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 PDFInfo
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- 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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- 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
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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
- 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
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- 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
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- 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
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- 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
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- 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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Abstract
Description
また、本発明は、転写フィルムを用いる、積層体の製造方法及び回路配線の製造方法の提供も課題とする。
仮支持体が、仮支持体本体と、仮支持体本体の一方の表面上に配置された第1層と、仮支持体本体の他方の表面上に配置された第2層とを有し、
第1層及び第2層のうち、第1層が感光性組成物層側に配置され、
第1層が、平均粒子径100~1000nmの第1有機粒子と、平均粒子径70nm以下の第1無機粒子とを含み、第1層の感光性組成物層と接する面のクルトシスRkuが、2.0~100であり、
第2層が、平均粒子径70nm以下の第2無機粒子を含むか、又は、無機粒子を含まない、転写フィルム。
〔2〕 第1有機粒子が、ポリスチレン樹脂粒子を含む、〔1〕に記載の転写フィルム。
〔3〕 第1有機粒子の平均粒子径が、350~800nmである、〔1〕又は〔2〕に記載の転写フィルム。
〔4〕 第1無機粒子及び第2無機粒子の少なくとも一方が、ケイ素原子及びアルミニウム原子からなる群から選択される少なくとも1つを含む、〔1〕~〔3〕のいずれか1つに記載の転写フィルム。
〔5〕 第1無機粒子及び第2無機粒子の少なくとも一方が、酸化アルミニウムを含む、〔1〕~〔4〕のいずれか1つに記載の転写フィルム。
〔6〕 第1無機粒子の平均粒子径及び第2無機粒子の平均粒子径が、10~50nmである、〔1〕~〔5〕のいずれか1つに記載の転写フィルム。
〔7〕 仮支持体本体の厚みが、6.0~30.0μmであり、
第1層及び第2層の厚みが、0.8~3.0μmである、〔1〕~〔6〕のいずれか1つに記載の転写フィルム。
〔8〕 第1有機粒子の平均粒子径が、350~800nmであり、
第1無機粒子が、酸化アルミニウムを含み、
第1無機粒子の平均粒子径が、10~50nmである、〔1〕~〔7〕のいずれか1つに記載の転写フィルム。
〔9〕 第2層が、平均粒子径350~800nmの第2有機粒子を含み、
第2無機粒子が、酸化アルミニウムを含み、
第2無機粒子の平均粒子径が、10~50nmである、〔1〕~〔8〕のいずれか1つに記載の転写フィルム。
〔10〕 第1層の表面のクルトシスRkuが、2.5~10である、〔1〕~〔9〕のいずれか1つに記載の転写フィルム。
〔11〕 第1層の表面のクルトシスRkuが、3.0~5.0であり、第1無機粒子及び第2無機粒子が酸化アルミニウムを含む、〔1〕~〔10〕のいずれか1つに記載の転写フィルム。
〔12〕 感光性組成物層が、バインダーポリマー、重合性化合物、及び、重合開始剤を含む、〔1〕~〔11〕のいずれか1つに記載の転写フィルム。
〔13〕 感光性組成物層と保護フィルムとの間に、屈折率調整層を更に有する、〔1〕~〔12〕のいずれか1つに記載の転写フィルム。
〔14〕 感光性組成物層が、タッチパネル用電極保護膜形成に用いられる、〔1〕~〔13〕のいずれか1つに記載の転写フィルム。
〔15〕 〔1〕~〔14〕のいずれか1つに記載の転写フィルムから保護フィルムを剥離して、仮支持体とは反対側の表面を、導電層を有する基板に貼り合わせ、導電層、感光性組成物層、及び、仮支持体をこの順に有する感光性組成物層付き基板を得る貼合工程と、
感光性組成物層をパターン露光する露光工程と、
露光された感光性組成物層を現像して、パターンを形成する現像工程と、を有し、
更に、貼合工程と露光工程との間、又は、露光工程と現像工程との間に、感光性組成物層付き基板から仮支持体を剥離する剥離工程と、を有する、積層体の製造方法。
〔16〕 〔1〕~〔14〕のいずれか1つに記載の転写フィルムから保護フィルムを剥離して、仮支持体とは反対側の表面を、導電層を有する基板に貼り合わせ、導電層、感光性組成物層、及び、仮支持体をこの順に有する感光性組成物層付き基板を得る貼合工程と、
感光性組成物層をパターン露光する露光工程と、
露光された感光性組成物層を現像して、パターンを形成する現像工程と、
パターンが配置されていない領域における導電層をエッチング処理するエッチング工程と、
更に、貼合工程と露光工程との間、又は、露光工程と現像工程との間に、感光性組成物層付き基板から仮支持体を剥離する剥離工程と、を有する、回路配線の製造方法。
本明細書において、「~」を用いて表される数値範囲は、「~」の前後に記載される数値を下限値及び上限値として含む範囲を意味する。
本明細書において、段階的に記載されている数値範囲において、ある数値範囲で記載された上限値又は下限値は、他の段階的な記載の数値範囲の上限値又は下限値に置き換えてもよい。本明細書に記載されている数値範囲において、ある数値範囲で記載された上限値又は下限値は、実施例に示されている値に置き換えてもよい。
本明細書において、可視光の平均透過率は、分光光度計を用いて測定される値であり、例えば、日立製作所株式会社製の分光光度計U-3310を用いて測定できる。
本明細書において、特段の断りがない限り、分子量分布が有する化合物の分子量は、重量平均分子量である。
本明細書において、特段の断りがない限り、重合体の構成単位の比は、質量比である。
(置換基T)
置換基Tとしては、例えば、フッ素原子、塩素原子、臭素原子、及び、ヨウ素原子等のハロゲン原子;メトキシ基、エトキシ基、及び、tert-ブトキシ基等のアルコキシ基;フェノキシ基及びp-トリルオキシ基等のアリールオキシ基;メトキシカルボニル基、ブトキシカルボニル基、及び、フェノキシカルボニル基等のアルコキシカルボニル基;アセトキシ基、プロピオニルオキシ基、及び、ベンゾイルオキシ基等のアシルオキシ基;アセチル基、ベンゾイル基、イソブチリル基、アクリロイル基、メタクリロイル基、及び、メトキサリル基等のアシル基;メチルスルファニル基及びtert-ブチルスルファニル基等のアルキルスルファニル基;フェニルスルファニル基及びp-トリルスルファニル基等のアリールスルファニル基;アルキル基;シクロアルキル基;アリール基;ヘテロアリール基;水酸基;カルボキシ基;ホルミル基;スルホ基;シアノ基;ニトロ基;エーテル基;アルキルアミノカルボニル基;アリールアミノカルボニル基;スルホンアミド基;シリル基;アミノ基;モノアルキルアミノ基;ジアルキルアミノ基;アリールアミノ基;並びにこれらの組み合わせが挙げられる。
転写フィルムは、仮支持体と、仮支持体上に配置された感光性組成物層と、保護フィルムとをこの順で有する。仮支持体は、仮支持体本体と、仮支持体本体の一方の表面上に配置された第1層と、仮支持体本体の他方の表面上に配置された第2層とを有し、第1層及び第2層のうち、第1層が感光性組成物層側に配置される。つまり、転写フィルムは、第2層、仮支持体本体、第1層、感光性組成物層、及び、保護フィルムをこの順で有する。
本発明者らは、上述したように、従来の転写フィルムについて検討したところ、パターニング性及び剥離性の両立ができていないことを知見した。
それに対して、本発明では、第1層と第2層とを有する仮支持体を有する場合、所望の効果が得られた。その機構については、本発明らは以下のように推測している。
各層に含まれ得る第1無機粒子が所定の平均粒子径に制御されることにより、露光時の光の散乱を抑制し、均一に露光されて樹脂パターンの線幅のばらつきが少なくなる。また、第1層に含まれる所定の粒径を有する有機粒子を含むことで、クルトシスRkuが所定の範囲に調整され、感光性組成物層と仮支持体との間、及び、感光性組成物層と保護フィルムとの間での所望の剥離性を付与できたと推測される。
以下、本明細書において、転写フィルムのパターニング性がより優れること、及び、転写フィルムの剥離性がより優れることの少なくとも一方の効果が得られることを本発明の効果がより優れるともいう。
(1)「仮支持体/感光性組成物層/屈折率調整層/保護フィルム」
(2)「仮支持体/感光性組成物層/保護フィルム」
(3)「仮支持体/中間層/感光性組成物層/保護フィルム」
(4)「仮支持体/熱可塑性樹脂層/中間層/感光性組成物層/保護フィルム」
なお、上記各構成において、感光性組成物層は、ネガ型感光性組成物層であることが好ましい。また、感光性組成物層が着色樹脂層であることも好ましい。
本発明の転写フィルムは、後述するように配線保護膜用の転写フィルムとして使用されてもよいし、エッチングレジスト用の転写フィルムとして使用されてもよい。
配線保護膜用の転写フィルムとする場合、転写フィルムの構成としては、上述した(1)~(2)の構成であることが好ましい。また、エッチングレジスト用の転写フィルムとする場合、転写フィルムの構成としては、上述した(2)~(4)の構成であることが好ましい。
具体的には、例えば、後述する第1実施形態、及び、第2実施形態が挙げられる。
図1に示す転写フィルム10は、仮支持体1と、感光性組成物層3及び屈折率調整層5を含む組成物層2と、保護フィルム7とを、この順に有する。
また、図1で示す転写フィルム10は屈折率調整層5を配置した形態であるが、屈折率調整層5は、配置されなくてもよい。
図2に示す転写フィルム20は、仮支持体11と、熱可塑性樹脂層13、中間層15、及び、感光性組成物層17を含む組成物層12と、保護フィルム19とを、この順に有する。
また、図2で示す転写フィルム20は熱可塑性樹脂層13及び中間層15を配置した形態であるが、熱可塑性樹脂層13及び中間層15は、配置されなくてもよい。
第2実施形態の転写フィルムにおいて、仮支持体11及び保護フィルム17としては、上述した第1実施形態の仮支持体1及び保護フィルム9と同じものが挙げられる。
以下、転写フィルムの各構成について詳述する。
転写フィルムは、仮支持体を有する。
仮支持体は、仮支持体本体と、後述する第1層と、後述する第2層とを有する。
仮支持体は、感光性組成物層を支持する部材であり、最終的には剥離処理により除去される。
以下、仮支持体を構成する各部材について詳述する。
仮支持体は、仮支持体本体を有する。
仮支持体本体は、第1層と第2層との間に配置される部材である。
仮支持体本体としては、例えば、ガラス基板及びフィルムが挙げられ、樹脂フィルムが好ましい。また、仮支持体本体としては、加圧下、又は、加圧下及び加熱下において、著しい変形、収縮、又は、伸びを生じない、かつ、可撓性を有するフィルムが好ましい。
なかでも、仮支持体本体としては、ポリエステルフィルムが好ましく、2軸延伸ポリエステルフィルムがより好ましく、2軸延伸PETフィルムが更に好ましい。また、仮支持体本体は、シワ等の変形及び傷がないことも好ましい。
2軸延伸とは、2軸延伸処理を行い、2軸方向に分子配向性を有することを意味する。
分子配向性は、マイクロ波透過型分子配向計(例えば、MOA-6004、王子計測機器社製)を用いて測定する。2軸方向のなす角は、90°±5°であることが好ましく、90°±3°であることがより好ましく、90°±1°であることが更に好ましい。
上記2軸延伸ポリエステルフィルムは、長手方向及び幅方向に分子配向性を有することが好ましい。
幅方向とは、長手方向に直交する方向を意味する。なお、幅方向が不明である場合、マイクロ波透過型分子配向計(例えば、MOA-6004、王子計測機器社製)を用いて測定される配向度のうち、最も配向度が強い方向を幅方向とする。また、直交とは、厳密な直交に限られず、略直交を含む。略直交とは、90°±5°で交わることを意味し、90°±3°で交わることが好ましく、90°±1°で交わることがより好ましい。
ポリエステルとしては、例えば、ポリエチレンテレフタレート(PET)、及び、ポリエチレン-2,6-ナフタレート(PEN)が挙げられる。なかでも、ポリエステルとしては、PETが好ましい。
ポリエステルの含有量は、2軸延伸ポリエステルフィルム中の重合体の全質量に対して、85質量%以上が好ましく、90質量%以上がより好ましく、95質量%以上が更に好ましく、98質量%以上が特に好ましい。上限は特に制限されず、2軸延伸ポリエステルフィルム中の重合体の全質量に対して、100質量%以下が好ましい。
ポリエステルの含有量は、2軸延伸ポリエステルフィルムの全質量に対して、85質量%以上が好ましく、90質量%以上がより好ましく、95質量%以上が更に好ましく、98質量%以上が特に好ましい。上限は特に制限されず、2軸延伸ポリエステルフィルムの全質量に対して、100質量%以下が好ましい。
2軸延伸ポリエステルフィルムがPETを含む場合、PETの含有量は、2軸延伸ポリエステルフィルム中のポリエステルの全質量に対して、90~100質量%が好ましく、95~100質量%がより好ましく、98~100質量%が更に好ましく、100質量%が特に好ましい。
ポリエステルの製造方法としては、例えば、触媒存在下で、少なくとも1つのジカルボン酸化合物と、少なくとも1つのジオール化合物とを重縮合させることによりポリエステルを製造できる。
ジカルボン酸化合物としては、例えば、脂肪族ジカルボン酸化合物、脂環式ジカルボン酸化合物、及び、芳香族ジカルボン酸化合物が挙げられる。
ジオール化合物としては、例えば、脂肪族ジオール化合物、脂環式ジオール化合物、及び、芳香族ジオール化合物が挙げられる。
触媒としては、例えば、アルカリ金属化合物、アルカリ土類金属化合物、亜鉛化合物、鉛化合物、マンガン化合物、コバルト化合物、アルミニウム化合物、アンチモン化合物、チタン化合物、ゲルマニウム化合物、及び、リン化合物が挙げられる。
ポリエステルの製造には、必要に応じて、公知の末端封止剤を用いることができる。末端封止剤としては、例えば、オキサゾリン系化合物、カルボジイミド化合物、及び、エポキシ化合物が挙げられる。
具体的には、仮支持体のヘイズは、0.5%未満が好ましく、0.4%以下がより好ましい。下限は特に制限されず、0%以上が好ましい。
なお、ヘイズは、ヘイズメーターを用いて、JIS K 7105:1981に準ずる方法により測定でき、本明細書に記載のヘイズは、ヘイズメーター(NDH-2000、日本電色工業社製)を用いて測定した値である。
仮支持体本体のL*a*b*表色系におけるb*値は分光色差計(例えば、SE-2000、日本電色工業社製)を用いて、透過法により測定する。
また、幅方向のF-5としては、80MPa以上160MPa未満が好ましい。
幅方向のF-5が上記の範囲であることで、強度不足による傷の発生等による加工特性の低下が抑制され、長手方向のF-5との両立も良好となる。90MPa以上150MPa未満がより好ましく、100MPa以上140MPa未満が更に好ましい。
F-5及び破断強度は、縦方向及び横方向の延伸温度及び延伸倍率を適宜調整することで達成できる。
仮支持体は、感光性組成物層側に配置された第1層を有する。
第1層は、平均粒子径100~1000nmの第1有機粒子と、平均粒子径70nm以下の第1無機粒子とを含み、第1層の感光性組成物層と接する面のクルトシスRkuが、2~100である。
第1層の感光性組成物層と接する面のクルトシスRku(以下、単に「クルトシスRku)ともいう。)は、2.5~80が好ましく、2.5~10がより好ましく、2.5~6.0が更に好ましく、3.0~5.0が特に好ましい。
クルトシスRkuの測定は、第1層の感光性組成物層と接する面(仮支持体本体と反対側の表面)のうち、無作為に選択した10箇所をZygo社製、New View 6000を用いて測定し、得られた測定値のうち最小値及び最大値を除いた平均値とする。
第1有機粒子の平均粒子径は、100~1000nmであり、本発明の効果がより優れる点で、350~800nmが好ましく、350~700nmがより好ましく、400~600nmが更に好ましい。
第1有機粒子の平均粒子径は、透過型電子顕微鏡(TEM:Transmission Electron Microscope)の画像から無作為に選択した50個の第1有機粒子の粒子径を算術平均することにより求める。具体的には、仮支持体の断面を切り出した後に、仮支持体の断面をTEMで観察し、TEMの観察画像から無作為に粒子を50個選択する。選択された粒子に対して、エネルギー分散型X線分析(EDX:Energy dispersive X-ray spectroscopy)を行い、EDXの結果から、無機元素を含まない粒子を有機粒子とし、無機元素を含む粒子を無機粒子として、各粒子の粒子径を算術平均することにより求めることができる。また、各粒子が球形ではない場合、各粒子の平均粒子径は、仮支持体の断面TEM画像から得られる有機粒子又は無機粒子の断面積を求め、その断面積と同じ面積の円に置き換えた際の直径を、各粒子の平均粒子径とする。なお、平均粒子径とは、断面TEM画像での直径を算術平均した値を意味する。
樹脂粒子としては、例えば、ポリスチレン樹脂粒子、アクリル樹脂粒子、ポリエステル樹脂粒子、シリコーン有機粒子、及び、スチレン-アクリル有機粒子が挙げられ、ポリスチレン樹脂粒子が好ましい。
また、第1有機粒子は、架橋構造を有することが好ましい。
第1有機粒子の含有量は、第1層の全質量に対して、0.01~10.0質量%が好ましく、0.05~1.0質量%がより好ましく、0.1~1.0質量%が更に好ましく、0.1~0.3質量%が特に好ましい。
第1無機粒子の平均粒子径は、70nm以下であり、本発明の効果がより優れる点で、65nm以下が好ましく、50nm以下がより好ましい。下限は特に制限されず、1nm以上が好ましく、5nm以上がより好ましく、8nm以上が更に好ましく、10nm以上が特に好ましい。
第1無機粒子の平均粒子径は、上述した有機粒子の平均粒子径の測定方法を用いて測定できる。
第1無機粒子としては、例えば、二酸化ケイ素粒子(シリカ粒子)、チタニア粒子(酸化チタン粒子)、炭酸カルシウム、硫酸バリウム、及び、酸化アルミニウム粒子(アルミナ粒子)が挙げられる。なかでも、無機粒子としては、ヘイズ及び耐久性の点で、酸化アルミニウム粒子、又は、二酸化ケイ素粒子が好ましく、酸化アルミニウム粒子がより好ましい。
二酸化ケイ素粒子としては、例えば、ヒュームドシリカ粒子、及び、コロイダルシリカ粒子が挙げられる。
ヒュームドシリカ粒子としては、例えば、ケイ素原子を含む化合物を気相中で酸素及び水素と反応させることによって得ることができる。原料となるケイ素化合物としては、例えば、ハロゲン化ケイ素(例えば、塩化ケイ素)が挙げられる。
コロイダルシリカ粒子としては、例えば、原料化合物を加水分解及び縮合するゾルゲル法により合成することができる。コロイダルシリカの原料化合物としては、例えば、アルコキシケイ素(例えば、テトラエトキシシラン)、及び、ハロゲン化シラン化合物(例えば、ジフェニルジクロロシラン)が挙げられる。
二酸化ケイ素粒子の形態は、1次粒子であってもよく、1次粒子の凝集体(凝集シリカ粒子)であってもよい。
第1無機粒子の含有量は、第1層の全質量に対して、0.01~10.0質量%が好ましく、0.05~1.0質量%がより好ましく、0.1~1.0質量%が更に好ましく、0.2~0.5質量%が特に好ましい。
第1層は、上述した成分以外に、他の成分を含んでいてもよい。
他の成分としては、例えば、樹脂、界面活性剤、架橋剤、及び、造膜助剤が挙げられ、樹脂が好ましい。
第1層は、他の成分を1種のみ含んでいてもよく、2種以上含んでいてもよい。
樹脂とは、重量平均分子量が3000以上のポリマーを意味する。
樹脂の重量平均分子量は、ゲルパーミエーションクロマトグラフィ(GPC)を用いて測定できる。
樹脂としては、オレフィン樹脂、上述した仮支持体本体を構成する樹脂、及び、後述する感光性組成物層に含まれるバインダーポリマーが挙げられ、仮支持体本体を構成する樹脂、又は、バインダーポリマーが好ましく、ポリエステル樹脂がより好ましく、PET樹脂が更に好ましい。
オレフィン樹脂としては、例えば、公知のオレフィン樹脂が挙げられる。オレフィン樹脂としては、例えば、ポリエチレン及びポリプロピレンが挙げられる。
界面活性剤としては、例えば、アニオン系界面活性剤、カチオン系界面活性剤、ノニオン系界面活性剤、及び、両性界面活性剤が挙げられ、アニオン系界面活性剤又はノニオン系界面活性剤が好ましい。
アニオン系界面活性剤としては、例えば、ラピゾール(登録商標)A-90(日油社製)、サンデッドBL(三洋化成工業社製)、及び、ニッコールSCS(日光ケミカルズ社製)が挙げられる。
ノニオン系界面活性剤としては、例えば、ナロアクティー(登録商標)CL95(三洋化成工業社製)が挙げられる。
界面活性剤としては、上記以外に、例えば、界面活性剤物性性能要覧(技術情報協会)に記載の界面活性剤も挙げられる。
架橋剤としては、例えば、カルボジイミド化合物、オキサゾリン化合物、エポキシ化合物、メラミン化合物、及び、イソシアネート化合物の公知の架橋剤が挙げられる。
架橋剤としては、例えば、カルボジライト(登録商標)V-02-L2(日清紡ケミカル社製)、エポクロス(登録商標)WS-700(日本触媒社製)、デナコール(登録商標)EX614B(ナガセケムテックス社製)、及び、デュラネート(登録商標)WM44(旭化成ケミカルズ社製)が挙げられる。
第2層は、平均粒子径70nm以下の第2無機粒子を含む層であるか、又は、無機粒子を含まない層である。換言すると、第2層は、第2無機粒子を含むか、又は、平均粒子径を問わず無機粒子を含まない。なかでも、第2層は、第2無機粒子を含むことが好ましい。
第2層が平均粒子径70nm以下の第2無機粒子を含む場合、第2層に含まれる第2無機粒子の平均粒子径は、本発明の効果がより優れる点で、65nm以下が好ましく、50nm以下がより好ましい。下限は特に制限されず、1nm以上が好ましく、5nm以上がより好ましく、8nm以上が更に好ましく、10nm以上が特に好ましい。
第2無機粒子の平均粒子径は、上述した第1有機粒子の平均粒子径の測定方法を用いて測定できる。
第2無機粒子としては、例えば、二酸化ケイ素粒子(シリカ粒子)、チタニア粒子(酸化チタン粒子)、炭酸カルシウム、硫酸バリウム、及び、酸化アルミニウム粒子(アルミナ粒子)が挙げられる。なかでも、無機粒子としては、ヘイズ及び耐久性の点で、酸化アルミニウム粒子、又は、二酸化ケイ素粒子が好ましく、酸化アルミニウム粒子がより好ましい。
二酸化ケイ素粒子の態様は、上述した通りである。
第2無機粒子の含有量は、第2層の全質量に対して、0.01~10.0質量%が好ましく、0.05~1.0質量%がより好ましく、0.1~1.0質量%が更に好ましく、0.2~0.5質量%が特に好ましい。
第2有機粒子の定義としては、上述した第1層に含まれる第1有機粒子と同義であり、好適態様も同じである。
第2有機粒子の含有量は、第2層の全質量に対して、0.01~10.0質量%が好ましく、0.05~1.0質量%がより好ましく、0.1~1.0質量%が更に好ましく、0.1~0.3質量%が特に好ましい。
第2層は、上述した成分以外に、他の成分を含んでいてもよい。
他の成分としては、上述した第1層に含まれる他の成分と同義であり、好適態様も同じである。
第1層に含まれる第1有機粒子と、第2層に含まれる第2有機粒子とが、同一の有機粒子又は異なる有機粒子であってもよい。なかでも、本発明の効果がより優れる点で、同一の有機粒子が好ましい。
また、第1層に含まれる第1有機粒子の含有量と、第2層に含まれる第2有機粒子の含有量とが、同一の含有量又は異なる含有量であってもよい。なかでも、本発明の効果がより優れる点で、同一の含有量が好ましい。
第1層に含まれる第1無機粒子と、第2層に含まれる第2無機粒子とが、同一の無機粒子又は異なる無機粒子であってもよい。なかでも、本発明の効果がより優れる点で、同一の無機粒子が好ましい。
また、第1層に含まれる第1無機粒子の含有量と、第2層に含まれる第2無機粒子の含有量とが、同一の含有量又は異なる含有量であってもよい。なかでも、本発明の効果がより優れる点で、同一の含有量が好ましい。
第1層の厚みと、第2層の厚みとが、同一の厚み又は異なる厚みであってもよい。なかでも、本発明の効果がより優れる点で、同一の厚みが好ましい。
仮支持体は、光透過性を有することが好ましい。
感光性組成物層を露光する際に、仮支持体を介して感光性組成物層を露光することができる。本明細書において、光透過性を有するとは、パターン露光に使用する波長の光の透過率が50%以上であることを意味する。
波長365nmの光の透過率は、仮支持体を介してパターン露光できる点から、60%以上が好ましく、70%以上がより好ましい。上限は特に制限されず、100%以下が好ましい。
なお、透過率とは、測定対象となる層の主面に垂直な方向(厚み方向)に光を入射させたときの入射光の強度に対する、測定対象となる層を通過して出射した出射光の強度の比率を意味する。例えば、透過率は、大塚電子社製のMCPD Seriesを用いて測定できる。
具体的には、仮支持体のヘイズは、0.5%未満が好ましく、0.4%以下がより好ましい。下限は特に制限されず、0%以上が好ましい。仮支持体のヘイズが上記の範囲にあることで、露光工程において、仮支持体が支持する感光性組成物層を露光した際の光の散乱が効果的に抑制され、現像工程後の樹脂パターンの歪み及び抜け等が抑制され、壁面の状態が良好な樹脂パターンが形成できる。
なお、ヘイズは、ヘイズメーターを用いて、JIS K 7105:1981に準ずる方法により測定でき、本明細書に記載のヘイズは、ヘイズメーター(NDH-2000、日本電色工業社製)を用いて測定した値である。
仮支持体の厚みは、特に制限されないが、200.0μm以下の場合が多く、本発明の効果がより優れる点で、100.0μm以下が好ましく、40.0μm以下がより好ましく、35.0μm以下が更に好ましい。下限は特に制限されず、1.0μm以上が好ましく、5.0μm以上がより好ましく、10.0μm以上が更に好ましい。
仮支持体の厚みは、走査型電子顕微鏡(SEM)による断面観察により測定した任意の5点の平均値として算出できる。
転写フィルムは、保護フィルムを有する。
保護フィルムを有することで、保護フィルムに接する層(例えば、感光性組成物層)の表面を保護することができる。
樹脂フィルムとしては、例えば、ポリエチレンフィルム、ポリプロピレンフィルム、ポリエチレンテレフタレートフィルム、トリ酢酸セルロースフィルム、ポリスチレンフィルム、及び、ポリカーボネートフィルムが挙げられる。なかでも、樹脂フィルムとしては、ポリエチレンフィルム、ポリプロピレンフィルム、又は、ポリエチレンテレフタレートフィルムが好ましく、ポリエチレンテレフタレートフィルムがより好ましい。
転写フィルムは、仮支持体上に配置された感光性組成物層を有する。
感光性組成物層は、後述するバインダーポリマー、重合性化合物、及び、重合開始剤を含むことが好ましい。
感光性組成物層を被転写物上に転写した後、露光及び現像を行うことにより、被転写物上にパターンを形成できる。
感光性組成物層としては、ポジ型感光性組成物層であっても、ネガ型感光性組成物層であってもよい。ポジ型感光性組成物層とは、露光により露光部が現像液に対する溶解性が向上する感光性組成物層である。ネガ型感光性組成物層とは、露光により露光部が現像液に対する溶解性が低下する感光性組成物層である。
なかでも、ネガ型感光性組成物層を用いることが好ましい。感光性組成物層がネガ型感光性組成物層である場合、形成されるパターンは保護膜に該当する。
感光性組成物層の厚みは、走査型電子顕微鏡(SEM)による断面観察により測定した任意の5点の平均値として算出する。
感光性組成物層の色相は、色差計(CR-221、ミノルタ社製)を用いて測定できる。
感光性組成物層は、バインダーポリマーを含んでいてもよい。
バインダーポリマーとしては、例えば、(メタ)アクリル樹脂、スチレン樹脂、エポキシ樹脂、アミド樹脂、アミドエポキシ樹脂、アルキド樹脂、フェノール樹脂、エステル樹脂、ウレタン樹脂、エポキシ樹脂と(メタ)アクリル酸との反応で得られるエポキシアクリレート樹脂、及び、エポキシアクリレート樹脂と酸無水物との反応で得られる酸変性エポキシアクリレート樹脂が挙げられる。
なお、本明細書において、(メタ)アクリル樹脂とは、(メタ)アクリル化合物に由来する構成単位を有する樹脂を意味する。(メタ)アクリル化合物に由来する構成単位の含有量は、(メタ)アクリル樹脂の全構成単位に対して、50質量%以上が好ましく、70質量%以上がより好ましい。
(メタ)アクリル樹脂は、(メタ)アクリル化合物に由来する構成単位のみで構成されていてもよく、(メタ)アクリル化合物以外の重合性単量体に由来する構成単位を有していてもよい。すなわち、(メタ)アクリル化合物に由来する構成単位の含有量の上限は、(メタ)アクリル樹脂の全構成単位に対して、100質量%以下が好ましい。
(メタ)アクリル酸エステルとしては、例えば、(メタ)アクリル酸アルキルエステル、(メタ)アクリル酸テトラヒドロフルフリルエステル、(メタ)アクリル酸ジメチルアミノエチルエステル、(メタ)アクリル酸ジエチルアミノエチルエステル、(メタ)アクリル酸グリシジルエステル、(メタ)アクリル酸ベンジルエステル、2,2,2-トリフルオロエチル(メタ)アクリレート、及び、2,2,3,3-テトラフルオロプロピル(メタ)アクリレートが挙げられ、(メタ)アクリル酸アルキルエステルが好ましい。
(メタ)アクリルアミドとしては、例えば、ジアセトンアクリルアミド等のアクリルアミドが挙げられる。
(メタ)アクリル酸エステルとしては、炭素数1~4のアルキル基を有する(メタ)アクリル酸アルキルエステルが好ましく、(メタ)アクリル酸メチル又は(メタ)アクリル酸エチルがより好ましい。
上記構成単位を形成する重合性単量体としては、(メタ)アクリル化合物と共重合可能な(メタ)アクリル化合物以外の化合物であれば特に制限されず、例えば、スチレン、ビニルトルエン及びα-メチルスチレン等のα位又は芳香族環に置換基を有してもよいスチレン化合物、アクリロニトリル及びビニル-n-ブチルエーテル等のビニルアルコールエステル、マレイン酸、マレイン酸無水物、マレイン酸モノメチル、マレイン酸モノエチル及びマレイン酸モノイソプロピル等のマレイン酸モノエステル、フマール酸、ケイ皮酸、α-シアノケイ皮酸、イタコン酸、並びに、クロトン酸が挙げられる。
これらの重合性単量体は、1種又は2種以上を組み合わせて用いてもよい。
なかでも、(メタ)アクリル樹脂は、カルボキシ基を有する構成単位を有することがより好ましく、上記の(メタ)アクリル酸に由来する構成単位を有することが更に好ましい。
(メタ)アクリル樹脂における(メタ)アクリル酸アルキルエステルに由来する構成単位の含有量は、(メタ)アクリル樹脂の全構成単位に対して、1~90質量%が好ましく、1~80質量%がより好ましく、5~60質量%が更に好ましい。
また、(メタ)アクリル樹脂としては、メタクリル酸に由来する構成単位、メタクリル酸メチルに由来する構成単位、及び、アクリル酸エチルに由来する構成単位を有するアクリル樹脂も好ましい。
(メタ)アクリル樹脂におけるメタクリル酸に由来する構成単位及びメタクリル酸アルキルエステルに由来する構成単位の合計含有量は、本発明の効果がより優れる点から、(メタ)アクリル樹脂の全構成単位に対して、40質量%以上が好ましく、60質量%以上がより好ましい。上限は特に制限されず、100質量%以下が好ましく、80質量%以下がより好ましい。
本発明の効果がより優れる点から、メタクリル酸に由来する構成単位及びメタクリル酸アルキルエステルに由来する構成単位の合計含有量は、アクリル酸に由来する構成単位及びアクリル酸アルキルエステルに由来する構成単位の合計含有量に対して、質量比で60/40~80/20が好ましい。
なお、(メタ)アクリル樹脂の末端部は、合成に用いた重合開始剤に由来する部位により構成される。末端にエステル基を有する(メタ)アクリル樹脂は、エステル基を有するラジカルを発生する重合開始剤を用いることにより合成できる。
なお、本開示において、「アルカリ可溶性」とは、22℃において炭酸ナトリウムの1質量%水溶液100gへの溶解度が0.1g以上であることを意味する。
バインダーポリマーは、例えば、現像性の点から、酸価60mgKOH/g以上のバインダーポリマーであることが好ましい。
また、バインダーポリマーは、例えば、加熱により架橋成分と熱架橋し、強固な膜を形成しやすいという点から、酸価60mgKOH/g以上のカルボキシ基を有する樹脂(いわゆる、カルボキシ基含有樹脂)であることがより好ましく、酸価60mgKOH/g以上のカルボキシ基を有する(メタ)アクリル樹脂(いわゆる、カルボキシ基含有(メタ)アクリル樹脂)であることが更に好ましい。
バインダーポリマーがカルボキシ基を有する樹脂であると、例えば、ブロックイソシアネート化合物等の熱架橋性化合物を添加して熱架橋することで、3次元架橋密度を高めることができる。また、カルボキシ基を有する樹脂のカルボキシ基が無水化され、疎水化すると、湿熱耐性が改善し得る。
例えば、特開2011-095716号公報の段落[0025]に記載のポリマーのうち、酸価60mgKOH/g以上のカルボキシ基含有アクリル樹脂、特開2010-237589号公報の段落[0033]~[0052]に記載のポリマーのうち、酸価60mgKOH/g以上のカルボキシ基含有アクリル樹脂等を好ましく用いることができる。
なお、本開示において、スチレン-アクリル共重合体とは、スチレン化合物に由来する構成単位と、(メタ)アクリル化合物に由来する構成単位とを有する樹脂を指し、上記スチレン化合物に由来する構成単位、及び、上記(メタ)アクリル化合物に由来する構成単位の合計含有量は、上記共重合体の全構成単位に対して、30質量%以上が好ましく、50質量%以上がより好ましい。下限は特に制限されないが、100質量%以下が好ましい。
また、スチレン化合物に由来する構成単位の含有量は、上記共重合体の全構成単位に対して、1質量%以上が好ましく、5質量%以上がより好ましく、5~80質量%が更に好ましい。
また、上記(メタ)アクリル化合物に由来する構成単位の含有量は、上記共重合体の全構成単位に対して、5質量%以上が好ましく、10質量%以上がより好ましく、20~95質量%が更に好ましい。
芳香環構造を有する構成単位を形成するモノマーとしては、アラルキル基を有するモノマー、スチレン、及び重合可能なスチレン誘導体(例えば、メチルスチレン、ビニルトルエン、tert-ブトキシスチレン、アセトキシスチレン、4-ビニル安息香酸、スチレンダイマー、及びスチレントリマー等)が挙げられる。なかでも、アラルキル基を有するモノマー、又はスチレンが好ましい。
アラルキル基としては、置換又は非置換のフェニルアルキル基(ベンジル基を除く)、及び置換又は非置換のベンジル基等が挙げられ、置換又は非置換のベンジル基が好ましい。
また、バインダーポリマーは、本発明の効果がより優れる点から、下記式(S)で表される構成単位(スチレンに由来する構成単位)を有することがより好ましい。
また、バインダーポリマーにおける芳香環構造を有する構成単位の含有量は、本発明の効果がより優れる点から、バインダーポリマーの全構成単位に対して、5~70モル%が好ましく、10~60モル%がより好ましく、20~60モル%が更に好ましい。
更に、バインダーポリマーにおける上記式(S)で表される構成単位の含有量は、本発明の効果がより優れる点から、バインダーポリマーの全構成単位に対して、5~70モル%が好ましく、10~60モル%がより好ましく、20~60モル%が更に好ましい。
なお、本開示において、「構成単位」の含有量をモル比で規定する場合、上記「構成単位」は「モノマー単位」と同義であるものとする。また、本開示において、上記「モノマー単位」は、高分子反応等により重合後に修飾されていてもよい。以下においても同様である。
なかでも、本発明の効果がより優れる点から、2環以上の脂肪族炭化水素環が縮環した環が好ましく、テトラヒドロジシクロペンタジエン環(トリシクロ[5.2.1.02,6]デカン環)がより好ましい。
脂肪族炭化水素環構造を有する構成単位を形成するモノマーとしては、ジシクロペンタニル(メタ)アクリレート、シクロヘキシル(メタ)アクリレート、及び、イソボルニル(メタ)アクリレートが挙げられる。
また、バインダーポリマーは、本発明の効果がより優れる点から、下記式(Cy)で表される構成単位を有することがより好ましく、上記式(S)で表される構成単位、及び、下記式(Cy)で表される構成単位を有することがより好ましい。
式(Cy)におけるRCyは、本発明の効果がより優れる点から、炭素数5~20の脂肪族炭化水素環構造を有する一価の基であることが好ましく、炭素数6~16の脂肪族炭化水素環構造を有する一価の基であることがより好ましく、炭素数8~14の脂肪族炭化水素環構造を有する一価の基であることが更に好ましい。
また、式(Cy)のRCyにおける脂肪族炭化水素環構造としては、本発明の効果がより優れる点から、シクロペンタン環構造、シクロヘキサン環構造、若しくは、イソボロン環構造等の単環の脂肪族炭化水素環構造、又は、テトラヒドロジシクロペンタジエン環構造、若しくは、ノルボルナン環構造等の多環の脂肪族炭化水素環構造であることが好ましく、シクロヘキサン環構造、又は、テトラヒドロジシクロペンタジエン環構造であることがより好ましく、テトラヒドロジシクロペンタジエン環構造であることが更に好ましい。
更に、式(Cy)のRCyにおける脂肪族炭化水素環構造は、本発明の効果がより優れる点から、多環の脂肪族炭化水素環であることが好ましく、2環以上の脂肪族炭化水素環が縮環した環構造であることがより好ましく、2~4環の脂肪族炭化水素環が縮環した環であることが更に好ましい。
更に、式(Cy)におけるRCyは、本発明の効果がより優れる点から、式(Cy)における-C(=O)O-の酸素原子と脂肪族炭化水素環構造(単環又は多環であってもよい)とが直接結合する基、すなわち、脂肪族炭化水素環基であることが好ましく、シクロヘキシル基、又は、ジシクロペンタニル基であることがより好ましく、ジシクロペンタニル基であることが更に好ましい。
バインダーポリマーが脂肪族炭化水素環構造を有する構成単位を有する場合、脂肪族炭化水素環構造を有する構成単位の含有量は、本発明の効果がより優れる点から、バインダーポリマーの全構成単位に対して、5~90質量%が好ましく、10~80質量%がより好ましく、20~70質量%が更に好ましい。
また、バインダーポリマーにおける脂肪族炭化水素環構造を有する構成単位の含有量は、本発明の効果がより優れる点から、バインダーポリマーの全構成単位に対して、5~70モル%が好ましく、10~60モル%がより好ましく、20~60モル%が更に好ましい。
更に、バインダーポリマーにおける上記式(Cy)で表される構成単位の含有量は、本発明の効果がより優れる点から、バインダーポリマーの全構成単位に対して、5~70モル%が好ましく、10~60モル%がより好ましく、20~60モル%が更に好ましい。
また、バインダーポリマーにおける芳香環構造を有する構成単位及び脂肪族炭化水素環構造を有する構成単位の総含有量は、本発明の効果がより優れる点から、バインダーポリマーの全構成単位に対して、10~80モル%が好ましく、20~70モル%がより好ましく、30~60モル%が更に好ましい。
更に、バインダーポリマーにおける上記式(S)で表される構成単位及び上記式(Cy)で表される構成単位の総含有量は、本発明の効果がより優れる点から、バインダーポリマーの全構成単位に対して、10~80モル%が好ましく、20~70モル%がより好ましく、30~60モル%が更に好ましい。
また、バインダーポリマーにおける上記式(S)で表される構成単位のモル量nSと上記式(Cy)で表される構成単位のモル量nCyは、本発明の効果がより優れる点から、下記式(SCy)に示す関係を満たすことが好ましく、下記式(SCy-1)を満たすことがより好ましく、下記式(SCy-2)を満たすことが更に好ましい。
0.20≦nS/(nS+nCy)≦0.80 式(SCy)
0.30≦nS/(nS+nCy)≦0.75 式(SCy-1)
0.40≦nS/(nS+nCy)≦0.70 式(SCy-2)
上記酸基としては、カルボキシ基、スルホ基、ホスホン酸基、及び、リン酸基が挙げられ、カルボキシ基が好ましい。
上記酸基を有する構成単位としては、下記に示す、(メタ)アクリル酸由来の構成単位が好ましく、メタクリル酸由来の構成単位がより好ましい。
バインダーポリマーが酸基を有する構成単位を有する場合、酸基を有する構成単位の含有量は、本発明の効果がより優れる点から、バインダーポリマーの全構成単位に対して、5~50質量%が好ましく、5~40質量%がより好ましく、10~30質量%が更に好ましい。
また、バインダーポリマーにおける酸基を有する構成単位の含有量は、本発明の効果がより優れる点から、バインダーポリマーの全構成単位に対して、5~70モル%が好ましく、10~50モル%がより好ましく、15~40モル%が更に好ましい。
更に、バインダーポリマーにおける(メタ)アクリル酸由来の構成単位の含有量は、本発明の効果がより優れる点から、バインダーポリマーの全構成単位に対して、5~70モル%が好ましく、10~50モル%がより好ましく、15~40モル%が更に好ましい。
反応性基としては、ラジカル重合性基が好ましく、エチレン性不飽和基がより好ましい。また、バインダーポリマーがエチレン性不飽和基を有している場合、バインダーポリマーは、側鎖にエチレン性不飽和基を有する構成単位を有することが好ましい。
本開示において、「主鎖」とは、樹脂を構成する高分子化合物の分子中で相対的に最も長い結合鎖を表し、「側鎖」とは、主鎖から枝分かれしている原子団を表す。
エチレン性不飽和基としては、(メタ)アクリル基が好ましく、(メタ)アクリロキシ基がより好ましい。
反応性基を有する構成単位の一例としては、下記に示すものが挙げられるが、これらに限定されない。
バインダーポリマーが反応性基を有する構成単位を有する場合、反応性基を有する構成単位の含有量は、本発明の効果がより優れる点から、バインダーポリマーの全構成単位に対して、5~70質量%が好ましく、10~50質量%がより好ましく、20~40質量%が更に好ましい。
また、バインダーポリマーにおける反応性基を有する構成単位の含有量は、本発明の効果がより優れる点から、バインダーポリマーの全構成単位に対して、5~70モル%が好ましく、10~60モル%がより好ましく、20~50モル%が更に好ましい。
反応性基をバインダーポリマーに導入する手段の好ましい例としては、カルボキシ基を有するポリマーを重合反応により合成した後、高分子反応により、得られたポリマーのカルボキシ基の一部にグリシジル(メタ)アクリレートを反応させて、(メタ)アクリロキシ基をポリマーに導入する手段が挙げられる。この手段により、側鎖に(メタ)アクリロキシ基を有するバインダーポリマーを得ることができる。
上記重合反応は、70~100℃の温度条件で行うことが好ましく、80~90℃の温度条件で行うことがより好ましい。上記重合反応に用いる重合開始剤としては、アゾ系開始剤が好ましく、例えば、富士フイルム和光純薬社製のV-601(商品名)又はV-65(商品名)がより好ましい。上記高分子反応は、80~110℃の温度条件で行うことが好ましい。上記高分子反応においては、アンモニウム塩等の触媒を用いることが好ましい。
以下に示す各構成単位の含有比率aは、以下のバインダーポリマーの全構成単位に対して、20~60質量%が好ましい。bは、以下のバインダーポリマーの全構成単位に対して、10~50質量%が好ましい。cは、以下のバインダーポリマーの全構成単位に対して、5.0~25質量%が好ましい。dは、以下のバインダーポリマーの全構成単位に対して、10~50質量%が好ましい。
カルボン酸無水物構造は、鎖状カルボン酸無水物構造、及び環状カルボン酸無水物構造のいずれであってもよいが、環状カルボン酸無水物構造であることが好ましい。
環状カルボン酸無水物構造の環としては、5~7員環が好ましく、5員環又は6員環がより好ましく、5員環が更に好ましい。
Z1aとしては、炭素数2~4のアルキレン基が好ましく、炭素数2又は3のアルキレン基がより好ましく、炭素数2のアルキレン基が更に好ましい。
n1aは、0以上の整数を表す。Z1aが炭素数2~4のアルキレン基を表す場合、n1aは、0~4の整数であることが好ましく、0~2の整数であることがより好ましく、0であることが更に好ましい。
n1aが2以上の整数を表す場合、複数存在するRA1aは、同一でも異なっていてもよい。また、複数存在するRA1aは、互いに結合して環を形成してもよいが、互いに結合して環を形成していないことが好ましい。
感光性組成物層が重合体Xを含む場合、本発明の効果がより優れる点から、重合体Xの含有量は、感光性組成物層の全質量に対して、0.10~30.00質量%が好ましく、0.20~20.00質量%がより好ましく、0.20~5.00質量%が更に好ましく、0.50~1.50質量%が特に好ましい。
バインダーポリマーの分散度(重量平均分子量Mw/数平均分子量Mn)は、現像残渣低減の点から、1.0~3.0が好ましく、2.0~3.0がより好ましい。
バインダーポリマーの酸価は、JIS K0070:1992に記載の方法に従って、測定される値である。
バインダーポリマーが重合体Aである場合、感光性組成物層はネガ型感光性組成物層であることが好ましい。
重合体Aは、アルカリ可溶性樹脂であることが好ましい。
重合体Aの酸価は、現像液による感光性組成物層の膨潤を抑制することにより、解像性がより優れる観点から、220mgKOH/g以下が好ましく、200mgKOH/g未満がより好ましく、190mgKOH/g未満が更に好ましい。
重合体Aの酸価の下限は特に制限されないが、現像性がより優れる観点から、60mgKOH/g以上が好ましく、120mgKOH/g以上がより好ましく、150mgKOH/g以上が更に好ましく、170mgKOH/g以上が特に好ましい。
重合体Aの酸価は、重合体Aを構成する構成単位の種類及び酸基を含む構成単位の含有量により調整すればよい。
重合体Aにおける第一の単量体に基づく構成単位の含有量は、重合体Aの全質量に対して、5~50質量%が好ましく、10~40質量%がより好ましく、10~30質量%が更に好ましい。
上記含有量を5質量%以上にすることは、良好な現像性を発現させる観点、エッジフューズ性を制御する等の観点から好ましい。上記含有量を50質量%以下にすることは、レジストパターンの高解像性及びスソ形状の観点から、更にはレジストパターンの耐薬品性の観点から好ましい。
重合体Aにおける第二の単量体に基づく構成単位の含有量は、重合体Aの全質量に対して、5~90質量%が好ましく、15~60質量%がより好ましく、20~45質量%が更に好ましい。
一態様において、重合体Aは、芳香族炭化水素基を有する単量体に基づく構成単位を25~55質量%、第一の単量体に基づく構成単位を20~35質量%、第二の単量体に基づく構成単位を15~45質量%含む重合体であることが好ましい。また、別の態様において、芳香族炭化水素基を有する単量体に基づく構成単位を70~90質量%、第一の単量体に基づく構成単位を10~25質量%含む重合体であることが好ましい。
側鎖に分岐構造を有する基を含むモノマーの具体例としては、(メタ)アクリル酸i-プロピル、(メタ)アクリル酸i-ブチル、(メタ)アクリル酸s-ブチル、(メタ)アクリル酸t-ブチル、(メタ)アクリル酸i-アミル、(メタ)アクリル酸t-アミル、(メタ)アクリル酸sec-iso-アミル、(メタ)アクリル酸2-オクチル、(メタ)アクリル酸3-オクチル、及び(メタ)アクリル酸t-オクチルが挙げられる。これらのなかでも、(メタ)アクリル酸i-プロピル、(メタ)アクリル酸i-ブチル、又はメタクリル酸t-ブチルが好ましく、メタクリル酸i-プロピル又はメタクリル酸t-ブチルがより好ましい。
側鎖に脂環構造を有する基を含むモノマーの具体例としては、単環の脂肪族炭化水素基を有するモノマー、及び、多環の脂肪族炭化水素基を有するモノマーが挙げられる。また、炭素原子数5~20個の脂環式炭化水素基を有する(メタ)アクリレートが挙げられる。より具体的な例としては、(メタ)アクリル酸(ビシクロ〔2.2.1]ヘプチル-2)、(メタ)アクリル酸-1-アダマンチル、(メタ)アクリル酸-2-アダマンチル、(メタ)アクリル酸-3-メチル-1-アダマンチル、(メタ)アクリル酸-3,5-ジメチル-1-アダマンチル、(メタ)アクリル酸-3-エチルアダマンチル、(メタ)アクリル酸-3-メチル-5-エチル-1-アダマンチル、(メタ)アクリル酸-3,5,8-トリエチル-1-アダマンチル、(メタ)アクリル酸-3,5-ジメチル-8-エチル-1-アダマンチル、(メタ)アクリル酸2-メチル-2-アダマンチル、(メタ)アクリル酸2-エチル-2-アダマンチル、(メタ)アクリル酸3-ヒドロキシ-1-アダマンチル、(メタ)アクリル酸オクタヒドロ-4,7-メンタノインデン-5-イル、(メタ)アクリル酸オクタヒドロ-4,7-メンタノインデン-1-イルメチル、(メタ)アクリル酸-1-メンチル、(メタ)アクリル酸トリシクロデカン、(メタ)アクリル酸-3-ヒドロキシ-2,6,6-トリメチル-ビシクロ〔3.1.1〕ヘプチル、(メタ)アクリル酸-3,7,7-トリメチル-4-ヒドロキシ-ビシクロ〔4.1.0〕ヘプチル、(メタ)アクリル酸(ノル)ボルニル、(メタ)アクリル酸イソボルニル、(メタ)アクリル酸フェンチル、(メタ)アクリル酸-2,2,5-トリメチルシクロヘキシル、及び(メタ)アクリル酸シクロヘキシルが挙げられる。これら(メタ)アクリル酸エステルのなかでも、(メタ)アクリル酸シクロヘキシル、(メタ)アクリル酸(ノル)ボルニル、(メタ)アクリル酸イソボルニル、(メタ)アクリル酸-1-アダマンチル、(メタ)アクリル酸-2-アダマンチル、(メタ)アクリル酸フェンチル、(メタ)アクリル酸1-メンチル、又は(メタ)アクリル酸トリシクロデカンが好ましく、(メタ)アクリル酸シクロヘキシル、(メタ)アクリル酸(ノル)ボルニル、(メタ)アクリル酸イソボルニル、(メタ)アクリル酸-2-アダマンチル、又は(メタ)アクリル酸トリシクロデカンがより好ましい。
2種以上を使用する場合には、芳香族炭化水素基を有する単量体に基づく構成単位を含む重合体Aを2種類混合使用すること、又は芳香族炭化水素基を有する単量体に基づく構成単位を含む重合体Aと芳香族炭化水素基を有する単量体に基づく構成単位を含まない重合体Aとを混合使用することが好ましい。後者の場合、芳香族炭化水素基を有する単量体に基づく構成単位を含む重合体Aの使用割合は、重合体Aの全質量に対して、50質量%以上が好ましく、70質量%以上がより好ましく、80質量%以上が更に好ましく、90質量%以上が特に好ましい。上限は特に制限されず、100質量%以下が好ましい。
その他の樹脂としては、アクリル樹脂、スチレン-アクリル系共重合体、ポリウレタン樹脂、ポリビニルアルコール、ポリビニルホルマール、ポリアミド樹脂、ポリエステル樹脂、ポリアミド樹脂、エポキシ樹脂、ポリアセタール樹脂、ポリヒドロキシスチレン樹脂、ポリイミド樹脂、ポリベンゾオキサゾール樹脂、ポリシロキサン樹脂、ポリエチレンイミン、ポリアリルアミン、及びポリアルキレングリコールが挙げられる。
バインダーポリマーの含有量は、本発明の効果がより優れる点から、感光性組成物層の全質量に対して、10.00~90.00質量%が好ましく、30.00~80.00質量%がより好ましく、40.00~70.00質量%が更に好ましく、45.00~60.00質量%が特に好ましい。
感光性組成物層は、重合開始剤を含んでいてもよい。
重合開始剤としては、特に制限されず、公知の重合開始剤を用いることができる。重合開始剤としては、光重合開始剤、又は、熱重合開始剤が好ましい。
重合開始剤は、ラジカル重合開始剤又はカチオン重合開始剤であってもよい。
重合開始剤としては、例えば、オキシムエステル構造を有する光重合開始剤(以下「オキシム系光重合開始剤」ともいう。)、α-アミノアルキルフェノン構造を有する光重合開始剤(以下「α-アミノアルキルフェノン系光重合開始剤」ともいう。)、α-ヒドロキシアルキルフェノン構造を有する光重合開始剤(以下「α-ヒドロキシアルキルフェノン系重合開始剤」ともいう。)、アシルフォスフィンオキサイド構造を有する光重合開始剤(以下「アシルフォスフィンオキサイド系光重合開始剤」ともいう。)、N-フェニルグリシン構造を有する光重合開始剤(以下「N-フェニルグリシン系光重合開始剤」ともいう。)が挙げられる。
2,4,5-トリアリールイミダゾール二量体の誘導体としては、例えば、2-(o-クロロフェニル)-4,5-ジフェニルイミダゾール二量体、2-(o-クロロフェニル)-4,5-ジ(メトキシフェニル)イミダゾール二量体、2-(o-フルオロフェニル)-4,5-ジフェニルイミダゾール二量体、2-(o-メトキシフェニル)-4,5-ジフェニルイミダゾール二量体、及び2-(p-メトキシフェニル)-4,5-ジフェニルイミダゾール二量体が挙げられる。
光カチオン重合開始剤としては、pKaが4以下の酸を発生する光カチオン重合開始剤が好ましく、pKaが3以下の酸を発生する光カチオン重合開始剤がより好ましく、pKaが2以下の酸を発生する光カチオン重合開始剤が特に好ましい。pKaの下限値は特に定めないが、例えば、-10.0以上が好ましい。
イオン性光カチオン重合開始剤として、例えば、ジアリールヨードニウム塩類及びトリアリールスルホニウム塩類等のオニウム塩化合物、並びに、第4級アンモニウム塩類が挙げられる。
イオン性光カチオン重合開始剤としては、特開2014-085643号公報の段落0114~0133に記載のイオン性光カチオン重合開始剤を用いてもよい。
感光性組成物層における重合開始剤の含有量は特に制限されないが、感光性組成物層の全質量に対して、0.10質量%以上が好ましく、0.50質量%以上がより好ましい。上限は特に制限されず、感光性組成物層の全質量に対して、10.00質量%以下が好ましく、5.00質量%以下がより好ましい。
感光性組成物層は、重合性化合物を含んでいてもよい。
重合性化合物は、重合性基を有する化合物である。重合性基としては、例えば、ラジカル重合性基、及び、カチオン重合性基が挙げられ、ラジカル重合性基が好ましい。
エチレン性不飽和基としては、(メタ)アクリロキシ基が好ましい。
本明細書において、エチレン性不飽和化合物は、上記バインダーポリマー以外の化合物であり、分子量5,000未満であることが好ましい。
Q2-R1a-Q1 式(M)
式(M)中、Q1及びQ2はそれぞれ独立に、(メタ)アクリロイルオキシ基を表し、R1は鎖状構造を有する2価の連結基を表す。
また、式(M)におけるQ1及びQ2は、反応性の点から、アクリロイルオキシ基であることが好ましい。
式(M)におけるR1aとしては、本発明の効果がより優れる点から、アルキレン基、アルキレンオキシアルキレン基(-L1-O-L1-)、又は、ポリアルキレンオキシアルキレン基(-(L1-O)p-L1-)が好ましく、炭素数2~20の炭化水素基、又は、ポリアルキレンオキシアルキレン基がより好ましく、炭素数4~20のアルキレン基が更に好ましく、炭素数6~18の直鎖アルキレン基が特に好ましい。
上記炭化水素基は、少なくとも一部に鎖状構造を有していればよく、上記鎖状構造以外の部分としては、特に制限はなく、例えば、分岐鎖状、環状、又は、炭素数1~5の直鎖状アルキレン基、アリーレン基、エーテル結合、及びそれらの組み合わせのいずれであってもよく、アルキレン基、又は、2つ以上のアルキレン基と1つ以上のアリーレン基とを組み合わせた基が好ましく、アルキレン基がより好ましく、直鎖アルキレン基が更に好ましい。
なお、上記L1は、それぞれ独立に、アルキレン基を表し、エチレン基、プロピレン基、又は、ブチレン基が好ましく、エチレン基、又は、1,2-プロピレン基がより好ましい。pは2以上の整数を表し、2~10の整数が好ましい。
本開示において、「Q1とQ2の間を連結する最短の連結鎖の原子数」とは、Q1に連結するR1における原子からQ2に連結するR1における原子までを連結する最短の原子数である。
なかでも、本発明の効果がより優れる点から、化合物Mとしては、1,6-ヘキサンジオールジ(メタ)アクリレート、1,9-ノナンジオールジ(メタ)アクリレート、1,10-デカンジオールジ(メタ)アクリレート、及びネオペンチルグリコールジ(メタ)アクリレートからなる群から選ばれた少なくとも1種の化合物であることが好ましく、1,6-ヘキサンジオールジ(メタ)アクリレート、1,9-ノナンジオールジ(メタ)アクリレート、及び1,10-デカンジオールジ(メタ)アクリレートからなる群から選ばれた少なくとも1種の化合物であることがより好ましく、1,9-ノナンジオールジ(メタ)アクリレート、及び、1,10-デカンジオールジ(メタ)アクリレートからなる群から選ばれた少なくとも1種の化合物であることが更に好ましい。
本明細書において、「2官能以上のエチレン性不飽和化合物」とは、一分子中にエチレン性不飽和基を2つ以上有する化合物を意味する。
エチレン性不飽和化合物におけるエチレン性不飽和基としては、(メタ)アクリロイル基が好ましい。
エチレン性不飽和化合物としては、(メタ)アクリレート化合物が好ましい。
上記化合物M以外の2官能のエチレン性不飽和化合物としては、トリシクロデカンジメタノールジ(メタ)アクリレート、及びトリシクロデカンジメナノールジ(メタ)アクリレートが挙げられる。
3官能以上のエチレン性不飽和化合物としては、ジペンタエリスリトール(トリ/テトラ/ペンタ/ヘキサ)(メタ)アクリレート、ペンタエリスリトール(トリ/テトラ)(メタ)アクリレート、トリメチロールプロパントリ(メタ)アクリレート、ジトリメチロールプロパンテトラ(メタ)アクリレート、イソシアヌル酸(メタ)アクリレート、及び、グリセリントリ(メタ)アクリレート骨格の(メタ)アクリレート化合物が挙げられる。
3官能以上のウレタン(メタ)アクリレート化合物としては、例えば、アクリット8UX-015A(大成ファインケミカル社製)、NKエステル UA-32P(新中村化学工業社製)、NKエステル UA-1100H(新中村化学工業社製)が挙げられる。
また、ウレタン(メタ)アクリレートとしては、3官能以上のウレタン(メタ)アクリレートも挙げられる。官能基数の下限としては、6官能以上がより好ましく、8官能以上が更に好ましい。なお、官能基数の上限としては、20官能以下が好ましい。3官能以上のウレタン(メタ)アクリレートとしては、例えば、8UX-015A(大成ファインケミカル(株)製)、UA-32P(新中村化学工業(株)製)、U-15HA(新中村化学工業(株)製)、UA-1100H(新中村化学工業(株)製)、共栄社化学(株)製のAH-600(商品名)、並びに、UA-306H、UA-306T、UA-306I、UA-510H、及びUX-5000(いずれも日本化薬(株)製)が挙げられる。
酸基としては、例えば、リン酸基、スルホ基、及び、カルボキシ基が挙げられる。
なかでも、酸基としては、カルボキシ基が好ましい。
酸基を有するエチレン性不飽和化合物としては、酸基を有する3~4官能のエチレン性不飽和化合物〔ペンタエリスリトールトリ及びテトラアクリレート(PETA)骨格にカルボキシ基を導入したもの(酸価:80~120mgKOH/g)〕、及び酸基を有する5~6官能のエチレン性不飽和化合物(ジペンタエリスリトールペンタ及びヘキサアクリレート(DPHA)骨格にカルボキシ基を導入したもの〔酸価:25~70mgKOH/g)〕が挙げられる。
これら酸基を有する3官能以上のエチレン性不飽和化合物は、必要に応じ、酸基を有する2官能のエチレン性不飽和化合物と併用してもよい。
酸基を有するエチレン性不飽和化合物が、カルボキシ基を有する2官能以上のエチレン性不飽和化合物及びそのカルボン酸無水物からなる群から選択される少なくとも1種であると、現像性及び膜強度がより高まる。
カルボキシ基を有する2官能以上のエチレン性不飽和化合物は、特に制限されず、公知の化合物の中から適宜選択できる。
カルボキシ基を有する2官能以上のエチレン性不飽和化合物としては、例えば、アロニックス(登録商標)TO-2349(東亞合成(株)製)、アロニックス(登録商標)M-520(東亞合成(株)製)、アロニックス(登録商標)M-510(東亞合成(株)製)が挙げられる。
これらは単独で又は2種類以上を組み合わせて使用される。
なかでも、上記化合物としては、テトラメチロールメタン構造又はトリメチロールプロパン構造を有するエチレン不飽和化合物が好ましく、テトラメチロールメタントリ(メタ)アクリレート、テトラメチロールメタンテトラ(メタ)アクリレート、トリメチロールプロパントリ(メタ)アクリレート、又は、ジ(トリメチロールプロパン)テトラアクリレートがより好ましい。
エステル結合を含むエチレン性不飽和化合物としては、分子内にエステル結合を含むものであれば特に制限されないが、本発明の効果が優れる点で、テトラメチロールメタン構造又はトリメチロールプロパン構造を有するエチレン不飽和化合物が好ましく、テトラメチロールメタントリ(メタ)アクリレート、テトラメチロールメタンテトラ(メタ)アクリレート、トリメチロールプロパントリ(メタ)アクリレート、又は、ジ(トリメチロールプロパン)テトラアクリレートがより好ましい。
エチレン性不飽和化合物としては、信頼性付与の点から、炭素数6~20の脂肪族基を有するエチレン性不飽和化合物と、上記のテトラメチロールメタン構造又はトリメチロールプロパン構造を有するエチレン不飽和化合物と、を含むことが好ましい。
炭素数6以上の脂肪族構造を有するエチレン性不飽和化合物としては、例えば、1,9-ノナンジオールジ(メタ)アクリレート、1,10-デカンジオールジ(メタ)アクリレート、及びトリシクロデカンジメタノールジ(メタ)アクリレートが挙げられる。
上記重合性化合物としては、2環以上の脂肪族炭化水素環が縮環した環構造(好ましくは、トリシクロデカン構造及びトリシクロデセン構造からなる群から選択される構造)を有する重合性化合物が好ましく、2環以上の脂肪族炭化水素環が縮環した環構造を有する2官能エチレン性不飽和化合物がより好ましく、トリシクロデカンジメタノールジ(メタ)アクリレートが更に好ましい。
上記脂肪族炭化水素環構造としては、本発明の効果がより優れる点から、シクロペンタン構造、シクロヘキサン構造、トリシクロデカン構造、トリシクロデセン構造、ノルボルナン構造、又は、イソボロン構造が好ましい。
感光性組成物層に含まれる重合性化合物のうち、分子量300以下の重合性化合物の含有量の割合は、感光性組成物層に含まれる全ての重合性化合物の含有量に対して、30質量%以下が好ましく、25質量%以下がより好ましく、20質量%以下が更に好ましい。
分子量300以下の重合性化合物の含有量の割合の下限は、特に制限されないが、1.0質量%以上が好ましい。
上記エチレン性不飽和化合物における2官能以上のエチレン性不飽和化合物の含有量は、感光性組成物層に含まれる全てのエチレン性不飽和化合物の総含有量に対して、60~100質量%が好ましく、80~100質量%がより好ましく、90~100質量%が更に好ましい。
感光性組成物層は、芳香環及び2つのエチレン性不飽和基を有する重合性化合物B1を含むことも好ましい。重合性化合物B1は、上述した重合性化合物Bのうち、一分子中に1つ以上の芳香環を有する2官能エチレン性不飽和化合物である。
重合性化合物B1は、芳香環を1つのみ有してもよく、2つ以上の芳香環を有してもよい。
ビスフェノール構造としては、例えば、ビスフェノールA(2,2-ビス(4-ヒドロキシフェニル)プロパン)に由来するビスフェノールA構造、ビスフェノールF(2,2-ビス(4-ヒドロキシフェニル)メタン)に由来するビスフェノールF構造、及びビスフェノールB(2,2-ビス(4-ヒドロキシフェニル)ブタン)に由来するビスフェノールB構造が挙げられ、ビスフェノールA構造が好ましい。
ビスフェノール構造の両端と2つの重合性基とは、直接結合してもよく、1つ以上のアルキレンオキシ基を介して結合してもよい。ビスフェノール構造の両端に付加するアルキレンオキシ基としては、エチレンオキシ基又はプロピレンオキシ基が好ましく、エチレンオキシ基がより好ましい。ビスフェノール構造に付加するアルキレンオキシ基の付加数は特に制限されないが、1分子あたり4~16個が好ましく、6~14個がより好ましい。
ビスフェノール構造を有する重合性化合物B1については、特開2016-224162号公報の段落[0072]~[0080]に記載されており、この公報に記載の内容は本明細書に組み込まれる。
2,2-ビス(4-((メタ)アクリロキシポリアルコキシ)フェニル)プロパンとしては、例えば、2,2-ビス(4-(メタクリロキシジエトキシ)フェニル)プロパン(FA-324M、日立化成社製)、EO変性ビスフェノールAジメタクリレート(FA-321M、日立化成社製)、エトキシ化ビスフェノールAジメタクリレート(BPE-80N、新中村化学工業社製)、ノニルフェノキシポリエチレングリコールアクリレート(FA-318AS、日立化成社製)、2,2-ビス(4-(メタクリロキシエトキシプロポキシ)フェニル)プロパン、2,2-ビス(4-(メタクリロキシペンタエトキシ)フェニル)プロパン(BPE-500、新中村化学工業社製)、2,2-ビス(4-(メタクリロキシドデカエトキシテトラプロポキシ)フェニル)プロパン(FA-3200MY、日立化成社製)、2,2-ビス(4-(メタクリロキシペンタデカエトキシ)フェニル)プロパン(BPE-1300、新中村化学工業社製)、2,2-ビス(4-(メタクリロキシジエトキシ)フェニル)プロパン(BPE-200、新中村化学工業社製)、及びエトキシ化(10)ビスフェノールAジアクリレート(NKエステルA-BPE-10、新中村化学工業社製)が挙げられる。
一態様において、n1+n2+n3+n4は、2~20が好ましく、2~16がより好ましく、4~12が更に好ましい。また、n2+n4は、0~10が好ましく、0~4がより好ましく、0~2が更に好ましく、0が特に好ましい。
重合性化合物B1の含有量は、解像性がより優れる観点から、感光性組成物層の全質量に対して、10質量%以上が好ましく、20質量%以上がより好ましい。上限は特に制限されないが、転写性及びエッジフュージョン(転写部材の端部から感光性樹脂が滲み出す現象)の観点から、70質量%以下が好ましく、60質量%以下がより好ましい。
感光性組成物層における重合性化合物(特に、エチレン性不飽和化合物)の含有量は、感光性組成物層の全質量に対して、1.00~70.00質量%が好ましく、10.00~70.00質量%がより好ましく、15.0~50.0質量%が更に好ましく、20.0~40.0質量%が特に好ましい。
感光性組成物層は、複素環化合物を含んでいてもよい。
複素環化合物が有する複素環は、単環及び多環のいずれの複素環でもよい。
複素環化合物が有するヘテロ原子としては、窒素原子、酸素原子、及び、硫黄原子が挙げられる。複素環化合物は、窒素原子、酸素原子、及び、硫黄原子からなる群から選択される少なくとも1種の原子を有することが好ましく、窒素原子を有することがより好ましい。
なかでも、複素環化合物としては、トリアゾール化合物、ベンゾトリアゾール化合物、テトラゾール化合物、チアジアゾール化合物、トリアジン化合物、ローダニン化合物、チアゾール化合物、ベンゾイミダゾール化合物、ベンゾオキサゾール化合物、及び、ピリジン化合物からなる群から選択される少なくとも1種の化合物が好ましく、トリアゾール化合物、ベンゾトリアゾール化合物、テトラゾール化合物、チアジアゾール化合物、チアゾール化合物、ベンゾチアゾール化合物、ベンゾイミダゾール化合物、及び、ベンゾオキサゾール化合物からなる群から選択される少なくとも1種の化合物がより好ましい。
トリアゾール化合物及びベンゾトリアゾール化合物としては、以下の化合物が例示できる。
感光性組成物層が複素環化合物を含む場合、複素環化合物の含有量は、感光性組成物層の全質量に対して、0.01~20.00質量%が好ましく、0.10~10.00質量%がより好ましく、0.10~5.00質量%が更に好ましく、0.10~1.00質量%が特に好ましい。
感光性組成物層は、脂肪族チオール化合物を含んでいてもよい。
なかでも、多官能の脂肪族チオール化合物としては、トリメチロールプロパントリス(3-メルカプトブチレート)、1,4-ビス(3-メルカプトブチリルオキシ)ブタン、及び、1,3,5-トリス(3-メルカプトブチリルオキシエチル)-1,3,5-トリアジン-2,4,6(1H,3H,5H)-トリオンからなる群より選ばれる少なくとも1種の化合物が好ましい。
感光性組成物層は、得られる硬化膜の強度、及び、得られる未硬化膜の粘着性の点から、熱架橋性化合物を含むことが好ましい。
なお、本明細書においては、後述するエチレン性不飽和基を有する熱架橋性化合物は、エチレン性不飽和化合物としては扱わず、熱架橋性化合物として扱うものとする。
また、熱架橋性化合物は、上述した感光性組成物層に含まれる成分(バインダーポリマー、重合開始剤、及び、重合性化合物等)とは異なる化合物である。
熱架橋性化合物としては、エポキシ化合物、オキセタン化合物、メチロール化合物、及び、ブロックイソシアネート化合物が挙げられる。
なかでも、得られる硬化膜の強度、及び、得られる未硬化膜の粘着性の点から、ブロックイソシアネート化合物が好ましい。
ブロックイソシアネート化合物は、ヒドロキシ基及びカルボキシ基と反応するため、例えば、バインダーポリマー及びエチレン性不飽和基を有するラジカル重合性化合物の少なくとも一方が、ヒドロキシ基及びカルボキシ基の少なくとも一方を有する場合には、形成される膜の親水性が下がり、保護膜としての機能が強化される傾向がある。
なお、ブロックイソシアネート化合物とは、「イソシアネートのイソシアネート基をブロック剤で保護(いわゆる、マスク)した構造を有する化合物」を指す。
ブロックイソシアネート化合物は、ブロックイソシアネート当量(以下「NCO価」ともいう。)が4.5mmol/g以上のブロックイソシアネート化合物(以下「第1ブロックイソシアネート化合物」ともいう。)を含むことが好ましい。これにより、曲げ耐性がより優れ、また、導電層の腐食も抑制できる。
第1ブロックイソシアネート化合物のNCO価の上限値は、本発明の効果がより優れる点から、6.0mmol/g以下が好ましく、5.8mmol/g未満がより好ましく、5.7mmol/g以下が更に好ましい。
本発明におけるブロックイソシアネート化合物のNCO価は、ブロックイソシアネート化合物1g当たりに含まれるブロックイソシアネート基のミリモル数を意味し、以下の式から算出できる。
式:ブロックイソシアネート化合物のNCO価=1000×(分子中に含まれるブロックイソシアネート基の個数)/(ブロックイソシアネート化合物の分子量)
脂肪族炭化水素環の具体例としては、シクロペンタン環、及びシクロヘキサン環が挙げられ、シクロヘキサン環が好ましい。
芳香族炭化水素環の具体例としては、ベンゼン環及びナフタレン環が挙げられ、ベンゼン環が好ましい。
複素環の具体例としては、イソシアヌレート環が挙げられる。
第1ブロックイソシアネート化合物が環構造を有する場合、環の個数は、本発明の効果がより優れる点から、1~2が好ましく、1がより好ましい。なお、第1ブロックイソシアネート化合物が縮合環を含む場合には、縮合環を構成する環の個数を数え、例えば、ナフタレン環における環の個数は2として数える。
B1-A1-L1-A2-B2 式Q
ブロックイソシアネート基としては、特に限定されないが、本発明の効果がより優れる点から、イソシアネート基がオキシム化合物でブロックされた基が好ましく、イソシアネート基がメチルエチルケトオキシムでブロックされた基(具体的には、*-NH-C(=O)-O-N=C(CH3)-C2H5で表される基。*は、A1又はA2との結合位置を表す。)がより好ましい。
B1及びB2は、同一の構造の基であることが好ましい。
アルキレン基は、直鎖状、分岐状、又は、環状であってもよく、直鎖状であることが好ましい。
アルキレン基の炭素数は、1~10であり、本発明の効果がより優れる点から、1~5が好ましく、1~3がより好ましく、1が更に好ましい。
A1及びA2は、同一の構造の基であることが好ましい。
2価の連結基の具体例としては、2価の炭化水素基が挙げられる。
2価の炭化水素基の具体例としては、2価の飽和炭化水素基、2価の芳香族炭化水素基、及び、これらの基が2つ以上連結されて形成される基が挙げられる。
2価の飽和炭化水素基としては、直鎖状、分岐状、又は、環状であってもよく、本発明の効果がより優れる点から、環状であることが好ましい。2価の飽和炭化水素基の炭素数は、本発明の効果がより優れる点から、4~15が好ましく、5~10がより好ましく、5~8が更に好ましい。
2価の芳香族炭化水素基としては、炭素数5~20であることが好ましく、例えば、フェニレン基が挙げられる。2価の芳香族炭化水素基は、置換基(例えば、アルキル基)を有していてもよい。
なかでも、2価の連結基としては、炭素数5~10の直鎖状、分岐状、若しくは、環状の2価の飽和炭化水素基、炭素数5~10の環状の飽和炭化水素基と炭素数1~3の直鎖状のアルキレン基とが連結した基、置換基を有していてもよい2価の芳香族炭化水素基、又は、2価の芳香族炭化水素基と炭素数1~3の直鎖状のアルキレン基とが連結した基が好ましく、炭素数5~10の環状の2価の飽和炭化水素基、又は、置換基を有していてもよいフェニレン基がより好ましく、シクロへキシレン基又は置換基を有していてもよいフェニレン基が更に好ましく、シクロへキシレン基が特に好ましい。
B1a-A1a-L1a-A2a-B2a 式QA
L1aにおける環状の2価の飽和炭化水素基の炭素数は、5~10が好ましく、5~8がより好ましく、5~6が更に好ましく、6が特に好ましい。
L1aにおける2価の芳香族炭化水素基の好適態様は、式QA中のL1と同様である。
なかでも、L1aは、環状の2価の飽和炭化水素基が好ましく、炭素数5~10の環状の2価の飽和炭化水素基がより好ましく、炭素数5~10の環状の2価の飽和炭化水素基が更に好ましく、炭素数5~6の環状の2価の飽和炭化水素基が特に好ましく、シクロへキシレン基が最も好ましい。
ブロックイソシアネート化合物は、NCO価が4.5mmol/g未満のブロックイソシアネート化合物(以下「第2ブロックイソシアネート化合物」ともいう。)を含むことが好ましい。これにより、感光性組成物層をパターン露光及び現像を行った後において、現像残渣の発生を抑制できる。
解離温度が100~160℃であるブロック剤の具体例は、上述した通りである。
重合性基としては、(メタ)アクリロキシ基、(メタ)アクリルアミド基、及び、スチリル基等のエチレン性不飽和基、並びに、グリシジル基等のエポキシ基を有する基が挙げられる。上記の中でも、重合性基としては、得られるパターンにおける表面の面状、現像速度、及び、反応性の点から、エチレン性不飽和基が好ましく、(メタ)アクリロキシ基がより好ましい。
感光性組成物層が熱架橋性化合物を含む場合、熱架橋性化合物の含有量は、感光性組成物層の全質量に対して、1.00~50.00質量%が好ましく、10.00~30.00質量%がより好ましく、10.00~20.00質量%が更に好ましい。
感光性組成物層層は、界面活性剤を含んでいてもよい。
界面活性剤としては、例えば、特許第4502784号公報の段落[0017]、及び特開2009-237362号公報の段落[0060]~[0071]に記載の界面活性剤が挙げられ、これらの内容は本明細書に組み込まれる。
界面活性剤としては、例えば、フッ素系界面活性剤、シリコーン系界面活性剤、及びノニオン系界面活性剤が挙げられ、フッ素系界面活性剤又はシリコーン系界面活性剤が好ましく、フッ素系界面活性剤がより好ましい。
また、フッ素系界面活性剤は、フッ素原子を含有する官能基を持つ分子構造を有し、熱を加えるとフッ素原子を含有する官能基の部分が切断されてフッ素原子が揮発するアクリル系化合物も好適に使用できる。このようなフッ素系界面活性剤としては、DIC社製のメガファック DSシリーズ(化学工業日報2016年2月22日、日経産業新聞2016年2月23日、例えば、メガファック DS-21)が挙げられる。
フッ素界面活性剤としては、環境適性向上の観点から、パーフルオロオクタン酸(PFOA)及びパーフルオロオクタンスルホン酸(PFOS)等の炭素数が7以上のパーフルオロアルキル基を有する化合物の代替材料に由来する界面活性剤であることが好ましい。
シリコーン系界面活性剤の市販品としては、DOWSIL 8032 ADDITIVE、トーレシリコーンDC3PA、トーレシリコーンSH7PA、トーレシリコーンDC11PA、トーレシリコーンSH21PA、トーレシリコーンSH28PA、トーレシリコーンSH29PA、トーレシリコーンSH30PA、及びトーレシリコーンSH8400(以上、東レ・ダウコーニング社製);X-22-4952、X-22-4272、X-22-6266、KF-351A、K354L、KF-355A、KF-945、KF-640、KF-642、KF-643、X-22-6191、X-22-4515、KF-6004、KP-341、KF-6001、KF-6002、KP-101KP-103、KP-104、KP-105、KP-106、KP-109、KP-109、KP-112、KP-120、KP-121、KP-124、KP-125、KP-301、KP-306、KP-310、KP-322、KP-323、KP-327、KP-341、KP-368、KP-369、KP-611、KP-620、KP-621、KP-626、KP-652(以上、信越シリコーン社製);F-4440、TSF-4300、TSF-4445、及びTSF-4460、TSF-4452(以上、モメンティブ・パフォーマンス・マテリアルズ社製);BYK300、BYK306、BYK307、BYK310、BYK320、BYK323、BYK325、BYK330、BYK313、BYK315N、BYK331、BYK333、BYK345、BYK347、BYK348、BYK349、BYK370、BYK377、BYK378、BYK323(以上、ビックケミー社製)が挙げられる。
ノニオン系界面活性剤の市販品としては、プルロニック(登録商標) L10、L31、L61、L62、10R5、17R2、25R2(以上、BASF社製);テトロニック 304、701、704、901、904、及び150R1(以上、BASF社製);ソルスパース 20000(以上、日本ルーブリゾール社製);NCW-101、NCW-1001、及びNCW-1002(以上、富士フイルム和光純薬社製);パイオニン D-6112、D-6112-W、及びD-6315(以上、竹本油脂社製)、オルフィンE1010、サーフィノール104、400、及び440(以上、日信化学工業社製)が挙げられる。
感光性組成物層が界面活性剤を含む場合、界面活性剤の含有量は、感光性組成物層の全質量に対して、0.01~3.0質量%が好ましく、0.05~1.0質量%がより好ましく、0.10~0.80質量%が更に好ましい。
感光性組成物層は、リン酸エステル化合物を含んでいてもよい。
リン酸エステル化合物としては、リン酸(O=P(OH)3)における3つの水素の少なくとも1つ以上が有機基で置換されたものであれば特に制限されず、ユニケミカル株式会社製のPhosmerシリーズ(Phosmer-M、Phosmer-CL、Phosmer-PE、Phosmer-MH、Phosmer-PP)、日本化薬株式会社製のKAYAMERシリーズ(KAYAMER PM-21、KAYAMER PM-2)、及び、共栄社化学株式会社製のライトエステルシリーズ(ライトエステルP-2M(商品名))が挙げられる。
リン酸エステル化合物の含有量は特に制限されないが、感光性組成物層の全質量に対して、0.05~3.0質量%が好ましく、0.1~2.0質量%がより好ましく、0.2~1.0質量%が更に好ましい。
感光性組成物層がリン酸エステル化合物を含む場合、リン酸エステル化合物の含有量は特に制限されないが、被転写体に対する密着性をより向上させる点で、バインダーポリマー及び重合性化合物の合計100質量部に対して、10質量部以下であることが好ましく、3質量部以下であることがより好ましい。また、上記含有量の上限は特に制限されないが、0.01質量部以上であることが好ましく、0.1質量部以上であることがより好ましい。
感光性組成物層は、重合禁止剤を含んでいてもよい。
重合禁止剤とは、重合反応を遅延又は禁止させる機能を有する化合物を意味する。重合禁止剤としては、例えば、重合禁止剤として用いられる公知の化合物を用いることができる。
なかでも、重合禁止剤としては、フェノチアジン化合物、ニトロソ化合物又はその塩、及び、ヒンダードフェノール化合物からなる群から選択される少なくとも1種が好ましく、フェノチアジン、ビス[3-(3-tert-ブチル-4-ヒドロキシ-5-メチルフェニル)プロピオン酸][エチレンビス(オキシエチレン)]2,4-ビス〔(ラウリルチオ)メチル〕-o-クレゾール、1,3,5-トリス(3,5-ジ-t-ブチル-4-ヒドロキシベンジル)、及び、N-ニトロソフェニルヒドロキシルアミンアルミニウム塩がより好ましい。
感光性組成物層が重合禁止剤を含む場合、重合禁止剤の含有量は、感光性組成物層の全質量に対して、0.01~10.0質量%が好ましく、0.01~5.00質量%がより好ましく、0.01~3.00質量%が更に好ましく、0.01~1.00質量%が特に好ましい。
感光性組成物層は、水素供与性化合物を含んでいてもよい。
水素供与性化合物は、光重合開始剤の活性光線に対する感度を一層向上させる、及び、酸素による重合性化合物の重合阻害を抑制する等の作用を有する。
なかでも、本発明の効果がより優れる点で、アミン類としては、4,4’-ビス(ジエチルアミノ)ベンゾフェノン、及び、トリス(4-ジメチルアミノフェニル)メタンからなる群から選択される少なくとも1種が好ましい。
なかでも、本発明の効果がより優れる点で、アミノ酸化合物としては、N-フェニルグリシンが好ましい。
感光性組成物層が水素供与性化合物を含む場合、水素供与性化合物の含有量は、重合成長速度と連鎖移動のバランスとによる硬化速度の向上の点から、感光性組成物層の全質量に対して、0.01~10.00質量%が好ましく、0.03~8.00質量%がより好ましく、0.05~5.00質量%が更に好ましい。
感光性組成物層は、顔料を含む着色樹脂層であってもよい。
近年の電子機器が有する液晶表示窓には、液晶表示窓を保護するために、透明なガラス基板等の裏面周縁部に黒色の枠状遮光層が形成されたカバーガラスが取り付けられている場合がある。このような遮光層を形成するために着色樹脂層が使用し得る。
顔料としては、所望とする色相に合わせて適宜選択すればよく、黒色顔料、白色顔料、黒色及び白色以外の有彩色の顔料の中から選択できる。なかでも、黒色系のパターンを形成する場合には、顔料として黒色顔料が好適に選択される。
ここで、粒径とは、電子顕微鏡で撮影した顔料粒子の写真像から顔料粒子の面積を求め、顔料粒子の面積と同面積の円を考えた場合の円の直径を指し、数平均粒径は、任意の100個の粒子について上記の粒径を求め、求められた100個の粒径を平均して得られる平均値である。
また、酸化チタンの表面は、シリカ処理、アルミナ処理、チタニア処理、ジルコニア処理、又は有機物処理が施されていてもよく、二つ以上の処理が施されてもよい。これにより、酸化チタンの触媒活性が抑制され、耐熱性及び褪光性等が改善される。
加熱後の感光性組成物層の厚みを薄くする観点から、酸化チタンの表面への表面処理としては、アルミナ処理及びジルコニア処理の少なくとも一方が好ましく、アルミナ処理及びジルコニア処理の両方が特に好ましい。
有彩色の顔料としては、例えば、ビクトリア・ピュアーブルーBO(Color Index(以下C.I.)42595)、オーラミン(C.I.41000)、ファット・ブラックHB(C.I.26150)、モノライト・エローGT(C.I.ピグメント・エロー12)、パーマネント・エローGR(C.I.ピグメント・エロー17)、パーマネント・エローHR(C.I.ピグメント・エロー83)、パーマネント・カーミンFBB(C.I.ピグメント・レッド146)、ホスターバームレッドESB(C.I.ピグメント・バイオレット19)、パーマネント・ルビーFBH(C.I.ピグメント・レッド11)、ファステル・ピンクBスプラ(C.I.ピグメント・レッド81)、モナストラル・ファースト・ブルー(C.I.ピグメント・ブルー15)、モノライト・ファースト・ブラックB(C.I.ピグメント・ブラック1)及びカーボン、C.I.ピグメント・レッド97、C.I.ピグメント・レッド122、C.I.ピグメント・レッド149、C.I.ピグメント・レッド168、C.I.ピグメント・レッド177、C.I.ピグメント・レッド180、C.I.ピグメント・レッド192、C.I.ピグメント・レッド215、C.I.ピグメント・グリーン7、C.I.ピグメント・ブルー15:1、C.I.ピグメント・ブルー15:4、C.I.ピグメント・ブルー22、C.I.ピグメント・ブルー60、C.I.ピグメント・ブルー64、及びC.I.ピグメント・バイオレット23が挙げられる。なかでも、C.I.ピグメント・レッド177が好ましい。
分散液は、黒色顔料と顔料分散剤とをあらかじめ混合して得られる混合物を、有機溶剤(又はビヒクル)に加えて分散機で分散させることによって調製されるものでもよい。顔料分散剤は、顔料及び溶剤に応じて選択すればよく、例えば市販の分散剤を使用することができる。なお、ビヒクルとは、顔料分散液とした場合に顔料を分散させている媒質の部分を指し、液状であり、黒色顔料を分散状態で保持するバインダー成分と、バインダー成分を溶解及び希釈する溶剤成分(有機溶剤)とを含む。
感光性組成物層は、上述したバインダーポリマーの各構造単位の残存モノマーを含む場合がある。
残存モノマーの含有量は、パターニング性、及び、信頼性の点から、バインダーポリマー全質量に対して、5,000質量ppm以下が好ましく、2,000質量ppm以下がより好ましく、500質量ppm以下が更に好ましい。下限は特に制限されないが、バインダーポリマー全質量に対して、1質量ppm以上が好ましく、10質量ppm以上がより好ましい。
バインダーポリマーの各構造単位の残存モノマーは、パターニング性、及び、信頼性の点から、感光性組成物層の全質量に対して、3,000質量ppm以下が好ましく、600質量ppm以下がより好ましく、100質量ppm以下が更に好ましい。下限は特に制限されないが、感光性組成物層の全質量に対して、0.1質量ppm以上が好ましく、1質量ppm以上がより好ましい。
残存モノマーの量は、液体クロマトグラフィー、及び、ガスクロマトグラフィー等の公知の方法で測定できる。
感光性組成物層は、既述の成分以外の成分(以下「他の成分」ともいう。)を含んでいてもよい。他の成分としては、例えば、増感剤、色素、酸化防止剤、粒子(例えば、金属酸化物粒子)が挙げられる。また、他の成分としては、特開2000-310706号公報の段落[0058]~[0071]に記載のその他の添加剤も挙げられる。
増感剤としては、特に制限されず、公知の増感剤、染料及び顔料を用いることができる。増感剤としては、例えば、ジアルキルアミノベンゾフェノン化合物、ピラゾリン化合物、アントラセン化合物、クマリン化合物、キサントン化合物、チオキサントン化合物、アクリドン化合物、オキサゾール化合物、ベンゾオキサゾール化合物、チアゾール化合物、ベンゾチアゾール化合物、トリアゾール化合物(例えば、1,2,4-トリアゾール)、スチルベン化合物、トリアジン化合物、チオフェン化合物、ナフタルイミド化合物、トリアリールアミン化合物、及び、アミノアクリジン化合物が挙げられる。
粒子としては、金属酸化物粒子が好ましい。
金属酸化物粒子における金属には、B、Si、Ge、As、Sb、及び、Te等の半金属も含まれる。
粒子の平均一次粒子径は、例えば、硬化膜の透明性の点から、1~200nmが好ましく、3~80nmがより好ましい。
粒子の平均一次粒子径は、電子顕微鏡を用いて任意の粒子200個の粒子径を測定し、測定結果を算術平均することにより算出される。なお、粒子の形状が球形でない場合には、最も長い辺を粒子径とする。
感光性組成物層は、粒子を含まないか、又は、感光性組成物層が粒子を含む場合には、粒子の含有量が、感光性組成物層の全質量に対して、0質量%超35質量%以下が好ましく、粒子を含まないか、又は、粒子の含有量が、感光性組成物層の全質量に対して、0質量%超10質量%以下がより好ましく、粒子を含まないか、又は、粒子の含有量が、感光性組成物層の全質量に対して、0質量%超5質量%以下が更に好ましく、粒子を含まないか、又は、粒子の含有量が、感光性組成物層の全質量に対して、0質量%超1質量%以下が更に好ましく、粒子を含まないことが特に好ましい。
感光性組成物層は、色素を含んでいてもよい。
色素としては、特に制限されず、公知の色素を用いることができ、例えば、ロイコ化合物が挙げられる。
酸化防止剤としては、例えば、1-フェニル-3-ピラゾリドン(別名:フェニドン)、1-フェニル-4,4-ジメチル-3-ピラゾリドン、及び、1-フェニル-4-メチル-4-ヒドロキシメチル-3-ピラゾリドン等の3-ピラゾリドン類;ハイドロキノン、カテコール、ピロガロール、メチルハイドロキノン、及び、クロルハイドロキノン等のポリヒドロキシベンゼン類;パラメチルアミノフェノール、パラアミノフェノール、パラヒドロキシフェニルグリシン、及び、パラフェニレンジアミンが挙げられる。
なかでも、本発明の効果がより優れる点で、酸化防止剤としては、3-ピラゾリドン類が好ましく、1-フェニル-3-ピラゾリドンがより好ましい。
感光性組成物層は、不純物を含んでいてもよい。
不純物としては、例えば、ナトリウム、カリウム、マグネシウム、カルシウム、鉄、マンガン、銅、アルミニウム、チタン、クロム、コバルト、ニッケル、亜鉛、スズ、ハロゲン、及び、これらのイオンが挙げられる。
なかでも、ハロゲン化物イオン、ナトリウムイオン、及び、カリウムイオンは不純物として混入し易いため、下記の含有量にすることが好ましい。
転写フィルムは、感光性組成物層上に配置された屈折率調整層を有していてもよい。
転写フィルムは、仮支持体と、感光性組成物層と、屈折率調整層とをこの順で有することが好ましい。
なお、転写フィルムが後述する保護フィルムを更に有する場合、仮支持体と、感光性組成物層と、屈折率調整層と、後述する保護フィルムとをこの順で有することが好ましい。
屈折率調整層が金属酸化抑制剤を含むことで、屈折率調整層に接する金属の酸化を抑制できる。
金属酸化抑制剤としては、例えば、分子内に窒素原子を含む芳香環を有する化合物が好ましい。金属酸化抑制剤としては、例えば、イミダゾール、ベンゾイミダゾール、テトラゾール、メルカプトチアジアゾール、及び、ベンゾトリアゾールが挙げられる。
屈折率調整層の厚みは、走査型電子顕微鏡(SEM)による断面観察により測定した任意の5点の平均値として算出する。
転写フィルムは、上述した仮支持体、感光性組成物層、屈折率調整層、及び、保護フィルム以外に、その他の層を有していてもよい。
その他の層としては、例えば、熱可塑性樹脂層、中間層、及び、帯電防止層が挙げられる。
熱可塑性樹脂層は、通常、仮支持体と感光性組成物層との間に配置される。転写フィルムが熱可塑性樹脂層を備えることで、転写フィルムと基板との貼合工程における基板への追従性が向上して、基板と転写フィルムとの間の気泡の混入を抑制できる。この結果として、熱可塑性樹脂層に隣接する層(例えば、仮支持体)との密着性を担保できる。
アルカリ可溶性樹脂としては、例えば、アクリル樹脂、ポリスチレン樹脂、スチレン-アクリル系共重合体、ポリウレタン樹脂、ポリビニルアルコール、ポリビニルホルマール、ポリアミド樹脂、ポリエステル樹脂、ポリアミド樹脂、エポキシ樹脂、ポリアセタール樹脂、ポリヒドロキシスチレン樹脂、ポリイミド樹脂、ポリベンゾオキサゾール樹脂、ポリシロキサン樹脂、ポリエチレンイミン、ポリアリルアミン、及びポリアルキレングリコールが挙げられる。
ここで、アクリル樹脂は、(メタ)アクリル酸に由来する構成単位、(メタ)アクリル酸エステルに由来する構成単位、及び(メタ)アクリル酸アミドに由来する構成単位からなる群から選ばれた少なくとも1種の構成単位を有する樹脂を意味する。
アクリル樹脂としては、(メタ)アクリル酸に由来する構成単位、(メタ)アクリル酸エステルに由来する構成単位、及び(メタ)アクリル酸アミドに由来する構成単位の合計含有量が、アクリル樹脂の全質量に対して50質量%以上であることが好ましい。
なかでも、(メタ)アクリル酸に由来する構成単位及び(メタ)アクリル酸エステルに由来する構成単位の合計含有量が、アクリル樹脂の全質量に対して、30~100質量%が好ましく、50~100質量%がより好ましい。
酸基としては、カルボキシ基、スルホ基、リン酸基、及びホスホン酸基が挙げられ、カルボキシ基が好ましい。
アルカリ可溶性樹脂は、現像性の観点から、酸価60mgKOH/g以上のアルカリ可溶性樹脂がより好ましく、酸価60mgKOH/g以上のカルボキシ基含有アクリル樹脂が更に好ましい。
アルカリ可溶性樹脂の酸価の上限は、特に制限されないが、300mgKOH/g以下が好ましく、250mgKOH/g以下がより好ましく、200mgKOH/g以下が更に好ましく、150mgKOH/g以下が特に好ましい。
例えば、特開2011-095716号公報の段落[0025]に記載のポリマーのうち酸価60mgKOH/g以上のカルボキシ基含有アクリル樹脂であるアルカリ可溶性樹脂、特開2010-237589号公報の段落[0033]~[0052]に記載のポリマーのうちの酸価60mgKOH/g以上のカルボキシ基含有アクリル樹脂、及び特開2016-224162号公報の段落[0053]~[0068]に記載のバインダーポリマーのうちの酸価60mgKOH/g以上のカルボキシ基含有アクリル樹脂が挙げられる。
上記カルボキシ基含有アクリル樹脂におけるカルボキシ基を有する構成単位の共重合比は、アクリル樹脂の全質量に対して、5~50質量%が好ましく、10~40質量%がより好ましく、12~30質量%が更に好ましい。
アルカリ可溶性樹脂としては、現像性及び隣接する層との密着性の観点から、(メタ)アクリル酸に由来する構成単位を有するアクリル樹脂が特に好ましい。
アルカリ可溶性樹脂の含有量は、現像性及び隣接する層との密着性の観点から、熱可塑性樹脂層の全質量に対して、10~99質量%が好ましく、20~90質量%がより好ましく、40~80質量%が更に好ましく、50~75質量%が特に好ましい。
転写フィルム10において、中間層5は、熱可塑性樹脂層3と感光性組成物層7との間に存在することにより、熱可塑性樹脂層3及び感光性組成物層7の塗布形成の際及び塗布形成後の保存の際に生じ得る成分の混合を抑制できる。
中間層としては、水溶性樹脂を含む水溶性樹脂層が使用できる。
また、中間層としては、特開平5-072724号公報に「分離層」として記載されている、酸素遮断機能のある酸素遮断層も使用できる。中間層が酸素遮断層であると、露光時の感度が向上し、露光機の時間負荷が低減し、生産性が向上するため、好ましい。
中間層として用いられる酸素遮断層は、上記公報等に記載された公知の層から適宜選択すればよい。なかでも、低い酸素透過性を示し、水又はアルカリ水溶液(22℃の炭酸ナトリウムの1質量%水溶液)に分散又は溶解する酸素遮断層が好ましい。
上記樹脂は、その一部又は全部として、水溶性樹脂を含む。
水溶性樹脂として使用可能な樹脂としては、例えば、ポリビニルアルコール系樹脂、ポリビニルピロリドン系樹脂、セルロース系樹脂、アクリルアミド系樹脂、ポリエチレンオキサイド系樹脂、ゼラチン、ビニルエーテル系樹脂、ポリアミド樹脂、及びこれらの共重合体等の樹脂が挙げられる。
また、水溶性樹脂としては、(メタ)アクリル酸/ビニル化合物の共重合体等も使用できる。(メタ)アクリル酸/ビニル化合物の共重合体としては、(メタ)アクリル酸/(メタ)アクリル酸アリルの共重合体が好ましく、メタクリル酸/メタクリル酸アリルの共重合体がより好ましい。
水溶性樹脂が(メタ)アクリル酸/ビニル化合物の共重合体である場合、各組成比(モル%)としては、例えば、90/10~20/80が好ましく、80/20~30/70がより好ましい。
水溶性樹脂の分散度(Mw/Mn)は、1~10が好ましく、1~5がより好ましい。
水溶性樹脂の含有量は特に制限されないが、酸素遮断性、並びに、層間混合抑制能をより向上させる点で、水溶性樹脂層(中間層)の全質量に対して、50質量%以上が好ましく、70質量%以上がより好ましく、80質量%以上が更に好ましく、90質量%以上が特に好ましい。なお、その上限値としては特に制限されないが、99.9質量%以下が好ましく、99.8質量%以下が更に好ましい。
転写フィルムが帯電防止層を有することで、帯電防止層上に配置されたフィルム等を剥離する際における静電気の発生を抑制でき、また、設備又は他のフィルム等との擦れによる静電気の発生も抑制できるため、例えば、電子機器における不具合の発生を抑止できる。
帯電防止層は、仮支持体と感光性組成物層との間に配置することが好ましい。
仮支持体の製造方法としては、特に制限されず、公知の方法が挙げられる。
仮支持体の製造方法としては、押出成形工程と塗布工程と有する製造方法であってもよく、共押出成形工程を有する製造方法であってもよい。また、上記工程に加えて、更に2軸延伸工程を有することが好ましい。
押出成形法としては、例えば、押出機を用いて原料樹脂を押し出すことによって、原料樹脂を所望の形状に成形する方法が挙げられる。
共押出形成工程としては、例えば、押出機を用いて複数の原料樹脂を押し出すことによって、原料樹脂を多層構造を有する形状に成形する方法が挙げられる。
仮支持体の製造方法は、ポリエステルを溶融押出することにより、未延伸仮支持体本体を形成する工程(以下「押出成形工程」ともいう。)と、塗布工程と、上記仮支持体本体を長手方向に延伸する工程(以下「縦延伸工程」ともいう。)と、上記長手方向に延伸された仮支持体本体を幅方向に延伸する工程(以下「横延伸工程」ともいう。)と、を有することが好ましい。また、仮支持体の製造方法は、第1層、第2層、及び、仮支持体本体の原料樹脂を同時に溶融押出することにより、未延伸仮支持体を形成する工程(以下「共押出成形工程」ともいう。)と、上記仮支持体を長手方向に延伸する工程(以下「縦延伸工程」ともいう。)と、上記長手方向に延伸された仮支持体を幅方向に延伸する工程(以下「横延伸工程」ともいう。)と、を有することも好ましい。
押出成形工程においては、原料樹脂(例えば、ポリエステル)を溶融押出することにより、未延伸仮支持体本体を形成する。
塗布工程は、第1層又は第2層を形成する工程である。
塗布工程としては、特に制限されず、公知の方法が挙げられる。
塗布工程においては、第1層又は第2層に含まれる成分を溶剤に溶解させて第1層又は第2層形成用塗布液を調製して用いることが好ましい。溶剤としては、例えば、水及び有機溶剤が挙げられる。
なかでも、2軸延伸工程後に設けることが好ましく、長手方向に延伸された仮支持体本体上に第1層又は第2層形成用塗布液を塗布し、次いで、横延伸することがより好ましい。
共押出成形工程としては、特に制限されず、公知の方法が挙げられる。共押出成形工程としては、例えば、特開2019-65271号公報に記載の方法が挙げられ、これらの内容は本明細書に組み込まれる。
2軸延伸工程は、特に制限されず、公知の方法が挙げられる。
2軸延伸工程としては、縦延伸工程及び横延伸工程を有することが好ましい。
縦延伸工程においては、上記未延伸フィルム(例えば、未延伸仮支持体及び未延伸仮支持体本体)を長手方向に延伸(以下「縦延伸」ともいう。)を行うことが好ましい。
横延伸工程においては、上記長手方向に延伸されたフィルム(例えば、長手方向に延伸された仮支持体及び長手方向に延伸された仮支持体本体)を幅方向に延伸(以下「横延伸」ともいう。)する。
仮支持体の製造方法としては、上記幅方向に延伸されたフィルム(例えば、幅方向に延伸された仮支持体及び幅方向に延伸された仮支持体本体)を加熱処理する工程(以下「加熱処理工程」ともいう。)を有することが好ましい。加熱処理工程としては、例えば、熱固定工程、及び、熱緩和工程が挙げられる。加熱処理工程は、熱固定工程、及び、熱緩和工程の少なくとも一方を有することが好ましく、熱固定工程、及び、熱緩和工程を有することがより好ましい。
熱固定工程においては、上記幅方向に延伸されたフィルム(例えば、幅方向に延伸された仮支持体及び幅方向に延伸された仮支持体本体)を加熱することで熱固定する。熱固定によって原料樹脂を結晶化させることができるため、上記フィルムの収縮を抑えることができる。
熱緩和工程においては、上記幅方向に延伸されたフィルム(例えば、幅方向に延伸された仮支持体及び幅方向に延伸された仮支持体本体)を加熱することで熱緩和する。熱緩和によってフィルム(例えば、幅方向に延伸された仮支持体及び幅方向に延伸された仮支持体本体)の残留歪みを緩和できる。
仮支持体の製造方法は、上記加熱処理されたフィルム(例えば、加熱処理された仮支持体及び加熱処理された仮支持体本体)を冷却する工程(以下「冷却工程」ともいう。)を有することが好ましい。
本発明の転写フィルムの製造方法は特に制限されず、公知の方法を用いることができる。
なかでも、生産性に優れる点で、仮支持体上に感光性組成物を塗布し、必要に応じて乾燥処理を施し、感光性組成物層を形成する方法が好ましい。
以下、上記方法について詳述する。
本明細書において、「乾燥」とは、感光性組成物に含まれる溶剤の少なくとも一部を除去することを意味する。
保護フィルムを感光性組成物層に貼り合わせる方法は特に制限されず、公知の方法が挙げられる。
保護フィルムを感光性組成物層に貼り合わせる装置としては、真空ラミネーター及びオートカットラミネーター等の公知のラミネーターが挙げられる。
ラミネーターは、ゴムローラー等の任意の加熱可能なローラーを備え、加圧及び加熱ができるものであることが好ましい。
上述した転写フィルムを用いることにより、被転写体へ感光性組成物層を転写することができる。
なかでも、転写フィルムから保護フィルムを剥離して、仮支持体とは反対側の表面を、導電部を有する基板に接触させて貼り合わせ、導電部、感光性組成物層、及び、仮支持体をこの順に有する感光性組成物層付き基板を得る貼合工程と、
感光性組成物層をパターン露光する露光工程と、
露光された感光性組成物層を現像して、パターンを形成する現像工程と、を有し、
更に、貼合工程と露光工程との間、又は、露光工程と現像工程との間に、感光性組成物層付き基板から仮支持体を剥離する剥離工程と、を有する、積層体の製造方法が好ましい。
以下、上記工程の手順について詳述する。
貼合工程は、転写フィルムから保護フィルムを剥離して、転写フィルムの仮支持体とは反対側の表面を、導電部を有する基板に接触させて貼り合わせ、導電層、感光性組成物層、及び、仮支持体をこの順に有する感光性組成物層付き基板を得る工程である。
転写フィルムの仮支持体とは反対側の表面とは、転写フィルムが屈折率調整層を有する場合は屈折率調整層であることが好ましく、転写フィルムが屈折率調整層を有さない場合は感光性組成物層であることが好ましい。つまり、貼合工程は、転写フィルムの屈折率調整層を、被転写体に接触させて貼り合わせるか、又は、転写フィルムの感光性組成物層を、被転写体に接触させて貼り合わせることが好ましい。
転写フィルムの仮支持体上の露出した感光性組成物層を、導電層に接触させて貼り合わせる。この貼合によって、導電層上に、感光性組成物層及び仮支持体が配置される。
上記貼合においては、上記導電層と上記感光性組成物層の表面と、が接触するように圧着させる。
上記圧着の方法としては特に制限はなく、公知の転写方法及びラミネート方法を用いることができる。なかでも、感光性組成物層の表面を、導電部を有する基板に重ね、ロール等による加圧及び加熱することに行われることが好ましい。
貼り合せには、真空ラミネーター及びオートカットラミネーター等の公知のラミネーターを使用できる。
基板の好ましい態様としては、例えば、国際公開第2018/155193号の段落[0140]に記載があり、この内容は本明細書に組み込まれる。
また、基板上には導電層を1層のみ配置してもよいし、2層以上配置してもよい。導電層を2層以上配置する場合は、異なる材質の導電層を有することが好ましい。
導電層の好ましい態様としては、例えば、国際公開第2018/155193号の段落[0141]に記載があり、この内容は本明細書に組み込まれる。
透明電極は、タッチパネル用電極として好適に機能し得る。透明電極は、ITO(酸化インジウムスズ)、及び、IZO(酸化インジウム亜鉛)等の金属酸化膜、並びに、金属メッシュ、及び、銀ナノワイヤー等の金属細線により構成されることが好ましい。
金属細線としては、銀、銅等の細線が挙げられる。なかでも、銀メッシュ、銀ナノワイヤー等の銀導電性材料が好ましい。
引き回し配線の材質である金属としては、金、銀、銅、モリブデン、アルミニウム、チタン、クロム、亜鉛、及び、マンガン、並びに、これらの金属元素の2種以上からなる合金が挙げられる。なかでも、引き回し配線の材質としては、銅、モリブデン、アルミニウム、又は、チタンが好ましく、銅がより好ましい。
露光工程は、感光性組成物層をパターン露光する工程である。
なお、ここで、「パターン露光」とは、パターン状に露光する形態、すなわち、露光部と非露光部とが存在する形態の露光を指す。
パターン露光におけるパターンの詳細な配置及び具体的サイズは、特に制限されない。なお、後述する現像工程によって形成されるパターンは、幅が500μm以下である細線を含むことが好ましく、幅が100μm以下の細線を含むことがより好ましい。
露光量は、5~200mJ/cm2が好ましく、10~200mJ/cm2がより好ましい。
剥離工程は、貼合工程と露光工程との間、又は、露光工程と後述する現像工程との間に、感光性組成物層付き基板から仮支持体を剥離する工程である。
剥離方法は特に制限されず、特開2010-072589号公報の段落[0161]~[0162]に記載されたカバーフィルム剥離機構と同様の機構を用いることができる。
現像工程は、露光された感光性組成物層を現像して、パターンを形成する工程である。
上記感光性組成物層の現像は、現像液を用いて行うことができる。
現像液として、アルカリ性水溶液が好ましい。アルカリ性水溶液に含まれ得るアルカリ性化合物としては、例えば、水酸化ナトリウム、水酸化カリウム、炭酸ナトリウム、炭酸カリウム、炭酸水素ナトリウム、炭酸水素カリウム、テトラメチルアンモニウムヒドロキシド、テトラエチルアンモニウムヒドロキシド、テトラプロピルアンモニウムヒドロキシド、テトラブチルアンモニウムヒドロキシド、及び、コリン(2-ヒドロキシエチルトリメチルアンモニウムヒドロキシド)が挙げられる。
好適に用いられる現像方式としては、例えば、国際公開第2015/093271号の段落[0195]に記載の現像方式が挙げられる。
上記積層体の製造方法は、上記現像工程によって得られたパターンを、露光する工程(ポスト露光工程)及び/又は加熱する工程(ポストベーク工程)を有していてもよい。
ポスト露光工程及びポストベーク工程の両方を含む場合、ポスト露光の後、ポストベークを実施することが好ましい。
転写フィルムは、回路配線の製造方法に用いることもできる。
回路配線の製造方法としては、特に制限されず、公知の製造方法が挙げられる。
なかでも、回路配線の製造方法としては、
転写フィルムから保護フィルムを剥離して、仮支持体上の感光性組成物層を、導電層を有する基板に貼り合わせ、導電層、感光性組成物層、及び、仮支持体をこの順に有する感光性組成物層付き基板を得る貼合工程と、
感光性組成物層をパターン露光する露光工程と、
露光された感光性組成物層を現像して、パターンを形成する現像工程と、
パターンが配置されていない領域における導電層をエッチング処理するエッチング工程と、
更に、貼合工程と露光工程との間、又は、露光工程と現像工程との間に、感光性組成物層付き基板から仮支持体を剥離する剥離工程と、を有する、積層体の製造方法が好ましい。
エッチング工程は、現像工程で得られたパターンが配置されていない領域にある導電層をエッチング処理する工程(エッチング工程)である。
つまり、エッチング工程は、感光性組成物層から形成されたパターンを、エッチングレジストとして使用し、導電層のエッチング処理を行うことである。
酸性のエッチング液としては、例えば、塩酸、硫酸、硝酸、酢酸、フッ酸、シュウ酸、及び、リン酸から選択される酸性成分単独の水溶液、並びに、酸性成分と、塩化第2鉄、フッ化アンモニウム及び過マンガン酸カリウムから選択される塩との混合水溶液が挙げられる。酸性成分は、複数の酸性成分を組み合わせた成分であってもよい。
アルカリ性のエッチング液としては、例えば、水酸化ナトリウム、水酸化カリウム、アンモニア、有機アミン、及び、有機アミンの塩(テトラメチルアンモニウムハイドロオキサイド等)から選択されるアルカリ成分単独の水溶液、並びに、アルカリ成分と塩(過マンガン酸カリウム等)との混合水溶液が挙げられる。アルカリ成分は、複数のアルカリ成分を組み合わせた成分であってもよい。
回路配線の製造方法は、残存するパターンを除去する工程(除去工程)を含んでいてもよい。
除去工程は、特に制限され、各工程前又は工程後に行ってもよく、エッチング工程の後に行うことが好ましい。
残存するパターンを除去する方法としては、特に制限されないが、薬品処理により除去する方法が挙げられ、除去液を用いて除去する方法が好ましい。
除去液を用いて除去する方法としては、撹拌中の除去液に、残存するパターンを有する被転写体を、1~30分間浸漬する方法が挙げられる。
除去液の液温としては、30~80℃が好ましく、50~80℃がより好ましい。
また、除去液を使用し、スプレー法、シャワー法及びパドル法等の公知の方法により除去してもよい。
積層体の製造方法、及び、回路配線の製造方法は、上述した工程以外の任意の工程(その他の工程)を含んでもよい。
その他の工程としては、例えば、国際公開第2019/022089号の段落[0172]に記載の可視光線反射率を低下させる工程、国際公開第2019/022089号の段落[0172]に記載の絶縁膜上に新たな導電層を形成する工程が挙げられる。が、これらの工程に制限されない。
積層体の製造方法、及び、回路配線の製造方法は、被転写体が有する複数の導電層の一部又は全ての可視光線反射率を低下させる処理を行う工程を含んでいてもよい。
可視光線反射率を低下させる処理としては、例えば、酸化処理が挙げられる。被転写体が銅を含む導電層を有する場合、銅を酸化処理して酸化銅とし、導電層を黒化することにより、導電層の可視光線反射率を低下させることができる。
可視光線反射率を低下させる処理については、特開2014-150118号公報の段落[0017]~[0025]、並びに、特開2013-206315号公報の段落[0041]~[0042]、段落[0048]、及び、段落[0058]に記載を援用でき、これらの内容は本明細書に組み込まれる。
回路配線の製造方法は、回路配線の表面に絶縁膜を形成する工程と、絶縁膜の表面に新たな導電層を形成する工程と、を含むことも好ましい。
上記の工程により、第1の電極パターンと、絶縁した第2の電極パターンとを形成することができる。
絶縁膜を形成する工程としては、特に制限されず、公知の永久膜を形成する方法が挙げられる。また、絶縁性を有する感光性材料を用いて、フォトリソグラフィにより所望のパターンの絶縁膜を形成してもよい。
絶縁膜上に新たな導電層を形成する工程は、特に制限されず、例えば、導電性を有する感光性組成物を用いて、フォトリソグラフィにより所望のパターンの新たな導電層を形成してもよい。
積層体の製造方法、及び、回路配線の製造方法により製造される積層体及び回路配線は、種々の装置に適用することができる。上記の製造方法により製造される積層体又は回路配線を備えた装置としては、例えば、表示装置、プリント配線板、半導体パッケージ、入力装置が挙げられ、タッチパネルが好ましく、静電容量型タッチパネルがより好ましい。また、上記入力装置は、有機EL表示装置及び液晶表示装置等の表示装置に適用できる。
転写フィルムは、電子デバイスの製造方法にも用いてもよい。
上記電子デバイスの製造方法としては、上述の転写フィルムを用いる電子デバイスの製造方法が好ましい。
なかでも、電子デバイスの製造方法は、上述した積層体の製造方法を含むことが好ましい。
上記電子デバイスとしては、例えば、入力装置等が挙げられ、タッチパネルであることが好ましい。また、上記入力装置は、有機エレクトロルミネッセンス表示装置、及び、液晶表示装置の表示装置に適用することができる。
また、タッチパネル用配線を形成する工程を含むタッチパネルの製造方法は、上述した以外の任意の工程(その他の工程)を含んでもよい。
タッチパネル用配線を形成する方法としては、例えば、国際公開第2016/190405号公報の図1に記載の方法も挙げられる。
タッチパネルにおける検出方法としては、例えば、抵抗膜方式、静電容量方式、超音波方式、電磁誘導方式、及び、光学方式等の公知の方式が挙げられ、静電容量方式が好ましい。
タッチパネルとしては、例えば、特開2017-120345号公報の段落[0229]に記載のものが挙げられる。
このような樹脂パターンの硬化膜は、電子デバイス(タッチパネル等)が有する電極等の一部又は全部を被覆する保護膜(永久膜)として使用できる。電極等の上に上記樹脂パターンの硬化膜を保護膜(永久膜)として配置することで、金属の腐食、電極と駆動用回路間の電気抵抗の増加、及び、断線といった不具合の防止が可能である。
以下の実施例において、重量平均分子量(Mw)は、ゲルパーミエーションクロマトグラフィ(GPC)によるポリスチレン換算で求めた重量平均分子量である。
下記の手順に従って、実施例1の仮支持体Z-1を作製した。
脱塩水(1500質量部)に、過硫酸カリウム(3.2質量部)と、ラウリル硫酸ナトリウム(0.15質量部)を添加し均一に溶解させた後、スチレン(92質量部)とジビニルベンゼン(8質量部)との混合溶液を加えた。窒素ガス雰囲気下で攪拌しながら70℃で24時間重合反応を行い、架橋ポリスチレン樹脂粒子を得た。
ペレットA及び混合物Xを含水率50ppm以下に乾燥させた後、中間層がペレットAとなるように押し出し機に投入し、290℃で溶融させ、層用合流ブロックで合流積層し、X層(混合物Xからなる層)/A層(ペレットAからなる層)/X層(混合物Xからなる層)の順に3層構造を有する未延伸の仮支持体を作製した。なお、押し出された溶融体(メルト)は、静電印加法を用い、冷却ロールに一方のX層側を密着させた。
得られた未延伸の仮支持体に対して、下記の方法により逐次2軸延伸を施した。
まず、未延伸の仮支持体を周速の異なる2対のニップロールの間に通すことにより縦方向(搬送方向)に延伸した。なお、縦延伸は、予熱温度75℃、延伸温度95℃、延伸倍率3.4倍、及び延伸速度1300%/秒として実施した。
次に、得られた縦方向に延伸された仮支持体に対して、テンターを用いて横方向に延伸した。なお、縦延伸は、予熱温度100℃、延伸温度120℃、延伸倍率4.2倍、及び延伸速度50%/秒として実施し、仮支持体Z-1を得た。なお、仮支持体Z-1の各層の厚みは、X層/A層/X層=1μm/14μm/1μmであった。
表2~3に従って、各成分を変更した以外は、上述した仮支持体Z-1と同様の手順で、各実施例及び各比較例の仮支持体を作製した。
下記の手順に従って、実施例1の転写フィルムを作製した。
まず、各転写フィルムに含まれる成分について、詳述する。
PGMEA(55.8質量部)とトルエン(55.8質量部)とを混合し、第1液を調製した。また、メタクリル酸(12質量部)、メタクリル酸メチル(58質量部)、及びアクリル酸エチル(30質量部)の混合液と、AIBN(アゾビスイソブチロニトリル)(1.0質量部)と、PGMEA(6.2質量部)と、トルエン(6.2質量部)とを混合し、室温にて1時間撹拌して第2液を調製した。
フラスコに上記第1液を入れ、窒素雰囲気下において80℃に昇温した。次に、得られた混合液を、攪拌下、液温を80℃に維持しながら、滴下ポンプを用いて、上記第2液を更にフラスコに4時間かけて添加した。添加終了後、攪拌下、得られた混合液の液温を80℃に維持して更に6時間反応させ、バインダーポリマーAを含む溶液を得た。得られたバインダーポリマーAの重量平均分子量は65,000であった。各モノマー由来の組成比(質量比)は、メタクリル酸/メタクリル酸メチル/アクリル酸エチル=12/58/30であった。
3つ口フラスコにPGMEA(116.5質量部)を入れ、窒素雰囲気下において90℃に昇温した。3つ口フラスコ内の液温を90℃±2℃に維持しながら、スチレン(52.0質量部)、メタクリル酸メチル(24.0質量部)、メタクリル酸(24.0質量部)、V-601(2,2’-アゾビス(イソ酪酸)ジメチル、富士フイルム社製(4.0質量部)及びPGMEA(116.5質量部)の混合液を、2時間かけて3つ口フラスコ内に滴下した。滴下終了後、液温を90℃±2℃に維持しながら混合液を2時間撹拌することで、バインダーポリマーBを含む溶液(固形分濃度は30.0質量%)を得た。なお、バインダーポリマーBの酸価は159mgKOH/g、重量平均分子量は60,000、ガラス転移温度は126℃であった。各モノマー由来の組成比(質量比)は、スチレン/メタクリル酸/メタクリル酸メチル=52/24/24であった。
プロピレングリコールモノメチルエーテル(82.4g)をフラスコに仕込み、窒素気流下90℃に加熱した。この液にスチレン(38.4g)、ジシクロペンタニルメタクリレート(30.1g)、メタクリル酸(34.0g)をプロピレングリコールモノメチルエーテル(20g)に溶解させた溶液、及び、重合開始剤V-601(富士フイルム和光純薬社製)(5.4g)をプロピレングリコールモノメチルエーテルアセテート(43.6g)に溶解させた溶液を同時に3時間かけて滴下した。滴下終了後、1時間おきに3回V-601を(0.75g)添加した。その後更に3時間反応させた。その後プロピレングリコールモノメチルエーテルアセテート(58.4g)、プロピレングリコールモノメチルエーテル(11.7g)で希釈した。空気気流下、反応液を100℃に昇温し、テトラエチルアンモニウムブロミド(0.53g)、p-メトキシフェノール(0.26g)を添加した。これにグリシジルメタクリレート(日油社製ブレンマーGH)(25.5g)を20分かけて滴下した。これを100℃で7時間反応させ、重合体P-1の溶液を得た。得られた溶液の固形分濃度は36.5質量%であった。GPCにおける標準ポリスチレン換算の重量平均分子量は17000、分散度は2.4、ポリマーの酸価は94.5mgKOH/gであった。ガスクロマトグラフィーを用いて測定した残存モノマー量はいずれのモノマーにおいてもポリマー固形分に対し0.1質量%未満であった。
バインダーポリマーC(式中の繰り返し単位はモル比)の構造を以下に示す。
感光性組成物Y-1~Y-5を調整した。
・トリシクロデカンジメタノールジアクリレート(重合性化合物、A-DCP、新中村化学工業社製):19.31質量部
・カルボン酸含有モノマー(重合性化合物、アロニックスTO2349、東亞合成社製):3.21質量部
・ウレタン-アクリルモノマー(重合性化合物、アクリット8UX-015A、大成ファインケミカル社製):9.65質量部
・下記バインダーポリマーP-1(酸価95mgKOH/g、Mw=27,000、固形分濃度36.3質量%):固形分換算で53.64質量部
・Irgacure OXE-02(光重合開始剤、BASF社製):0.37質量部
・Omnirad 907(光重合開始剤、IGM Resins B.V.社製):0.74質量部
・N-フェニルグリシン(水素供与性化合物、純正化学社製):0.10質量部
・ベンゾイミダゾール(複素環化合物、東京化成工業社製):0.30質量部
・メガファック F551(界面活性剤、DIC社製):0.16質量部
・1-メトキシ-2-プロピルアセテート(PGMEA)とメチルエチルケトン(MEK)との混合溶剤(PGMEA:MEK=4:6):感光性組成物Y-1の固形分濃度が29%になる量
・バインダーポリマーA:固形分換算で63.00質量部
・ペンタエリスリトールトリアクリレート(エチレン性不飽和化合物、新中村化学社製「A-TMM-3LM-N」):37.00質量部
・ビス(2,4,6-トリメチルベンゾイル)フェニルフォスフィンオキサイド(重合開始剤、IGM Resins B.V.社製「Omnirad 819」):10.00質量部
・ポリエーテル変性シリコーン(界面活性剤(レベリング剤)、東レ・ダウコーニング社製「8032 ADDITIVE」):0.06質量部
・MEK:感光性組成物Y-2の固形分濃度が30%になる量
・バインダーポリマーB(固形分濃度30.0質量%):53.27質量部
・NKエステルBPE-500(重合性化合物、2,2-ビス(4-(メタクリロキシペンタエトキシ)フェニル)プロパン、新中村化学工業社製):22.5質量部
・NKエステルBPE-200(重合性化合物、2,2-ビス(4-(メタクリロキシジエトキシ)フェニル)プロパン、新中村化学工業社製):10.0質量部
・NKエステルA-TMPT(重合性化合物、トリメチロールプロパントリアクリレート、新中村化学工業社製):10質量部
・B-CIM(重合開始剤、2-(2-クロロフェニル)-4,5-ジフェニルイミダゾール二量体、Hampford社製):3.00質量部
・SB-PI 701(増感剤、4,4’-ビス(ジエチルアミノ)ベンゾフェノン、三洋貿易社製):0.30質量部
・色素N-1(ロイコクリスタルバイオレット、東京化成工業社製、ラジカルにより発色):0.60質量部
・色素N-2(ブリリアントグリーン、東京化成工業社製):0.02質量部
・1-(2-ジ-n-ブチルアミノメチル)-5-カルボキシベンゾトリアゾールと1-(2-ジ-n-ブチルアミノメチル)-6-カルボキシベンゾトリアゾールの混合物((水素供与性化合物、質量比1:1):0.10質量部
・Irganox245(酸化防止剤、エチレンビス(オキシエチレン)ビス-(3-(5-tert-ブチル-4-ヒドロキシ-m-トリル)プロピオネート)、BASF社製):0.20質量部
・N-ニトロソフェニルヒドロキシルアミンアルミニウム塩(重合禁止剤):0.01質量部
・メチルエチルケトン(三協化学社製):感光性組成物Y-3の固形分濃度が30%になる量
・PGMEA(昭和電工社製):50.00質量部
・メタノール(三菱ガス化学社製):10.00質量部
・バインダーポリマーC:52.67質量部(固形分量)
・A-NOD-N(1,9-ノナンジオールジアクリレート、新中村化学工業(株)製):2.73質量部
・A-DCP(トリシクロデカンジメタノールジアクリレート、新中村化学工業(株)製):17.90質量部
・アロニックス TO-2349(カルボン酸基を有する多官能エチレン性不飽和化合物、東亞合成(株)製):2.98質量部
・DPHA:ジペンタエリスリトールヘキサアクリレート(東新油脂(株)製):7.99質量部
・ 1-[9-エチル-6-(2-メチルベンゾイル)-9H-カルバゾール-3-イル]エタノン-1-(O-アセチルオキシム)(D-1、Irgacure OXE-02、BASF社製):0.36部
・ 2-メチル-1-(4-メチルチオフェニル)-2-モルフォリノプロパン-1-オン(D-2、Irgacure 907、BASF社製):0.73部
・デュラネートWT32-B75P(E-3、ブロックイソシアネート化合物、旭化成ケミカルズ(株)製):12.50質量部
・イソニコチンアミド:0.52質量部
・ベンゾイミダゾール:0.13質量部
・N-フェニルグリシン(純正化学(株)製):0.10質量部
・スチレン/無水マレイン酸=4:1(モル比)の共重合体(酸無水物価1.94mmol/g、重量平均分子量10,500)(SMA EF-40、Cray Valley社製):1.20質量部
・BYK-330(BYK社製):0.10質量部
・PGMEA:70質量部
・MEK:30質量部
・バインダーポリマーC:40質量部(固形分量)
・ベンジルメタクリレート/メタクリル酸=80/20(質量比)の共重合体(重量平均分子量30000):12.67質量部(固形分量)
・A-NOD-N(1,9-ノナンジオールジアクリレート、新中村化学工業(株)製):2.73質量部
・KAYARAD R-604(日本化薬製):10質量部
・A-DCP(トリシクロデカンジメタノールジアクリレート、新中村化学工業(株)製):7.90質量部
・A-TMMT(ペンタエリスリトールテトラアクリレート、新中村化学工業(株)製):2.98質量部
・DPHA:ジペンタエリスリトールヘキサアクリレート(東新油脂(株)製):8質量部
・(1-(ビフェニル-4-イル)-2-メチル-2-モルフォリノプロパン-1-オン(商品名:APi-307、Shenzhen UV-ChemTech Ltd.社製):2.1質量部
・ナフタレンチオール:0.10質量部
・BYK-330(BYK社製):0.10質量部
・PGMEA:50質量部
・MEK:30質量部
下記表1に示す感光性組成物A~Cを調製した。表1中、各成分の数値は各成分の含有量(質量部)を表し、バインダーポリマーの量は、バインダーポリマー溶液(固形分濃度36.3質量%)の量を意味する。
なお、感光性組成物Bに含まれる1-フェニル-3-(4-メトキシスチリル)-5-(4-メトキシフェニル)ピラゾリンは、下記のスキームに従って方法で合成した。
得られた淡黄色個体(9.0g)及びフェニルヒドラジン(3.3g)を酢酸(100mL)に溶解させ、室温で3時間攪拌した後、氷冷した。得られた溶液をろ過し、酢酸(200mL)、蒸留水(200mL)、及びメタノール(200mL)の順でかけ洗いをした後、ろ過物を室温で送風乾燥することで淡黄色個体として1-フェニル-3-(4-メトキシスチリル)-5-(4-メトキシフェニル)ピラゾリン4.7g(収率40%)を得た。
上記で得られた仮支持体Z-1の上に、スリット状ノズルを用いて、感光性組成物Y-1を、乾燥後の厚みが8.8μmになるように調整して塗布し、100℃で2分間乾燥させた後、更に120℃で1分間乾燥させた。
その後、感光性組成物層の上に、保護フィルムとして厚み16μmのポリエチレンテレフタレートフィルム(16KS40、東レ社製)を圧着して、実施例1の転写フィルムを得た。
表2~3に従って各成分、及び各層の厚みを変更した以外は、実施例1と同様の手順で実施例2~14、16~28、30及び比較例1~5の転写フィルムを得た。
上記で得られた実施例1の転写フィルムに、更に感光性組成物層の上に、下記の屈折率調整層形成用組成物X-1を、乾燥後の厚みが73nmになるように調整して塗布し、80℃で1分間乾燥させた。その後、更に110℃で1分間乾燥させて、感光性組成物層上に直接配置された屈折率調整層を形成し、実施例15の転写フィルムを得た。
上記で得られた実施例28の転写フィルムに、更に感光性組成物層の上に、下記の屈折率調整層形成用組成物X-1を、乾燥後の厚みが73nmになるように調整して塗布し、80℃で1分間乾燥させた。その後、更に110℃で1分間乾燥させて、感光性組成物層上に直接配置された屈折率調整層を形成し、実施例29の転写フィルムを得た。
屈折率調整層形成用組成物は、下記の各成分を用いて調整した。
なお、屈折率調整層形成用組成物は、酸基を有する樹脂と、アンモニア水溶液とを用いて調製しており、酸基を有する樹脂はアンモニア水溶液で中和され、酸基を有する樹脂のアンモニウム塩を含む水系樹脂組成物である。
・酸基を有するバインダーポリマー(アクリル樹脂、ZB-015M、富士フイルムファインケミカル社製、メタクリル酸/メタクリル酸アリルの共重合樹脂(組成比(モル比)=20/80)、重量平均分子量2.5万、固形分濃度5.00%、アンモニア水溶液):固形分換算で14.78質量部
・酸基を有するバインダーポリマー(アクリル樹脂、ARUFON UC3920、東亞合成社製):0.53質量部
・エチレン性不飽和化合物(カルボン酸基を有する多官能エチレン性不飽和化合物、アロニックス TO-2349、東亞合成社製):2.00質量部
・界面活性剤(フッ素系界面活性剤、メガファックF-444、DIC社製):0.68質量部
・BT-LX(城北化学工業社製):2.00質量部
・メタノールと蒸留水と混合溶剤(メタノール:蒸留水=7:3(質量比)):屈折率調整層形成用組成物の固形分濃度が1.66質量%になる量
<パターニング性>
厚み100μmのシクロオレフィンポリマー(COP)フィルム上に、スパッタ法にて厚み200nmでの銅層を形成することで、銅層付きCOPフィルム基板を4枚作製した。上記で得た銅層付きCOPフィルム基板に、圧着ロールの温度:100℃、線圧:0.6MPa、及び線速度:4.0m/分のラミネート条件で、各転写フィルムをラミネートした後、3時間静置した。
その後、仮支持体を剥離せずに、線幅が100μmであるラインアンドスペースパターンを形成するためのマスク(Duty比=1:1)を介して転写フィルムの感光性組成物層を露光した。露光の光源として超高圧水銀灯を用いた。露光量は、現像によって形成される樹脂パターンの線幅が100μmになる範囲で調節した。
露光後の感光性組成物層の表面から仮支持体を剥離し、感光性組成物層を現像した。具体的には、33℃の1.0質量%炭酸ナトリウム水溶液を用いて、シャワー現像を45秒間行い、樹脂パターンを有する積層体を得た。
得られた樹脂パターンの任意箇所20点の線幅を測定した。測定した20点の線幅値について、標準偏差σ、及び、平均値αを算出した。更に、下記式で分散βを算出して、以下の評価基準に従って、パターニング性を評価した。なお、以下の評価基準において、Aがパターニング性が最も良く、Eが最も悪い。A、B及びCのいずれかであることが好ましく、A又はBであることがより好ましく、Aであることが更に好ましい。
分散β(%)=100×(標準偏差σ/平均値α)
(評価基準)
A:分散βが、3%未満
B:分散βが、3%以上5%未満
C:分散βが、5%以上8%未満
D:分散βが、8%以上10%未満
E:分散βが、10%以上
(感光性組成物層と仮支持体との間の剥離性)
上記で得られた各転写フィルムを、保護フィルムを剥離した後に、感光性組成物層を銅板にラミネートした。ラミネートの条件は、ラミロール温度100℃、線圧3N/cm、及び搬送速度4m/分とした。その後、仮支持体を垂直上方に0.01m/分の速さで剥離した後、銅板に残存した感光性組成物層を目視で確認し、以下の評価基準に従って、評価した。なお、下記の評価基準において、Aが剥離性が最も良く、Eが最も悪い。A、B及びCのいずれかであることが好ましく、A又はBであることがより好ましく、Aであることが更に好ましい。
感光性組成物層の銅板上の残存面積(%)=100×(剥離後の銅板上に残存した感光性組成物層の面積/剥離前の銅板上の感光性組成物層の面積)
(評価基準)
A:感光性組成物層の銅板上の残存面積が、100%
B:感光性組成物層の銅板上の残存面積が、99%以上100%未満
C:感光性組成物層の銅板上の残存面積が、95%以上99%未満
D:感光性組成物層の銅板上の残存面積が、90%以上95%未満
E:感光性組成物層の銅板上の残存面積が、90%未満
保護フィルムを垂直上方に0.01m/分の速さで剥離した後、仮支持体に残存した感光性組成物層を目視で確認し、以下の評価基準に従って、評価した。なお、下記の評価基準において、Aが剥離性が最も良く、Eが最も悪い。A、B及びCのいずれかであることが好ましく、A又はBであることがより好ましく、Aであることが更に好ましい。
感光性組成物層の仮支持体上の残存面積(%)=100×(剥離後の仮支持体上に残存した感光性組成物層の面積/剥離前の仮支持体上の感光性組成物層の面積)
(評価基準)
A:感光性組成物層の仮支持体上の残存面積が、100%
B:感光性組成物層の仮支持体上の残存面積が、99%以上100%未満
C:感光性組成物層の仮支持体上の残存面積が、95%以上99%未満
D:感光性組成物層の仮支持体上の残存面積が、90%以上95%未満
E:感光性組成物層の仮支持体上の残存面積が、90%未満
Zygo社製 New View 6000を用い、ISO 4287:1997準拠した方法で、仮支持体の第1層の感光性組成物層と接する面のクルトシスRkuを評価した。
「感光性組成物層/仮支持体」の欄は、感光性組成物層と仮支持体との間の剥離性を示す。
「感光性組成物層/保護フィルム」の欄は、感光性組成物層と保護フィルムとの間の剥離性を示す。
実施例1及び8~10と、実施例7及び11との比較から、第1有機粒子の平均粒子径が350~800nmである場合、本発明の効果がより優れることが確認された。
また、同様の比較から、第1層の表面のクルトシスRkuが、2.5~10である場合、本発明の効果がより優れることが確認された。
実施例1等と、実施例12及び13との比較から、第1無機粒子の平均粒子径及び第2無機粒子の平均粒子径が10~50nmである場合、本発明の効果がより優れることが確認された。
実施例1等と、実施例14及び21との比較から、第1無機粒子及び第2無機粒子が酸化アルミニウムを含む場合、本発明の効果がより優れることが確認された。
実施例1等と、実施例21との比較から、第1層及び第2層に含まれる成分、並びに、第1層及び第2層の厚みが同一である場合、本発明の効果がより優れることが確認された。
実施例1等と、実施例7、11~14及び21との比較から、第1層の表面のクルトシスRkuが3.0~5.0であり、第1無機粒子及び第2無機粒子が酸化アルミニウムを含む場合、本発明の効果がより優れることが確認された。
2、12 組成物層
3、17 感光性組成物層
5 屈折率調整層
7、19 保護フィルム
10、20 転写フィルム
13 熱可塑性樹脂層
15 中間層
Claims (16)
- 仮支持体と、前記仮支持体上に配置された感光性組成物層と、保護フィルムとをこの順で有する転写フィルムであって、
前記仮支持体が、仮支持体本体と、前記仮支持体本体の一方の表面上に配置された第1層と、前記仮支持体本体の他方の表面上に配置された第2層とを有し、
前記第1層及び前記第2層のうち、前記第1層が前記感光性組成物層側に配置され、
前記第1層が、平均粒子径100~1000nmの第1有機粒子と、平均粒子径70nm以下の第1無機粒子とを含み、前記第1層の前記感光性組成物層と接する面のクルトシスRkuが、2.0~100であり、
前記第2層が、平均粒子径70nm以下の第2無機粒子を含むか、又は、無機粒子を含まない、転写フィルム。 - 前記第1有機粒子が、ポリスチレン樹脂粒子を含む、請求項1に記載の転写フィルム。
- 前記第1有機粒子の平均粒子径が、350~800nmである、請求項1又は2に記載の転写フィルム。
- 前記第1無機粒子及び前記第2無機粒子の少なくとも一方が、ケイ素原子及びアルミニウム原子からなる群から選択される少なくとも1つを含む、請求項1~3のいずれか1項に記載の転写フィルム。
- 前記第1無機粒子及び前記第2無機粒子の少なくとも一方が、酸化アルミニウムを含む、請求項1~4のいずれか1項に記載の転写フィルム。
- 前記第1無機粒子の平均粒子径及び前記第2無機粒子の平均粒子径が、10~50nmである、請求項1~5のいずれか1項に記載の転写フィルム。
- 前記仮支持体本体の厚みが、6.0~30.0μmであり、
前記第1層及び前記第2層の厚みが、0.8~3.0μmである、請求項1~6のいずれか1項に記載の転写フィルム。 - 前記第1有機粒子の平均粒子径が、350~800nmであり、
前記第1無機粒子が、酸化アルミニウムを含み、
前記第1無機粒子の平均粒子径が、10~50nmである、請求項1~7のいずれか1項に記載の転写フィルム。 - 前記第2層が、平均粒子径350~800nmの第2有機粒子を含み、
前記第2無機粒子が、酸化アルミニウムを含み、
前記第2無機粒子の平均粒子径が、10~50nmである、請求項1~8のいずれか1項に記載の転写フィルム。 - 前記第1層の表面の前記クルトシスRkuが、2.5~10である、請求項1~9のいずれか1項に記載の転写フィルム。
- 前記第1層の表面の前記クルトシスRkuが、3.0~5.0であり、
前記第1無機粒子及び前記第2無機粒子が酸化アルミニウムを含む、請求項1~10のいずれか1項に記載の転写フィルム。 - 前記感光性組成物層が、バインダーポリマー、重合性化合物、及び、重合開始剤を含む、請求項1~11のいずれか1項に記載の転写フィルム。
- 前記感光性組成物層と前記保護フィルムとの間に、屈折率調整層を更に有する、請求項1~12のいずれか1項に記載の転写フィルム。
- 前記感光性組成物層が、タッチパネル用電極保護膜形成に用いられる、請求項1~13のいずれか1項に記載の転写フィルム。
- 請求項1~14のいずれか1項に記載の転写フィルムから保護フィルムを剥離して、前記仮支持体とは反対側の表面を、導電層を有する基板に貼り合わせ、前記導電層、前記感光性組成物層、及び、前記仮支持体をこの順に有する感光性組成物層付き基板を得る貼合工程と、
前記感光性組成物層をパターン露光する露光工程と、
露光された前記感光性組成物層を現像して、パターンを形成する現像工程と、を有し、
更に、前記貼合工程と前記露光工程との間、又は、前記露光工程と前記現像工程との間に、前記感光性組成物層付き基板から前記仮支持体を剥離する剥離工程と、を有する、積層体の製造方法。 - 請求項1~14のいずれか1項に記載の転写フィルムから保護フィルムを剥離して、前記仮支持体とは反対側の表面を、導電層を有する基板に貼り合わせ、前記導電層、前記感光性組成物層、及び、前記仮支持体をこの順に有する感光性組成物層付き基板を得る貼合工程と、
前記感光性組成物層をパターン露光する露光工程と、
露光された前記感光性組成物層を現像して、パターンを形成する現像工程と、
前記パターンが配置されていない領域における前記導電層をエッチング処理するエッチング工程と、
更に、前記貼合工程と前記露光工程との間、又は、前記露光工程と前記現像工程との間に、前記感光性組成物層付き基板から前記仮支持体を剥離する剥離工程と、を有する、回路配線の製造方法。
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| 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 |
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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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