotriazole compound, a tetrazole compound, a thiadiazol compound, a thiazole compound, a benzothiazole compound, a benzoimidazole compound, and a benzoxazole compound is preferable. More preferred.
  • heterocyclic compound Preferred specific examples of the heterocyclic compound are shown below.
  • examples of the triazole compound and the benzotriazole compound include the following compounds.
  • Examples of the tetrazole compound include the following compounds.
  • Examples of the thiadiazole compound include the following compounds.
  • Examples of the triazine compound include the following compounds.
  • Examples of the loadonine compound include the following compounds.
  • Examples of the thiazole compound include the following compounds.
  • benzothiazole compound examples include the following compounds.
  • Examples of the benzimidazole compound include the following compounds.
  • benzoxazole compound examples include the following compounds.
  • Examples of the pyridine compound include (iso) nicotinic acid and (iso) nicotinamide.
  • the photosensitive composition layer may contain one kind of heterocyclic compound alone, or may contain two or more kinds of heterocyclic compounds.
  • the content of the heterocyclic compound is preferably 0.01 to 20.00% by mass, preferably 0.10 to 10% by mass, based on the total mass of the photosensitive composition layer. It is more preferably 0.00% by mass, further preferably 0.10 to 5.00% by mass, and particularly preferably 0.10 to 1.00% by mass.
  • the photosensitive composition layer may contain an aliphatic thiol compound.
  • aliphatic thiol compound a monofunctional aliphatic thiol compound or a polyfunctional aliphatic thiol compound (that is, a bifunctional or higher functional aliphatic thiol compound) is preferable, and the adhesion (particularly, exposure) of the formed pattern is preferable.
  • Polyfunctional aliphatic thiol compounds are more preferable from the viewpoint of adhesion later).
  • polyfunctional aliphatic thiol compound means an aliphatic compound having two or more thiol groups (also referred to as “mercapto groups”) in the molecule.
  • the molecular weight of the polyfunctional aliphatic thiol compound is preferably 100 or more, more preferably 100 to 1,500, still more preferably 150 to 1,000.
  • the number of functional groups of the polyfunctional aliphatic thiol compound for example, 2 to 10 functionalities are preferable, 2 to 8 functionalities are more preferable, and 2 to 6 functionalities are further preferable, from the viewpoint of adhesion of the formed pattern.
  • polyfunctional aliphatic thiol compound examples include trimethylolpropanetris (3-mercaptobutylate), 1,4-bis (3-mercaptobutylyloxy) butane, pentaerythritol tetrakis (3-mercaptobutyrate), and the like.
  • the polyfunctional aliphatic thiol compounds include trimethylolpropane tris (3-mercaptobutyrate), 1,4-bis (3-mercaptobutylyloxy) butane, and 1,3,5-tris (3,5-tris). At least one compound selected from the group consisting of 3-mercaptobutylyloxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione is preferable.
  • Examples of the monofunctional aliphatic thiol compound include 1-octanethiol, 1-dodecanethiol, ⁇ -mercaptopropionic acid, methyl-3-mercaptopropionate, 2-ethylhexyl-3-mercaptopropionate, and n-. Examples thereof include octyl-3-mercaptopropionate, methoxybutyl-3-mercaptopropionate, and stearyl-3-mercaptopropionate.
  • the photosensitive composition layer may contain one kind of aliphatic thiol compound alone, or may contain two or more kinds of aliphatic thiol compounds.
  • the content of the aliphatic thiol compound is preferably 5% by mass or more, more preferably 5 to 50% by mass, based on the total mass of the photosensitive composition layer. 5 to 30% by mass is more preferable, and 8 to 20% by mass is particularly preferable.
  • the photosensitive composition layer preferably contains a heat-crosslinkable compound from the viewpoint of the strength of the obtained cured film and the adhesiveness of the obtained uncured film.
  • the thermally crosslinkable compound having an ethylenically unsaturated group described later is not treated as an ethylenically unsaturated compound, but is treated as a thermally crosslinkable compound.
  • the heat-crosslinkable compound is a compound different from the components (binder polymer, polymerization initiator, polymerizable compound, etc.) contained in the above-mentioned photosensitive composition layer.
  • the heat-crosslinkable compound examples include an epoxy compound, an oxetane compound, a methylol compound, and a blocked isocyanate compound.
  • the blocked isocyanate compound is preferable from the viewpoint of the strength of the obtained cured film and the adhesiveness of the obtained uncured film. Since the blocked isocyanate compound reacts with a hydroxy group and a carboxy group, for example, when at least one of the binder polymer and the radically polymerizable compound having an ethylenically unsaturated group has at least one of the hydroxy group and the carboxy group, The hydrophilicity of the formed film tends to decrease, and the function as a protective film tends to be strengthened.
  • the blocked isocyanate compound refers to "a compound having a structure in which the isocyanate group of isocyanate is protected (so-called masked) with a blocking agent".
  • the blocked isocyanate compound preferably contains a blocked isocyanate compound having a blocked isocyanate equivalent (hereinafter, also referred to as “NCO value”) of 4.5 mmol / g or more (hereinafter, also referred to as “first blocked isocyanate compound”).
  • NCO value blocked isocyanate equivalent
  • the NCO value of the first block isocyanate compound is 4.5 mmol / g or more, and 5.0 mmol / g or more is more preferable, and 5.3 mmol / g or more is further preferable, from the viewpoint that the effect of the present invention is more excellent.
  • the upper limit of the NCO value of the first block isocyanate compound is preferably 6.0 mmol / g or less, more preferably less than 5.8 mmol / g, and further preferably 5.7 mmol / g or less, because the effect of the present invention is more excellent. preferable.
  • the NCO value of the blocked isocyanate compound in the present invention means the number of millimoles of the blocked isocyanate group contained in 1 g of the blocked isocyanate compound, and can be calculated from the following formula.
  • NCO value of blocked isocyanate compound 1000 ⁇ (number of blocked isocyanate groups contained in the molecule) / (molecular weight of blocked isocyanate compound)
  • the dissociation temperature of the first block isocyanate compound is preferably 100 to 160 ° C, more preferably 110 to 150 ° C.
  • the "dissociation temperature of the blocked isocyanate compound” is the heat absorption peak associated with the deprotection reaction of the blocked isocyanate compound when measured by DSC (Differential scanning calorimetry) analysis using a differential scanning calorimeter. Means temperature.
  • the differential scanning calorimeter is not particularly limited, and for example, a differential scanning calorimeter (model: DSC6200) manufactured by Seiko Instruments Inc. can be preferably used.
  • the oxime compound is preferable as the blocking agent having a dissociation temperature of 100 to 160 ° C. from the viewpoint of storage stability.
  • the first block isocyanate compound preferably has a ring structure from the viewpoint that the effect of the present invention is more excellent.
  • the ring structure include an aliphatic hydrocarbon ring, an aromatic hydrocarbon ring, and a heterocyclic ring. From the viewpoint that the effect of the present invention is more excellent, the aliphatic hydrocarbon ring and the aromatic hydrocarbon ring are preferable, and the fat Group hydrocarbon rings are more preferred.
  • Specific examples of the aliphatic hydrocarbon ring include a cyclopentane ring and a cyclohexane ring, and a cyclohexane ring is preferable.
  • the aromatic hydrocarbon ring include a benzene ring and a naphthalene ring, and a benzene ring is preferable.
  • Specific examples of the heterocycle include an isocyanurate ring.
  • the number of rings is preferably 1 to 2 and more preferably 1 from the viewpoint that the effect of the present invention is more excellent.
  • the first block isocyanate compound contains a fused ring, the number of rings constituting the fused ring is counted, for example, the number of rings in the naphthalene ring is counted as 2.
  • the number of blocked isocyanate groups contained in the first blocked isocyanate compound is preferably 2 to 5 and more preferably 2 to 3 from the viewpoint of excellent strength of the formed pattern and more excellent effect of the present invention. Is more preferable.
  • the first blocked isocyanate compound is preferably a blocked isocyanate compound represented by the formula Q from the viewpoint that the effect of the present invention is more excellent.
  • B 1 and B 2 each independently represent a blocked isocyanate group.
  • the blocked isocyanate group is not particularly limited, but a group in which the isocyanate group is blocked with an oxime compound is preferable, and a group in which the isocyanate group is blocked with a methylethylketooxime (specifically, a group in which the isocyanate group is blocked with an oxime compound) is preferable because the effect of the present invention is more excellent.
  • a 1 and A 2 independently represent a single bond or an alkylene group having 1 to 10 carbon atoms, and an alkylene group having 1 to 10 carbon atoms is preferable.
  • the alkylene group may be linear, branched, or cyclic, and is preferably linear.
  • the alkylene group has 1 to 10 carbon atoms, and is preferably 1 to 5, more preferably 1 to 3, and even more preferably 1 because the effect of the present invention is more excellent. It is preferable that A 1 and A 2 are groups having the same structure.
  • L 1 represents a divalent linking group.
  • the divalent linking group include a divalent hydrocarbon group.
  • the divalent hydrocarbon group include a divalent saturated hydrocarbon group, a divalent aromatic hydrocarbon group, and a group formed by linking two or more of these groups.
  • the divalent saturated hydrocarbon group may be linear, branched, or cyclic, and is preferably cyclic from the viewpoint that the effect of the present invention is more excellent.
  • the number of carbon atoms of the divalent saturated hydrocarbon group is preferably 4 to 15, more preferably 5 to 10, and even more preferably 5 to 8 from the viewpoint that the effect of the present invention is more excellent.
  • the divalent aromatic hydrocarbon group preferably has 5 to 20 carbon atoms, and examples thereof include a phenylene group.
  • the divalent aromatic hydrocarbon group may have a substituent (for example, an alkyl group).
  • the divalent linking group includes a linear, branched or cyclic divalent saturated hydrocarbon group having 5 to 10 carbon atoms, a cyclic saturated hydrocarbon group having 5 to 10 carbon atoms and carbon.
  • a group linked with the linear alkylene group of 3 is preferable, a cyclic divalent saturated hydrocarbon group having 5 to 10 carbon atoms, or a phenylene group which may have a substituent is more preferable, and a cyclo A phenylene group which may have a hexylene group or a substituent is more preferable, and a cyclohexylene group is particularly preferable.
  • the blocked isocyanate compound represented by the formula Q is preferably a blocked isocyanate compound represented by the formula QA because the effect of the present invention is more excellent.
  • B 1a and B 2a each independently represent a blocked isocyanate group.
  • the preferred embodiments of B 1a and B 2a are the same as those of B 1 and B 2 in the formula Q.
  • a 1a and A 2a each independently represent a divalent linking group.
  • the preferred embodiment of the divalent linking group in A 1a and A 2a is the same as A 1a and A 2a in the formula Q.
  • L 1a represents a cyclic divalent saturated hydrocarbon group or a divalent aromatic hydrocarbon group.
  • the number of carbon atoms of the cyclic divalent saturated hydrocarbon group in L 1a is preferably 5 to 10, more preferably 5 to 8, further preferably 5 to 6, and particularly preferably 6.
  • the preferred embodiment of the divalent aromatic hydrocarbon group in L 1a is the same as that of L 1 in the formula QA.
  • L 1a is preferably a cyclic divalent saturated hydrocarbon group, more preferably a cyclic divalent saturated hydrocarbon group having 5 to 10 carbon atoms, and more preferably a cyclic divalent saturated hydrocarbon group having 5 to 10 carbon atoms.
  • Hydrocarbon groups are more preferred, cyclic divalent saturated hydrocarbon groups having 5 to 6 carbon atoms are particularly preferred, and cyclohexylene groups are most preferred.
  • first block isocyanate compound Specific examples of the first block isocyanate compound are shown below, but the first block isocyanate compound is not limited to this.
  • the photosensitive composition layer may contain one kind of first block isocyanate compound alone, or may contain two or more kinds of first block isocyanate compounds.
  • the content of the first block isocyanate compound is preferably 0.50 to 25.00% by mass, more preferably 1.00 to 20.00% by mass, and 1.50 with respect to the total mass of the photosensitive composition layer. It is more preferably ⁇ 5.00% by mass.
  • the first blocked isocyanate compound is obtained, for example, by reacting the isocyanate group of a compound having an isocyanate group (for example, a compound in which B 1 and B 2 in the above formula Q are isocyanate groups) with the blocking agent.
  • a compound having an isocyanate group for example, a compound in which B 1 and B 2 in the above formula Q are isocyanate groups
  • the blocked isocyanate compound preferably contains a blocked isocyanate compound having an NCO value of less than 4.5 mmol / g (hereinafter, also referred to as “second blocked isocyanate compound”). This makes it possible to suppress the generation of development residues after pattern exposure and development of the photosensitive composition layer.
  • the NCO value of the second block isocyanate compound is less than 4.5 mmol / g, preferably 2.0 to 4.5 mmol / g, and more preferably 2.5 to 4.0 mmol / g.
  • the dissociation temperature of the second block isocyanate compound is preferably 100 to 160 ° C, more preferably 110 to 150 ° C.
  • Specific examples of the blocking agent having a dissociation temperature of 100 to 160 ° C. are as described above.
  • the second block isocyanate compound preferably has an isocyanurate structure from the viewpoint of improving the brittleness of the membrane or improving the adhesion to the transferred material.
  • the blocked isocyanate compound having an isocyanurate structure can be obtained, for example, by subjecting hexamethylene diisocyanate to isocyanurate to protect it.
  • an oxime structure using an oxime compound as a blocking agent is used because it is easier to set the dissociation temperature in a preferable range and to reduce the amount of development residue as compared with a compound having no oxime structure.
  • the compound to have is preferable.
  • the second block isocyanate compound may have a polymerizable group in terms of the strength of the formed pattern.
  • a radically polymerizable group is preferable.
  • the polymerizable group include a (meth) acryloxy group, a (meth) acrylamide group, an ethylenically unsaturated group such as a styryl group, and a group having an epoxy group such as a glycidyl group.
  • an ethylenically unsaturated group is preferable, and a (meth) acryloxy group is more preferable, from the viewpoint of surface surface condition, development speed, and reactivity in the obtained pattern.
  • second block isocyanate compound Specific examples of the second block isocyanate compound are shown below, but the second block isocyanate compound is not limited to this.
  • the second block isocyanate compound a commercially available product can be used.
  • examples of commercially available blocked isocyanate compounds include, for example, Karenz (registered trademark) AOI-BM, Karenz (registered trademark) MOI-BM, Karenz (registered trademark) AOI-BP, Karenz (registered trademark) MOI-BP [above. , Showa Denko Corporation], and block-type Duranate series [for example, Duranate (registered trademark) TPA-B80E, WT32-B75P, Asahi Kasei Chemicals Co., Ltd.].
  • the photosensitive composition layer may contain one type of second-block isocyanate compound alone, or may contain two or more types of second-block isocyanate compounds.
  • the content of the second block isocyanate compound is 1. From the viewpoint that the generation of development residue can be further reduced with respect to the total mass of the photosensitive composition layer. It is preferably 00 to 25.00% by mass, more preferably 1.00 to 20.0% by mass, still more preferably 10.00 to 15.00% by mass.
  • the mass ratio of the content of the first block isocyanate compound to the content of the second block isocyanate compound is preferably 0.10 to 9.00, more preferably 0.18 to 2.35, still more preferably 0.18 to 1.00, from the viewpoint of bending resistance and reduction of moisture permeability.
  • the heat-crosslinkable compound may be used alone or in combination of two or more.
  • the content of the heat-crosslinkable compound is preferably 1.00 to 50.00% by mass with respect to the total mass of the photosensitive composition layer, and is 10.00. It is more preferably from 30.00% by mass, still more preferably from 10.00 to 20.00% by mass.
  • the photosensitive composition layer may contain a surfactant.
  • the surfactant include the surfactants described in paragraphs [0017] of Japanese Patent No. 4502784 and paragraphs [0060] to [0071] of JP-A-2009-237362, and the contents thereof include. Incorporated herein.
  • the surfactant include a fluorine-based surfactant, a silicone-based surfactant, and a nonionic surfactant, and a fluorine-based surfactant or a silicone-based surfactant is preferable, and a fluorine-based surfactant is preferable. More preferred.
  • fluorine-based surfactants include, for example, Megafuck F-171, F-172, F-173, F-176, F-177, F-141, F-142, F-143, F-144. , F-437, F-475, F-477, F-479, F-482, F-551-A, F-552, F-554, F-555-A, F-556, F-557, F -558, F-559, F-560, F-561, F-565, F-563, F-568, F-575, F-780, EXP. MFS-330, EXP. MFS-578, EXP. MFS-578-2, EXP. MFS-579, EXP. MFS-586, EXP.
  • the fluorine-based surfactant has a molecular structure having a functional group containing a fluorine atom, and an acrylic compound in which a portion of the functional group containing a fluorine atom is cut off and the fluorine atom volatilizes when heat is applied.
  • a fluorine-based surfactant include the Megafuck DS series manufactured by DIC (The Chemical Daily, February 22, 2016, Nikkei Sangyo Shimbun, February 23, 2016, for example, Megafuck DS-21). Be done.
  • fluorine-based surfactant it is also preferable to use a polymer of a fluorine atom-containing vinyl ether compound having a fluorinated alkyl group or a fluorinated alkylene ether group and a hydrophilic vinyl ether compound.
  • a block polymer can also be used as the fluorine-based surfactant.
  • the fluorine-based surfactant has a repeating unit derived from a (meth) acrylate compound having a fluorine atom and 2 or more (preferably 5 or more) alkyleneoxy groups (preferably ethyleneoxy groups and propyleneoxy groups) (meth).
  • a fluorine-containing polymer compound containing a repeating unit derived from an acrylate compound can also be preferably used.
  • a fluorine-based surfactant a fluorine-containing polymer having an ethylenically unsaturated bond-containing group in the side chain can also be used.
  • the fluorine surfactant is derived from a substitute material for a compound having a perfluoroalkyl group having 7 or more carbon atoms, such as perfluorooctanoic acid (PFOA) and perfluorooctanesulfonic acid (PFOS), from the viewpoint of improving environmental suitability. It is preferably a surfactant.
  • silicone-based surfactant examples include a linear polymer composed of a siloxane bond and a modified siloxane polymer having an organic group introduced into a side chain or a terminal.
  • Commercially available silicone-based surfactants include DOWNIL 8032 ADDITIVE, Torre Silicone DC3PA, Torre Silicone SH7PA, Torre Silicone DC11PA, Torre Silicone SH21PA, Torre Silicone SH28PA, Torre Silicone SH29PA, Torre Silicone SH30PA, and Torre Silicone SH8400.
  • Nonionic surfactants include, for example, glycerol, trimethylolpropane, trimethylolethane, and their ethoxylates and propoxylates (eg, glycerol propoxylate, glycerol ethoxylate, etc.); polyoxyethylene lauryl ether, poly. Examples thereof include oxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, and sorbitan fatty acid ester.
  • nonionic surfactants include Pluronic® L10, L31, L61, L62, 10R5, 17R2, 25R2 (all manufactured by BASF); Tetronic 304, 701, 704, 901, 904, and 150R1 (above, manufactured by BASF); Solspers 20000 (above, manufactured by Japan Lubrizol); NCW-101, NCW-1001, and NCW-1002 (above, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.); Pionin D-6112, Examples thereof include D-6112-W, D-6315 (all manufactured by Takemoto Oil & Fat Co., Ltd.), Orfin E1010, Surfinol 104, 400, and 440 (all manufactured by Nissin Chemical Industries, Ltd.).
  • the surfactant may be used alone or in combination of two or more.
  • the content of the surfactant is preferably 0.01 to 3.0% by mass, preferably 0.05 to 1% by mass, based on the total mass of the photosensitive composition layer. 9.0% by mass is more preferable, and 0.10 to 0.80% by mass is further preferable.
  • the photosensitive composition layer may contain a phosphoric acid ester compound.
  • the light ester series (light ester P-2M (trade name)) manufactured by the company can be mentioned.
  • the phosphoric acid ester compound may be used alone or in combination of two or more.
  • the content of the phosphoric acid ester compound is not particularly limited, but is preferably 0.05 to 3.0% by mass, more preferably 0.1 to 2.0% by mass, based on the total mass of the photosensitive composition layer. 0.2 to 1.0% by mass is more preferable.
  • the content of the phosphoric acid ester compound is not particularly limited, but the total mass of the binder polymer and the polymerizable compound is 100 mass in terms of further improving the adhesion to the transferred material. It is preferably 10 parts by mass or less, and more preferably 3 parts by mass or less.
  • the upper limit of the content is not particularly limited, but is preferably 0.01 parts by mass or more, and more preferably 0.1 parts by mass or more.
  • the photosensitive composition layer may contain a polymerization inhibitor.
  • the polymerization inhibitor means a compound having a function of delaying or prohibiting a polymerization reaction.
  • a known compound used as a polymerization inhibitor can be used.
  • polymerization inhibitor examples include phenothiazine compounds such as phenothiazine, bis- (1-dimethylbenzyl) phenothiazine, and 3,7-dioctylphenothiazine; bis [3- (3-tert-butyl-4-hydroxy-5-.
  • Methylphenyl) propionic acid [ethylene bis (oxyethylene)] 2,4-bis [(laurylthio) methyl] -o-cresol, 1,3,5-tris (3,5-di-t-butyl-4-) Hydroxybenzyl), 1,3,5-tris (4-t-butyl-3-hydroxy-2,6-dimethylbenzyl), 2,4-bis- (n-octylthio) -6- (4-hydroxy-3) , 5-Di-t-butylanilino) -1,3,5-triazine, and hindered phenol compounds such as pentaerythritol tetrakis 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate; 4 -Nitroso compounds such as nitrosophenol, N-nitrosodiphenylamine, N-nitrosocyclohexylhydroxylamine, and N-nitrosophenylhydroxylamine or salts thereof;
  • quinone compounds such as 4-benzoquinone; phenolic compounds such as 4-methoxyphenol, 4-methoxy-1-naphthol, and t-butylcatechol; copper dibutyldithiocarbamate, copper diethyldithiocarbamate, manganese diethyldithiocarbamate, And a metal salt compound such as manganese diphenyldithiocarbamate can be mentioned.
  • the polymerization inhibitor at least one selected from the group consisting of a phenothiazine compound, a nitroso compound or a salt thereof, and a hindered phenol compound is preferable, and phenothiazine and bis [3- (3-tert-butyl-) are preferable.
  • 4-Hydroxy-5-methylphenyl) propionic acid] [ethylenebis (oxyethylene)] 2,4-bis [(laurylthio) methyl] -o-cresol, 1,3,5-tris (3,5-di-) t-butyl-4-hydroxybenzyl) and N-nitrosophenylhydroxylamine aluminum salt are more preferred.
  • the polymerization inhibitor may be used alone or in combination of two or more.
  • the content of the polymerization inhibitor is preferably 0.01 to 10.0% by mass, preferably 0.01 to 5% by mass, based on the total mass of the photosensitive composition layer. It is more preferably 0.00% by mass, further preferably 0.01 to 3.00% by mass, and particularly preferably 0.01 to 1.00% by mass.
  • the photosensitive composition layer may contain a hydrogen donating compound.
  • the hydrogen donating compound has an action of further improving the sensitivity of the photopolymerization initiator to active light rays and suppressing the inhibition of the polymerization of the polymerizable compound by oxygen.
  • Examples of the hydrogen donating compound include amines and amino acid compounds.
  • Examples of amines include M.I. R. Sander et al., "Journal of Polymer Society", Vol. 10, pp. 3173 (1972), Japanese Patent Application Laid-Open No. 44-020189, Japanese Patent Application Laid-Open No. 51-082102, Japanese Patent Application Laid-Open No. 52-134692, Japanese Patent Application Laid-Open No. 59-138205. Examples thereof include the compounds described in Japanese Patent Application Laid-Open No. 60-0843305, Japanese Patent Application Laid-Open No. 62-018537, Japanese Patent Application Laid-Open No. 64-033104, and Research Disclosure No. 33825.
  • 4,4'-bis (diethylamino) benzophenone tris (4-dimethylaminophenyl) methane (also known as leucocrystal violet), triethanolamine, p-dimethylaminobenzoic acid ethyl ester, p-formyl.
  • examples thereof include dimethylaniline and p-methylthiodimethylaniline.
  • amino acid compound examples include N-phenylglycine, N-methyl-N-phenylglycine, and N-ethyl-N-phenylglycine.
  • N-phenylglycine is preferable as the amino acid compound because the effect of the present invention is more excellent.
  • Examples of the hydrogen donor compound include an organometallic compound (tributyltin acetate, etc.) described in JP-A-48-042965, a hydrogen donor described in JP-A-55-0344414, and JP-A-6. Sulfur compounds (Trithian and the like) described in JP-A-308727 can also be mentioned.
  • organometallic compound tributyltin acetate, etc.
  • Sulfur compounds Trithian and the like
  • the hydrogen donating compound may be used alone or in combination of two or more.
  • the content of the hydrogen donating compound is the total mass of the photosensitive composition layer in terms of improving the curing rate due to the balance between the polymerization growth rate and the chain transfer.
  • 0.01 to 10.00% by mass is preferable, 0.03 to 8.00% by mass is more preferable, and 0.05 to 5.00% by mass is further preferable.
  • the photosensitive composition layer may be a colored resin layer containing a pigment.
  • the liquid crystal display window of an electronic device may have a cover glass having a black frame-shaped light-shielding layer formed on the peripheral edge of the back surface of a transparent glass substrate or the like to protect the liquid crystal display window. be.
  • a colored resin layer can be used to form such a light-shielding layer.
  • the pigment may be appropriately selected according to the desired hue, and can be selected from black pigments, white pigments, and chromatic pigments other than black and white. Among them, when forming a black pattern, a black pigment is preferably selected as the pigment.
  • the black pigment a known black pigment (organic pigment, inorganic pigment, etc.) can be appropriately selected as long as the effect of the present invention is not impaired.
  • the black pigment for example, carbon black, titanium oxide, titanium carbide, iron oxide, titanium oxide, graphite and the like are preferably mentioned from the viewpoint of optical density, and carbon black is particularly preferable.
  • carbon black from the viewpoint of surface resistance, carbon black having at least a part of the surface coated with a resin is preferable.
  • the particle size of the black pigment is preferably 0.001 to 0.1 ⁇ m, more preferably 0.01 to 0.08 ⁇ m in terms of number average particle size.
  • the particle size refers to the diameter of the circle when the area of the pigment particles is obtained from the photographic image of the pigment particles taken with an electronic microscope and the circle having the same area as the area of the pigment particles is considered, and the number average particle size. Is an average value obtained by obtaining the above particle size for any 100 particles and averaging the obtained 100 particle sizes.
  • the white pigment described in paragraphs [0015] and [0114] of JP-A-2005-007765 can be used as the white pigment.
  • the white pigments as the inorganic pigment, titanium oxide, zinc oxide, lithopone, light calcium carbonate, white carbon, aluminum oxide, aluminum hydroxide, or barium sulfate is preferable, and titanium oxide or zinc oxide is more preferable. Titanium oxide is preferable, and titanium oxide is more preferable.
  • rutile-type or anatase-type titanium oxide is more preferable, and rutile-type titanium oxide is particularly preferable.
  • the surface of titanium oxide may be treated with silica, alumina, titania, zirconia, or an organic substance, or may be subjected to two or more treatments.
  • the catalytic activity of titanium oxide is suppressed, and heat resistance, fading and the like are improved.
  • at least one of alumina treatment and zirconia treatment is preferable as the surface treatment of the surface of titanium oxide, and both alumina treatment and zirconia treatment are particularly preferable.
  • the photosensitive composition layer is a colored resin layer
  • the photosensitive composition layer further contains a chromatic pigment other than the black pigment and the white pigment from the viewpoint of transferability.
  • a chromatic pigment is contained, the particle size of the chromatic pigment is preferably 0.1 ⁇ m or less, more preferably 0.08 ⁇ m or less, in that the dispersibility is more excellent.
  • the lower limit is not particularly limited, but 0.001 ⁇ m or more is preferable.
  • chromatic pigments include Victoria Pure Blue BO (Color Index (hereinafter CI) 42595), Auramine (CI41000), Fat Black HB (CI26150), and Monolite.
  • the content of the pigment is preferably more than 3% by mass and 40% by mass or less, preferably more than 3% by mass and 35% by mass or less, based on the total mass of the photosensitive composition layer. More preferably, it is more preferably more than 5% by mass and 35% by mass or less, and particularly preferably 10 to 35% by mass.
  • the content of the pigment other than the black pigment is preferably 30% by mass or less with respect to the black pigment, and is preferably 1 to 20.
  • the mass% is more preferable, and 3 to 15% by mass is further preferable.
  • the black pigment (preferably carbon black) is photosensitive in the form of a pigment dispersion. It is preferably introduced into the resin composition.
  • the dispersion liquid may be prepared by adding a mixture obtained by previously mixing a black pigment and a pigment dispersant to an organic solvent (or vehicle) and dispersing it with a disperser.
  • the pigment dispersant may be selected depending on the pigment and the solvent, and for example, a commercially available dispersant can be used.
  • the vehicle refers to a portion of the medium in which the pigment is dispersed when the pigment is dispersed, and is a liquid, a binder component that holds the black pigment in a dispersed state, and a solvent component that dissolves and dilutes the binder component. (Organic solvent) and included.
  • the disperser is not particularly limited, and examples thereof include known dispersers such as a kneader, a roll mill, an attritor, a super mill, a dissolver, a homomixer, and a sand mill. Further, it may be finely pulverized by mechanical grinding using frictional force.
  • disperser and fine pulverization the description of "Encyclopedia of Pigments" (Kunizo Asakura, First Edition, Asakura Shoten, 2000, 438, 310) can be referred to.
  • the photosensitive composition layer may contain residual monomers of each structural unit of the binder polymer described above.
  • the content of the residual monomer is preferably 5,000 mass ppm or less, more preferably 2,000 mass ppm or less, and 500 mass ppm or less with respect to the total mass of the binder polymer from the viewpoint of patterning property and reliability. More preferred.
  • the lower limit is not particularly limited, but is preferably 1 mass ppm or more, more preferably 10 mass ppm or more, based on the total mass of the binder polymer.
  • the residual monomer of each structural unit of the binder polymer is preferably 3,000 mass ppm or less, more preferably 600 mass ppm or less, based on the total mass of the photosensitive composition layer from the viewpoint of patterning property and reliability. , 100 mass ppm or less is more preferable.
  • the lower limit is not particularly limited, but is preferably 0.1 mass ppm or more, and more preferably 1 mass ppm or more, with respect to the total mass of the photosensitive composition layer.
  • the amount of residual monomer of the monomer when synthesizing the binder polymer by the polymer reaction is also preferably in the above range.
  • the content of glycidyl acrylate is preferably in the above range.
  • the amount of the residual monomer can be measured by a known method such as liquid chromatography and gas chromatography.
  • the photosensitive composition layer may contain components other than the above-mentioned components (hereinafter, also referred to as “other components”).
  • Other components include, for example, sensitizers, dyes, antioxidants, particles (eg, metal oxide particles).
  • sensitizers for example, sensitizers, dyes, antioxidants, particles (eg, metal oxide particles).
  • particles eg, metal oxide particles.
  • other additives described in paragraphs [0058] to [0071] of JP-A-2000-310706 can also be mentioned.
  • the sensitizer is not particularly limited, and known sensitizers, dyes and pigments can be used.
  • the sensitizer include dialkylaminobenzophenone compounds, pyrazoline compounds, anthracene compounds, coumarin compounds, xanthone compounds, thioxanthone compounds, acridone compounds, oxazole compounds, benzoxazole compounds, thiazole compounds, benzothiazole compounds, and triazole compounds (for example,). 1,2,4-triazole), stylben compounds, triazine compounds, thiophene compounds, naphthalimide compounds, triarylamine compounds, and aminoacridin compounds.
  • metal oxide particles are preferable.
  • the metal in the metal oxide particles also includes metalloids such as B, Si, Ge, As, Sb, and Te.
  • the average primary particle diameter of the particles is preferably 1 to 200 nm, more preferably 3 to 80 nm, for example, from the viewpoint of transparency of the cured film.
  • the average primary particle size of the particles is calculated by measuring the particle size of 200 arbitrary particles using an electron microscope and arithmetically averaging the measurement results. If the shape of the particle is not spherical, the longest side is the particle diameter.
  • the photosensitive composition layer When the photosensitive composition layer contains particles, it may contain only one kind of metal type and particles having different sizes, etc., or may contain two or more kinds of particles.
  • the photosensitive composition layer does not contain particles, or when the photosensitive composition layer contains particles, the content of the particles exceeds 0% by mass with respect to the total mass of the photosensitive composition layer. Whether it is preferably 35% by mass or less and contains no particles, or the content of the particles is more preferably more than 0% by mass and 10% by mass or less based on the total mass of the photosensitive composition layer, and is free of particles.
  • the content of the particles is more preferably more than 0% by mass and 5% by mass or less with respect to the total mass of the photosensitive composition layer, and the particles are not contained or the content of the particles is the photosensitive composition. It is more preferably more than 0% by mass and 1% by mass or less with respect to the total mass of the material layer, and it is particularly preferable that particles are not contained.
  • the photosensitive composition layer may contain a dye.
  • the dye is not particularly limited, and known dyes can be used, and examples thereof include leuco compounds.
  • the antioxidant examples include 1-phenyl-3-pyrazolidone (also known as phenidone), 1-phenyl-4,4-dimethyl-3-pyrazolidone, and 1-phenyl-4-methyl-4-hydroxymethyl-.
  • 3-Pyrazoridones such as 3-pyrazolidone; polyhydroxybenzenes such as hydroquinone, catechol, pyrogallol, methylhydroquinone, and chlorhydroquinone; paramethylaminophenol, paraaminophenol, parahydroxyphenylglycine, and paraphenylenediamine. Be done.
  • 3-pyrazolidones are preferable, and 1-phenyl-3-pyrazolidone is more preferable as the antioxidant because the effect of the present invention is more excellent.
  • the content of the antioxidant is preferably 0.001% by mass or more, more preferably 0.005% by mass or more, based on the total mass of the photosensitive composition layer. It is preferable, and 0.01% by mass or more is more preferable.
  • the upper limit is not particularly limited, but is preferably 1% by mass or less with respect to the total mass of the photosensitive composition layer.
  • the photosensitive composition layer may contain impurities.
  • impurities include sodium, potassium, magnesium, calcium, iron, manganese, copper, aluminum, titanium, chromium, cobalt, nickel, zinc, tin, halogen, and ions thereof.
  • halide ions, sodium ions, and potassium ions are easily mixed as impurities, so the following content is preferable.
  • the content of impurities in the photosensitive composition layer is preferably 80% by mass or less, more preferably 10% by mass or less, still more preferably 2% by mass or less, based on the total mass of the photosensitive composition layer.
  • the lower limit is not particularly limited, and is preferably 1 mass ppb or more, more preferably 0.1 mass ppm or more, based on the total mass of the photosensitive composition layer.
  • a raw material having a low impurity content is selected as a raw material contained in the photosensitive composition layer, and prevention of contamination of impurities during formation of the photosensitive composition layer, and cleaning. And remove it.
  • the amount of impurities can be kept within the above range.
  • Impurities can be quantified by known methods such as ICP (Inductively Coupled Plasma) emission spectroscopy, atomic absorption spectroscopy, and ion chromatography.
  • ICP Inductively Coupled Plasma
  • the content of compounds such as benzene, formaldehyde, trichlorethylene, 1,3-butadiene, carbon tetrachloride, chloroform, N, N-dimethylformamide, N, N-dimethylacetamide, and hexane in the photosensitive composition layer is Less is preferable.
  • These compounds are preferably 100 mass ppm or less, more preferably 20 mass ppm or less, still more preferably 4 mass ppm or less, based on the total mass of the photosensitive composition layer.
  • the lower limit is not particularly limited, and is preferably 10 mass ppb or more, more preferably 100 mass ppb or more, based on the total mass of the photosensitive composition layer.
  • the content of these compounds can be suppressed in the same manner as the above-mentioned metal impurities. Further, it can be quantified by a known measurement method.
  • the water content in the photosensitive composition layer is preferably 0.01 to 1.0% by mass, preferably 0.05, with respect to the total mass of the photosensitive composition layer from the viewpoint of improving reliability and laminateability. ⁇ 0.5% by mass is more preferable.
  • the transfer film may have a refractive index adjusting layer arranged on the photosensitive composition layer.
  • the transfer film preferably has a temporary support, a photosensitive composition layer, and a refractive index adjusting layer in this order.
  • the transfer film further has a protective film described later, it is preferable to have a temporary support, a photosensitive composition layer, a refractive index adjusting layer, and a protective film described later in this order.
  • the refractive index adjusting layer As the refractive index adjusting layer, a known refractive index adjusting layer can be applied. Examples of the material contained in the refractive index adjusting layer include a binder and particles.
  • binder examples include a binder polymer contained in the photosensitive composition layer and a polymer containing a structural unit having a carboxylic acid anhydride structure.
  • the particles include zirconium oxide particles (ZrO 2 particles), niobium oxide particles (Nb 2 O 5 particles), titanium oxide particles (TiO 2 particles), and silicon dioxide particles (SiO 2 particles).
  • the refractive index adjusting layer preferably contains a metal oxidation inhibitor.
  • a metal oxidation inhibitor for example, a compound having an aromatic ring containing a nitrogen atom in the molecule is preferable.
  • the metal oxidation inhibitor include imidazole, benzimidazole, tetrazole, mercaptothiadiazole, and benzotriazole.
  • the refractive index of the refractive index adjusting layer is preferably 1.60 or more, more preferably 1.63 or more.
  • the upper limit is not particularly limited, and is preferably 2.10 or less, and more preferably 1.85 or less.
  • the thickness of the refractive index adjusting layer is preferably 500 nm or less, more preferably 110 nm or less, still more preferably 100 nm or less.
  • the lower limit is not particularly limited, and is preferably 20 nm or more, and more preferably 50 nm or more.
  • the thickness of the refractive index adjusting layer is calculated as an average value of any five points measured by cross-sectional observation with a scanning electron microscope (SEM).
  • the transfer film may have other layers in addition to the temporary support, the photosensitive composition layer, the refractive index adjusting layer, and the protective film described above.
  • the other layer include a thermoplastic resin layer, an intermediate layer, and an antistatic layer.
  • thermoplastic resin layer The thermoplastic resin layer is usually arranged between the temporary support and the photosensitive composition layer.
  • the transfer film When the transfer film is provided with the thermoplastic resin layer, the followability to the substrate in the bonding process between the transfer film and the substrate is improved, and the mixing of air bubbles between the substrate and the transfer film can be suppressed. As a result, the adhesion to the layer adjacent to the thermoplastic resin layer (for example, a temporary support) can be ensured.
  • the thermoplastic resin layer contains resin.
  • the resin contains a thermoplastic resin in part or in whole. That is, in one embodiment, it is also preferable that the resin of the thermoplastic resin layer is a thermoplastic resin.
  • the thermoplastic resin is preferably an alkali-soluble resin.
  • alkali-soluble resin include acrylic resin, polystyrene resin, styrene-acrylic copolymer, polyurethane resin, polyvinyl alcohol, polyvinyl formal, polyamide resin, polyester resin, polyamide resin, epoxy resin, polyacetal resin, and polyhydroxystyrene resin.
  • an acrylic resin is preferable from the viewpoint of developability and adhesion to an adjacent layer.
  • the acrylic resin is at least selected from the group consisting of a structural unit derived from (meth) acrylic acid, a structural unit derived from (meth) acrylic acid ester, and a structural unit derived from (meth) acrylic acid amide. It means a resin having one kind of structural unit.
  • the acrylic resin the total content of the structural unit derived from (meth) acrylic acid, the structural unit derived from (meth) acrylic acid ester, and the structural unit derived from (meth) acrylic acid amide is the total content of the acrylic resin. It is preferably 50% by mass or more with respect to the mass.
  • the total content of the structural unit derived from (meth) acrylic acid and the structural unit derived from (meth) acrylic acid ester is preferably 30 to 100% by mass, preferably 50 to 100% by mass, based on the total mass of the acrylic resin. 100% by mass is more preferable.
  • the alkali-soluble resin is preferably a polymer having an acid group.
  • the acid group include a carboxy group, a sulfo group, a phosphoric acid group, and a phosphonic acid group, and a carboxy group is preferable.
  • the alkali-soluble resin is more preferably an alkali-soluble resin having an acid value of 60 mgKOH / g or more, and further preferably a carboxy group-containing acrylic resin having an acid value of 60 mgKOH / g or more.
  • the upper limit of the acid value of the alkali-soluble resin is not particularly limited, but is preferably 300 mgKOH / g or less, more preferably 250 mgKOH / g or less, further preferably 200 mgKOH / g or less, and particularly preferably 150 mgKOH / g or less.
  • the carboxy group-containing acrylic resin having an acid value of 60 mgKOH / g or more is not particularly limited and can be appropriately selected from known resins and used.
  • an alkali-soluble resin which is a carboxy group-containing acrylic resin having an acid value of 60 mgKOH / g or more
  • paragraph [0033] of JP-A-2010-237589 Acrylic resin containing a carboxy group having an acid value of 60 mgKOH / g or more among the polymers described in [0052], and acids among the binder polymers described in paragraphs [0053] to [0068] of JP2016-224162A.
  • Examples thereof include a carboxy group-containing acrylic resin having a value of 60 mgKOH / g or more.
  • the copolymerization ratio of the structural unit having a carboxy group in the carboxy group-containing acrylic resin is preferably 5 to 50% by mass, more preferably 10 to 40% by mass, and 12 to 30% by mass with respect to the total mass of the acrylic resin. Is more preferable.
  • an acrylic resin having a structural unit derived from (meth) acrylic acid is particularly preferable from the viewpoint of developability and adhesion to an adjacent layer.
  • the alkali-soluble resin may have a reactive group.
  • the reactive group may be any addition-polymerizable group, and an ethylenically unsaturated group; a polycondensable group such as a hydroxy group and a carboxy group; a polyaddition reactive group such as an epoxy group and a (block) isocyanate group may be used. Can be mentioned.
  • the weight average molecular weight (Mw) of the alkali-soluble resin is preferably 1,000 or more, more preferably 10,000 to 100,000, and even more preferably 20,000 to 50,000.
  • the alkali-soluble resin may be used alone or in combination of two or more.
  • the content of the alkali-soluble resin is preferably 10 to 99% by mass, more preferably 20 to 90% by mass, based on the total mass of the thermoplastic resin layer from the viewpoint of developability and adhesion to the adjacent layer. 40 to 80% by mass is more preferable, and 50 to 75% by mass is particularly preferable.
  • the intermediate layer 5 is present between the thermoplastic resin layer 3 and the photosensitive composition layer 7, so that the thermoplastic resin layer 3 and the photosensitive composition layer 7 are formed and coated. It is possible to suppress the mixing of components that may occur during storage after formation.
  • a water-soluble resin layer containing a water-soluble resin can be used.
  • an oxygen blocking layer having an oxygen blocking function which is described as a “separation layer” in JP-A-5-07724, can also be used.
  • the intermediate layer is an oxygen blocking layer, the sensitivity at the time of exposure is improved, the time load of the exposure machine is reduced, and the productivity is improved, which is preferable.
  • the oxygen blocking layer used as the intermediate layer may be appropriately selected from the known layers described in the above publications and the like. Of these, an oxygen blocking layer that exhibits low oxygen permeability and is dispersed or dissolved in water or an alkaline aqueous solution (1% by mass aqueous solution of sodium carbonate at 22 ° C.) is preferable.
  • the water-soluble resin layer contains a resin.
  • the resin contains a water-soluble resin in part or in whole.
  • the resin that can be used as the water-soluble resin include polyvinyl alcohol-based resin, polyvinylpyrrolidone-based resin, cellulose-based resin, acrylamide-based resin, polyethylene oxide-based resin, gelatin, vinyl ether-based resin, polyamide resin, and their co-weight. Examples include resins such as coalescing.
  • a (meth) acrylic acid / vinyl compound copolymer or the like can also be used as the water-soluble resin.
  • the copolymer of (meth) acrylic acid / vinyl compound a copolymer of (meth) acrylic acid / allyl (meth) acrylic acid is preferable, and a copolymer of methacrylic acid / allyl methacrylate is more preferable.
  • the water-soluble resin is a copolymer of (meth) acrylic acid / vinyl compound
  • the composition ratio (mol%) is preferably 90/10 to 20/80, preferably 80/20 to 30/70. More preferred.
  • the lower limit of the weight average molecular weight of the water-soluble resin is preferably 5,000 or more, more preferably 7,000 or more, and even more preferably 10,000 or more.
  • the upper limit thereof is preferably 200,000 or less, more preferably 100,000 or less, and even more preferably 50,000 or less.
  • the dispersity (Mw / Mn) of the water-soluble resin is preferably 1 to 10, more preferably 1 to 5.
  • the resin in the water-soluble resin layer (intermediate layer) is arranged on one surface side of the water-soluble resin layer (intermediate layer) in order to further improve the ability to suppress interlayer mixing of the water-soluble resin layer (intermediate layer). It is preferable that the resin is different from the resin contained in the layer to be formed and the resin contained in the layer arranged on the other surface side.
  • the resin of the water-soluble resin layer (intermediate layer) 15 is a resin. It is preferable that the resin is different from the polymer A and the thermoplastic resin (alkali-soluble resin).
  • the water-soluble resin preferably contains polyvinyl alcohol, and more preferably contains both polyvinyl alcohol and polyvinylpyrrolidone, in terms of further improving the oxygen blocking property and the ability to suppress interlayer mixing.
  • the water-soluble resin may be used alone or in combination of two or more.
  • the content of the water-soluble resin is not particularly limited, but is preferably 50% by mass or more with respect to the total mass of the water-soluble resin layer (intermediate layer) in terms of further improving the oxygen blocking property and the ability to suppress interlayer mixing. , 70% by mass or more is more preferable, 80% by mass or more is further preferable, and 90% by mass or more is particularly preferable.
  • the upper limit is not particularly limited, but is preferably 99.9% by mass or less, and more preferably 99.8% by mass or less.
  • the layer thickness of the water-soluble resin layer (intermediate layer) is not particularly limited, but is preferably 0.1 to 5 ⁇ m, more preferably 0.5 to 3 ⁇ m.
  • the thickness of the water-soluble resin layer (intermediate layer) is within the above range, the oxygen blocking property is not lowered and the ability to suppress interlaminar mixing is excellent. Further, it is possible to suppress an increase in the time for removing the water-soluble resin layer (intermediate layer) during development.
  • the transfer film Since the transfer film has an antistatic layer, it is possible to suppress the generation of static electricity when peeling off the film or the like arranged on the antistatic layer, and also suppress the generation of static electricity due to rubbing against equipment or other films or the like. Therefore, for example, it is possible to suppress the occurrence of a defect in an electronic device.
  • the antistatic layer is preferably placed between the temporary support and the photosensitive composition layer.
  • the antistatic layer is a layer having antistatic properties and contains at least an antistatic agent.
  • the antistatic agent is not particularly limited, and a known antistatic agent can be applied.
  • the method for producing the temporary support is not particularly limited, and examples thereof include known methods.
  • the temporary support may be manufactured by a manufacturing method having an extrusion molding step and a coating step, or a manufacturing method having a coextrusion molding step. Further, it is preferable to have a biaxial stretching step in addition to the above steps.
  • the extrusion molding method include a method of molding a raw material resin into a desired shape by extruding the raw material resin using an extruder.
  • Examples of the coextrusion forming step include a method of molding a plurality of raw material resins into a shape having a multilayer structure by extruding a plurality of raw material resins using an extruder.
  • the biaxial stretching step may be simultaneous biaxial stretching in which longitudinal stretching and transverse stretching are performed at the same time, or sequential biaxial stretching in which longitudinal stretching and transverse stretching are performed in two stages or in multiple stages of two or more stages.
  • the forms of sequential biaxial stretching include, for example, [in order of longitudinal stretching and transverse stretching], [in order of longitudinal stretching, transverse stretching and longitudinal stretching], [in order of longitudinal stretching, longitudinal stretching and transverse stretching], and [ The form of lateral stretching and longitudinal stretching] can be mentioned. Above all, it is preferable to carry out in the order of longitudinal stretching and transverse stretching.
  • the method for manufacturing the temporary support includes a step of forming an unstretched temporary support main body by melt-extruding polyester (hereinafter, also referred to as “extrusion molding step”), a coating step, and a lengthening of the temporary support main body.
  • a step of stretching in the direction hereinafter, also referred to as “longitudinal stretching step”
  • a step of stretching the temporary support main body stretched in the longitudinal direction in the width direction hereinafter, also referred to as “transverse stretching step”. It is preferable to have.
  • the method for manufacturing the temporary support is a step of forming an unstretched temporary support by simultaneously melt-extruding the raw material resins of the first layer, the second layer, and the temporary support body (hereinafter, “coextrusion molding”).
  • a step of stretching the temporary support in the longitudinal direction hereinafter, also referred to as a “longitudinal stretching step”
  • a step of stretching the temporary support stretched in the longitudinal direction in the width direction also referred to as a “step”.
  • the raw material resin for example, polyester
  • the raw material resin is melt-extruded to form an unstretched temporary support body.
  • melt extrusion method examples include a method using an extruder.
  • a raw material resin for example, polyester
  • an extruder equipped with one or two or more screws and the screw is rotated to melt and knead. Will be done.
  • Polyester is melted in an extruder by heating and kneading with a screw to form a melt.
  • the melt is extruded from an extrusion die (hereinafter, also referred to as "die") through a gear pump, a filter, or the like (JIS B8650: 2006, a, extrusion molding machine, No. 134).
  • the melt may be extruded in a single layer or in multiple layers.
  • the extruder In melt extrusion, it is preferable to replace the inside of the extruder with nitrogen from the viewpoint of suppressing thermal decomposition (for example, hydrolysis of polyester) in the extruder. Further, the extruder is preferably a twin-screw extruder in that the kneading temperature can be kept low.
  • the melt extruded from the extrusion die is cooled to form a film.
  • the melt can be formed into a film by bringing the melt into contact with a casting roll and cooling and solidifying the melt on the casting roll. In cooling the melt, it is more preferable to blow air (preferably cold air) on the melt.
  • the temperature of the casting roll is preferably more than ⁇ 10 ° C. + 30 ° C., more preferably ⁇ 7 to + 20 ° C., and even more preferably ⁇ 5 + 10 ° C. with respect to the glass transition temperature (Tg) of the polyester.
  • the method for improving the adhesion include an electrostatic application method, an air knife method, an air chamber method, a vacuum nozzle method, and a touch roll method.
  • the temporary support body cooled by using a casting roll or the like is stripped from the cooling member such as a casting roll by using a stripping member such as a stripping roll.
  • the coating step is a step of forming the first layer or the second layer.
  • the coating step is not particularly limited, and examples thereof include known methods.
  • the coating step is not particularly limited, and examples thereof include known methods.
  • the reverse roll coat method, the gravure coat method, the kiss coat method, the die coater method, the roll brush method, the spray coat method, the air knife coat method, the wire bar coat method, the pipe doctor method, the impregnation coat method, and the curtain coat method can be mentioned. Be done. Moreover, you may use these methods alone or in combination.
  • the solvent include water and organic solvents.
  • the coating step may be provided before and after any step in the manufacturing step of the temporary support. Specifically, it may be provided after the extrusion molding step or after the biaxial stretching step. Further, it may be performed once or a plurality of times. Among them, it is preferable to provide the coating liquid after the biaxial stretching step, and it is more preferable to apply the coating liquid for forming the first layer or the second layer on the temporary support main body stretched in the longitudinal direction, and then laterally stretch the coating liquid.
  • the coextrusion molding step is not particularly limited, and examples thereof include known methods.
  • Examples of the coextrusion molding step include the methods described in JP-A-2019-65271, and the contents thereof are incorporated in the present specification.
  • the biaxial stretching step is not particularly limited, and a known method can be mentioned.
  • the biaxial stretching step preferably includes a longitudinal stretching step and a transverse stretching step.
  • the longitudinal stretching step it is preferable to stretch the unstretched film (for example, the unstretched temporary support and the main body of the unstretched temporary support) in the longitudinal direction (hereinafter, also referred to as “longitudinal stretching”).
  • the longitudinal stretching step it is preferable to preheat the unstretched film (for example, the unstretched temporary support and the unstretched temporary support main body) before the longitudinal stretching.
  • the unstretched film for example, the unstretched temporary support and the unstretched temporary support main body.
  • the preheating temperature is preferably ⁇ 10 to + 60 ° C., more preferably 0 to + 50 ° C. with respect to the Tg of the unstretched film (for example, the unstretched temporary support and the unstretched temporary support body). .. Specifically, the preheating temperature is preferably 60 to 100 ° C, more preferably 65 to 80 ° C.
  • the longitudinal stretching is performed, for example, by applying tension between two or more pairs of nip rolls installed in the transport direction while transporting the unstretched film (for example, the unstretched temporary support and the unstretched temporary support main body) in the longitudinal direction. It can be carried out. For example, when a pair of nip rolls A and a pair of nip rolls B are installed on the upstream side in the transport direction, the rotation speed of the nip rolls B is set to the rotation speed of the nip roll A when the unstretched polyester film is transported. By increasing the speed, the unstretched film (for example, the unstretched temporary support and the unstretched temporary support body) is stretched in the longitudinal direction.
  • the unstretched film for example, the unstretched temporary support and the unstretched temporary support body
  • the draw ratio in the longitudinal stretching step is preferably smaller than the stretching ratio in the transverse stretching step described later.
  • the stretching ratio in the longitudinal stretching step is preferably 2.0 to 5.0 times, more preferably 2.5 to 4.0 times, and further preferably 2.8 to 4.0 times. preferable.
  • the heating temperature in the longitudinal stretching step is preferably ⁇ 20 to + 50 ° C., preferably ⁇ 10 to + 40 ° C. with respect to the Tg of the unstretched film (for example, the unstretched temporary support and the unstretched temporary support main body). It is more preferable that the temperature is 0 to + 30 ° C. Specifically, the heating temperature in the longitudinal stretching step is preferably 70 to 120 ° C, more preferably 80 to 110 ° C, and even more preferably 85 to 100 ° C.
  • a nip roll or the like in contact with the unstretched film for example, the unstretched temporary support and the unstretched temporary support body
  • a method of heating the roll of the film is mentioned. Examples of the method for heating the roll include a method of providing a heater or a pipe through which a hot solvent can flow inside the roll.
  • a method of applying warm air to an unstretched film for example, an unstretched temporary support and an unstretched temporary support body
  • a method of contacting with a heat source such as a heater, and passing in the vicinity of the heat source.
  • This includes a method of heating an unstretched film (for example, an unstretched temporary support and an unstretched temporary support body).
  • the stretching speed in the longitudinal stretching step is preferably 800 to 1500% / sec, more preferably 1000 to 1400% / sec, and even more preferably 1200 to 1400% / sec.
  • the "stretching speed" is a value expressed as a percentage by dividing the length ⁇ d stretched for 1 second from the length d 0 before stretching by the length d 0 before stretching.
  • the film stretched in the longitudinal direction (for example, a temporary support stretched in the longitudinal direction and a temporary support main body stretched in the longitudinal direction) is stretched in the width direction (hereinafter, also referred to as “lateral stretching”).
  • the transverse stretching step it is preferable to preheat the film stretched in the longitudinal direction (for example, the temporary support stretched in the longitudinal direction and the temporary support body stretched in the longitudinal direction) before the transverse stretching.
  • the film stretched in the longitudinal direction for example, the temporary support stretched in the longitudinal direction and the temporary support body stretched in the longitudinal direction
  • the film can be easily stretched laterally.
  • the preheating temperature is preferably ⁇ 10 to + 60 ° C., more preferably 0 to + 50 ° C. with respect to the Tg of the unstretched film (for example, the unstretched temporary support and the unstretched temporary support body). .. Specifically, the preheating temperature is preferably 80 to 120 ° C, more preferably 90 to 110 ° C.
  • the draw ratio in the transverse stretching step is preferably larger than the draw ratio in the longitudinal stretching step.
  • the stretching ratio in the transverse stretching step is preferably 3.0 to 6.0 times, more preferably 3.5 to 5.0 times, and further preferably 3.5 to 4.5 times. preferable.
  • the area magnification represented by the product of the stretching ratio in the longitudinal stretching step and the stretching ratio in the transverse stretching step is preferably 12.8 to 15.5 times, and preferably 13.5 to 15.2 times. Is more preferable, and 14.0 to 15.0 times is further preferable.
  • the area magnification is 12.8 times or more, the molecular orientation in the film width direction becomes good. Further, when the area magnification is 15.5 times or less, it is easy to maintain a state in which the molecular orientation is difficult to be relaxed when subjected to heat treatment.
  • the heating temperature in the transverse stretching step is preferably ⁇ 10 to + 80 ° C., preferably 0 to + 70 ° C. with respect to the Tg of the unstretched film (for example, the unstretched temporary support and the unstretched temporary support main body). More preferably, it is more preferably 0 to + 60 ° C. Specifically, the heating temperature in the transverse stretching step is preferably 100 to 140 ° C, more preferably 110 to 135 ° C, and even more preferably 115 to 130 ° C.
  • the stretching speed in the transverse stretching step is preferably 10 to 100% / sec, more preferably 10 to 70% / sec, and even more preferably 20 to 60% / sec.
  • a step of heat-treating a film stretched in the width direction (for example, a temporary support stretched in the width direction and a temporary support main body stretched in the width direction) (hereinafter, “heating”). It is preferable to have a "treatment step").
  • the heat treatment step include a heat fixing step and a heat relaxation step.
  • the heat treatment step preferably includes at least one of a heat fixing step and a heat relaxation step, and more preferably has a heat fixing step and a heat relaxation step.
  • the film stretched in the width direction (for example, the temporary support stretched in the width direction and the temporary support main body stretched in the width direction) is heat-fixed by heating. Since the raw material resin can be crystallized by heat fixing, shrinkage of the film can be suppressed.
  • the heating temperature in the heat fixing step is preferably 190 to 240 ° C, more preferably 200 to 240 ° C, and even more preferably 210 to 230 ° C.
  • the variation in the maximum ultimate film surface temperature in the film width direction is preferably 0.5 to 10.0 ° C, more preferably 0.5 to 7.0 ° C, and 0.5. It is more preferably to 5.0 ° C, and particularly preferably 0.5 to 4.0 ° C.
  • Examples of the heating method include a method of applying hot air to the film and a method of radiant heating of the film.
  • Examples of the device used in the method of radiant heating include an infrared heater.
  • the heating time in the heat fixing step is preferably 5 to 50 seconds, more preferably 5 to 30 seconds, and even more preferably 5 to 10 seconds.
  • Heat relaxation process In the heat relaxation step, heat is relaxed by heating the film stretched in the width direction (for example, a temporary support stretched in the width direction and a temporary support main body stretched in the width direction). By thermal relaxation, the residual strain of the film (for example, the temporary support stretched in the width direction and the temporary support main body stretched in the width direction) can be relaxed.
  • the heating temperature in the heat relaxation step is preferably 5 ° C. or higher, more preferably 15 ° C. or higher, and even more preferably 25 ° C. or higher lower than the heating temperature in the heat fixing step. It is particularly preferable that the temperature is as low as 30 ° C. or higher.
  • the lower limit of the heating temperature in the heat relaxation step is preferably 100 ° C. or higher, more preferably 110 ° C. or higher, and even more preferably 120 ° C. or higher.
  • Examples of the heating method include a method of applying hot air to the film and a method of radiant heating of the film.
  • Examples of the device used in the method of radiant heating include an infrared heater.
  • the method for manufacturing a temporary support includes a step of cooling the heat-treated film (for example, a heat-treated temporary support and a heat-treated temporary support main body) (hereinafter, also referred to as a “cooling step”). Is preferable.
  • Examples of the cooling method include a method of blowing air (preferably cold air) on the film and a method of bringing the film into contact with a temperature-adjustable member (for example, a temperature control roll).
  • a temperature-adjustable member for example, a temperature control roll
  • the average cooling rate in the cooling step is preferably 500 to 4000 ° C./min, more preferably 1000 to 3500 ° C./min, and even more preferably 1500 to 3000 ° C./min.
  • the average cooling rate is determined using a non-contact thermometer (for example, a radiation thermometer). For example, from the distance Z between the point where the surface temperature of the film (for example, the temporary support and the temporary support body) becomes 150 ° C. and the point where the film surface temperature becomes 70 ° C., and the film transport speed S, 150 ° C. The cooling time (Z / S) from to 70 ° C. is determined. Next, the average cooling rate is obtained by calculating (150-70) / (Z / S).
  • the method for producing the transfer film of the present invention is not particularly limited, and a known method can be used. Among them, from the viewpoint of excellent productivity, a method of applying a photosensitive composition on a temporary support and subjecting it to a drying treatment as necessary to form a photosensitive composition layer is preferable. Hereinafter, the above method will be described in detail.
  • Examples of the method for applying the photosensitive composition include a printing method, a spray method, a roll coating method, a bar coating method, a curtain coating method, a spin coating method, and a die coating method (that is, a slit coating method).
  • drying means removing at least a portion of the solvent contained in the photosensitive composition.
  • the transfer film has a refractive index adjusting layer on the photosensitive composition layer
  • the composition for forming the refractive index adjusting layer is applied on the photosensitive composition layer and dried as necessary to refract.
  • a rate adjustment layer can be formed.
  • the transfer film can be manufactured by adhering the protective film to the photosensitive composition layer.
  • the method of adhering the protective film to the photosensitive composition layer is not particularly limited, and known methods can be mentioned.
  • Examples of the device for adhering the protective film to the photosensitive composition layer include known laminators such as a vacuum laminator and an auto-cut laminator. It is preferable that the laminator is provided with an arbitrary heatable roller such as a rubber roller and can be pressurized and heated.
  • the photosensitive composition layer can be transferred to the transferred object.
  • the protective film is peeled off from the transfer film, and the surface opposite to the temporary support is brought into contact with the substrate having the conductive portion and bonded to the conductive portion, the photosensitive composition layer, and the temporary support.
  • An exposure process for pattern exposure of the photosensitive composition layer and It comprises a developing step of developing an exposed photosensitive composition layer to form a pattern.
  • a method for producing a laminated body comprising a peeling step of peeling a temporary support from a substrate with a photosensitive composition layer between a bonding step and an exposure step, or between an exposure step and a developing step. Is preferable.
  • the procedure of the above process will be described in detail.
  • the protective film is peeled off from the transfer film, and the surface of the transfer film on the opposite side of the temporary support is brought into contact with a substrate having a conductive portion and bonded to the conductive layer, the photosensitive composition layer, and the like. Further, it is a step of obtaining a substrate with a photosensitive composition layer having a temporary support in this order.
  • the method for peeling the protective film from the transfer film is not particularly limited, and a known method can be used.
  • the surface opposite to the temporary support of the transfer film is preferably a refractive index adjusting layer when the transfer film has a refractive index adjusting layer, and is photosensitive when the transfer film does not have the refractive index adjusting layer. It is preferably a sex composition layer. That is, in the bonding step, the refractive index adjusting layer of the transfer film may be brought into contact with the transferred body to be bonded, or the photosensitive composition layer of the transfer film may be brought into contact with the transferred body to be bonded. preferable. The exposed photosensitive composition layer on the temporary support of the transfer film is brought into contact with the conductive layer and bonded.
  • the photosensitive composition layer and the temporary support are arranged on the conductive layer.
  • the conductive layer and the surface of the photosensitive composition layer are pressure-bonded so as to be in contact with each other.
  • the crimping method is not particularly limited, and known transfer methods and laminating methods can be used. Above all, it is preferable to superimpose the surface of the photosensitive composition layer on a substrate having a conductive portion, pressurize and heat it with a roll or the like.
  • a known laminator such as a vacuum laminator and an auto-cut laminator can be used for bonding.
  • the substrate having a conductive layer has a conductive layer on the substrate, and any layer may be formed if necessary. That is, the substrate having the conductive layer is a conductive substrate having at least a substrate and a conductive layer arranged on the substrate.
  • the substrate examples include a resin substrate, a glass substrate, and a semiconductor substrate. Preferred embodiments of the substrate are described, for example, in paragraph [0140] of WO 2018/155193, the contents of which are incorporated herein.
  • 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 from the viewpoint of conductivity and fine wire forming property. It is preferable to have it. Further, only one conductive layer may be arranged on the substrate, or two or more layers may be arranged. When two or more conductive layers are arranged, it is preferable to have conductive layers made of different materials. Preferred embodiments of the conductive layer are described, for example, in paragraph [0141] of WO 2018/155193, the contents of which are incorporated herein.
  • a substrate having at least one of a transparent electrode and a routing wire is preferable.
  • the above-mentioned substrate can be suitably used as a touch panel substrate.
  • the transparent electrode may function suitably as a touch panel electrode.
  • the transparent electrode is preferably composed of a metal oxide film such as ITO (indium tin oxide) and IZO (indium zinc oxide), a metal mesh, and a fine metal wire such as silver nanowire.
  • the thin metal wire include thin wires such as silver and copper. Of these, silver conductive materials such as silver mesh and silver nanowires are preferable.
  • Metal is preferable as the material of the routing wiring.
  • the metal that is the material of the routing wiring include gold, silver, copper, molybdenum, aluminum, titanium, chromium, zinc, and manganese, and alloys composed of two or more of these metal elements.
  • copper, molybdenum, aluminum, or titanium is preferable, and copper is more preferable as the material of the routing wiring.
  • the electrode protective film for a touch panel formed by using the photosensitive composition layer in the transfer film of the present invention has an electrode or the like for the purpose of protecting the electrode or the like (that is, at least one of the electrode for the touch panel and the wiring for the touch panel). It is preferably provided so as to cover it directly or via another layer.
  • the exposure step is a step of pattern-exposing the photosensitive composition layer.
  • the "pattern exposure” refers to an exposure in a form of exposure in a pattern, that is, a form in which an exposed portion and a non-exposed portion are present.
  • the detailed arrangement and specific size of the pattern in the pattern exposure are not particularly limited.
  • the pattern formed by the development step described later preferably includes thin lines having a width of 500 ⁇ m or less, and more preferably contains thin lines having a width of 100 ⁇ m or less.
  • any light source in a wavelength range capable of curing the photosensitive composition layer (for example, a wavelength of 365 nm or 405 nm) can be appropriately selected and used.
  • the main wavelength of the exposure light for pattern exposure is preferably a wavelength of 365 nm.
  • the main wavelength is the wavelength having the highest intensity.
  • Examples of the light source include various lasers, light emitting diodes (LEDs), ultra-high pressure mercury lamps, high pressure mercury lamps, and metal halide lamps.
  • the exposure amount is preferably 5 to 200 mJ / cm 2 , more preferably 10 to 200 mJ / cm 2 .
  • the peeling step is a step of peeling the temporary support from the substrate with the photosensitive composition layer between the bonding step and the exposure step, or between the exposure step and the development step described later.
  • the peeling method is not particularly limited, and a mechanism similar to the cover film peeling mechanism described in paragraphs [0161] to [0162] of JP2010-072589 can be used.
  • the developing step is a step of developing the exposed photosensitive composition layer to form a pattern.
  • the development of the photosensitive composition layer can be performed using a developing solution.
  • An alkaline aqueous solution is preferable as the developing solution.
  • the alkaline compound that can be contained in the alkaline aqueous solution include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogencarbonate, potassium hydrogencarbonate, tetramethylammonium hydroxide, tetraethylammonium hydroxide, and tetrapropylammonium hydroxide. Do, tetrabutylammonium hydroxide, and choline (2-hydroxyethyltrimethylammonium hydroxide) can be mentioned.
  • Examples of the development method include paddle development, shower development, spin development, and dip development.
  • the developer preferably used includes, for example, the developer described in paragraph [0194] of International Publication No. 2015/093271, and examples of the developing method preferably used include International Publication No. 1.
  • the development method described in paragraph [0195] of 2015/093271 can be mentioned.
  • the method for producing the laminate may include a step of exposing the pattern obtained by the development step (post-exposure step) and / or a step of heating (post-baking step).
  • post-exposure step a step of exposing the pattern obtained by the development step
  • post-baking step a step of heating
  • the transfer film can also be used in a method for manufacturing circuit wiring.
  • the method for manufacturing the circuit wiring is not particularly limited, and examples thereof include known manufacturing methods.
  • the protective film is peeled off from the transfer film, the photosensitive composition layer on the temporary support is attached to the substrate having the conductive layer, and the photosensitive layer, the photosensitive composition layer, and the photosensitive composition have the temporary support in this order.
  • the bonding process to obtain a substrate with a sex composition layer An exposure process for pattern exposure of the photosensitive composition layer, and A developing step of developing an exposed photosensitive composition layer to form a pattern, An etching process that etches the conductive layer in the area where the pattern is not arranged,
  • a method for producing a laminated body comprising a peeling step of peeling a temporary support from a substrate with a photosensitive composition layer between a bonding step and an exposure step, or between an exposure step and a developing step. Is preferable.
  • the bonding step, the exposure step, the developing step, and the peeling step are synonymous with each step of the above-mentioned ⁇ manufacturing method of laminated body>, and the preferable range is also the same.
  • the etching step is a step (etching step) of etching the conductive layer in the region where the pattern obtained in the developing step is not arranged. That is, the etching step is to use the pattern formed from the photosensitive composition layer as an etching resist and perform the etching treatment of the conductive layer.
  • etching step a known method can be applied. For example, the method described in paragraphs [0209] to [0210] of JP-A-2017-120435, paragraphs [0048] to [0054] of JP-A-2010-152155. ], A wet etching method of immersing in an etching solution, and a dry etching method by plasma etching can be mentioned.
  • an acidic or alkaline etching solution may be appropriately selected according to the etching target.
  • the acidic etching solution include an aqueous solution of an acidic component alone selected from hydrochloric acid, sulfuric acid, nitric acid, acetic acid, hydrofluoric acid, oxalic acid, and phosphoric acid, as well as an acidic component, ferric chloride, and fluoride. Examples thereof include a mixed aqueous solution with a salt selected from ammonium and potassium permanganate.
  • the acidic component may be a component in which a plurality of acidic components are combined.
  • the alkaline etching solution examples include an aqueous solution of an alkaline component alone selected from sodium hydroxide, potassium hydroxide, ammonia, an organic amine, and a salt of an organic amine (tetramethylammonium hydroxide, etc.), and an alkaline component. And a mixed aqueous solution of salt (potassium permanganate, etc.) can be mentioned.
  • the alkaline component may be a component in which a plurality of alkaline components are combined.
  • the method for manufacturing a circuit wiring may include a step (removal step) of removing the remaining pattern.
  • the removal step is particularly limited and may be performed before or after each step, preferably after the etching step.
  • the method for removing the remaining pattern is not particularly limited, and examples thereof include a method for removing by chemical treatment, and a method for removing with a removing liquid is preferable. Examples of the method of removing using the removing liquid include a method of immersing the transferred body having the remaining pattern in the removing liquid being stirred for 1 to 30 minutes.
  • the liquid temperature of the removing liquid is preferably 30 to 80 ° C, more preferably 50 to 80 ° C.
  • the removing liquid examples include a removing liquid in which an inorganic alkaline component or an organic alkaline component is dissolved in water, dimethyl sulfoxide, N-methylpyrrolidone, or a mixed solution thereof.
  • examples of the inorganic alkaline component include sodium hydroxide and potassium hydroxide.
  • examples of the organic alkali component include a primary amine compound, a secondary amine compound, a tertiary amine compound and a quaternary ammonium salt compound.
  • the removing liquid may be used and removed by a known method such as a spray method, a shower method and a paddle method.
  • the method for manufacturing the laminate and the method for manufacturing the circuit wiring may include any step (other steps) other than the above-mentioned steps.
  • Other steps include, for example, a step of reducing the visible light reflectance described in paragraph [0172] of International Publication No. 2019/022089, and a step on the insulating film described in paragraph [0172] of International Publication No. 2019/022089.
  • a step of forming a new conductive layer can be mentioned. However, it is not limited to these steps.
  • the method for manufacturing the laminate and the method for manufacturing the circuit wiring may include a step of reducing the visible light reflectance of a part or all of the plurality of conductive layers included in the transferred body.
  • the treatment for reducing the visible light reflectance include an oxidation treatment.
  • the visible light reflectance of the conductive layer can be lowered by oxidizing copper to copper oxide and blackening the conductive layer.
  • paragraphs [0017] to [0025] of JP-A-2014-150118, and paragraphs [0041] to [0042] and paragraphs [0048] of JP-A-2013-206315. ] can be incorporated, the contents of which are incorporated herein.
  • the method for manufacturing a circuit wiring preferably includes a step of forming an insulating film on the surface of the circuit wiring and a step of forming a new conductive layer on the surface of the insulating film.
  • the step of forming the insulating film is not particularly limited, and examples thereof include a known method of forming a permanent film.
  • an insulating film having a desired pattern may be formed by photolithography using a photosensitive material having an insulating property.
  • the step of forming the new conductive layer on the insulating film is not particularly limited, and for example, a new conductive layer having a desired pattern may be formed by photolithography using a photosensitive composition having conductivity. ..
  • a substrate having a plurality of conductive layers on both surface sides of the substrate it is also preferable to use a substrate having a plurality of conductive layers on both surface sides of the substrate, and to form a circuit sequentially or simultaneously with respect to the conductive layers arranged on both surface sides of the substrate.
  • a circuit wiring for a touch panel in which a first conductive pattern is formed on one surface of a substrate and a second conductive pattern is formed on the surface of the other substrate. It is also preferable to form the touch panel circuit wiring having such a configuration from both sides of the substrate by roll-to-roll.
  • the laminated body and the circuit wiring manufactured by the manufacturing method of the laminated body and the manufacturing method of the circuit wiring can be applied to various devices.
  • Examples of the device provided with the laminate or circuit wiring manufactured by the above manufacturing method include a display device, a printed wiring board, a semiconductor package, and an input device, and a touch panel is preferable, and a capacitance type touch panel is more preferable. ..
  • the input device can be applied to a display device such as an organic EL display device and a liquid crystal display device.
  • the transfer film may also be used in a method for manufacturing an electronic device.
  • the method for manufacturing the electronic device the method for manufacturing the electronic device using the transfer film described above is preferable.
  • the method for manufacturing an electronic device includes the above-mentioned method for manufacturing a laminate.
  • the electronic device include an input device and the like, and a touch panel is preferable.
  • the input device can be applied to an organic electroluminescence display device and a display device of a liquid crystal display device.
  • a transferred body for example, a substrate, a conductive layer (a conductive layer possessed by the substrate)
  • a laminated body in which patterns manufactured using the above transfer film are laminated in this order for example, a transferred body (for example, a substrate, a conductive layer (a conductive layer possessed by the substrate)), and a laminated body in which patterns manufactured using the above transfer film are laminated in this order.
  • a method including a step of forming wiring for a touch panel by etching a conductive layer in a region where a resin pattern is not arranged is also preferable, and the bonding step, the exposure step, and the developing step are performed.
  • a method using a pattern manufactured by a manufacturing method including is more preferable.
  • the touch panel manufacturing method including the step of forming the touch panel wiring the specific embodiment of each step and the embodiment such as the order in which each step is performed are as described in the above-mentioned ⁇ Circuit wiring manufacturing method>. The same applies to the preferred embodiment. Further, the touch panel manufacturing method including the step of forming the touch panel wiring may include any step (other steps) other than those described above. As a method for forming the wiring for the touch panel, for example, the method described in FIG. 1 of International Publication No. 2016/190405 can be mentioned.
  • a touch panel having at least touch panel wiring is manufactured.
  • the touch panel preferably has a transparent substrate, electrodes, and an insulating layer or a protective layer.
  • Examples of the detection method on the touch panel include known methods such as a resistance film method, a capacitance method, an ultrasonic method, an electromagnetic induction method, and an optical method, and the capacitance method is preferable.
  • the touch panel includes, for example, an in-cell type (for example, the one shown in FIGS. 5 to 8 of JP-A-2012-51751), an on-cell type (for example, the one described in FIG. 19 of JP-A-2013-168125), and the touch panel.
  • an in-cell type for example, the one shown in FIGS. 5 to 8 of JP-A-2012-51751
  • an on-cell type for example, the one described in FIG. 19 of JP-A-2013-168125
  • the touch panel for example, Of Japanese Patent Application Laid-Open No. 2012-089102
  • OGS One Glass Solution
  • TOR Touch-on-Lens type (for example, FIG. 2 of Japanese Patent Application Laid-Open No. 2013-054727). (For example, those described in FIG.
  • Examples of the touch panel include those described in paragraph [0229] of JP-A-2017-120345.
  • the manufactured electronic device contains a resin pattern as a cured film.
  • the cured film of such a resin pattern can be used as a protective film (permanent film) that covers a part or all of electrodes and the like of an electronic device (touch panel and the like).
  • the present invention will be specifically described with reference to examples.
  • the materials, amounts, ratios, treatment contents, treatment procedures, etc. shown in the following examples may be appropriately and changed as long as they do not deviate from the gist of the present specification. Therefore, the scope of the present invention is not limited to the specific examples shown below.
  • “parts” and “%” are based on mass.
  • the weight average molecular weight (Mw) is the weight average molecular weight determined in terms of polystyrene by gel permeation chromatography (GPC).
  • Pellets A of polyethylene terephthalate produced by using the titanium compound (citrate chelated titanium complex, VERTEC AC-420, manufactured by Johnson Matthey) described in Japanese Patent No. 5575671 as a polymerization catalyst were obtained.
  • a master batch A containing 1% by mass of crosslinked polystyrene resin particles (organic particles) was obtained by supplying the particles to a smelting extruder and keeping the vent holes at a reduced pressure of 1 kPa or less to remove water.
  • Pellet A (90 parts by mass) and 10% by mass water slurry (alumina sol, manufactured by Nissan Chemical Industries, Ltd.) (10 parts by mass) of alumina particles having an average particle diameter of 30 nm were supplied to a twin-screw kneading extruder to vent holes. was kept at a reduced pressure of 1 kPa or less and water was removed to obtain a master batch B containing 1% by mass of alumina particles.
  • pellet A 70 parts by mass
  • masterbatch A 10 parts by mass
  • masterbatch B 20 parts by mass
  • the pellet A and the mixture X are dried to a water content of 50 ppm or less, they are put into an extruder so that the intermediate layer becomes pellet A, melted at 290 ° C., merged and laminated with a layer merging block, and the X layer (mixture) is formed.
  • An unstretched temporary support having a three-layer structure in the order of X layer) / A layer (layer composed of pellet A) / X layer (layer composed of mixture X) was prepared.
  • the obtained unstretched temporary support was sequentially biaxially stretched by the following method.
  • the unstretched temporary support was stretched in the vertical direction (transport direction) by passing it between two pairs of nip rolls having different peripheral speeds.
  • the longitudinal stretching was carried out at a preheating temperature of 75 ° C., a stretching temperature of 95 ° C., a stretching ratio of 3.4 times, and a stretching speed of 1300% / sec.
  • the obtained temporary support stretched in the vertical direction was stretched in the horizontal direction using a tenter.
  • the longitudinal stretching was carried out at a preheating temperature of 100 ° C., a stretching temperature of 120 ° C., a stretching ratio of 4.2 times, and a stretching speed of 50% / sec to obtain a temporary support Z-1.
  • Temporary supports of each Example and each Comparative Example were prepared by the same procedure as the above-mentioned provisional support Z-1 except that each component was changed according to Tables 2 to 3.
  • Transfer film The transfer film of Example 1 was prepared according to the following procedure. First, the components contained in each transfer film will be described in detail.
  • PGMEA 55.8 parts by mass
  • toluene 55.8 parts by mass
  • PGMEA 6.2 parts by mass
  • AIBN azobisisobutyronitrile
  • the obtained mixed liquid was further added to the flask over 4 hours using a dropping pump while maintaining the liquid temperature at 80 ° C. under stirring. After completion of the addition, the mixture was kept at a temperature of 80 ° C. and reacted for another 6 hours under stirring to obtain a solution containing the binder polymer A.
  • the weight average molecular weight of the obtained binder polymer A was 65,000.
  • ⁇ Binder polymer B> PGMEA (116.5 parts by mass) was placed in a three-necked flask, and the temperature was raised to 90 ° C. under a nitrogen atmosphere.
  • Styrene (52.0 parts by mass), methyl methacrylate (24.0 parts by mass), methacrylic acid (24.0 parts by mass), V while maintaining the liquid temperature in the three-necked flask at 90 ° C ⁇ 2 ° C.
  • a mixed solution of -601 (2,2'-azobis (isobutyric acid) dimethyl, manufactured by Fujifilm (4.0 parts by mass) and PGMEA (116.5 parts by mass) was placed in a three-necked flask over 2 hours.
  • the mixed solution was stirred for 2 hours while maintaining the liquid temperature at 90 ° C. ⁇ 2 ° C. to obtain a solution containing the binder polymer B (solid content concentration: 30.0% by mass).
  • the acid value of the binder polymer B was 159 mgKOH / g, the weight average molecular weight was 60,000, and the glass transition temperature was 126 ° C.
  • ⁇ Binder polymer C Propylene glycol monomethyl ether (82.4 g) was placed in a flask and heated to 90 ° C. under a nitrogen stream. A solution in which styrene (38.4 g), dicyclopentanyl methacrylate (30.1 g), and methacrylic acid (34.0 g) are dissolved in propylene glycol monomethyl ether (20 g) in this solution, and a polymerization initiator V-601. A solution prepared by dissolving (5.4 g) of (Fuji Film Wako Pure Chemical Industries, Ltd.) in propylene glycol monomethyl ether acetate (43.6 g) was simultaneously added dropwise over 3 hours.
  • V-601 (0.75 g) was added 3 times every 1 hour. After that, it was reacted for another 3 hours. Then, it was diluted with propylene glycol monomethyl ether acetate (58.4 g) and propylene glycol monomethyl ether (11.7 g). The temperature of the reaction solution was raised to 100 ° C. under an air flow, and tetraethylammonium bromide (0.53 g) and p-methoxyphenol (0.26 g) were added. Glycidyl methacrylate (NOF Corporation Blemmer GH) (25.5 g) was added dropwise to this over 20 minutes. This was reacted at 100 ° C.
  • the solid content concentration of the obtained solution was 36.5% by mass.
  • the weight average molecular weight in terms of standard polystyrene in GPC was 17,000, the dispersity was 2.4, and the acid value of the polymer was 94.5 mgKOH / g.
  • the amount of residual monomer measured by gas chromatography was less than 0.1% by mass with respect to the polymer solid content in any of the monomers.
  • the structure of the binder polymer C (the repeating unit in the formula is a molar ratio) is shown below.
  • Photosensitive composition The photosensitive compositions Y-1 to Y-5 were prepared.
  • Photosensitive composition Y-2) -Binder polymer A 63.00 parts by mass in terms of solid content-Pentaerythritol triacrylate (ethylenically unsaturated compound, "A-TMM-3LM-N” manufactured by Shin-Nakamura Chemical Co., Ltd.): 37.00 parts by mass-bis ( 2,4,6-trimethylbenzoyl) Phenylphosphine oxide (polymerization initiator, "Omnirad 819" manufactured by IGM Resins B.V.): 10.00 parts by mass, polyether-modified silicone (surface active agent (leveling agent)) , Toray Dow Corning Co., Ltd. "8032 ADDITION”): 0.06 parts by mass ⁇ MEK: Amount at which the solid content concentration of the photosensitive composition Y-2 becomes 30%
  • Binder polymer C 52.67 parts by mass (solid content) -A-NOD-N (1,9-nonandiol diacrylate, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.): 2.73 parts by mass-A-DCP (tricyclodecanedimethanol diacrylate, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.) ): 17.90 parts by mass, Aronix TO-2349 (polyfunctional ethylenically unsaturated compound having a carboxylic acid group, manufactured by Toa Synthetic Co., Ltd.): 2.98 parts by mass, DPHA: dipentaerythritol hexaacrylate (manufactured by Toa Synthetic Co., Ltd.) Toshin Oil & Fat Co., Ltd.): 7.9 parts by mass 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-3-yl] etanone-1-
  • photosensitive compositions A to C The photosensitive compositions A to C shown in Table 1 below were prepared.
  • the numerical value of each component represents the content (parts by mass) of each component, and the amount of the binder polymer means the amount of the binder polymer solution (solid content concentration 36.3% by mass).
  • the 1-phenyl-3- (4-methoxystyryl) -5- (4-methoxyphenyl) pyrazoline contained in the photosensitive composition B was synthesized by a method according to the following scheme.
  • Anisaldehyde (20.4 g), acetone (4.4 g), sodium hydroxide (15.0 g), and distilled water (120 mL) were dissolved in ethanol (150 mL) and stirred at room temperature for 3 hours.
  • the obtained solution was filtered, washed with distilled water (500 mL), and then blown to dry at room temperature to obtain a pale yellow solid (18.7 g).
  • the obtained pale yellow solid (9.0 g) and phenylhydrazine (3.3 g) were dissolved in acetic acid (100 mL), stirred at room temperature for 3 hours, and then ice-cooled.
  • Examples 1 to 14, 16 to 28, 30 and Comparative Examples 1 to 5 Using a slit-shaped nozzle, the photosensitive composition Y-1 was adjusted and applied onto the temporary support Z-1 obtained above so that the thickness after drying was 8.8 ⁇ m, and the mixture was applied to 100. After drying at ° C. for 2 minutes, it was further dried at 120 ° C. for 1 minute. Then, a polyethylene terephthalate film (16KS40, manufactured by Toray Industries, Inc.) having a thickness of 16 ⁇ m was pressure-bonded onto the photosensitive composition layer as a protective film to obtain a transfer film of Example 1. Transfer films of Examples 2 to 14, 16 to 28, 30 and Comparative Examples 1 to 5 were obtained in the same procedure as in Example 1 except that the thickness of each component and each layer was changed according to Tables 2 to 3.
  • Example 15 On the transfer film of Example 1 obtained above, and further on the photosensitive composition layer, the following composition X-1 for forming a refractive index adjusting layer is adjusted so that the thickness after drying is 73 nm. And dried at 80 ° C. for 1 minute. Then, it was further dried at 110 ° C. for 1 minute to form a refractive index adjusting layer directly arranged on the photosensitive composition layer, and a transfer film of Example 15 was obtained.
  • Example 29 On the transfer film of Example 28 obtained above, and further on the photosensitive composition layer, the following composition X-1 for forming a refractive index adjusting layer is adjusted so that the thickness after drying is 73 nm. And dried at 80 ° C. for 1 minute. Then, it was further dried at 110 ° C. for 1 minute to form a refractive index adjusting layer directly arranged on the photosensitive composition layer, and the transfer film of Example 29 was obtained.
  • composition for forming a refractive index adjusting layer The composition for forming the refractive index adjusting layer was adjusted using each of the following components.
  • the composition for forming the refractive index adjusting layer is prepared by using a resin having an acid group and an aqueous ammonia solution.
  • the resin having an acid group is neutralized with the aqueous ammonia solution, and the ammonium resin having an acid group is used. It is an aqueous resin composition containing a salt.
  • COP film substrates with a copper layer were produced by forming a copper layer having a thickness of 200 nm on a cycloolefin polymer (COP) film having a thickness of 100 ⁇ m by a sputtering method. After laminating each transfer film on the COP film substrate with a copper layer obtained above under the laminating conditions of the pressure-bonding roll temperature: 100 ° C., linear pressure: 0.6 MPa, and linear velocity: 4.0 m / min, 3 I left it for a while.
  • COP cycloolefin polymer
  • An ultra-high pressure mercury lamp was used as the light source for the exposure.
  • the exposure amount was adjusted within a range in which the line width of the resin pattern formed by development was 100 ⁇ m.
  • the temporary support was peeled off from the surface of the photosensitive composition layer after exposure, and the photosensitive composition layer was developed. Specifically, shower development was carried out for 45 seconds using a 1.0 mass% sodium carbonate aqueous solution at 33 ° C. to obtain a laminate having a resin pattern.
  • the line widths of 20 points at arbitrary points of the obtained resin pattern were measured.
  • the standard deviation ⁇ and the mean value ⁇ were calculated for the measured line width values at 20 points. Further, the dispersion ⁇ was calculated by the following formula, and the patterning property was evaluated according to the following evaluation criteria. In the following evaluation criteria, A has the best patterning property and E has the worst patterning property. It is preferably any of A, B and C, more preferably A or B, and even more preferably A.
  • Dispersion ⁇ 100 ⁇ (standard deviation ⁇ / mean value ⁇ ) (Evaluation criteria) A: Dispersion ⁇ is less than 3% B: Dispersion ⁇ is 3% or more and less than 5% C: Dispersion ⁇ is 5% or more and less than 8% D: Dispersion ⁇ is 8% or more and less than 10% E: Dispersion ⁇ is 10% or more
  • ⁇ Removability> (Removability between the photosensitive composition layer and the temporary support) After peeling off the protective film from each of the transfer films obtained above, the photosensitive composition layer was laminated on the copper plate.
  • the laminating conditions were a lamirol temperature of 100 ° C., a linear pressure of 3 N / cm, and a transport speed of 4 m / min. Then, after the temporary support was peeled vertically upward at a speed of 0.01 m / min, the photosensitive composition layer remaining on the copper plate was visually confirmed and evaluated according to the following evaluation criteria. In the following evaluation criteria, A has the best peelability and E has the worst. It is preferably any of A, B and C, more preferably A or B, and even more preferably A.
  • Remaining area (%) on the copper plate of the photosensitive composition layer 100 ⁇ (Area of the photosensitive composition layer remaining on the copper plate after peeling / Area of the photosensitive composition layer on the copper plate before peeling) (Evaluation criteria)
  • the photosensitive composition layer remaining on the temporary support was visually confirmed and evaluated according to the following evaluation criteria.
  • A has the best peelability and E has the worst. It is preferably any of A, B and C, more preferably A or B, and even more preferably A.
  • Remaining area of the photosensitive composition layer on the temporary support (%) 100 ⁇ (Area of the photosensitive composition layer remaining on the temporary support after peeling / Photosensitive composition on the temporary support before peeling) Layer area) (Evaluation criteria) A: The remaining area of the photosensitive composition layer on the temporary support is 100%.
  • the remaining area of the photosensitive composition layer on the temporary support is 99% or more and less than 100%
  • C The remaining area of the photosensitive composition layer on the temporary support is 95% or more and less than 99%
  • D Photosensitive The remaining area of the composition layer on the temporary support is 90% or more and less than 95%.
  • E The remaining area of the photosensitive composition layer on the temporary support is less than 90%.
  • each description shows the following.
  • the column “Photosensitive composition layer / temporary support” indicates the peelability between the photosensitive composition layer and the temporary support.
  • the column “Photosensitive composition layer / protective film” indicates the peelability between the photosensitive composition layer and the protective film.

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WO2012081680A1 (ja) * 2010-12-16 2012-06-21 日立化成工業株式会社 感光性エレメント、レジストパターンの形成方法及びプリント配線板の製造方法
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JP2017013387A (ja) 2015-07-02 2017-01-19 三菱樹脂株式会社 基材レス両面粘着シート用離型フィルム
WO2019146380A1 (ja) 2018-01-24 2019-08-01 富士フイルム株式会社 感光性転写材料及びその製造方法、樹脂パターンの製造方法、並びに、回路配線の製造方法
JPWO2020158316A1 (ja) * 2019-01-29 2021-12-09 富士フイルム株式会社 感光性転写材料、樹脂パターンの製造方法、回路配線の製造方法、タッチパネルの製造方法、並びに、フィルム及びその製造方法
JP7463905B2 (ja) 2019-09-27 2024-04-09 東レ株式会社 ドライフィルムレジスト用二軸配向ポリエステルフィルム
JP6954502B1 (ja) * 2020-03-26 2021-10-27 東洋紡株式会社 薄膜層転写用積層体
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JP2009092818A (ja) * 2007-10-05 2009-04-30 Fujifilm Corp 感光性転写材料、カラーフィルタおよびその製造方法
WO2012081680A1 (ja) * 2010-12-16 2012-06-21 日立化成工業株式会社 感光性エレメント、レジストパターンの形成方法及びプリント配線板の製造方法
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