WO2022181455A1 - 転写フィルム及び導体パターンの製造方法 - Google Patents
転写フィルム及び導体パターンの製造方法 Download PDFInfo
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- WO2022181455A1 WO2022181455A1 PCT/JP2022/006481 JP2022006481W WO2022181455A1 WO 2022181455 A1 WO2022181455 A1 WO 2022181455A1 JP 2022006481 W JP2022006481 W JP 2022006481W WO 2022181455 A1 WO2022181455 A1 WO 2022181455A1
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- Prior art keywords
- layer
- mass
- transfer
- temporary support
- photosensitive layer
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- 238000004528 spin coating Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- PJANXHGTPQOBST-UHFFFAOYSA-N stilbene Chemical class C=1C=CC=CC=1C=CC1=CC=CC=C1 PJANXHGTPQOBST-UHFFFAOYSA-N 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 125000000547 substituted alkyl group Chemical group 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 239000000375 suspending agent Substances 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 description 1
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 description 1
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 description 1
- 150000003557 thiazoles Chemical class 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 150000003577 thiophenes Chemical class 0.000 description 1
- YRHRIQCWCFGUEQ-UHFFFAOYSA-N thioxanthen-9-one Chemical class C1=CC=C2C(=O)C3=CC=CC=C3SC2=C1 YRHRIQCWCFGUEQ-UHFFFAOYSA-N 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- 125000005259 triarylamine group Chemical group 0.000 description 1
- 239000001003 triarylmethane dye Substances 0.000 description 1
- 125000005409 triarylsulfonium group Chemical group 0.000 description 1
- 150000003918 triazines Chemical class 0.000 description 1
- 150000003852 triazoles Chemical group 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 239000013638 trimer Substances 0.000 description 1
- MTPVUVINMAGMJL-UHFFFAOYSA-N trimethyl(1,1,2,2,2-pentafluoroethyl)silane Chemical compound C[Si](C)(C)C(F)(F)C(F)(F)F MTPVUVINMAGMJL-UHFFFAOYSA-N 0.000 description 1
- LZTRCELOJRDYMQ-UHFFFAOYSA-N triphenylmethanol Chemical compound C=1C=CC=CC=1C(C=1C=CC=CC=1)(O)C1=CC=CC=C1 LZTRCELOJRDYMQ-UHFFFAOYSA-N 0.000 description 1
- JODJRDDQVZMRIY-UHFFFAOYSA-N trityloxyboronic acid Chemical compound C=1C=CC=CC=1C(C=1C=CC=CC=1)(OB(O)O)C1=CC=CC=C1 JODJRDDQVZMRIY-UHFFFAOYSA-N 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 230000004304 visual acuity Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000012463 white pigment Substances 0.000 description 1
- 230000037303 wrinkles Effects 0.000 description 1
- 239000001018 xanthene dye Substances 0.000 description 1
- 150000007964 xanthones Chemical class 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/02—Physical, chemical or physicochemical properties
- B32B7/022—Mechanical properties
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/20—Exposure; Apparatus therefor
-
- G—PHYSICS
- G06—COMPUTING; CALCULATING OR 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
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/02—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding
- H05K3/06—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding the conductive material being removed chemically or electrolytically, e.g. by photo-etch process
Definitions
- the present disclosure relates to a method of manufacturing a transfer film and a conductor pattern.
- Transfer films are widely used in various pattern forming methods such as photolithography.
- Transfer films typically include a transfer layer.
- a transfer layer is placed on an object (eg, substrate) by transfer to the object.
- a transfer layer disposed on an object can be patterned, for example, through exposure and development.
- Patent Document 1 discloses a transfer film including a support film and a photosensitive resin layer made of a specific photosensitive resin composition provided on the support film.
- Patent document 1 JP 2020-086238
- the resolution may be lowered for the following reasons. Transfer of the transfer layer to the object is performed, for example, by laminating the transfer film and the object. However, if the adhesion between the transfer layer and the object is low, for example, the developer may enter the gap between the transfer layer and the object during development, resulting in a decrease in resolution. Furthermore, when the transfer film includes a transfer layer and a protective film, in the process of peeling the protective film from the transfer film, part of the transfer layer may adhere to the surface of the peeled protective film. In other words, part of the transfer layer may be removed along with the protective film. If a part of the transfer layer is removed along with the protective film, the original characteristics of the transfer layer may not be exhibited, and, for example, the resolution may be lowered.
- An object of one embodiment of the present disclosure is to provide a transfer film having excellent resolution.
- Another embodiment of the present disclosure aims to provide a method for manufacturing a conductor pattern using a transfer film having excellent resolution.
- the present disclosure includes the following aspects. ⁇ 1> A temporary support, a transfer layer, and a protective film are included in this order, and the storage elastic modulus of the protective film side of the transfer layer at 25° C. is 1.0 ⁇ 10 6 Pa to 3.0 ⁇ A transfer film at 10 8 Pa. ⁇ 2> The transfer film according to ⁇ 1>, wherein a storage elastic modulus of the temporary support side of the transfer layer at 25° C. is 1.0 ⁇ 10 6 Pa or more. ⁇ 3> The transfer film according to ⁇ 1> or ⁇ 2>, wherein the surface roughness Ra of the transfer layer facing the temporary support is 0.1 nm to 15 nm.
- ⁇ 4> The transfer film according to any one of ⁇ 1> to ⁇ 3>, wherein the surface roughness Ra of the temporary support facing the transfer layer is 0.1 nm to 15 nm.
- the transfer layer is a photosensitive layer.
- the intermediate layer contains an alkali-soluble resin and a polymerizable compound, and the ratio of the mass of the polymerizable compound to the mass of the alkali-soluble resin in the intermediate layer is 0.5 or more; Transfer film as described.
- ⁇ 8> The transfer film according to ⁇ 6> or ⁇ 7>, wherein the intermediate layer has a thickness of 10 ⁇ m or less.
- ⁇ 9> The transfer film according to any one of ⁇ 6> to ⁇ 8>, wherein the intermediate layer includes a thermoplastic resin layer and a water-soluble resin layer.
- the photosensitive layer contains an alkali-soluble resin and a polymerizable compound, and the ratio of the mass of the polymerizable compound to the mass of the alkali-soluble resin in the photosensitive layer is 0.6 or more.
- ⁇ 11> The transfer film according to any one of ⁇ 5> to ⁇ 10>, wherein the photosensitive layer has a thickness of 10 ⁇ m or less.
- ⁇ 12> peeling off the protective film of the transfer film according to any one of ⁇ 1> to ⁇ 11>; disposing the transfer layer and the temporary support on the layer in this order; exposing the transfer layer; developing the transfer layer to form a resist pattern; A method of manufacturing a conductor pattern, comprising, in this order, etching or plating the metal layer that is not coated, and stripping the resist pattern.
- ⁇ 13> peeling off the protective film of the transfer film according to any one of ⁇ 1> to ⁇ 11>; Arranging the transfer layer and the temporary support on the layer in this order, peeling the temporary support, exposing the transfer layer, developing the transfer layer, and forming a resist pattern.
- a transfer film with excellent resolution is provided.
- a method for manufacturing a conductor pattern using a transfer film with excellent resolution is provided.
- FIG. 3 is a schematic plan view showing pattern A;
- FIG. 3 is a schematic plan view showing a pattern B;
- FIG. 3 is a schematic plan view showing a pattern A;
- symbol may be abbreviate
- a numerical range represented using “to” means a range including the numerical values described before and after "to” as lower and upper limits.
- (meth)acrylic represents both or either acrylic and methacrylic
- (meth)acrylate represents both or either acrylate and methacrylate
- (meth)acryloyl represents either or both acryloyl and methacryloyl.
- the amount of each component in the composition means the total amount of the corresponding multiple substances present in the composition when there are multiple substances corresponding to each component in the composition, unless otherwise specified. do.
- the term "process” includes not only an independent process, but also a process that cannot be clearly distinguished from other processes as long as the intended purpose of the process is achieved.
- groups (atomic groups) in the present disclosure notations that do not describe substitution and unsubstituted include not only those not having substituents but also those having substituents.
- alkyl group includes not only alkyl groups having no substituents (unsubstituted alkyl groups) but also alkyl groups having substituents (substituted alkyl groups).
- exposure includes not only exposure using light but also drawing using particle beams such as electron beams and ion beams, unless otherwise specified.
- the light used for exposure generally includes the emission line spectrum of a mercury lamp, far ultraviolet rays represented by excimer lasers, extreme ultraviolet rays (EUV light), X-rays, and active rays (active energy rays) such as electron beams. mentioned.
- Chemical structural formulas in the present disclosure may be described as simplified structural formulas omitting hydrogen atoms.
- “% by mass” and “% by weight” are synonymous, and “parts by mass” and “parts by weight” are synonymous.
- a combination of two or more preferred aspects is a more preferred aspect.
- “transparent” means that the average transmittance of visible light with a wavelength of 400 nm to 700 nm is 80% or more, preferably 90% or more.
- the average transmittance of visible light is a value measured using a spectrophotometer, and can be measured using a spectrophotometer U-3310 manufactured by Hitachi, Ltd., for example.
- the weight-average molecular weight (Mw) and number-average molecular weight (Mn) in the present disclosure are obtained by gel permeation using columns of TSKgel GMHxL, TSKgel G4000HxL, and TSKgel G2000HxL (all trade names manufactured by Tosoh Corporation).
- the content of metal elements is a value measured using an inductively coupled plasma (ICP) spectrometer.
- the refractive index is a value measured using an ellipsometer at a wavelength of 550 nm.
- hue is a value measured using a color difference meter (CR-221, manufactured by Minolta Co., Ltd.).
- alkali-soluble means that the solubility in 100 g of a 1% by mass aqueous solution of sodium carbonate at a liquid temperature of 22° C. is 0.1 g or more.
- water-soluble means that the solubility in 100 g of water at pH 7.0 at a liquid temperature of 22° C. is 0.1 g or more.
- solids means all components except solvent.
- the thickness of each layer included in the transfer film is obtained by observing a cross section in a direction perpendicular to the main surface of the transfer film with a scanning electron microscope (SEM), and measuring the thickness of each layer based on the obtained observation image. is measured at any five points or more and the average value is calculated.
- SEM scanning electron microscope
- a transfer film according to an embodiment of the present disclosure includes a temporary support, a transfer layer, and a protective film in this order, and the storage elastic modulus of the transfer layer on the protective film side at 25° C. is 1.0. ⁇ 10 6 Pa to 3.0 ⁇ 10 8 Pa.
- the storage modulus of the protective film side of the transfer layer is defined by the storage modulus of the layer in the transfer layer that is closest to the protective film. For example, when the transfer layer has a multi-layer structure, the storage elastic modulus of the layer closest to the protective film among the layers included in the transfer layer is the "storage elastic modulus of the protective film side of the transfer layer".
- the storage elastic modulus of the single transfer layer is referred to as "the storage elastic modulus of the protective film side of the transfer layer".
- the storage elastic modulus of the protective film side of the transfer layer at 25° C. is 1.0 ⁇ 10 6 Pa or more, adhesion of the transfer layer to the surface of the peeled protective film is suppressed, and a decrease in resolution is also suppressed. be done.
- the storage elastic modulus of the protective film side of the transfer layer at 25° C. is 3.0 ⁇ 10 8 Pa or less, the adhesion between the transfer layer and the object during transfer of the transfer layer to the object (for example, substrate) is low. and improve resolution. Therefore, according to one embodiment of the present disclosure, a transfer film with excellent resolution is provided.
- Each layer in the transfer film may have a single layer structure or a multilayer structure.
- the transfer layer include a photosensitive layer and an intermediate layer.
- the intermediate layer include a thermoplastic resin layer and a water-soluble resin layer.
- a configuration example of the transfer film is shown below. However, the configuration of the transfer film is not limited to the following examples.
- the photosensitive layer is preferably a negative photosensitive layer. It is also preferable that the photosensitive layer is a colored resin layer.
- FIG. 1 is a schematic diagram showing the configuration of a transfer film according to one embodiment.
- the transfer film 100 shown in FIG. 1 includes a temporary support 10, an intermediate layer 20, a photosensitive layer 30, and a protective film 40 in this order.
- the maximum width of the undulations of the transfer film is preferably 300 ⁇ m or less, more preferably 200 ⁇ m or less, and even more preferably 60 ⁇ m or less.
- the maximum width of the undulations of the transfer film is preferably 0 ⁇ m or more, more preferably 0.1 ⁇ m or more, and even more preferably 1 ⁇ m or more.
- the maximum width of the waviness of the transfer film is measured by the following procedure. First, the transfer film is cut in a direction perpendicular to the main surface so as to have a size of 20 cm long and 20 cm wide to prepare a test sample.
- a protective film is peeled. Then, the test sample is placed on a flat and horizontal stage so that the surface of the temporary support faces the stage. After standing, the surface of the test sample is scanned with a laser microscope (for example, VK-9700SP manufactured by Keyence Corporation) for a 10 cm square range at the center of the test sample to obtain a three-dimensional surface image, and the resulting three-dimensional surface Subtract the minimum concave height from the maximum convex height observed in the image. The above operation is performed for 10 test samples, and the arithmetic average value is taken as the "maximum width of undulation of the transfer film".
- a laser microscope for example, VK-9700SP manufactured by Keyence Corporation
- a transfer film according to one embodiment of the present disclosure includes a temporary support.
- a temporary support is a support that supports the transfer layer and is peelable.
- the surface roughness Ra of the temporary support facing the transfer layer is preferably 0.1 nm to 15 nm, more preferably 0.1 nm to 10 nm, even more preferably 0.1 nm to 6 nm. , 0.1 nm to 2 nm.
- the surface of the temporary support facing the transfer layer specifically refers to the surface of the temporary support that faces the transfer layer.
- the surface roughness Ra of the temporary support facing the transfer layer is increased, the peelability of the temporary support is improved, and, for example, adhesion of the transfer layer to the peeled surface of the temporary support is suppressed.
- the surface roughness Ra of the temporary support facing the transfer layer is reduced, an increase in the surface roughness Ra of the transfer layer due to the temporary support is suppressed.
- the surface roughness Ra of the temporary support facing the transfer layer is small, light scattering is suppressed in the exposure of the transfer layer through the temporary support. As a result of these, the resolution is improved.
- the roughness Ra of the surface of the temporary support facing the transfer layer is the arithmetic mean roughness Ra measured by the following method.
- a three-dimensional optical profiler (New View 7300, Zygo) is used to obtain the surface profile of the target surface.
- "Microscope Application” of "MetroPro ver 8.3.2” is used as measurement and analysis software.
- the "Surface Map” screen is displayed by the above software, and histogram data is obtained in the "Surface Map” screen.
- the arithmetic average roughness Ra of the target surface is calculated from the obtained histogram data. If the target surface is covered by another layer, the arithmetic mean roughness Ra of the target surface is measured after exposing the target surface by peeling off the other layer.
- the temporary support may have a single-layer structure or a multi-layer structure.
- the temporary support is preferably a film, more preferably a resin film.
- the temporary support is preferably a film that has flexibility and does not undergo significant deformation, shrinkage, or elongation under pressure or under pressure and heat.
- films examples include polyethylene terephthalate (PET) film (eg, biaxially stretched polyethylene terephthalate film), polymethyl methacrylate film, cellulose triacetate film, polystyrene film, polyimide film, and polycarbonate film.
- PET polyethylene terephthalate
- a polyethylene terephthalate film is preferred as the temporary support. It is preferable that the film used as the temporary support be free from deformation such as wrinkles and flaws.
- the transparency of the temporary support is preferably high.
- the transmittance of the temporary support at 365 nm is preferably 60% or more, more preferably 70% or more.
- the haze of the temporary support is small.
- the haze of the temporary support is preferably 2% or less, more preferably 0.5% or less, and even more preferably 0.1% or less.
- the number of coarse particles, foreign matter, and defects contained in the temporary support is preferably as small as possible.
- the number of particles with a diameter of 1 ⁇ m or more, foreign matter, and defects in the temporary support is preferably 50/10 mm 2 or less, more preferably 10/10 mm 2 or less, and 3/10 mm 2 or less. It is more preferably less than or equal to, and particularly preferably 0/10 mm 2 .
- the thickness of the temporary support is not particularly limited, it is preferably 5 ⁇ m to 200 ⁇ m, more preferably 10 ⁇ m to 150 ⁇ m, more preferably 10 ⁇ m to 50 ⁇ m from the viewpoint of ease of handling and versatility. preferable.
- Examples of the temporary support include a biaxially stretched polyethylene terephthalate film with a thickness of 16 ⁇ m, a biaxially stretched polyethylene terephthalate film with a thickness of 12 ⁇ m, and a biaxially stretched polyethylene terephthalate film with a thickness of 9 ⁇ m.
- Preferred embodiments of the temporary support include, for example, paragraphs 0017 to 0018 of JP-A-2014-85643, paragraphs 0019-0026 of JP-A-2016-27363, paragraphs 0041 to 0057 of WO 2012/081680, Paragraphs 0029 to 0040 of WO 2018/179370 and paragraphs 0012 to 0032 of JP 2019-101405 A are described, and the contents of these publications are incorporated herein.
- a layer containing fine particles may be provided on the surface of the temporary support.
- the lubricant layer may be provided on one side or both sides of the temporary support.
- the diameter of the particles contained in the lubricant layer is preferably 0.05 ⁇ m to 0.8 ⁇ m.
- the thickness of the lubricant layer is preferably 0.05 ⁇ m to 1.0 ⁇ m.
- a transfer film according to one embodiment of the present disclosure includes a transfer layer.
- the storage elastic modulus of the protective film side of the transfer layer at 25° C. is 1.0 ⁇ 10 6 Pa to 3.0 ⁇ 10 8 Pa.
- the storage elastic modulus of the protective film side of the transfer layer at 25° C. is 1.0 ⁇ 10 6 Pa or more, adhesion of the transfer layer to the surface of the peeled protective film is suppressed, and a decrease in resolution is also suppressed. be done.
- the storage elastic modulus of the protective film side of the transfer layer at 25° C. is 3.0 ⁇ 10 8 Pa or less, the adhesion between the transfer layer and the object during transfer of the transfer layer to the object (for example, substrate) is low. and improve resolution.
- the storage elastic modulus of the protective film side of the transfer layer at 25° C. is preferably 1.0 ⁇ 10 6 Pa to 2.0 ⁇ 10 8 Pa, more preferably 1.0 ⁇ 10 7 Pa. It is more preferably ⁇ 1.0 ⁇ 10 8 Pa.
- the storage elastic modulus of the temporary support side of the transfer layer at 25° C. is preferably 1.0 ⁇ 10 6 Pa or more.
- the "storage modulus of the transfer layer on the temporary support side" is defined by the storage modulus of the layer in the transfer layer that is closest to the temporary support.
- the storage elastic modulus of the layer closest to the temporary support among the plurality of layers included in the transfer layer is defined as the storage elastic modulus of the temporary support side of the transfer layer.
- the storage elastic modulus of the single transfer layer is referred to as the "temporary support-side storage elastic modulus of the transfer layer.”
- the storage elastic modulus of the temporary support side of the transfer layer at 25° C. is 1.0 ⁇ 10 6 Pa or more, the adhesion of the transfer layer to the surface of the peeled temporary support is suppressed, and the resolution is also lowered. Suppressed.
- the storage elastic modulus of the temporary support side of the transfer layer at 25° C. becomes small, for example, the resolution is improved in an exposure method in which the transfer layer and the photomask are brought into contact with each other.
- the storage elastic modulus of the temporary support side of the transfer layer at 25° C. is preferably 1.0 ⁇ 10 6 Pa to 3.0 ⁇ 10 8 Pa, more preferably 1.0 ⁇ 10 6 Pa. It is more preferably 2.0 ⁇ 10 8 Pa, and even more preferably 1.0 ⁇ 10 7 Pa to 1.0 ⁇ 10 8 Pa.
- the storage elastic modulus is measured using a viscoelasticity measuring device (T.A Instruments Rheometer DHR-2), a 20 mm ⁇ parallel plate and a Peltier plate (Gap: about 0.5 mm) at a temperature of 20 ° C. 125° C., temperature increase rate of 5° C./min, frequency of 1 Hz, and strain of 0.5%. Specifically, before measurement, the sample is melted on a Peltier plate at 80° C. to 95° C., cooled to 20° C. at a cooling rate of 5° C./min, and then measured in the Gap constant mode. The value at 25°C is adopted for the storage modulus.
- a viscoelasticity measuring device T.A Instruments Rheometer DHR-2
- a 20 mm ⁇ parallel plate and a Peltier plate (Gap: about 0.5 mm) at a temperature of 20 ° C. 125° C., temperature increase rate of 5° C./min, frequency of 1 Hz, and strain of 0.5%.
- the sample
- the method of adjusting the storage modulus of the transfer layer is not limited. Factors that affect the storage modulus of the transfer layer include, for example, the composition of the transfer layer.
- the storage elastic modulus of the transfer layer is adjusted by, for example, the type of alkali-soluble resin, the type of polymerizable compound, the ratio of the mass of the polymerizable compound to the mass of the alkali-soluble resin, and the type of additives.
- the surface roughness Ra of the transfer layer facing the temporary support is preferably 0.1 nm to 15 nm, more preferably 0.1 nm to 10 nm, and more preferably 0.1 nm to It is more preferably 6 nm, and particularly preferably 0.1 nm to 2 nm.
- the surface of the transfer layer facing the temporary support specifically refers to the surface of the transfer layer that faces the temporary support.
- the surface roughness Ra of the transfer layer facing the temporary support is measured by a method according to the method for measuring the surface roughness Ra of the temporary support facing the transfer layer described in the section "Temporary support" above. be done.
- the transfer layer may have a single layer structure or a multilayer structure.
- the transfer layer includes a photosensitive layer.
- the transfer layer may be a photosensitive layer.
- the transfer layer may further include layers other than the photosensitive layer.
- the transfer layer may include an intermediate layer and a photosensitive layer.
- the intermediate layer improves lamination properties of the transfer film. According to the intermediate layer, for example, when the transfer film and the substrate are bonded together, the followability to the substrate is improved, air bubbles are suppressed from entering between the substrate and the transfer film, and the adhesion between the substrate and the transfer film is improved. improves.
- the intermediate layer is preferably arranged between the temporary support and the photosensitive layer.
- the transfer film preferably includes a temporary support, an intermediate layer, a photosensitive layer, and a protective film in this order.
- the intermediate layer include a thermoplastic resin layer and a water-soluble resin layer. Specific aspects of each layer constituting the transfer layer will be described below.
- the photosensitive layer can be patterned, for example, by exposure and development after it has been transferred onto a substrate.
- the photosensitive layer may be a negative photosensitive layer or a positive photosensitive layer.
- the photosensitive layer is preferably a negative photosensitive layer.
- the formed pattern corresponds to the cured layer.
- the photosensitive layer is a negative photosensitive layer
- the negative photosensitive layer preferably contains a resin, a polymerizable compound and a polymerization initiator. Further, when the photosensitive layer is a negative photosensitive layer, it is also preferable that part or all of the resin contains an alkali-soluble resin.
- the photosensitive layer preferably contains a resin containing an alkali-soluble resin, a polymerizable compound, and a polymerization initiator.
- the photosensitive layer contains 10% to 90% by weight of an alkali-soluble resin, 5% to 70% by weight of an ethylenically unsaturated compound, and 0.01% to 20% by weight of photopolymerization, based on the total weight of the photosensitive layer. It preferably contains an initiator.
- the photosensitive layer preferably contains an alkali-soluble resin.
- suitable alkali-soluble resins include known alkali-soluble resins used for etching resists.
- the alkali-soluble resin is preferably a binder polymer.
- the alkali-soluble resin is preferably an alkali-soluble resin having an acid group. As the alkali-soluble resin, polymer A described later is preferable.
- the photosensitive layer preferably contains polymer A as 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, in terms of better resolution by suppressing swelling of the photosensitive layer by the developer. , less than 190 mg KOH/g.
- the lower limit of the acid value of polymer A is not particularly limited. From the viewpoint of better developability, the acid value of polymer A is preferably 60 mgKOH/g or more, more preferably 120 mgKOH/g or more, still more preferably 150 mgKOH/g or more, and 170 mgKOH/g. g or more is particularly preferred.
- the acid value is the mass [mg] of potassium hydroxide required to neutralize 1 g of a sample, and the unit is expressed as mgKOH/g in the present disclosure.
- 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 structural units constituting the polymer A and the content of structural units containing an acid group.
- the weight average molecular weight of polymer A is preferably from 5,000 to 500,000.
- a weight average molecular weight of 500,000 or less is preferable from the viewpoint of improving resolution and developability.
- the weight average molecular weight of polymer A is more preferably 100,000 or less, still more preferably 60,000 or less, and particularly preferably 50,000 or less.
- a weight-average molecular weight of 5,000 or more is preferable from the viewpoint of controlling properties of development aggregates and properties of an unexposed film such as edge-fuse properties and cut-chip properties in a photosensitive layer.
- the weight average molecular weight of polymer A is more preferably 10,000 or more, still more preferably 20,000 or more, and particularly preferably 30,000 or more.
- Edge fuseability refers to the degree of ease with which the photosensitive layer protrudes from the end face of the roll when the transfer film is wound into a roll.
- the cut chip property refers to the degree of easiness of chip flying when the unexposed film is cut with a cutter. If this chip adheres to the upper surface of the photosensitive layer or the like, it will be transferred to the mask in the subsequent exposure process or the like, resulting in defective products.
- the dispersity of polymer A is preferably 1.0 to 6.0, more preferably 1.0 to 5.0, even more preferably 1.0 to 4.0, and 1 0 to 3.0 is particularly preferred.
- weight average molecular weight (Mw) and number average molecular weight (Mn) are values measured using gel permeation chromatography. Further, the dispersity is the ratio of the weight average molecular weight to the number average molecular weight (weight average molecular weight/number average molecular weight).
- the polymer A preferably has an aromatic hydrocarbon group, and has a structural unit having an aromatic hydrocarbon group. is more preferable.
- aromatic hydrocarbon groups include substituted or unsubstituted phenyl groups and substituted or unsubstituted aralkyl groups.
- the content of the structural unit 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. It is more preferably at least 45% by mass, most preferably at least 50% by mass.
- the upper limit is not particularly limited, it is preferably 95% by mass or less, more preferably 85% by mass or less.
- the content ratio of the constitutional unit having an aromatic hydrocarbon group is obtained as a weight average value.
- Examples of monomers forming structural units having an aromatic hydrocarbon group include monomers having an aralkyl group, styrene, and polymerizable styrene derivatives (e.g., methylstyrene, vinyltoluene, tert-butoxystyrene, acetoxy styrene, 4-vinylbenzoic acid, styrene dimer, styrene trimer, etc.).
- a monomer having an aralkyl group or styrene is preferred.
- the content of the structural unit derived from styrene is 20 based on the total mass of the polymer A. It is preferably from 25% by mass to 50% by mass, more preferably from 25% by mass to 45% by mass, even more preferably from 30% by mass to 40% by mass, and from 30% by mass to 35% by mass. is particularly preferred.
- the aralkyl group includes a substituted or unsubstituted phenylalkyl group and the like, preferably a substituted or unsubstituted benzyl group.
- Examples of monomers having a phenylalkyl group other than a substituted or unsubstituted benzyl group include phenylethyl (meth)acrylate.
- Monomers having a substituted or unsubstituted benzyl group include (meth)acrylates having a substituted or unsubstituted benzyl group (e.g., benzyl (meth)acrylate, chlorobenzyl (meth)acrylate, etc.); vinyl monomers (eg, vinylbenzyl chloride, vinylbenzyl alcohol, etc.); Among them, benzyl (meth)acrylate is preferred.
- the content of the structural unit derived from benzyl (meth) acrylate is the polymer A Based on the total mass of, preferably 50% by mass to 95% by mass, more preferably 60% by mass to 90% by mass, even more preferably 70% by mass to 90% by mass, 75% by mass % to 90% by mass is particularly preferred.
- Polymer A having a structural unit having an aromatic hydrocarbon group is a monomer having an aromatic hydrocarbon group, at least one of the first monomer described later and / or the second monomer described later preferably obtained by polymerizing at least one of the
- the polymer A having no structural unit having an aromatic hydrocarbon group is preferably obtained by polymerizing at least one of the first monomers described later, and at least one of the first monomers and at least one of the second monomers described below are more preferably obtained by copolymerization.
- the first monomer is a monomer having a carboxy group in its molecule.
- the first monomer include (meth)acrylic acid, fumaric acid, cinnamic acid, crotonic acid, itaconic acid, 4-vinylbenzoic acid, maleic anhydride, and maleic acid half ester.
- (meth)acrylic acid is preferred.
- the content of the structural unit derived from the first monomer in the polymer A is preferably 5% by mass to 50% by mass, based on the total mass of the polymer A, and 10% by mass to 40% by mass. more preferably 15% by mass to 30% by mass.
- the content of structural units derived from the first monomer is preferably 10% by mass to 50% by mass based on the total mass of polymer A.
- the above ratio of 10% by mass or more is preferable from the viewpoint of developing good developability and controlling edge fuse properties, more preferably 15% by mass or more, and even more preferably 20% by mass or more.
- the above-mentioned content ratio of 50% by mass or less is preferable from the viewpoint of high resolution and groove shape of the resist pattern, and further from the viewpoint of chemical resistance of the resist pattern, and from these viewpoints, 35% by mass or less is more preferable, 30% by mass or less is even more preferable, and 27% by mass or less is particularly preferable.
- the second monomer is a monomer that is non-acidic and has at least one ethylenically 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.
- tert-butyl (meth)acrylate 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate and other (meth)acrylates; vinyl acetate esters of vinyl alcohol such as; and (meth)acrylonitrile.
- methyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, and n-butyl (meth)acrylate are preferred, and methyl (meth)acrylate is particularly preferred.
- the content of the structural unit derived from the second monomer in the polymer A is preferably 5% by mass to 60% by mass, based on the total mass of the polymer A, and 15% by mass to 50% by mass. more preferably 20% by mass to 45% by mass.
- the polymer A contains at least one structural unit selected from the group consisting of a structural unit having an aralkyl group and a structural unit derived from styrene. This is preferable from the viewpoint of suppressing widening of line width and deterioration of resolution.
- a copolymer containing methacrylic acid, benzyl methacrylate and styrene, a copolymer containing methacrylic acid, methyl methacrylate, benzyl methacrylate and styrene, and the like are preferable.
- the polymer A contains 25% to 40% by mass of structural units having an aromatic hydrocarbon group, 20% to 35% by mass of structural units derived from the first monomer, and the second It is preferable that the polymer contains 30% by mass to 45% by mass of structural units derived from the monomer. In another aspect, a polymer containing 70% to 90% by mass of structural units having an aromatic hydrocarbon group and 10% to 25% by mass of structural units derived from the first monomer. is preferred.
- the polymer A may have a branched structure and/or an alicyclic structure in its side chain.
- a branched structure or an alicyclic structure can be introduced into the side chain of the polymer A by using a monomer containing a group having a branched structure in the side chain or a monomer containing a group having an alicyclic structure in the side chain.
- the alicyclic structure may be a monocyclic structure or a polycyclic structure.
- monomers containing a group having a branched structure in the side chain include i-propyl (meth)acrylate, i-butyl (meth)acrylate, s-butyl (meth)acrylate, and t (meth)acrylate.
- -butyl i-amyl (meth)acrylate, t-amyl (meth)acrylate, isoamyl (meth)acrylate, 2-octyl (meth)acrylate, 3-octyl (meth)acrylate, and (meth)acrylate and t-octyl acrylate.
- i-propyl (meth)acrylate, i-butyl (meth)acrylate, and t-butyl methacrylate are preferred, and i-propyl methacrylate and t-butyl methacrylate are more preferred.
- monomers containing a group having an alicyclic structure in the side chain include monomers having a monocyclic aliphatic hydrocarbon group and monomers having a polycyclic aliphatic hydrocarbon group.
- (Meth)acrylates having an alicyclic hydrocarbon group with 5 to 20 carbon atoms (the number of carbon atoms) are also included.
- More specific examples include (meth)acrylic acid (bicyclo[2.2.1]heptyl-2), (meth)acrylate-1-adamantyl, (meth)acrylate-2-adamantyl, (meth) 3-methyl-1-adamantyl acrylate, 3,5-dimethyl-1-adamantyl (meth)acrylate, 3-ethyladamantyl (meth)acrylate, 3-methyl-5-(meth)acrylate Ethyl-1-adamantyl, (meth)acrylate-3,5,8-triethyl-1-adamantyl, (meth)acrylate-3,5-dimethyl-8-ethyl-1-adamantyl, (meth)acrylic acid 2 -methyl-2-adamantyl, 2-ethyl-2-adamantyl (meth)acrylate, 3-hydroxy-1-adamantyl (meth)acrylate, octahydro-4,7-mentanoindene-5- (meth
- cyclohexyl (meth)acrylate, (nor)bornyl (meth)acrylate, isobornyl (meth)acrylate, -1-adamantyl (meth)acrylate, (meth)acrylate - 2-adamantyl, fenchyl (meth)acrylate, 1-menthyl (meth)acrylate or tricyclodecane (meth)acrylate are preferred, cyclohexyl (meth)acrylate, (nor)bornyl (meth)acrylate, ( More preferred are isobornyl meth)acrylate, 2-adamantyl (meth)acrylate and tricyclodecane (meth)acrylate.
- the photosensitive layer may contain the polymer A singly or in combination of two or more.
- a mixture of two types of polymer A having an aromatic hydrocarbon group is used, or a polymer A having an aromatic hydrocarbon group and a polymer A having no aromatic hydrocarbon group are used. It is preferable to use the polymer A in combination.
- the content of the polymer A having an aromatic hydrocarbon group is preferably 50% by mass or more, more preferably 70% by mass or more, relative to the total mass of the polymer A. It is more preferably 80% by mass or more, and particularly preferably 90% by mass or more.
- Synthesis of polymer A is carried out by adding a radical polymerization initiator such as benzoyl peroxide and azoisobutyronitrile to a solution obtained by diluting one or more of the monomers described above with a solvent such as acetone, methyl ethyl ketone, or isopropanol. is preferably added in an appropriate amount and heated and stirred. In some cases, the synthesis is performed while part of the mixture is added dropwise to the reaction solution. After completion of the reaction, a solvent may be further added to adjust the desired concentration. As a means of synthesis, bulk polymerization, suspension polymerization, or emulsion polymerization may be used in addition to solution polymerization.
- a radical polymerization initiator such as benzoyl peroxide and azoisobutyronitrile
- the glass transition temperature Tg of polymer A is preferably 30°C or higher and 135°C or lower.
- the Tg of polymer A is more preferably 130° C. or lower, still more preferably 120° C. or lower, and particularly preferably 110° C. or lower.
- the polymer A having a Tg of 30° C. or more from the viewpoint of improving the edge fuse resistance.
- the Tg of the polymer A is more preferably 40° C. or higher, still more preferably 50° C. or higher, particularly preferably 60° C. or higher, and most preferably 70° C. or higher. .
- Alkali-soluble resin may be used individually by 1 type, or may be used in mixture of 2 or more types.
- the ratio of the alkali-soluble resin to the total weight of the photosensitive layer is preferably 10% by mass to 90% by mass, more preferably 30% by mass to 70% by mass, and still more preferably 40% by mass to 60% by mass. be. It is preferable from the viewpoint of controlling the developing time that the ratio of the alkali-soluble resin to the photosensitive layer is 90% by mass or less. On the other hand, from the viewpoint of improving the edge fuse resistance, it is preferable to set the ratio of the alkali-soluble resin to 10% by mass or more relative to the photosensitive layer.
- the photosensitive layer may contain resins other than alkali-soluble resins.
- Resins other than alkali-soluble resins may be resins having a solubility of less than 0.1 g in 100 g of a 1% by mass aqueous solution of sodium carbonate at a liquid temperature of 22° C. Examples include acrylic resins and styrene-acrylic copolymers.
- polyurethane resin polyvinyl alcohol, polyvinyl formal, polyamide resin, polyester resin, epoxy resin, polyacetal resin, polyhydroxystyrene resin, polyimide resin, polybenzoxazole resin , polysiloxane resins, polyethyleneimines, polyallylamines, and polyalkylene glycols.
- the photosensitive layer When the photosensitive layer is a negative photosensitive layer, the negative photosensitive layer preferably contains a polymerizable compound having a polymerizable group.
- the term “polymerizable compound” means a compound that polymerizes under the action of a polymerization initiator and is different from the alkali-soluble resin described above.
- the molecular weight of the polymerizable compound is preferably 1,500 or less.
- the molecular weight of the polymerizable compound is preferably 150 or more.
- the type of polymerizable group is not limited as long as it participates in the polymerization reaction.
- examples of polymerizable groups include groups having ethylenically unsaturated groups such as vinyl groups, acryloyl groups, methacryloyl groups, styryl groups, and maleimide groups.
- the group which has cationic polymerizable groups such as an epoxy group and an oxetane group, is mentioned, for example.
- a group having an ethylenically unsaturated group is preferable, and an acryloyl group or a methacryloyl group is more preferable.
- the polymerizable compound preferably contains a polymerizable compound having two or more polymerizable groups. More preferably, the polymerizable compound includes a polymerizable compound having two or more polymerizable groups and a polymerizable compound having three or more polymerizable groups.
- a compound having one or more ethylenically unsaturated groups i.e., an ethylenically unsaturated compound
- the photosensitivity of the negative photosensitive layer is more excellent, and two or more in one molecule.
- polyfunctional ethylenically unsaturated compounds are more preferred.
- the number of ethylenically unsaturated groups that the ethylenically unsaturated compound has in one molecule is preferably 6 or less, more preferably 3 or less, and 2 or less. More preferred.
- the photosensitive layer contains a compound having two or three ethylenically unsaturated groups in one molecule (i.e., bifunctional or It preferably contains a trifunctional ethylenically unsaturated compound), and more preferably contains a compound having two ethylenically unsaturated groups in one molecule (that is, a bifunctional ethylenically unsaturated compound).
- the content of the bifunctional ethylenically unsaturated compound with respect to the total weight of the polymerizable compound is preferably 20% by weight or more, more preferably more than 40% by weight, from the viewpoint of excellent peelability with respect to the total weight of the negative photosensitive layer. Preferably, 55% by mass or more is more preferable.
- the upper limit is not particularly limited, and may be 100% by mass. That is, all polymerizable compounds may be difunctional ethylenically unsaturated compounds.
- a (meth)acrylate compound having a (meth)acryloyl group as a polymerizable group is preferable.
- the photosensitive layer preferably contains an ethylenically unsaturated compound B1 having an aromatic ring and two ethylenically unsaturated groups.
- the ethylenically unsaturated compound B1 is a bifunctional ethylenically unsaturated compound having one or more aromatic rings in one molecule among the ethylenically unsaturated compounds described above.
- the mass ratio of the content of the ethylenically unsaturated compound B1 to the content of the ethylenically unsaturated compound is preferably 40% by mass or more, more preferably 50% by mass or more, from the viewpoint of better resolution. is more preferably 55% by mass or more, and particularly preferably 60% by mass or more.
- the upper limit is not particularly limited, it is preferably 99% by mass or less, more preferably 95% by mass or less, even more preferably 90% by mass or less, and particularly preferably 85% by mass or less, from the viewpoint of releasability.
- Examples of the aromatic ring of the ethylenically unsaturated compound B1 include aromatic hydrocarbon rings such as benzene ring, naphthalene ring and anthracene ring, thiophene ring, furan ring, pyrrole ring, imidazole ring, triazole ring, pyridine ring and the like. Examples include aromatic heterocycles and condensed rings thereof, preferably aromatic hydrocarbon rings, and more preferably benzene rings. In addition, the said aromatic ring may have a substituent. Ethylenically unsaturated compound B1 may have only one aromatic ring, or may have two or more aromatic rings.
- the ethylenically unsaturated compound B1 preferably has a bisphenol structure from the viewpoint of improving the resolution by suppressing the swelling of the photosensitive layer due to the developer.
- the bisphenol structure includes, for example, 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).
- the F structure and the bisphenol B structure derived from bisphenol B (2,2-bis(4-hydroxyphenyl)butane) can be mentioned, with the bisphenol A structure being preferred.
- Examples of the ethylenically unsaturated compound B1 having a bisphenol structure include compounds 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 bonded via one or more alkyleneoxy groups.
- the alkyleneoxy group added to both ends of the bisphenol structure is preferably an ethyleneoxy group or a propyleneoxy group, more preferably an ethyleneoxy group.
- the number of alkyleneoxy groups added to the bisphenol structure is not particularly limited, but is preferably 4 to 16, more preferably 6 to 14 per molecule.
- the ethylenically unsaturated compound B1 is preferably a bifunctional ethylenically unsaturated compound having a bisphenol A structure, more preferably 2,2-bis(4-((meth)acryloxypolyalkoxy)phenyl)propane.
- 2,2-bis(4-((meth)acryloxypolyalkoxy)phenyl)propane examples include 2,2-bis(4-(methacryloxydiethoxy)phenyl)propane (FA-324M, Hitachi Chemical Co., Ltd.) company), 2,2-bis(4-(methacryloxyethoxypropoxy)phenyl)propane, 2,2-bis(4-(methacryloxypentaethoxy)phenyl)propane (BPE-500, Shin-Nakamura Chemical Co., Ltd.) ), 2,2-bis(4-(methacryloxydodecaethoxytetrapropoxy)phenyl)propane (FA-3200MY, manufactured by Hitachi Chemical Co., Ltd.), 2,2-bis(4-(methacryloxypentadecaethoxy)phenyl ) Propane (BPE-1300, manufactured by Shin-Nakamura Chemical Co., Ltd.), 2,2-bis (4-(methacryloxydiethoxy) phenyl
- the ethylenically unsaturated compound B1 preferably contains a compound represented by the following formula (Bis) from the viewpoint of line width change over time, development temperature line width change, and sensitivity.
- R 1 and R 2 each independently represent a hydrogen atom or a methyl group
- A is C 2 H 4
- B is C 3 H 6
- n 1 and n 3 are each independently , an integer of 1 to 39
- n 1 + n 3 is an integer of 2 to 40
- n 2 and n 4 are each independently an integer of 0 to 29, and n 2 + n 4 is 0 to It is an integer of 30, and the arrangement of repeating units of -(AO)- and -(B-O)- may be random or block. In the case of a block, either -(AO)- or -(B-O)- may be on the bisphenol structure side.
- n 1 +n 2 +n 3 +n 4 is preferably an integer of 2-20, more preferably an integer of 2-16, and even more preferably an integer of 4-12. Also, n 2 +n 4 is preferably an integer of 0 to 10, more preferably an integer of 0 to 4, even more preferably an integer of 0 to 2, and particularly preferably 0.
- the ethylenically unsaturated compound B1 may be used singly or in combination of two or more.
- the content of the ethylenically unsaturated compound B1 in the photosensitive layer is preferably 10% by mass or more, more preferably 20% by mass or more, based on the total mass of the photosensitive layer, from the viewpoint of better resolution.
- the upper limit is not particularly limited, it is preferably 70% by mass or less, more preferably 60% by mass or less, from the viewpoint of transferability and edge fusion (a phenomenon in which components in the photosensitive layer ooze out from the edges of the transfer film).
- the photosensitive layer may contain an ethylenically unsaturated compound other than the ethylenically unsaturated compound B1 described above.
- Ethylenically unsaturated compounds other than the ethylenically unsaturated compound B1 are not particularly limited and can be appropriately selected from known compounds. For example, a compound having one ethylenically unsaturated group in one molecule (monofunctional ethylenically unsaturated compound), a bifunctional ethylenically unsaturated compound having no aromatic ring, and a trifunctional or higher ethylenically unsaturated compound.
- Examples of monofunctional ethylenically unsaturated compounds include ethyl (meth)acrylate, ethylhexyl (meth)acrylate, 2-(meth)acryloyloxyethyl succinate, polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate. , and phenoxyethyl (meth)acrylate.
- bifunctional ethylenically unsaturated compounds having no aromatic ring examples include alkylene glycol di(meth)acrylate, polyalkylene glycol di(meth)acrylate, urethane di(meth)acrylate, and trimethylolpropane diacrylate. be done.
- Alkylene glycol di(meth)acrylates include, for example, tricyclodecanedimethanol diacrylate (A-DCP, manufactured by Shin-Nakamura Chemical Co., Ltd.), tricyclodecanedimethanol dimethacrylate (DCP, manufactured by Shin-Nakamura Chemical Co., Ltd.
- A-DCP tricyclodecanedimethanol diacrylate
- DCP tricyclodecanedimethanol dimethacrylate
- Polyalkylene glycol di(meth)acrylates include, for example, polyethylene glycol di(meth)acrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, and polypropylene glycol di(meth)acrylate.
- Urethane di(meth)acrylates include, for example, propylene oxide-modified urethane di(meth)acrylates, and ethylene oxide and propylene oxide-modified urethane di(meth)acrylates.
- Examples of commercially available urethane di(meth)acrylates include 8UX-015A (manufactured by Taisei Fine Chemical Co., Ltd.), UA-32P (manufactured by Shin-Nakamura Chemical Co., Ltd.), and UA-1100H (manufactured by Shin-Nakamura Chemical Co., Ltd.). ).
- trifunctional or higher ethylenically unsaturated compounds include dipentaerythritol (tri/tetra/penta/hexa) (meth) acrylate, pentaerythritol (tri/tetra) (meth) acrylate, trimethylolpropane tri(meth) Acrylate, ditrimethylolpropane tetra(meth)acrylate, trimethylolethane tri(meth)acrylate, isocyanuric acid tri(meth)acrylate, glycerin tri(meth)acrylate, and alkylene oxide-modified products thereof.
- (tri/tetra/penta/hexa) (meth)acrylate is a concept including tri(meth)acrylate, tetra(meth)acrylate, penta(meth)acrylate, and hexa(meth)acrylate.
- (tri/tetra)(meth)acrylate” is a concept including tri(meth)acrylate and tetra(meth)acrylate.
- the photosensitive layer preferably contains the above-described ethylenically unsaturated compound B1 and a trifunctional or higher ethylenically unsaturated compound, and the above-described ethylenically unsaturated compound B1 and two or more trifunctional or higher functional ethylene More preferably, it contains a polyunsaturated compound.
- the mass ratio of the ethylenically unsaturated compound B1 and the tri- or higher functional ethylenically unsaturated compound is (total mass of the ethylenically unsaturated compound B1):(total mass of the tri- or higher functional ethylenically unsaturated compound).
- the photosensitive layer preferably contains the above-described ethylenically unsaturated compound B1 and two or more trifunctional ethylenically unsaturated compounds.
- alkylene oxide-modified trifunctional or higher ethylenically unsaturated compounds examples include caprolactone-modified (meth)acrylate compounds (KAYARAD (registered trademark) DPCA-20 manufactured by Nippon Kayaku Co., Ltd., A-9300 manufactured by Shin-Nakamura Chemical Co., Ltd. -1CL, etc.), alkylene oxide-modified (meth)acrylate compounds (KAYARAD RP-1040 manufactured by Nippon Kayaku Co., Ltd., ATM-35E and A-9300 manufactured by Shin-Nakamura Chemical Co., Ltd., EBECRYL (registered trademark) manufactured by Daicel Allnex Co., Ltd.
- ethoxylated glycerin triacrylate (A-GLY-9E etc. manufactured by Shin-Nakamura Chemical Co., Ltd.), Aronix (registered trademark) TO-2349 (manufactured by Toagosei Co., Ltd.), Aronix M-520 (Toagosei Co., Ltd. (manufactured by Toagosei Co., Ltd.) and Aronix M-510 (manufactured by Toagosei Co., Ltd.).
- an ethylenically unsaturated compound having an acid group described in paragraphs 0025 to 0030 of JP-A-2004-239942 may be used.
- the ratio Mm/Mb between the content Mm of the ethylenically unsaturated compound and the content Mb of the alkali-soluble resin in the photosensitive layer is preferably 1.0 or less from the viewpoint of resolution and linearity. It is more preferably 0.9 or less, and particularly preferably 0.5 or more and 0.9 or less.
- the ethylenically unsaturated compound in the photosensitive layer preferably contains a (meth)acrylic compound, more preferably a (meth)acrylate compound, from the viewpoint of curability and resolution.
- the ethylenically unsaturated compound in the photosensitive layer contains a (meth)acrylic compound, and the total mass of the (meth)acrylic compound contained in the photosensitive layer. More preferably, the content of the compound is 60% by mass or less.
- the molecular weight of the ethylenically unsaturated compound containing the ethylenically unsaturated compound B1 is preferably 200 to 3,000, more preferably 280 to 2,200, and 300 ⁇ 2,200 is more preferred.
- the polymerizable compound preferably contains an oxyethylene chain.
- An oxyethylene chain is a partial structure represented by -CH 2 -CH 2 -O-.
- Polymerizable compounds containing an oxyethylene chain include, for example, 2,2-bis(4-(methacryloxydiethoxy)phenyl)propane (FA-324M, manufactured by Hitachi Chemical Co., Ltd.), 2,2-bis(4- (Methacryloxyethoxypropoxy)phenyl)propane, 2,2-bis(4-(methacryloxypentaethoxy)phenyl)propane (BPE-500, manufactured by Shin-Nakamura Chemical Co., Ltd.), 2,2-bis(4-( methacryloxydodecaethoxytetrapropoxy)phenyl)propane (FA-3200MY, manufactured by Hitachi Chemical Co., Ltd.), 2,2-bis(4-(methacryloxypentadecaethoxy)phenyl)propane (BPE-1300, Shin
- the polymerizable compound may be used singly or in combination of two or more.
- the content of the polymerizable compound in the photosensitive layer is preferably 10% by mass to 70% by mass, more preferably 20% by mass to 60% by mass, and even more preferably 20% by mass to 50% by mass, relative to the total mass of the photosensitive layer. .
- the ratio of the weight of the polymerizable compound to the weight of the alkali-soluble resin in the photosensitive layer is preferably 0.6 or more, preferably 0.7 to 1.1. more preferably 0.8 to 1.0.
- the ratio of the mass of the polymerizable compound to the mass of the alkali-soluble resin in the photosensitive layer affects the storage modulus of the photosensitive layer. For example, when the ratio of the mass of the polymerizable compound to the mass of the alkali-soluble resin in the photosensitive layer increases, the storage elastic modulus of the photosensitive layer decreases.
- the storage elastic modulus of the photosensitive layer becomes small, the adhesion between the transfer layer and the object is improved when the transfer layer is transferred to the object (for example, substrate), and the resolution is also improved.
- the ratio of the mass of the polymerizable compound to the mass of the alkali-soluble resin in the photosensitive layer decreases, the storage elastic modulus of the photosensitive layer increases.
- the storage elastic modulus of the photosensitive layer increases, adhesion of the transfer layer to the surface of the peeled temporary support or protective film is suppressed, and deterioration in resolution is also suppressed.
- the negative photosensitive layer preferably contains a polymerization initiator.
- the polymerization initiator is selected according to the type of polymerization reaction, and examples thereof include thermal polymerization initiators and photopolymerization initiators. Moreover, a radical polymerization initiator and a cationic polymerization initiator are mentioned as a polymerization initiator.
- the negative photosensitive layer preferably contains a photopolymerization initiator.
- a photopolymerization initiator is a compound that initiates polymerization of a polymerizable compound upon exposure to actinic rays such as ultraviolet rays, visible rays, and X-rays.
- the photopolymerization initiator is not particularly limited, and known photopolymerization initiators can be used. Examples of photopolymerization initiators include radical photopolymerization initiators and cationic photopolymerization initiators, and radical photopolymerization initiators are preferred.
- photoradical polymerization initiators examples include photopolymerization initiators having an oxime ester structure, photopolymerization initiators having an ⁇ -aminoalkylphenone structure, photopolymerization initiators having an ⁇ -hydroxyalkylphenone structure, and acylphosphine oxide. structure and a photopolymerization initiator having an N-phenylglycine structure.
- the negative photosensitive layer contains 2,4,5-triarylimidazole dimer and its derivative as a photoradical polymerization initiator. It is preferable to include at least one selected from the group consisting of The two 2,4,5-triarylimidazole structures in the 2,4,5-triarylimidazole dimer and its derivative may be the same or different.
- 2,4,5-triarylimidazole dimer examples include, for example, 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer, 2-(o-chlorophenyl)-4,5-di (Methoxyphenyl)imidazole dimer, 2-(o-fluorophenyl)-4,5-diphenylimidazole dimer, 2-(o-methoxyphenyl)-4,5-diphenylimidazole dimer, and 2 -(p-methoxyphenyl)-4,5-diphenylimidazole dimer.
- radical photopolymerization initiator for example, polymerization initiators described in paragraphs 0031 to 0042 of JP-A-2011-95716 and paragraphs 0064-0081 of JP-A-2015-14783 may be used.
- photoradical polymerization initiators examples include ethyl dimethylaminobenzoate (DBE, CAS No. 10287-53-3), benzoin methyl ether, anisyl (p,p'-dimethoxybenzyl), TAZ-110 (trade name: Midori Chemical Co., Ltd.), benzophenone, TAZ-111 (product name: Midori Chemical Co., Ltd.), Irgacure OXE01, OXE02, OXE03, OXE04 (manufactured by BASF), Omnirad 651 and 369 (product name: IGM Resins B.V.) ), and 2,2′-bis(2-chlorophenyl)-4,4′,5,5′-tetraphenyl-1,2′-biimidazole (manufactured by Tokyo Chemical Industry Co., Ltd.).
- DBE ethyl dimethylaminobenzoate
- anisyl p,p'-dimethoxybenzyl
- photoradical polymerization initiators include, for example, 1-[4-(phenylthio)phenyl]-1,2-octanedione-2-(O-benzoyloxime) (trade name: IRGACURE (registered trademark) OXE- 01, manufactured by BASF), 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone-1-(O-acetyloxime) (trade name: IRGACURE OXE-02, BASF), IRGACURE OXE-03 (BASF), 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone (trade name: Omnirad 379EG, manufactured by IGM Resins B.V.), 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one (trade name: Omnirad 907, IGM Resins
- a photocationic polymerization initiator is a compound that generates an acid upon receiving an actinic ray.
- the photocationic polymerization initiator is preferably a compound that responds to an actinic ray with a wavelength of 300 nm or more, preferably 300 to 450 nm, and generates an acid, but its chemical structure is not limited.
- the sensitizer can be used for photocationic polymerization initiators that do not directly react to actinic rays with a wavelength of 300 nm or more, if they are compounds that react to actinic rays with a wavelength of 300 nm or more and generate an acid by using them in combination with a sensitizer. It can be preferably used in combination with.
- the photocationic polymerization initiator is preferably a photocationic polymerization initiator that generates an acid with a pKa of 4 or less, more preferably a photocationic polymerization initiator that generates an acid with a pKa of 3 or less, and an acid with a pKa of 2 or less.
- Photocationic polymerization initiators generated are particularly preferred.
- the lower limit of pKa is not particularly defined, it is preferably -10.0 or more, for example.
- photocationic polymerization initiators examples include ionic photocationic polymerization initiators and nonionic photocationic polymerization initiators.
- Ionic photocationic polymerization initiators include, for example, onium salt compounds such as diaryliodonium salts and triarylsulfonium salts, and quaternary ammonium salts.
- the ionic photocationic polymerization initiator the ionic photocationic polymerization initiators described in paragraphs 0114 to 0133 of JP-A-2014-85643 may be used.
- nonionic photocationic polymerization initiators include trichloromethyl-s-triazines, diazomethane compounds, imidosulfonate compounds, and oximesulfonate compounds.
- trichloromethyl-s-triazines, diazomethane compounds and imidosulfonate compounds compounds described in paragraphs 0083 to 0088 of JP-A-2011-221494 may be used.
- oxime sulfonate compound compounds described in paragraphs 0084 to 0088 of WO 2018/179640 may be used.
- the photosensitive layer may contain one type of photopolymerization initiator alone, or may contain two or more types.
- the content of the photopolymerization initiator in the photosensitive layer is not particularly limited, but is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and 1.0% by mass or more relative to the total mass of the photosensitive layer. is more preferred.
- the upper limit is not particularly limited, it is preferably 10% by mass or less, more preferably 5% by mass or less, relative to the total mass of the photosensitive layer.
- the photosensitive layer preferably contains a dye from the viewpoint of the visibility of the exposed and unexposed areas, the visibility of the pattern after development, and the resolution. is 450 nm or more, and the dye whose maximum absorption wavelength is changed by an acid, a base, or a radical (also simply referred to as “dye N”) is more preferably contained.
- the dye N is contained, although the detailed mechanism is unknown, the adhesion to the adjacent layers (for example, the temporary support and the intermediate layer) is improved and the resolution is improved.
- the fact that the dye "changes the maximum absorption wavelength due to acid, base or radical” means that the dye in the colored state is decolored by acid, base or radical, and the dye in the decolored state is acid or base.
- it may mean either a mode in which a color is developed by a radical, or a mode in which a dye in a coloring state changes to a coloring state of another hue.
- the dye N may be a compound that changes from a decolored state to develop color upon exposure, or may be a compound that changes from a colored state to decolor upon exposure.
- it may be a dye that changes the state of coloring or decoloring by the action of acid, base or radical generated in the photosensitive layer by exposure, and the state (e.g. pH) in the photosensitive layer due to the acid, base or radical. It may be a dye that changes the state of coloring or decoloring due to the change of . Further, it may be a dye that changes its coloring or decoloring state by directly receiving an acid, a base or a radical as a stimulus without being exposed to light.
- the dye N is preferably a dye whose maximum absorption wavelength is changed by acid or radicals, more preferably a dye whose maximum absorption wavelength is changed by radicals.
- the photosensitive layer preferably contains both a dye whose maximum absorption wavelength is changed by radicals as dye N and a radical photopolymerization initiator.
- the dye N is preferably a dye that develops color with an acid, a base, or a radical.
- a photoradical polymerization initiator i.e., a photoacid generator
- a photobase generator i.e., a photoacid generator
- Radical-reactive dyes, acid-reactive dyes, or base-reactive dyes develop colors by radicals, acids, or bases generated from initiators, photocationic polymerization initiators, or photobase generators. .
- the dye N preferably has a maximum absorption wavelength of 550 nm or more in the wavelength range of 400 nm to 780 nm during color development, more preferably 550 nm to 700 nm, and 550 nm. ⁇ 650 nm is more preferred. Further, the dye N may have only one maximum absorption wavelength in the wavelength range of 400 nm to 780 nm during color development, or may have two or more. When the dye N has two or more maximum absorption wavelengths in the wavelength range of 400 nm to 780 nm during color development, the maximum absorption wavelength with the highest absorbance among the two or more maximum absorption wavelengths should be 450 nm or more.
- the maximum absorption wavelength of Dye N is measured in the range of 400 nm to 780 nm using a spectrophotometer: UV3100 (manufactured by Shimadzu Corporation) in an air atmosphere. and detecting the wavelength at which the intensity of light is minimal (that is, the maximum absorption wavelength).
- a leuco compound is an example of a dye that develops or decolors upon exposure.
- dyes that are decolorized by exposure include leuco compounds, diarylmethane dyes, oxazine dyes, xanthene dyes, iminonaphthoquinone dyes, azomethine dyes, and anthraquinone dyes.
- the dye N a leuco compound is preferable from the viewpoint of the visibility of the exposed area and the non-exposed area.
- leuco compounds include leuco compounds having a triarylmethane skeleton (i.e., triarylmethane dyes), leuco compounds having a spiropyran skeleton (i.e., spiropyran dyes), and leuco compounds having a fluorane skeleton (i.e., fluoran dyes ), a leuco compound having a diarylmethane skeleton (i.e., diarylmethane dye), a leuco compound having a rhodamine lactam skeleton (i.e., rhodamine lactam dye), a leuco compound having an indolylphthalide skeleton (i.e., indolylphthalide and leuco compounds having a leuco auramine skeleton (ie, leuco auramine dyes).
- a triarylmethane skeleton i.e., triarylmethane dyes
- triarylmethane-based dyes or fluoran-based dyes are preferable, and leuco compounds having a triphenylmethane skeleton (that is, triphenylmethane-based dyes) or fluoran-based dyes are more preferable.
- the leuco compound preferably has a lactone ring, a sultine ring, or a sultone ring from the viewpoint of the visibility of the exposed and non-exposed areas.
- the lactone ring, sultine ring, or sultone ring of the leuco compound is reacted with a radical generated from a radical photopolymerization initiator or an acid generated from a photocationic polymerization initiator to change the leuco compound into a ring-closed state. It can be decolored, or it can be colored by changing the leuco compound into a ring-opened state.
- the leuco compound is preferably a compound that has a lactone ring, a sultine ring or a sultone ring and develops a color when the lactone ring, sultine ring or sultone ring is opened by a radical or an acid.
- a compound that develops color by ring-opening of the lactone ring is more preferred.
- Examples of the dye N include the following dyes and leuco compounds. Specific examples of dyes among dyes N include brilliant green, ethyl violet, methyl green, crystal violet, basic fuchsine, methyl violet 2B, quinaldine red, rose bengal, methanil yellow, thymolsulfophtalein, xylenol blue, methyl Orange, Paramethyl Red, Congo Fred, Benzopurpurin 4B, ⁇ -Naphthyl Red, Nile Blue 2B, Nile Blue A, Methyl Violet, Malachite Green, Parafuchsin, Victoria Pure Blue-Naphthalene Sulfonate, Victoria Pure Blue BOH (protective Tsuchiya Chemical Industry Co., Ltd.), Oil Blue #603 (Orient Chemical Industry Co., Ltd.), Oil Pink #312 (Orient Chemical Industry Co., Ltd.), Oil Red 5B (Orient Chemical Industry Co., Ltd.), Oil Scarlet #308 (Orient Chemical Industry Co., Ltd.), Oil Red OG (Orient Chemical
- leuco compounds among dyes N include p,p′,p′′-hexamethyltriaminotriphenylmethane (also referred to as leuco crystal violet), Pergascript Blue SRB (manufactured by Ciba-Geigy), and crystal violet lactone.
- Dye N is preferably a dye whose maximum absorption wavelength changes with radicals from the viewpoint of visibility of exposed and unexposed areas, pattern visibility after development, and resolution, and is a dye that develops color with radicals. is more preferable.
- Preferred dyes N are leuco crystal violet, crystal violet lactone, brilliant green, or victoria pure blue-naphthalene sulfonate.
- the dyes may be used singly or in combination of two or more.
- the content of the dye is preferably 0.1% by mass or more based on the total mass of the photosensitive layer, from the viewpoints of the visibility of the exposed and unexposed areas, the visibility of the pattern after development, and the resolution. .1 mass % to 10 mass % is more preferable, 0.1 mass % to 5 mass % is still more preferable, and 0.1 mass % to 1 mass % is particularly preferable.
- the content of dye N is 0.1% by mass or more with respect to the total mass of the photosensitive layer from the viewpoints of visibility of exposed and unexposed areas, pattern visibility after development, and resolution. It is preferably 0.1% by mass to 10% by mass, more preferably 0.1% by mass to 5% by mass, and particularly preferably 0.1% by mass to 1% by mass.
- the content of the dye N means the content of the dye when all the dyes N contained in the photosensitive layer are in a colored state.
- a method for quantifying the content of dye N will be described below using a dye that develops color by radicals as an example.
- Two solutions are prepared by dissolving 0.001 g or 0.01 g of dye in 100 mL of methyl ethyl ketone.
- a photoradical polymerization initiator Irgacure OXE01 (trade name, manufactured by BASF) is added to each of the solutions obtained, and radicals are generated by irradiation with light of 365 nm to bring all the dyes into a colored state. Thereafter, the absorbance of each solution having a liquid temperature of 25° C.
- the absorbance of the solution in which all the dyes are developed is measured in the same manner as described above except that 3 g of the photosensitive layer is dissolved in methyl ethyl ketone instead of the dyes. From the absorbance of the obtained solution containing the photosensitive layer, the content of the dye contained in the photosensitive layer is calculated based on the calibration curve.
- the photosensitive layer preferably contains a thermally crosslinkable compound from the viewpoint of the strength of the resulting cured film and the adhesiveness of the resulting uncured film.
- a thermally crosslinkable compound having an ethylenically unsaturated group which will be described later, is not treated as an ethylenically unsaturated compound, but as a thermally crosslinkable compound.
- Thermally crosslinkable compounds include methylol compounds and blocked isocyanate compounds. Among them, a blocked isocyanate compound is preferable from the viewpoint of the strength of the cured film to be obtained and the adhesiveness of the uncured film to be obtained.
- the blocked isocyanate compound reacts with a hydroxy group and a carboxy group, for example, when the alkali-soluble resin and/or the ethylenically unsaturated compound has at least one of a hydroxy group and a carboxy group, Hydrophilicity tends to decrease, and the function when a film obtained by curing a photosensitive layer is used as a protective film tends to be enhanced.
- the blocked isocyanate compound refers to "a compound having a structure in which the isocyanate group of isocyanate is protected (so-called masked) with a blocking agent".
- the dissociation temperature of the blocked isocyanate compound is not particularly limited, it is preferably 100°C to 160°C, more preferably 130°C to 150°C.
- the dissociation temperature of the blocked isocyanate means "the temperature of the endothermic peak associated with the deprotection reaction of the blocked isocyanate when measured by DSC (Differential Scanning Calorimetry) analysis using a differential scanning calorimeter".
- DSC Different Scanning Calorimetry
- a differential scanning calorimeter for example, a differential scanning calorimeter (model: DSC6200) manufactured by Seiko Instruments Inc. can be preferably used. However, the differential scanning calorimeter is not limited to this.
- the blocking agent having a dissociation temperature of 100° C. to 160° C. preferably contains an oxime compound, for example, from the viewpoint of storage stability.
- the blocked isocyanate compound preferably has an isocyanurate structure from the viewpoint of, for example, improving the brittleness of the film and improving the adhesion to the transferred material.
- a blocked isocyanate compound having an isocyanurate structure is obtained, for example, by isocyanurating hexamethylene diisocyanate and protecting it.
- compounds having an oxime structure using an oxime compound as a blocking agent tend to have a dissociation temperature within a preferred range and can reduce development residues more easily than compounds having no oxime structure. This is preferable from the viewpoint of ease of use.
- the blocked isocyanate compound may have a polymerizable group.
- the polymerizable group is not particularly limited, and any known polymerizable group can be used, and a radically polymerizable group is preferred.
- the polymerizable group include ethylenically unsaturated groups such as (meth)acryloxy groups, (meth)acrylamide groups and styryl groups, and groups having epoxy groups such as glycidyl groups.
- the polymerizable group is preferably an ethylenically unsaturated group, more preferably a (meth)acryloxy group, and still more preferably an acryloxy group.
- a commercially available product can be used as the blocked isocyanate compound.
- Examples of commercially available blocked isocyanate compounds include Karenz (registered trademark) AOI-BM, Karenz (registered trademark) MOI-BM, Karenz (registered trademark) MOI-BP, etc. (manufactured by Showa Denko K.K.), block type Duranate series (for example, Duranate (registered trademark) TPA-B80E, Duranate (registered trademark) WT32-B75P, etc., manufactured by Asahi Kasei Chemicals Corporation).
- the compound of the following structure can also be used as a blocked isocyanate compound.
- the thermally crosslinkable compound may be used singly or in combination of two or more.
- the content of the thermally crosslinkable compound is preferably 1% by mass to 50% by mass, more preferably 5% by mass to 30% by mass, based on the total mass of the photosensitive layer.
- the photosensitive layer may contain other components than those mentioned above.
- Other components include, for example, radical polymerization inhibitors, surfactants, sensitizers, and various additives.
- Other components may be used individually by 1 type, and may be used 2 or more types.
- the photosensitive layer may contain a radical polymerization inhibitor.
- radical polymerization inhibitors include thermal polymerization inhibitors described in paragraph 0018 of Japanese Patent No. 4502784. Among them, phenothiazine, phenoxazine and 4-methoxyphenol are preferred.
- Other radical polymerization inhibitors include naphthylamine, cuprous chloride, nitrosophenylhydroxyamine aluminum salt, and diphenylnitrosamine. In order not to impair the sensitivity of the photosensitive layer, it is preferred to use a nitrosophenylhydroxyamine aluminum salt as a radical polymerization inhibitor.
- the radical polymerization inhibitor may be used singly or in combination of two or more.
- the content of the radical polymerization inhibitor is preferably 0.001% by mass to 5.0% by mass, more preferably 0.01% by mass to 3% by mass, based on the total mass of the photosensitive layer. 0% by mass is more preferred, and 0.02% to 2.0% by mass is even more preferred.
- the content of the radical polymerization inhibitor is preferably 0.005% by mass to 5.0% by mass, more preferably 0.01% by mass to 3.0% by mass, relative to the total mass of the polymerizable compound. , more preferably 0.01% by mass to 1.0% by mass.
- the photosensitive layer preferably contains a surfactant.
- surfactants include surfactants described in paragraph 0017 of Japanese Patent No. 4502784 and paragraphs 0060 to 0071 of JP-A-2009-237362.
- a nonionic surfactant, a fluorine-based surfactant, or a silicone-based surfactant is preferable.
- fluorosurfactants include, for example, Megafac (trade name) F-171, F-172, F-173, F-176, F-177, F-141, F-142, F-143 , F-144, F-437, F-444, F-475, F-477, F-479, F-482, F-551-A, F-552, F-554, F-555-A, F -556, F-557, F-558, F-559, F-560, F-561, F-565, F-563, F-568, F-575, F-780, EXP.MFS-330, EXP . MFS-578, EXP. MFS-578-2, EXP. MFS-579, EXP.
- Fluorine-based surfactants also include acrylic compounds that have a molecular structure with a functional group containing a fluorine atom, and when heat is applied, the portion of the functional group containing a fluorine atom is cleaved and the fluorine atom volatilizes. It can be used preferably.
- fluorine-based surfactants include Megafac (trade name) DS series manufactured by DIC Corporation (The Chemical Daily (February 22, 2016), Nikkei Sangyo Shimbun (February 23, 2016)), For example, Megafac (trade name) DS-21 can be mentioned.
- the fluorosurfactant 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 fluorosurfactant.
- the fluorosurfactant has 2 or more (preferably 5 or more) structural units derived from a (meth)acrylate compound having a fluorine atom and an alkyleneoxy group (preferably an ethyleneoxy group and a propyleneoxy group) (meta).
- a fluorine-containing polymer compound containing structural units derived from an acrylate compound can also be preferably used.
- a fluorine-containing polymer having an ethylenically unsaturated group in a side chain can also be used as the fluorine-based surfactant.
- the fluorosurfactant for example, a compound having a linear perfluoroalkyl group with 7 or more carbon atoms may be used.
- PFOA perfluorooctanoic acid
- PFOS perfluorooctane sulfonic acid
- Nonionic surfactants include glycerol, trimethylolpropane, trimethylolethane and their ethoxylates and propoxylates (e.g., glycerol propoxylate, glycerol ethoxylate, etc.), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, Polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester, specific examples include Pluronic (trade name) L10, L31, L61, L62, 10R5, 17R2, 25R2 (manufactured by BASF), Tetronic (trade names) 304, 701, 704, 901, 904, 150R1, HYDROPALAT WE 3323 (manufactured by BASF), Solsperse (trade name) 20000 (manufactured by Nippo
- silicone-based surfactants include straight-chain polymers composed of siloxane bonds, and modified siloxane polymers in which organic groups are introduced into side chains and terminals.
- Specific examples of silicone surfactants include EXP. S-309-2, EXP. S-315, EXP. S-503-2, EXP.
- the photosensitive layer may contain one type of surfactant alone, or may contain two or more types.
- the content of the surfactant is preferably 0.001% by mass to 10% by mass, more preferably 0.01% by mass to 3% by mass, based on the total mass of the photosensitive layer.
- the photosensitive layer may contain a sensitizer.
- the sensitizer is not particularly limited, and known sensitizers, dyes and pigments can be used.
- Sensitizers include, for example, dialkylaminobenzophenone compounds, pyrazoline compounds, anthracene compounds, coumarin compounds, xanthone compounds, thioxanthone compounds, acridone compounds, oxazole compounds, benzoxazole compounds, thiazole compounds, benzothiazole compounds, triazole compounds (e.g., 1,2,4-triazoles), stilbene compounds, triazine compounds, thiophene compounds, naphthalimide compounds, triarylamine compounds, and aminoacridine compounds.
- the sensitizer may be used singly or in combination of two or more.
- the content of the sensitizer can be appropriately selected depending on the purpose. 0.01% by mass to 5% by mass, more preferably 0.05% by mass to 1% by mass, based on the total mass of
- the photosensitive layer may contain known additives as necessary in addition to the above components.
- additives include plasticizers, heterocyclic compounds, benzotriazoles, carboxybenzotriazoles, pyridines (such as isonicotinamide), purine bases (such as adenine), and solvents.
- the photosensitive layer may contain each additive singly or in combination of two or more.
- benzotriazoles include 1,2,3-benzotriazole, 1-chloro-1,2,3-benzotriazole, bis(N-2-ethylhexyl)aminomethylene-1,2,3-benzotriazole, bis(N-2-ethylhexyl)aminomethylene-1,2,3-tolyltriazole, bis(N-2-hydroxyethyl)aminomethylene-1,2,3-benzotriazole and the like.
- Carboxybenzotriazoles include, for example, 4-carboxy-1,2,3-benzotriazole, 5-carboxy-1,2,3-benzotriazole, N-(N,N-di-2-ethylhexyl)aminomethylene carboxybenzotriazole, N-(N,N-di-2-hydroxyethyl)aminomethylene carboxybenzotriazole, N-(N,N-di-2-ethylhexyl)aminoethylene carboxybenzotriazole and the like.
- carboxybenzotriazoles for example, commercial products such as CBT-1 (manufactured by Johoku Chemical Industry Co., Ltd., trade name) can be used.
- the total content of benzotriazoles and carboxybenzotriazoles is preferably 0.01% by mass to 3% by mass, more preferably 0.05% by mass to 1% by mass, based on the total mass of the photosensitive layer. is more preferable.
- a content of 0.01% by mass or more is preferable from the viewpoint of imparting storage stability to the photosensitive layer.
- setting the content to 3% by mass or less is preferable from the viewpoint of maintaining sensitivity and suppressing decolorization of the dye.
- the photosensitive layer may contain at least one selected from the group consisting of plasticizers and heterocyclic compounds.
- Plasticizers and heterocyclic compounds include compounds described in paragraphs 0097-0103 and 0111-0118 of WO2018/179640.
- the photosensitive layer may contain a solvent.
- the solvent may remain in the photosensitive layer.
- the photosensitive layer contains metal oxide particles, antioxidants, dispersants, acid multipliers, development accelerators, conductive fibers, thermal acid generators, ultraviolet absorbers, thickeners, cross-linking agents, and organic or It may further contain known additives such as inorganic suspending agents. Additives contained in the photosensitive layer are described in paragraphs 0165 to 0184 of JP-A-2014-85643, and the contents of this publication are incorporated herein.
- the photosensitive layer may contain a certain amount of impurities.
- impurities include sodium, potassium, magnesium, calcium, iron, manganese, copper, aluminum, titanium, chromium, cobalt, nickel, zinc, tin, halogens and ions thereof.
- halide ions, sodium ions, and potassium ions are likely to be mixed as impurities, so the following contents are preferable.
- the content of impurities in the photosensitive layer is preferably 80 ppm or less, more preferably 10 ppm or less, and even more preferably 2 ppm or less on a mass basis.
- the content of impurities can be 1 ppb or more, and may be 0.1 ppm or more, on a mass basis.
- Methods for adjusting the impurity content to the above range include selecting a material with a low impurity content as the raw material of the composition, preventing contamination of the impurity during the preparation of the photosensitive layer, and removing the impurity by washing. By such a method, the amount of impurities can be made 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 layer is preferably small. .
- the content of these compounds with respect to the total mass of the photosensitive layer is preferably 100 ppm or less, more preferably 20 ppm or less, and even more preferably 4 ppm or less, based on mass.
- the lower limit may be 10 ppb or more, and may be 100 ppb or more based on the total weight of the photosensitive layer.
- the content of these compounds can be suppressed in the same manner as the metal impurities described above. Moreover, it can quantify by a well-known measuring method.
- the water content in the photosensitive layer is preferably 0.01% by mass to 1.0% by mass, more preferably 0.05% by mass to 0.5% by mass, from the viewpoint of improving reliability and lamination properties.
- the photosensitive layer may contain residual monomers corresponding to the constituent units of the alkali-soluble resin described above.
- the content of the residual monomer is preferably 5,000 mass ppm or less, more preferably 2,000 mass ppm or less, and 500 mass ppm or less with respect to the total mass of the alkali-soluble resin, from the viewpoints of patterning properties and reliability. is more preferred.
- the lower limit is not particularly limited, it is preferably 1 mass ppm or more, more preferably 10 mass ppm or more.
- the residual monomer of each structural unit of the alkali-soluble resin is preferably 3,000 ppm by mass or less, more preferably 600 ppm by mass or less, more preferably 100 ppm by mass or less, based on the total mass of the photosensitive layer. Mass ppm or less is more preferable. Although the lower limit is not particularly limited, it is preferably 0.1 mass ppm or more, more preferably 1 mass ppm or more.
- the amount of residual monomers when synthesizing an alkali-soluble resin in a polymer reaction is also preferably within the above range.
- the content of glycidyl acrylate is preferably within the above range.
- the amount of residual monomers can be measured by known methods such as liquid chromatography and gas chromatography.
- the thickness of the photosensitive layer is preferably 20 ⁇ m or less, more preferably 10 ⁇ m or less, even more preferably 8 ⁇ m or less, and 5 ⁇ m or less from the viewpoint of developability and resolution. is particularly preferable, and it is most preferably 1 ⁇ m or more and 5 ⁇ m or less.
- the transmittance of light with a wavelength of 365 nm of the photosensitive layer is preferably 10% or more, preferably 30% or more, and more preferably 50% or more, from the viewpoint of better adhesion. Although the upper limit is not particularly limited, 99.9% or less is preferable.
- the method for forming the photosensitive layer is not particularly limited as long as it is a method capable of forming a layer containing the above components.
- a method for forming the photosensitive layer for example, a photosensitive resin composition containing an alkali-soluble resin, an ethylenically unsaturated compound, a photopolymerization initiator, a solvent, etc. is prepared, and the surface of the intermediate layer or the like is coated with the photosensitive resin composition. and drying the coating film of the photosensitive resin composition. Heat drying and reduced pressure drying are preferable as a method for drying the coating film of the photosensitive resin composition.
- drying means removing at least part of the solvent contained in the composition.
- Drying methods include, for example, natural drying, heat drying, and vacuum drying. The methods described above can be applied singly or in combination.
- the drying temperature is preferably 80° C. or higher, more preferably 90° C. or higher. Further, the upper limit thereof is preferably 130° C. or lower, more preferably 120° C. or lower. Drying can also be performed by changing the temperature continuously.
- the drying time is preferably 20 seconds or longer, more preferably 40 seconds or longer, and even more preferably 60 seconds or longer. Although the upper limit is not particularly limited, it is preferably 600 seconds or less, more preferably 300 seconds or less.
- Examples of the photosensitive resin composition used for forming the photosensitive layer include compositions containing an alkali-soluble resin, an ethylenically unsaturated compound, a photopolymerization initiator, the above optional components, and a solvent.
- the photosensitive resin composition preferably contains a solvent in order to adjust the viscosity of the photosensitive resin composition and facilitate the formation of the photosensitive layer.
- the solvent contained in the photosensitive resin composition is not particularly limited as long as it is capable of dissolving or dispersing the alkali-soluble resin, the ethylenically unsaturated compound, the photopolymerization initiator and the above optional components, and known solvents are used. can.
- solvents include alkylene glycol ether solvents, alkylene glycol ether acetate solvents, alcohol solvents (methanol, ethanol, etc.), ketone solvents (acetone, methyl ethyl ketone, etc.), aromatic hydrocarbon solvents (toluene, etc.), aprotic polar solvents.
- the photosensitive resin composition preferably contains at least one selected from the group consisting of alkylene glycol ether solvents and alkylene glycol ether acetate solvents.
- a mixed solvent containing at least one selected from the group consisting of alkylene glycol ether solvents and alkylene glycol ether acetate solvents and at least one selected from the group consisting of ketone solvents and cyclic ether solvents is more preferable.
- a mixed solvent containing at least one selected from the group consisting of a glycol ether solvent and an alkylene glycol ether acetate solvent, a ketone solvent, and a cyclic ether solvent is more preferable.
- Alkylene glycol ether solvents include, for example, ethylene glycol monoalkyl ether, ethylene glycol dialkyl ether, propylene glycol monoalkyl ether, propylene glycol dialkyl ether, diethylene glycol dialkyl ether, dipropylene glycol monoalkyl ether and dipropylene glycol dialkyl ether.
- Alkylene glycol ether acetate solvents include, for example, ethylene glycol monoalkyl ether acetate, propylene glycol monoalkyl ether acetate, diethylene glycol monoalkyl ether acetate and dipropylene glycol monoalkyl ether acetate.
- the solvent described in paragraphs 0092 to 0094 of WO 2018/179640, and the solvent described in paragraph 0014 of JP 2018-177889 may be used, the contents of which are herein incorporated into the book.
- the photosensitive resin composition may contain one type of solvent alone, or may contain two or more types.
- the content of the solvent when applying the photosensitive resin composition is preferably 50 parts by mass to 1,900 parts by mass, and 100 parts by mass to 900 parts by mass with respect to 100 parts by mass of the total solid content in the photosensitive resin composition. part is more preferred.
- the method for preparing the photosensitive resin composition is not particularly limited, for example, by preparing a solution in which each component is dissolved in the solvent in advance and mixing the resulting solution in a predetermined ratio, the photosensitive resin composition and a method for preparing the
- the photosensitive resin composition is preferably filtered using a filter with a pore size of 0.2 ⁇ m to 30 ⁇ m before forming the photosensitive layer.
- the method of applying the photosensitive resin composition is not particularly limited, and may be applied by a known method. Examples of coating methods include slit coating, spin coating, curtain coating, and inkjet coating. Alternatively, the photosensitive layer may be formed by applying a photosensitive resin composition onto a protective film described later and drying the composition.
- the intermediate layer preferably contains an alkali-soluble resin and a polymerizable compound.
- the alkali-soluble resin includes, for example, an alkali-soluble resin that is a component of the photosensitive layer described above and an alkali-soluble resin that is a component of the thermoplastic resin layer described later.
- the polymerizable compound include the polymerizable compound that is the component of the photosensitive layer described above.
- the ratio of the mass of the polymerizable compound to the mass of the alkali-soluble resin in the intermediate layer is preferably 0.5 or more, and is 0.6 to 1.1. more preferably 0.6 to 0.9.
- the ratio of the mass of the polymerizable compound to the mass of the alkali-soluble resin in the intermediate layer affects the storage modulus of the intermediate layer. For example, when the ratio of the mass of the polymerizable compound to the mass of the alkali-soluble resin in the intermediate layer increases, the storage modulus of the intermediate layer decreases.
- the storage elastic modulus of the intermediate layer becomes small, the adhesion between the transfer layer and the object is improved when the transfer layer is transferred to the object (for example, substrate), and the resolution is also improved.
- the ratio of the mass of the polymerizable compound to the mass of the alkali-soluble resin in the intermediate layer becomes small, the storage elastic modulus of the intermediate layer increases.
- the storage elastic modulus of the intermediate layer increases, adhesion of the transfer layer to the surface of the peeled temporary support or protective film is suppressed, and deterioration in resolution is also suppressed.
- the thickness of the intermediate layer is preferably 1 ⁇ m or more, more preferably 2 ⁇ m or more. From the viewpoint of developability and resolution, the thickness of the intermediate layer is preferably 20 ⁇ m or less, more preferably 10 ⁇ m or less, and particularly preferably 5 ⁇ m or less.
- the intermediate layer may have a single layer structure or a multilayer structure.
- Preferred intermediate layers include, for example, thermoplastic resin layers and water-soluble resin layers.
- the intermediate layer may include a thermoplastic resin layer, a water-soluble resin layer, or both a thermoplastic resin layer and a water-soluble resin layer.
- the intermediate layer preferably includes a thermoplastic resin layer and a water-soluble resin layer.
- the transfer film should include a temporary support, a thermoplastic resin layer, a water-soluble resin layer, a photosensitive layer, and a protective film in this order. is preferred.
- the intermediate layer may also include an oxygen-blocking layer having an oxygen-blocking function, which is described as a "separation layer" in JP-A-5-72724.
- an oxygen-blocking layer having an oxygen-blocking function, which is described as a "separation layer" in JP-A-5-72724.
- thermoplastic resin layer (Constituent element of intermediate layer: thermoplastic resin layer)
- the thermoplastic resin layer improves the followability to the substrate in bonding the transfer film and the substrate, suppresses the inclusion of air bubbles between the substrate and the transfer film, and improves the adhesion between the substrate and the transfer film. Improve.
- thermoplastic resin layer preferably contains an alkali-soluble resin as the thermoplastic resin.
- alkali-soluble resins include acrylic resins, polystyrene resins, styrene-acrylic copolymers, polyurethane resins, polyvinyl alcohol, polyvinyl formal, polyamide resins, polyester resins, polyamide resins, epoxy resins, polyacetal resins, polyhydroxystyrene resins, Polyimide resins, polybenzoxazole resins, polysiloxane resins, polyethyleneimines, polyallylamines and polyalkylene glycols.
- an acrylic resin is preferable from the viewpoint of developability and adhesion to adjacent layers.
- the acrylic resin is selected from the group consisting of structural units derived from (meth)acrylic acid, structural units derived from (meth)acrylic acid esters, and structural units derived from (meth)acrylic acid amides. It means a resin having at least one structural unit.
- the acrylic resin the total content of structural units derived from (meth) acrylic acid, structural units derived from (meth) acrylic acid ester, and structural units derived from (meth) acrylic acid amide is It is preferably at least 50% by mass with respect to the total mass.
- the total content of structural units derived from (meth)acrylic acid and structural units derived from (meth)acrylic ester is preferably 30% by mass to 100% by mass with respect to the total mass of the acrylic resin. , more preferably 50% by mass to 100% by mass.
- the alkali-soluble resin is preferably a polymer having an acid group.
- the acid group includes a carboxy group, a sulfo group, a phosphoric acid group and a phosphonic acid group, with the carboxy group being preferred.
- the alkali-soluble resin is more preferably an alkali-soluble resin having an acid value of 60 mgKOH/g or more, and more 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, it is preferably 200 mgKOH/g or less, more preferably 150 mgKOH/g or less.
- the carboxy group-containing acrylic resin having an acid value of 60 mgKOH/g or more is not particularly limited, and can be appropriately selected from known resins and used.
- an alkali-soluble resin that is a carboxy group-containing acrylic resin having an acid value of 60 mgKOH/g or more, described in 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 among the polymers, and a carboxy group having an acid value of 60 mgKOH/g or more among the alkali-soluble resins described in paragraphs 0053 to 0068 of JP-A-2016-224162.
- the copolymerization ratio of the structural unit having a carboxy group in the carboxy group-containing acrylic resin is preferably 5% by mass to 50% by mass, more preferably 10% by mass to 40% by mass, based on the total mass of the acrylic resin. % to 30% by mass is more preferred.
- 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 a polymerizable group, for example, a group capable of addition polymerization, polycondensation or polyaddition, and includes an ethylenically unsaturated group; a polycondensable group such as a hydroxy group and a carboxy group; , (blocked) isocyanate groups and the like.
- 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 thermoplastic resin layer may contain one type of alkali-soluble resin alone, or may contain two or more types.
- the content of the alkali-soluble resin is preferably 10% to 99% by mass, preferably 20% to 90% by mass, based on the total mass of the thermoplastic resin layer, from the viewpoint of developability and adhesion to adjacent layers. is more preferable, 40% by mass to 80% by mass is more preferable, and 50% by mass to 70% by mass is particularly preferable.
- thermoplastic resin layer has a maximum absorption wavelength of 450 nm or more in a wavelength range of 400 nm to 780 nm during color development, and contains a dye (simply referred to as “dye B”) whose maximum absorption wavelength changes with acid, base, or radicals. preferably.
- dye B a dye whose maximum absorption wavelength changes with acid, base, or radicals. preferably.
- Preferred embodiments of the dye B are the same as preferred embodiments of the dye N, except for the points described below.
- Dye B is preferably a dye whose maximum absorption wavelength changes with acid or radicals, more preferably a dye whose maximum absorption wavelength changes with acid, from the viewpoint of visibility and resolution of exposed and unexposed areas.
- the thermoplastic resin layer contains both a dye whose maximum absorption wavelength is changed by an acid as the dye B and a compound that generates an acid by light, which will be described later. It is preferable to contain
- the dye B may be used alone or in combination of two or more.
- the content of the dye B is preferably 0.2% by mass or more, more preferably 0.2% by mass to 6% by mass, based on the total mass of the thermoplastic resin layer, from the viewpoint of visibility of the exposed and unexposed areas. It is more preferably 0.2% by mass to 5% by mass, and particularly preferably 0.25% by mass to 3.0% by mass.
- the content of the dye B means the content of the dye when all of the dye B contained in the thermoplastic resin layer is in a colored state.
- a method for quantifying the content of the dye B will be described below using a dye that develops color by radicals as an example.
- Two solutions are prepared by dissolving 0.001 g or 0.01 g of dye in 100 mL of methyl ethyl ketone.
- a photoradical polymerization initiator Irgacure OXE01 (trade name, manufactured by BASF) is added to each of the solutions obtained, and radicals are generated by irradiation with light of 365 nm to bring all the dyes into a colored state. Thereafter, the absorbance of each solution having a liquid temperature of 25° C.
- thermoplastic resin layer is dissolved in methyl ethyl ketone instead of the dyes. From the absorbance of the obtained solution containing the thermoplastic resin layer, the amount of dye contained in the thermoplastic resin layer is calculated based on the calibration curve.
- thermoplastic resin layer compound that generates acid, base or radical upon exposure to light
- the thermoplastic resin layer may contain a compound that generates an acid, a base, or a radical upon exposure to light (also simply referred to as "compound C").
- Compound C is preferably a compound that generates an acid, a base, or a radical upon receiving actinic rays such as ultraviolet rays and visible rays.
- known photoacid generators, photobase generators, and photoradical polymerization initiators that is, photoradical generators
- a photoacid generator is preferable.
- the thermoplastic resin layer preferably contains a photoacid generator.
- the photoacid generator include photocationic polymerization initiators that may be contained in the photosensitive layer described above, and the preferred embodiments are the same except for the points described later.
- the photoacid generator preferably contains at least one compound selected from the group consisting of onium salt compounds and oxime sulfonate compounds. From the viewpoint of adhesion, it is more preferable to contain an oxime sulfonate compound. Moreover, as a photo-acid generator, the photo-acid generator which has the following structures is also preferable.
- the thermoplastic resin layer may contain a radical photopolymerization initiator.
- examples of the radical photopolymerization initiator include the radical photopolymerization initiators that may be contained in the photosensitive layer described above, and preferred embodiments are also the same.
- the thermoplastic resin layer may contain a photobase generator.
- the photobase generator is not particularly limited as long as it is a known photobase generator, and examples thereof include 2-nitrobenzylcyclohexylcarbamate, triphenylmethanol, O-carbamoylhydroxylamide, O-carbamoyloxime, 6-dinitrobenzyl)oxy]carbonyl ⁇ cyclohexylamine, bis ⁇ [(2-nitrobenzyl)oxy]carbonyl ⁇ hexane-1,6-diamine, 4-(methylthiobenzoyl)-1-methyl-1-morpholinoethane, ( 4-morpholinobenzoyl)-1-benzyl-1-dimethylaminopropane, N-(2-nitrobenzyloxycarbonyl)pyrrolidine, hexaamminecobalt (III) tris(triphenylmethylborate), 2-benzyl-2-dimethylamino -1-(4-morpholinophenyl)butanone, 2,6-
- the thermoplastic resin layer may contain one type of compound C alone, or may contain two or more types.
- the content of compound C is preferably 0.1% by mass to 10% by mass, and 0.5% by mass, based on the total mass of the thermoplastic resin layer, from the viewpoint of visibility and resolution of exposed and unexposed areas. % by mass to 5% by mass is more preferred.
- thermoplastic resin layer preferably contains a plasticizer from the viewpoints of resolution, adhesion to adjacent layers, and developability.
- the plasticizer preferably has a smaller molecular weight (weight average molecular weight (Mw) if it is an oligomer or polymer) than the alkali-soluble resin.
- the molecular weight (weight average molecular weight (Mw)) of the plasticizer is preferably 200 to 2,000.
- the plasticizer is not particularly limited as long as it is a compound that exhibits plasticity by being compatible with the alkali-soluble resin, but from the viewpoint of imparting plasticity, the plasticizer preferably has an alkyleneoxy group in the molecule, such as polyalkylene glycol. Compounds are more preferred.
- the alkyleneoxy group contained in the plasticizer more preferably has a polyethyleneoxy structure or a polypropyleneoxy structure.
- the plasticizer preferably contains a (meth)acrylate compound from the viewpoint of resolution and storage stability.
- the alkali-soluble resin is an acrylic resin and the plasticizer contains a (meth)acrylate compound.
- the (meth)acrylate compound used as the plasticizer include the (meth)acrylate compounds described as the ethylenically unsaturated compounds contained in the photosensitive layer.
- both the thermoplastic resin layer and the photosensitive layer contain the same (meth)acrylate compound. This is because when the same (meth)acrylate compound is contained in the thermoplastic resin layer and the photosensitive layer, the diffusion of components between the layers is suppressed and the storage stability is improved.
- thermoplastic resin layer contains a (meth)acrylate compound as a plasticizer
- the (meth)acrylate compound does not polymerize even in the exposed areas after exposure from the viewpoint of adhesion to adjacent layers.
- the (meth)acrylate compound used as a plasticizer is a polyfunctional compound having two or more (meth)acryloyl groups in one molecule from the viewpoint of resolution, adhesion with adjacent layers, and developability. (Meth)acrylate compounds are preferred.
- the (meth)acrylate compound used as a plasticizer a (meth)acrylate compound having an acid group or a urethane (meth)acrylate compound is also preferable.
- the thermoplastic resin layer may contain one type of plasticizer alone, or may contain two or more types.
- the content of the plasticizer is preferably 1% by mass to 70% by mass, preferably 10% by mass to 60% by mass, based on the total mass of the thermoplastic resin layer, from the viewpoints of resolution, adhesion with adjacent layers, and developability. % by mass is more preferred, and 20% to 50% by mass is particularly preferred.
- thermoplastic resin layer preferably contains a surfactant.
- surfactants include the surfactants that may be contained in the photosensitive layer described above, and preferred embodiments are also the same.
- the thermoplastic resin layer may contain one surfactant alone, or may contain two or more surfactants.
- the content of the surfactant is preferably 0.001% by mass to 10% by mass, more preferably 0.01% by mass to 3% by mass, relative to the total mass of the thermoplastic resin layer.
- thermoplastic resin layer may contain a sensitizer.
- the sensitizer is not particularly limited, and includes sensitizers that may be contained in the photosensitive layer described above.
- the thermoplastic resin layer may contain one type of sensitizer alone, or may contain two or more types.
- the content of the sensitizer can be appropriately selected depending on the purpose, but from the viewpoint of improving the sensitivity to the light source and visibility of the exposed area and the non-exposed area, it is 0.01 mass with respect to the total mass of the thermoplastic resin layer. % to 5% by mass, more preferably 0.05% to 1% by mass.
- thermoplastic resin layer may contain known additives, if necessary, in addition to the above components. Further, the thermoplastic resin layer is described in paragraphs 0189 to 0193 of JP-A-2014-85643, and the contents described in this publication are incorporated herein.
- the layer thickness of the thermoplastic resin layer is not particularly limited, it is preferably 1 ⁇ m or more, more preferably 2 ⁇ m or more, from the viewpoint of adhesion to adjacent layers.
- the upper limit is not particularly limited, it is preferably 20 ⁇ m or less, more preferably 10 ⁇ m or less, and even more preferably 5 ⁇ m or less from the viewpoint of developability and resolution.
- the method for forming the thermoplastic resin layer is not particularly limited as long as it is a method capable of forming a layer containing the above components.
- a method for forming a thermoplastic resin layer for example, a thermoplastic resin composition containing the above components and a solvent is prepared, the thermoplastic resin composition is applied to the surface of a temporary support or the like, and the thermoplastic resin composition is formed. A method of forming by drying a coating film of a product can be mentioned.
- the thermoplastic resin composition preferably contains a solvent in order to adjust the viscosity of the thermoplastic resin composition and facilitate the formation of the thermoplastic resin layer.
- the solvent contained in the thermoplastic resin composition is not particularly limited as long as it can dissolve or disperse the above components contained in the thermoplastic resin layer.
- Examples of the solvent contained in the thermoplastic resin composition include the solvent that may be contained in the photosensitive resin composition described above, and preferred embodiments are also the same.
- the solvent contained in the thermoplastic resin composition may be of one type alone, or may be of two or more types.
- the content of the solvent when applying the thermoplastic resin composition is preferably 50 parts by mass to 1,900 parts by mass, and 100 parts by mass to 900 parts by mass with respect to 100 parts by mass of the total solid content in the thermoplastic resin composition. part is more preferred.
- thermoplastic resin composition and formation of the thermoplastic resin layer may be carried out according to the method of preparing the photosensitive resin composition and the method of forming the photosensitive layer described above.
- the thermoplastic resin composition is prepared by previously preparing a solution in which each component contained in the thermoplastic resin layer is dissolved in the solvent, and mixing the resulting solution in a predetermined ratio, A thermoplastic resin layer is formed by applying the obtained thermoplastic resin composition to the surface of a temporary support and drying the coating film of the thermoplastic resin composition.
- the thermoplastic resin layer may be formed on the surface of the intermediate layer.
- the water-soluble resin layer preferably contains a water-soluble resin.
- water-soluble resins include polyvinyl alcohol-based resins, polyvinylpyrrolidone-based resins, cellulose-based resins, acrylamide-based resins, polyethylene oxide-based resins, gelatin, vinyl ether-based resins, polyamide resins, and resins such as copolymers thereof. is mentioned.
- the resins contained in the water-soluble resin layer are the polymer A contained in the photosensitive layer and the thermoplastic resin (for example, alkali soluble resin).
- the water-soluble resin layer preferably contains polyvinyl alcohol from the viewpoint of oxygen barrier properties and suppression of mixing of components during coating of multiple layers and storage after coating. It is more preferable to contain both.
- the water-soluble resin layer may contain one type of water-soluble resin alone, or may contain two or more types.
- the content of the water-soluble resin in the water-soluble resin layer is not particularly limited, but from the viewpoint of oxygen barrier properties and suppression of mixing of components during coating of multiple layers and storage after coating, a water-soluble resin is used. It is preferably 50% to 100% by weight, more preferably 70% to 100% by weight, even more preferably 80% to 100% by weight, and particularly preferably 90% to 100% by weight, relative to the total weight of the layer.
- the water-soluble resin layer may contain additives such as surfactants as necessary.
- the layer thickness of the water-soluble resin layer is not particularly limited, it is preferably 0.1 ⁇ m to 5 ⁇ m, more preferably 0.5 ⁇ m to 3 ⁇ m.
- the thickness of the water-soluble resin layer is within the above range, it is possible to suppress mixing of components during coating of multiple layers and during storage after coating without lowering the oxygen barrier properties, and during development. This is because an increase in the water-soluble resin layer removal time can be suppressed.
- the method for forming the water-soluble resin layer is not particularly limited. A method of forming a water-soluble resin layer by drying a coating film of a resin composition can be mentioned.
- the water-soluble resin composition preferably contains a solvent in order to adjust the viscosity of the water-soluble resin composition and facilitate the formation of the water-soluble resin layer.
- the solvent contained in the water-soluble resin composition is not particularly limited as long as it can dissolve or disperse the resin, and is preferably at least one selected from the group consisting of water and water-miscible organic solvents. Alternatively, a mixed solvent of water and a water-miscible organic solvent is more preferable.
- water-miscible organic solvents include alcohols having 1 to 3 carbon atoms, acetone, ethylene glycol and glycerin, with alcohols having 1 to 3 carbon atoms being preferred, and methanol or ethanol being more preferred.
- a transfer film according to one embodiment of the present disclosure includes a protective film.
- Materials constituting the protective film include resin films and paper, and resin films are preferable from the viewpoint of strength and flexibility.
- Resin films include polyethylene films, polypropylene films, polyethylene terephthalate films, cellulose triacetate films, polystyrene films, and polycarbonate films. Among them, polyethylene film, polypropylene film, or polyethylene terephthalate film is preferable.
- the thickness (layer thickness) of the protective film is not particularly limited, but is preferably 1 ⁇ m to 100 ⁇ m, more preferably 5 ⁇ m to 50 ⁇ m, even more preferably 5 ⁇ m to 40 ⁇ m, and particularly preferably 15 ⁇ m to 30 ⁇ m.
- the arithmetic mean roughness Ra value of the surface of the protective film in contact with the photosensitive layer (hereinafter simply referred to as "protective film surface”) is preferably 0.3 ⁇ m or less, and 0.1 ⁇ m or less, from the viewpoint of better resolution. is more preferable, and 0.05 ⁇ m or less is even more preferable.
- the thickness uniformity of the photosensitive layer and the formed resin pattern is improved when the Ra value of the surface of the protective film is within the above range.
- the lower limit of the Ra value of the surface of the protective film is not particularly limited, it is preferably 0.001 ⁇ m or more.
- the Ra value of the protective film surface is measured by the following method. Using a three-dimensional optical profiler (New View 7300, manufactured by Zygo), the surface of the protective film is measured under the following conditions to obtain the surface profile of the optical film. As measurement/analysis software, Microscope Application of MetroPro ver 8.3.2 is used. Next, the Surface Map screen is displayed using the above analysis software, and histogram data is obtained on the Surface Map screen. From the obtained histogram data, the arithmetic average roughness is calculated to obtain the surface Ra value of the protective film. When the protective film is attached to the transfer film, the protective film may be peeled off from the transfer film and the Ra value of the peeled surface may be measured.
- the protective film is arranged on the transfer layer by laminating the transfer layer and the protective film.
- Apparatuses used for bonding the transfer layer and the protective film include, for example, known laminators such as a vacuum laminator and an autocut laminator.
- the laminator is equipped with any heatable roller, such as a rubber roller, and can be applied with pressure and heat.
- the transfer layer and the temporary support may be formed in this order on the protective film.
- the cured film obtained by curing the photosensitive layer has a breaking elongation at 120 ° C. of 15% or more, and the arithmetic average roughness Ra of the surface of the temporary support on the photosensitive layer side is 50 nm or less. and the arithmetic mean roughness Ra of the surface of the protective film on the photosensitive layer side is preferably 150 nm or less.
- the transfer film according to the present disclosure preferably satisfies the following formula (R1).
- X ⁇ Y ⁇ 1,500 Formula (R1) X represents the breaking elongation value (%) of the cured film obtained by curing the photosensitive layer at 120 ° C.
- Y represents the arithmetic mean roughness of the surface of the temporary support on the photosensitive layer side. It represents the value of Ra (nm).
- X ⁇ Y is more preferably 750 or less.
- the elongation at break at 120°C is at least twice as large as the elongation at break at 23°C of the cured film obtained by curing the photosensitive layer.
- the elongation at break was measured by exposing a 20 ⁇ m-thick photosensitive layer at 120 mJ/cm 2 with an ultra-high pressure mercury lamp to cure it, then additionally exposing at 400 mJ/cm 2 with a high pressure mercury lamp, and heating at 145° C. for 30 minutes. measured by a tensile test using a cured film of
- the transfer film according to the present disclosure preferably satisfies the following formula (R2).
- Y ⁇ Z Formula (R2) Y represents the value (nm) of the arithmetic mean roughness Ra of the photosensitive layer side surface of the temporary support, and Z represents the arithmetic average of the photosensitive layer side surface of the protective film. It represents the value (nm) of roughness Ra.
- the production method of the transfer film according to the present disclosure is not particularly limited, and known production methods, for example, known methods of forming each layer can be used.
- a method for manufacturing a transfer film according to the present disclosure will be described with reference to FIG.
- the transfer film according to the present disclosure is not limited to having the configuration shown in FIG.
- the method for producing the transfer film 100 includes, for example, a step of applying the intermediate layer composition to the surface of the temporary support 10 and then drying the coating film of the intermediate layer composition to form the intermediate layer 20; a step of applying a photosensitive resin composition containing an alkali-soluble resin and an ethylenically unsaturated compound to the surface of the layer 20, and then drying the coating film of the photosensitive resin composition to form the photosensitive layer 30. is mentioned.
- an intermediate layer composition containing at least one selected from the group consisting of water and a water-miscible organic solvent is used, and an alkali-soluble resin, an ethylenically unsaturated compound, and an alkylene
- a photosensitive resin composition containing at least one selected from the group consisting of glycol ether solvents and alkylene glycol ether acetate solvents is preferable to use.
- the transfer film 100 is manufactured by pressing the protective film 40 onto the photosensitive layer 30 of the laminate manufactured by the manufacturing method described above.
- the method for producing the transfer film used in the present disclosure includes the step of providing the protective film 40 so as to contact the surface of the photosensitive layer 30 opposite to the side on which the temporary support 10 is provided. 10, an intermediate layer 20, a photosensitive layer 30 and a protective film 40.
- the transfer film 100 is preferably manufactured. After manufacturing the transfer film 100 by the manufacturing method described above, the transfer film 100 may be wound up to produce and store a roll-shaped transfer film.
- the transfer film in roll form can be provided as it is to the process of laminating the transfer film to a substrate in a roll-to-roll method, which will be described later.
- a transfer film according to an embodiment of the present disclosure can be suitably used for various applications that require precision microfabrication by photolithography. After patterning the photosensitive layer, etching may be performed using the photosensitive layer as a film, or electroforming, which is mainly electroplating, may be performed. Moreover, the cured film obtained by patterning may be used as a permanent film, for example, as an interlayer insulating film, a wiring protective film, a wiring protective film having an index matching layer, and the like.
- a transfer film according to an embodiment of the present disclosure is preferably used for forming a resist pattern.
- the transfer film according to one embodiment of the present disclosure is used for various wiring formation applications of semiconductor packages, printed circuit boards, sensor substrates, touch panels, electromagnetic wave shielding materials, conductive films such as film heaters, liquid crystal sealing materials, micromachines and micromachines. It can be suitably used for applications such as formation of structures in the field of electronics.
- the transfer film according to an embodiment of the present disclosure preferably includes an aspect in which the photosensitive layer is a colored resin layer containing a pigment.
- the photosensitive layer is a colored resin layer containing a pigment.
- the colored resin layer for example, liquid crystal display devices (LCD) and solid-state imaging devices [e.g., CCD (charge-coupled device) and CMOS (complementary metal oxide semiconductor)]. It is suitable for use in forming colored pixels such as filters or a black matrix.
- a cover glass with a black frame-shaped light-shielding layer formed on the periphery of the back surface of a transparent glass substrate or the like is attached to the liquid crystal display window.
- a colored resin layer may be used to form such a light shielding layer. Aspects other than the pigment in the colored resin layer are the same as those described above.
- the pigment used in the colored resin layer may be appropriately selected according to the desired hue, and may 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.
- black pigment a known black pigment (organic pigment, inorganic pigment, etc.) can be appropriately selected as long as it does not impair the effects of the present disclosure.
- black pigments include, for example, carbon black, titanium oxide, titanium carbide, iron oxide, titanium oxide and graphite, and carbon black is particularly preferred.
- 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 number average particle size of the black pigment is preferably 0.001 ⁇ m to 0.1 ⁇ m, more preferably 0.01 ⁇ m to 0.08 ⁇ m.
- the particle size refers to the diameter of a circle obtained by obtaining the area of a pigment particle from a photographic image of the pigment particle taken with an electron microscope and considering a circle having the same area as the area of the pigment particle. is an average value obtained by obtaining the above particle size for 100 arbitrary particles and averaging the obtained 100 particle sizes.
- white pigments other than black pigments white pigments described in paragraphs 0015 and 0114 of JP-A-2005-007765 can be used.
- white pigments titanium oxide, zinc oxide, lithopone, light calcium carbonate, white carbon, aluminum oxide, aluminum hydroxide, or barium sulfate are preferable as inorganic pigments, and titanium oxide or zinc oxide is more preferable.
- titanium oxide or zinc oxide is more preferable.
- titanium oxide is more preferred, and more preferred is titanium oxide.
- rutile-type or anatase-type titanium oxide is more preferable, and rutile-type titanium oxide is particularly preferable.
- the surface of titanium oxide may be subjected to silica treatment, alumina treatment, titania treatment, zirconia treatment, or organic substance treatment, or may be subjected to two or more treatments.
- the catalytic activity of titanium oxide is suppressed, and the heat resistance, fade resistance, and the like are improved.
- the surface treatment of the titanium oxide surface is preferably at least one of alumina treatment and zirconia treatment, and particularly preferably both alumina treatment and zirconia treatment.
- the photosensitive layer when the photosensitive layer is a colored resin layer, from the viewpoint of transferability, the photosensitive layer preferably further contains a chromatic pigment other than the black pigment and the white pigment.
- a chromatic pigment when a chromatic pigment is included, the particle size of the chromatic pigment is preferably 0.1 ⁇ m or less, more preferably 0.08 ⁇ m or less, from the viewpoint of better dispersibility.
- chromatic pigments include Victoria Pure Blue BO (Color Index (hereinafter C.I.) 42595), Auramine (C.I. 41000), Fat Black HB (C.I. 26150), Monolite ⁇ Yellow GT (C.I. Pigment Yellow 12), Permanent Yellow GR (C.I. Pigment Yellow 17), Permanent Yellow HR (C.I.
- Pigment Yellow 83 Permanent Carmine FBB (C) Pigment Red 146), Hoster Balm Red ESB (C.I. Pigment Violet 19), Permanent Ruby FBH (C.I. Pigment Red 11), Fastel Pink B Spra (C.I. Pigment Red 81), Monastral Fast Blue (C.I. Pigment Blue 15), Monolite Fast Black B (C.I. Pigment Black 1) and Carbon, C.I. I. Pigment Red 97, C.I. I. Pigment Red 122, C.I. I. Pigment Red 149, C.I. I. Pigment Red 168, C.I. I. Pigment Red 177, C.I. I. Pigment Red 180, C.I. I. Pigment Red 192, C.I. I.
- Pigment Red 215, C.I. I. Pigment Green 7, C.I. I. Pigment Blue 15:1, C.I. I. Pigment Blue 15:4, C.I. I. Pigment Blue 22, C.I. I. Pigment Blue 60, C.I. I. Pigment Blue 64, and C.I. I. Pigment Violet 23 may be mentioned.
- C.I. I. Pigment Red 177 is preferred.
- the content of the pigment is preferably more than 3% by mass and 40% by mass or less, more preferably more than 3% by mass and 35% by mass or less, based on the total mass of the photosensitive layer. More than 35% by mass is more preferable, and 10% by mass or more and 35% by mass or less is particularly preferable.
- the content of pigments other than black pigments is preferably 30% by mass or less, and 1% to 20% by mass, relative to black pigments. % is more preferred, and 3% by mass to 15% by mass is even more preferred.
- the black pigment (preferably carbon black) is introduced into the photosensitive resin composition in the form of a pigment dispersion.
- 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 the mixture with a dispersing machine.
- a pigment dispersant may be selected according to the pigment and solvent, and for example, a commercially available dispersant can be used.
- the vehicle refers to the part of the medium in which the pigment is dispersed when it is made into a pigment dispersion, and is a liquid binder component that holds the black pigment in a dispersed state, and a solvent component that dissolves and dilutes the binder component. (preferably an organic solvent).
- the disperser is not particularly limited, and includes known dispersers such as kneaders, roll mills, attritors, super mills, dissolvers, homomixers, and sand mills. Furthermore, it may be finely pulverized using frictional force by mechanical grinding. Regarding the dispersing machine and the fine pulverization, reference can be made to the description in "Encyclopedia of Pigment” (Kunizo Asakura, 1st edition, Asakura Shoten, 2000, pp. 438, 310).
- a method for manufacturing a conductor pattern according to an embodiment of the present disclosure includes peeling a protective film of a transfer film according to an embodiment of the present disclosure (hereinafter sometimes referred to as “protective film peeling step”); Laminating the transfer film and a substrate containing a metal layer, and arranging the transfer layer and the temporary support in this order on the metal layer of the substrate (hereinafter referred to as “bonding step” ), exposing the transfer layer (hereinafter sometimes referred to as “exposure step”), and developing the transfer layer to form a resist pattern (hereinafter referred to as “resist pattern forming step” ), performing etching or plating on the metal layer not covered with the resist pattern (hereinafter sometimes referred to as an “etching or plating step”), and stripping the resist pattern.
- protective film peeling step Laminating the transfer film and a substrate containing a metal layer, and arranging the transfer layer and the temporary support in this order on the metal layer of the substrate (hereinafter referred to as “bond
- the above-described method for producing a conductive pattern may include peeling off the temporary support (hereinafter sometimes referred to as “temporary support peeling step”) between the bonding step and the exposure step.
- the above-described method for producing a conductive pattern may include a step of removing the temporary support before the exposure step.
- a method for manufacturing a conductor pattern according to another embodiment of the present disclosure includes peeling a protective film of a transfer film according to an embodiment of the present disclosure (that is, “protective film peeling step”), and the transfer film. and a substrate containing a metal layer are bonded together, and the transfer layer and the temporary support are arranged in this order on the metal layer of the substrate (i.e., a “bonding step”); exposing the transfer layer (that is, the “exposure step”); and developing the transfer layer to form a resist pattern. (i.e., “resist pattern forming step”), etching or plating the metal layer not covered with the resist pattern (i.e., "etching or plating step”), and removing the resist pattern. (that is, “resist pattern stripping step”), and , in this order.
- the protective film peeling step the protective film of the transfer film is peeled.
- a peeling method of the protective film a known method is applied.
- a mechanism similar to the cover film peeling mechanism described in paragraphs 0161 to 0162 of JP-A-2010-072589 can be used.
- the peel strength of the protective film when peeling the protective film is preferably 0.3 mN/mm to 2.0 mN/mm, more preferably 0.3 mN/mm to 1.5 mN/mm, and 0.5 mN /mm to 1.0 mN/mm is particularly preferred.
- the peel strength of the protective film is measured by the following method.
- the transfer film and the substrate including the metal layer are bonded together, and the transfer layer and the temporary support are arranged in this order on the metal layer of the substrate.
- the bonding of the transfer film and the substrate preferably includes pressing the transfer film and the substrate together.
- the method for crimping the transfer film and the substrate is not particularly limited, and known transfer methods and lamination methods can be used.
- the transfer film and the substrate are preferably laminated together by stacking the transfer film and the substrate and applying pressure and heat using means such as rolls.
- a known laminator such as a laminator, a vacuum laminator, and an autocut laminator that can further improve productivity can be used for bonding.
- the lamination temperature is not particularly limited, it is preferably 70° C. to 130° C., for example.
- the manufacturing method of the conductor pattern including the bonding process is preferably carried out by a roll-to-roll method.
- the roll-to-roll method will be described below.
- the roll-to-roll method uses a substrate that can be wound and unwound as a substrate, and the step of unwinding the substrate or a structure including the substrate before any of the steps included in the method of manufacturing a conductor pattern ( Also referred to as an "unwinding step"), and after any of the steps, a step of winding up the substrate or a structure containing the substrate (also referred to as a "winding step"), at least any of the steps ( Preferably, all the steps, or all the steps other than the heating step) are performed while transporting the substrate or a structure including the substrate.
- the unwinding method in the unwinding step and the winding method in the winding step are not particularly limited, and known methods may be used in manufacturing methods to which a roll-to-roll system is applied.
- substrates include resin substrates, glass substrates, and semiconductor substrates. Preferred aspects of the substrate include, for example, the description in paragraph 0140 of WO2018/155193, the contents of which are incorporated herein. Preferred materials for the resin substrate are cycloolefin polymer and polyimide.
- the thickness of the resin substrate is preferably 5 ⁇ m to 200 ⁇ m, more preferably 10 ⁇ m to 100 ⁇ m.
- the substrate includes a metal layer.
- the substrate may include two or more metal layers. Examples of metals contained in the metal layer include Al, Zn, Cu, Fe, Ni, Cr, Mo, Ag and Au.
- the metal layer preferably contains at least one selected from the group consisting of copper and silver, more preferably copper or silver.
- the substrate may include layers other than metal layers.
- Layers other than metal layers include, for example, conductive metal oxide layers, graphene layers, carbon nanotube layers, and conductive polymer layers.
- Conductive metal oxides include ITO (Indium Tin Oxide), IZO (Indium Zinc Oxide) and SiO2 .
- ITO Indium Tin Oxide
- IZO Indium Zinc Oxide
- SiO2 SiO2 .
- “conductivity” means having a volume resistivity of less than 1 ⁇ 10 6 ⁇ cm.
- the volume resistivity of the conductive metal oxide is preferably less than 1 ⁇ 10 4 ⁇ cm.
- the substrate may include at least one of a transparent electrode and lead wiring.
- the substrate as described above can be suitably used as a touch panel substrate.
- a transparent electrode can function suitably as an electrode for touch panels.
- the transparent electrode is preferably composed of metal oxide films such as ITO (indium tin oxide) and IZO (indium zinc oxide), metal meshes, and thin metal wires such as metal nanowires.
- Fine metal wires include fine wires of silver, copper, and the like. Among them, silver conductive materials such as silver mesh and silver nanowire are preferable.
- a metal is preferable as the material of the routing wiring.
- metals for the routing wiring include gold, silver, copper, molybdenum, aluminum, titanium, chromium, zinc, manganese, and alloys composed of two or more of these metal elements. Copper, molybdenum, aluminum, or titanium is preferable as the material of the routing wiring, and copper is particularly preferable.
- the temporary support is removed. Specifically, the temporary support of the laminate obtained by the bonding step is peeled off. Peeling the temporary support usually exposes the transfer layer. A known method is applied as a peeling method of the temporary support. In the step of peeling off the temporary support, for example, a mechanism similar to the cover film peeling mechanism described in paragraphs 0161 to 0162 of JP-A-2010-072589 can be used.
- the peel strength of the temporary support during peeling of the temporary support is preferably 0.3 mN/mm to 2.5 mN/mm, more preferably 0.3 mN/mm to 1.5 mN/mm. 0.5 mN/mm to 1.0 mN/mm is particularly preferred.
- the peel strength of the temporary support is increased, the temporary support is prevented from being peeled off unintentionally, thereby improving handleability.
- the peel strength of the temporary support is low, the transfer layer is less likely to adhere to the peeled surface of the temporary support.
- the peel strength of the temporary support is higher than the peel strength of the protective film.
- the peel strength of the temporary support is measured by the following method.
- the protective film was peeled off from the transfer film, and the transfer film and substrate (specifically, copper substrate) were attached under the conditions of a laminating roll temperature of 100°C, a linear pressure of 0.6 MPa, and a linear speed (laminating speed) of 4.0 m/min.
- a laminate is obtained by combining.
- a tape PRINTACK manufactured by NITTO
- the tape is cut into a size of 70 mm ⁇ 10 mm to prepare a sample.
- a sample substrate is fixed on the sample stage.
- the tape is pulled at 5.5 mm / sec in the direction of 180 degrees to peel the temporary support, and the peel strength of the temporary support is measured.
- the matters related to the peel strength of the temporary support described above may also be applied to the temporary support described in the above section "Component of Transfer Film: Temporary Support”.
- the above-mentioned matters related to the peel strength of the temporary support are applied to the temporary support described in the section "Constituent of the transfer film: temporary support", it is used to measure the peel strength of the temporary support.
- the laminate is obtained by peeling off the protective film from the transfer film and bonding the transfer film and the substrate together under the conditions of a laminating roll temperature of 100° C., a linear pressure of 0.6 MPa, and a linear speed (laminating speed) of 4.0 m/min. be done.
- the transfer layer is exposed.
- the transfer layer is preferably pattern-exposed.
- Pattern exposure refers to exposure in a patterned form, that is, exposure in which an exposed portion and a non-exposed portion are present.
- the positional relationship between the exposed portion and the unexposed portion in pattern exposure is not particularly limited, and is adjusted as appropriate. Exposure may be performed along the direction from the substrate toward the transfer layer, or along the direction from the transfer layer toward the substrate.
- the detailed arrangement and specific size of the pattern in pattern exposure are not particularly limited.
- at least part of the pattern preferably the electrode pattern of the touch panel and/or or a portion of the lead-out wiring
- the light source used for exposure can be appropriately selected and used as long as it is a light source that irradiates the transfer layer (especially the photosensitive layer) with light of a wavelength (for example, 365 nm or 405 nm) that can be exposed.
- a wavelength for example, 365 nm or 405 nm
- ultra-high pressure mercury lamps, high pressure mercury lamps, metal halide lamps and LEDs Light Emitting Diodes
- the exposure dose is preferably 5 mJ/cm 2 to 200 mJ/cm 2 , more preferably 10 mJ/cm 2 to 100 mJ/cm 2 .
- Preferred embodiments of the light source, exposure amount and exposure method used for exposure include, for example, paragraphs 0146 to 0147 of WO 2018/155193, the contents of which are incorporated herein.
- the exposure step may be performed after the temporary support is peeled off, or may be performed before the temporary support is peeled off.
- the mask may be exposed in contact with the transfer layer (especially the photosensitive layer) or may be exposed in proximity without contact.
- the mask may be exposed in contact with the temporary support, or may be exposed in close proximity without contact.
- pattern exposure is preferably performed without peeling off the temporary support.
- the exposure method may be a contact exposure method in the case of contact exposure, a proximity exposure method in the case of a non-contact exposure method, a projection exposure method using a lens system or a mirror system, or a direct exposure method using an exposure laser or the like. It can be selected and used.
- an exposing machine having an appropriate lens numerical aperture (NA) can be used according to the required resolving power and depth of focus.
- NA lens numerical aperture
- the transfer layer particularly the photosensitive layer
- the transfer layer particularly the photosensitive layer
- the exposure may be performed not only in the atmosphere but also in a reduced pressure or a vacuum, and the exposure may be performed by interposing a liquid such as water between the light source and the transfer layer (especially the photosensitive layer). .
- resist pattern forming step In the resist pattern forming step, the transfer layer is developed to form a resist pattern. Development can be performed using a developer.
- the developer for example, a known developer such as the developer described in JP-A-5-72724 can be used.
- the developer is preferably an alkaline aqueous solution containing a compound having a pKa of 7 to 13 at a concentration of 0.05 mol/L to 5 mol/L.
- the developer may contain a water-soluble organic solvent and/or a surfactant.
- Alkaline compounds that can be contained in the alkaline aqueous solution include, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, and choline (2-hydroxyethyltrimethylammonium hydroxide).
- the developer described in paragraph 0194 of International Publication No. 2015/093271 is also preferably used.
- a development method that is preferably used includes, for example, the development method described in paragraph 0195 of International Publication No. 2015/093271.
- the development method is not particularly limited, and may be any of puddle development, shower development, shower and spin development, and dip development.
- Shower development is a development process in which an exposed portion or a non-exposed portion is removed by spraying a developing solution onto the exposed photosensitive layer by showering. After the development, it is preferable to remove the development residue by spraying the cleaning agent with a shower and rubbing it with a brush.
- the liquid temperature of the developer is not particularly limited, it is preferably 20°C to 40°C.
- the metal layer not covered with the resist pattern is etched or plated.
- the metal layer not covered with the resist pattern is removed to form a conductor pattern.
- a conductor pattern is formed on the metal layer not covered with the resist pattern.
- the latter method is sometimes called a semi-additive method.
- etching method a known method can be applied, for example, the method described in paragraphs 0209 to 0210 of JP-A-2017-120435, the method described in paragraphs 0048 to 0054 of JP-A-2010-152155. , a wet etching method in which the substrate is immersed in an etchant, and a dry etching method such as plasma etching.
- an acidic or alkaline etchant may be appropriately selected according to the object to be etched.
- acidic etching solutions include aqueous solutions of acidic components alone selected from hydrochloric acid, sulfuric acid, nitric acid, acetic acid, hydrofluoric acid, oxalic acid and phosphoric acid, and acidic components, ferric chloride, ammonium fluoride and A mixed aqueous solution with a salt selected from potassium permanganate can be mentioned.
- the acidic component may be a combination of multiple acidic components.
- Alkaline etchants include aqueous solutions of alkali components alone selected from sodium hydroxide, potassium hydroxide, ammonia, organic amines, and salts of organic amines (tetramethylammonium hydroxide, etc.), and alkali components and salts. (potassium permanganate, etc.).
- the alkaline component may be a component obtained by combining a plurality of alkaline components.
- Plating is preferably electroplating, and more preferably electroplating of copper.
- Components of the plating solution used in electroplating include, for example, water-soluble copper salts.
- the water-soluble copper salt a water-soluble copper salt that is commonly used as a component of a plating solution can be used.
- the water-soluble copper salt is preferably, for example, at least one selected from the group consisting of inorganic copper salts, alkanesulfonate copper salts, alkanol sulfonate copper salts, and organic acid copper salts.
- Inorganic copper salts include, for example, copper sulfate, copper oxide, copper chloride, and copper carbonate.
- Alkanesulfonic acid copper salts include, for example, copper methanesulfonate and copper propanesulfonate.
- Alkanol sulfonate copper salts include, for example, copper isethionate and copper propanol sulfonate.
- Organic acid copper salts include, for example, copper acetate, copper citrate, and copper tart
- the plating solution may contain sulfuric acid. By including sulfuric acid in the plating solution, the pH and sulfate ion concentration of the plating solution can be adjusted.
- a conductive pattern can be formed on a conductive pattern by supplying the transparent base material after the development process to a plating tank containing a plating solution.
- a conductive pattern can be formed by controlling the current density and the transport speed of the transparent substrate.
- the temperature of the plating solution used for electroplating is preferably 70°C or less, more preferably 10°C to 40°C.
- the current density in electroplating is preferably 0.1 A/dm 2 to 100 A/dm 2 , more preferably 0.5 A/dm 2 to 20 A/dm 2 .
- the resist pattern stripping step the resist pattern is stripped.
- the method of stripping the resist pattern is not particularly limited, but a method of removing by chemical treatment can be mentioned, and a method of removing using a remover is preferable.
- the substrate having the resist pattern is immersed for 1 minute to 30 minutes in a stirring removing liquid having a liquid temperature of preferably 30° C. to 80° C., more preferably 50° C. to 80° C. method.
- the removing liquid examples include a removing liquid obtained by dissolving an inorganic alkaline component or an organic alkaline component in water, dimethylsulfoxide, N-methylpyrrolidone, or a mixed solution thereof.
- inorganic alkaline components include sodium hydroxide and potassium hydroxide.
- Organic alkaline components include primary amine compounds, secondary amine compounds, tertiary amine compounds and quaternary ammonium salt compounds. Alternatively, it may be removed by a known method such as a spray method, a shower method, or a paddle method using a remover.
- a method for manufacturing a conductor pattern includes a step of exposing a resist pattern obtained by a resist pattern forming step (post-exposure step) and/or a step of heating (post-baking step). good too. If the method for manufacturing a conductor pattern includes both a post-exposure step and a post-bake step, post-baking is preferably performed after post-exposure.
- the exposure amount of post-exposure is preferably 100 mJ/cm 2 to 5,000 mJ/cm 2 , more preferably 200 mJ/cm 2 to 3,000 mJ/cm 2 .
- the post-baking temperature is preferably 80°C to 250°C, more preferably 90°C to 160°C.
- the post-baking time is preferably 1 to 180 minutes, more preferably 10 to 60 minutes.
- Examples of steps applicable to the method of manufacturing a conductor pattern include the steps described in paragraphs 0035 to 0051 of JP-A-2006-23696.
- Examples of steps applicable to the method for producing a conductor pattern include, for example, the step of reducing visible light reflectance described in paragraph 0172 of WO 2019/022089 and the step of reducing visible light reflectance described in paragraph 0172 of WO 2019/022089.
- a process of forming a new conductive layer over the insulating film is also included, but is not limited to these processes.
- a method for manufacturing a conductor pattern may include a step of performing a process for reducing the visible light reflectance of some or all of the multiple metal layers of the substrate.
- the treatment for reducing the visible light reflectance includes oxidation treatment.
- the visible light reflectance of the metal layer can be reduced by oxidizing the copper to form copper oxide and blackening the metal layer.
- the treatment for reducing the visible light reflectance is described in paragraphs 0017 to 0025 of JP-A-2014-150118, and paragraphs 0041, 0042, 0048 and 0058 of JP-A-2013-206315. , the contents of which are incorporated herein.
- a method of manufacturing a conductor pattern preferably includes a step of forming an insulating film on the surface of the conductor pattern, and a step of forming a new conductive layer on the surface of the insulating film.
- a second electrode pattern insulated from the first electrode pattern can be formed.
- the process of forming the insulating film is not particularly limited, and a known method of forming a permanent film can be used.
- an insulating film having a desired pattern may be formed by photolithography using an insulating photosensitive material.
- the step of forming a new conductive layer on the insulating film is not particularly limited.
- a conductive photosensitive material may be used to form a new conductive layer in a desired pattern by photolithography.
- the method of manufacturing the conductor pattern uses a substrate having a plurality of metal layers on both surfaces of the substrate, and sequentially or simultaneously forms circuits on the metal layers formed on both surfaces of the substrate.
- a circuit wiring for a touch panel in which the first conductor pattern is formed on one surface of the substrate and the second conductor pattern is formed on the other surface of the substrate.
- the touch panel circuit wiring having such a configuration from both sides of the substrate by roll-to-roll.
- Conductor patterns can be applied to various devices. Examples of the device provided with the conductive pattern manufactured by the above manufacturing method include an input device, preferably a touch panel, and more preferably a capacitive touch panel. Further, the input device can be applied to display devices such as an organic EL display device and a liquid crystal display device.
- a method for manufacturing a touch panel according to an embodiment of the present disclosure includes peeling a protective film of a transfer film according to an embodiment of the present disclosure (that is, “protective film peeling step”), the transfer film, and a metal Laminating a substrate including a layer, placing a transfer layer and a temporary support in this order on the metal layer of the substrate (i.e., a “lamination step”), and exposing the transfer layer (i.e., “exposure step”), developing the transfer layer to form a resist pattern (i.e., “resist pattern forming step”), and etching the metal layer not covered with the resist pattern.
- the above-described touch panel manufacturing method may include peeling off the temporary support (that is, “temporary support peeling step”) between the bonding step and the exposure step.
- the above-described touch panel manufacturing method may include a step of removing the temporary support before the exposure step.
- a method for manufacturing a touch panel according to another embodiment of the present disclosure includes peeling a protective film of a transfer film according to an embodiment of the present disclosure (that is, “protective film peeling step”), and , bonding a substrate containing a metal layer, arranging a transfer layer and a temporary support in this order on the metal layer of the substrate (i.e., a “bonding step”); exposing the transfer layer (i.e., the "exposure step”); and developing the transfer layer to form a resist pattern (i.e., “resist pattern forming step”), etching or plating the metal layer not covered with the resist pattern (i.e., “etching or plating step”), and stripping the resist pattern (i.e. , “resist pattern stripping step”), in this order.
- a resist pattern i.e., “resist pattern forming step”
- etching or plating step etching or plating the metal layer not covered with the resist pattern
- stripping the resist pattern
- each step in the touch panel manufacturing method and embodiments such as the order in which each step is performed are described in the above sections of "Method for manufacturing laminate” and “Method for manufacturing circuit wiring”. and preferred embodiments are also the same.
- a known method for manufacturing a touch panel may be referred to, except that the touch panel wiring is formed by the above method.
- the touch panel manufacturing method may include arbitrary steps (other steps) other than those described above.
- a touch panel having circuit wiring having pattern A corresponding to EX formed thereon can be manufactured. Specifically, it can be produced by the method described in FIG. 1 of International Publication No. 2016/190405.
- the central portion of the exposed portion EX (the pattern portion where the qualifications are connected) is the portion where the transparent electrode (touch panel electrode) is formed, and the peripheral portion (thin line portion) of the exposed portion EX is This is the portion where the wiring of the peripheral extracting portion is formed.
- a touch panel having at least touch panel wiring is manufactured by the touch panel manufacturing method described above.
- the touch panel preferably has a transparent substrate, electrodes, and an insulating layer or protective layer.
- a detection method for a touch panel known methods such as a resistive film method, a capacitance method, an ultrasonic method, an electromagnetic induction method, and an optical method can be used. Among them, the capacitance method is preferable.
- the touch panel type As the touch panel type, the so-called in-cell type (for example, those described in FIGS. 5, 6, 7 and 8 of JP-A-2012-517051), the so-called on-cell type (for example, JP 2013-168125) Those described in FIG. 19, and those described in FIGS. 1 and 5 of JP-A-2012-89102), OGS (One Glass Solution) type, TOL (Touch-on-Lens) type (for example, JP-A 2013-54727), various out-cell types (so-called GG, G1 G2, GFF, GF2, GF1 and G1F, etc.) and other configurations (for example, JP 2013-164871 6).
- touch panels include those described in paragraph 0229 of JP-A-2017-120435.
- Temporary support 1 was produced by the following method.
- particle-containing layer-forming composition 1 A particle-containing layer-forming composition 1 was obtained by mixing each component according to the formulation shown below. After preparing the particle-containing layer-forming composition 1, it was filtered through a 6 ⁇ m filter (F20, manufactured by Mahle Filter Systems Co., Ltd.), and then membrane degassed using a 2 ⁇ 6 radial flow superphobic (manufactured by Polypore Co., Ltd.). did.
- ⁇ Acrylic polymer AS-563A, manufactured by Daicel Finechem Co., Ltd., solid content 27.5% by mass
- ⁇ Nonionic surfactant Neloacty CL95, manufactured by Sanyo Chemical Industries, Ltd., solid content 100% by mass
- Anionic surfactant (Rapisol A-90, manufactured by NOF Corporation, diluted with water to a solid content of 1% by mass) 114.4 parts Carnauba wax dispersion (Cerosol 524, manufactured by Chukyo Yushi Co., Ltd., solid 30% by mass) 7 parts Carbodiimide compound (Carbodiimide V-02-L2, manufactured by Nisshinbo Chemical Co., Ltd., diluted with water to a solid content of 10% by mass) 20.9 parts Matting agent (Snowtex XL, Nissan Chemical Co., Ltd.) made, solid content 40% by mass, average particle diameter 50 nm): 2.8 parts, water: 690.2 parts
- the solidified unstretched film was sequentially biaxially stretched by the following method to obtain a temporary support including a polyester film with a thickness of 16 ⁇ m and a particle-containing layer with a thickness of 40 nm.
- Heat setting and heat relaxation The biaxially stretched film after longitudinal stretching and transverse stretching was heat-set under the following conditions. Heat setting temperature: 227°C Heat fixation time: 6 seconds
- the film thickness of the particle-containing layer was 40 nm as measured from a cross-sectional TEM photograph.
- the average particle diameter of the particles contained in the particle-containing layer was 50 nm when measured by the method described above using an HT-7700 transmission electron microscope (TEM) manufactured by Hitachi High-Technologies Corporation.
- ⁇ Water-soluble resin composition The following components were mixed to obtain a water-soluble resin composition used as material 1 for the water-soluble resin layer.
- ⁇ Ion-exchanged water 38.12 parts ⁇ Methanol (manufactured by Mitsubishi Gas Chemical Co., Ltd.): 57.17 parts ⁇ Kuraray Poval 4-88LA (polyvinyl alcohol, manufactured by Kuraray Co., Ltd.): 3.22 parts ⁇ Polyvinylpyrrolidone K-30 (manufactured by Nippon Shokubai Co., Ltd.): 1.49 parts Megafac F-444 (fluorosurfactant, manufactured by DIC Corporation): 0.0035 parts
- Photosensitive resin composition A mixed solvent containing methyl ethyl ketone (manufactured by Sankyo Chemical Co., Ltd., 60 parts) and propylene glycol monomethyl ether acetate (manufactured by Showa Denko KK, 40 parts) was prepared. Each component shown in Table 1 was mixed with a mixed solvent to prepare photosensitive resin compositions represented by Materials 1 to 4 and 5A to 5E in Table 1, respectively. The amount of the mixed solvent added was adjusted so that the solid content concentration of the photosensitive composition was 13% by mass.
- thermoplastic resin composition used as a material for the thermoplastic resin layer.
- A-2 benzyl methacrylate/methacrylic acid/acrylic acid copolymer (75% by mass/10% by mass/15% by mass, weight average molecular weight: 30,000, Tg: 75°C, acid value: 186 mgKOH/g)
- ⁇ B-1 A compound having the structure shown below (a dye that develops color with an acid)
- ⁇ C-1 A compound having the structure shown below (photoacid generator, compound described in paragraph 0227 of JP-A-2013-47765, synthesized according to the method described in paragraph 0227.)
- ⁇ D-3 NK Ester A-DCP (tricyclodecanedimethanol diacrylate, Shin-Nakamura Chemical Industry Co., Ltd.)
- ⁇ D-4 8UX-015A (polyfunctional urethane acrylate compound, Taisei Fine Chemical Co., Ltd.)
- ⁇ D-5 Aronix TO-2349 (polyfunctional acrylate compound having a carboxy group, Toagosei Co., Ltd.)
- E-1 Mega Fac F552 (DIC Corporation)
- F-1 Phenothiazine (Fujifilm Wako Pure Chemical Industries, Ltd.)
- ⁇ F-2 CBT-1 (Johoku Chemical Industry Co., Ltd.)
- ⁇ MEK Methyl ethyl ketone
- ⁇ PGME Propylene glycol monomethyl ether
- ⁇ PGMEA Propylene glycol monomethyl ether acetate
- thermoplastic resin layer if necessary, a water-soluble resin layer, and a photosensitive layer were formed in this order on the temporary support.
- a thermoplastic resin was formed by applying and drying a thermoplastic resin composition.
- a water-soluble resin layer was formed by applying and drying a water-soluble resin composition.
- a photosensitive layer was formed by applying and drying a photosensitive resin composition.
- a protective film was provided on the photosensitive layer to obtain a transfer film.
- a copper layer having a thickness of 200 nm was formed on the polyethylene terephthalate film by sputtering to obtain a copper substrate.
- the obtained copper substrate is used for the following evaluations.
- ⁇ Storage modulus> Using a viscoelasticity measuring device (Rheometer DHR-2 manufactured by TA Instruments), a parallel plate of 20 mm ⁇ and a Peltier plate (Gap: about 0.5 mm), the temperature is 20 ° C. to 125 ° C., and the heating rate is 5.
- the storage elastic moduli of the thermoplastic resin layer and the photosensitive layer were measured under the conditions of °C/min, frequency of 1 Hz, and strain of 0.5%. Specifically, before measurement, the sample was melted on a Peltier plate at 80° C. to 95° C., cooled to 20° C. at a cooling rate of 5° C./min, and then measured in the Gap constant mode. The value at 25°C is adopted for the storage modulus. Table 3 shows the measurement results.
- ⁇ Roughness Ra> The surface roughness Ra of the temporary support facing the transfer layer and the surface roughness Ra of the transfer layer facing the temporary support were measured by the following methods.
- the protective film was peeled off from the transfer film, and the transfer film was attached to the copper substrate under the conditions of a laminating roll temperature of 100° C., a linear pressure of 0.6 MPa, and a linear speed (laminating speed) of 4.0 m/min.
- a three-dimensional optical profiler (New View 7300, Zygo) was used to obtain the surface profile of the target surface.
- "Microscope Application” of "MetroPro ver8.3.2” was used as measurement and analysis software.
- a "Surface Map” screen was displayed by the above software, and histogram data was obtained in the "Surface Map” screen. The arithmetic average roughness Ra of the target surface was calculated from the obtained histogram data. Table 3 shows the measurement results.
- the peel strength of the protective film was measured by the following method.
- a tape PRINTACK manufactured by Nitto Denko Corporation
- a temporary support for the sample was fixed on the sample stage.
- SV-55 manufactured by Imada Seisakusho Co., Ltd.
- the tape is pulled at 5.5 mm / sec in the direction of 180 degrees, the protective film is peeled from the sample, and the peel strength of the protective film is measured. did.
- Table 3 shows the measurement results.
- the peel strength of the temporary support was measured by the following method.
- the protective film was peeled off from the transfer film, and the transfer film was attached to the copper substrate under the conditions of a laminating roll temperature of 100° C., a linear pressure of 0.6 MPa, and a linear speed (laminating speed) of 4.0 m/min.
- After sticking a tape (PRINTACK manufactured by NITTO) on the surface of the temporary support it was cut into a size of 70 mm ⁇ 10 mm to prepare a sample.
- a sample copper substrate was fixed on a sample table.
- the protective film was peeled off from the transfer film, and the transfer film was attached to the copper substrate under the conditions of a laminating roll temperature of 100° C., a linear pressure of 0.6 MPa, and a linear speed (laminating speed) of 4.0 m/min.
- the temporary support was peeled off from the resulting laminate, the transfer layer disposed on the copper substrate was brought into contact with a photomask having a line and space pattern, and the transfer layer was exposed using an ultra-high pressure mercury lamp. .
- the exposed transfer layer was subjected to shower development for 40 seconds using a 1.0 mass % sodium carbonate aqueous solution at 28°C.
- the protective film was peeled off from the transfer film, and the presence or absence of deposits of the transfer layer on the surface of the protective film was visually confirmed.
- the transfer film was attached to the copper substrate under the conditions of a laminating roll temperature of 100° C., a linear pressure of 0.6 MPa, and a linear speed (laminating speed) of 4.0 m/min.
- the temporary support was peeled off from the laminate thus obtained, and the presence or absence of a deposit of the transfer layer on the surface of the temporary support was visually confirmed.
- 16KS40 described in Table 3 means Lumirror 16KS40 manufactured by Toray Industries, Inc.
- 16FB40 described in Table 3 means Lumirror 16FB40 manufactured by Toray Industries, Inc.
- FG201 described in Table 3 means Alphan FG-201 manufactured by Oji F-Tech Co., Ltd.
- M/B described in Table 3 means the mass ratio of the polymerizable compound to the alkali-soluble resin.
- 10 ⁇ 5 described in Table 3 means 105.
- 10 ⁇ 6 described in Table 3 means 10 6 .
- 10 ⁇ 7 described in Table 3 means 107.
- 10 ⁇ 8 described in Table 3 means 10 8 .
- “Surface roughness Ra” described in the column “temporary support” in Table 3 means the roughness Ra of the surface of the temporary support facing the transfer layer.
- the “surface roughness Ra” described in the column “transfer layer” in Table 3 means the roughness Ra of the surface of the transfer layer facing the temporary support.
- the storage modulus of the protective film side of the transfer layer at 25° C. is in the range of 1.0 ⁇ 10 6 Pa to 3.0 ⁇ 10 8 Pa.
- Table 3 shows that the resolution of the examples is superior to that of the comparative examples.
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Abstract
Description
特許文献1:特開2020-086238号公報
<1> 仮支持体と、転写層と、保護フィルムと、をこの順に含み、25℃における上記転写層の上記保護フィルム側の貯蔵弾性率が、1.0×106Pa~3.0×108Paである、転写フィルム。
<2> 25℃における上記転写層の上記仮支持体側の貯蔵弾性率が、1.0×106Pa以上である、<1>に記載の転写フィルム。
<3> 上記仮支持体に面する上記転写層の表面の粗さRaが、0.1nm~15nmである、<1>又は<2>に記載の転写フィルム。
<4> 上記転写層に面する上記仮支持体の表面の粗さRaが、0.1nm~15nmである、<1>~<3>のいずれか1つに記載の転写フィルム。
<5> 上記転写層が、感光層である、<1>~<4>のいずれか1つに記載の転写フィルム。
<6> 上記転写層が、中間層及び感光層を含む、<1>~<4>のいずれか1つに記載の転写フィルム。
<7> 上記中間層が、アルカリ可溶性樹脂及び重合性化合物を含み、上記中間層における上記アルカリ可溶性樹脂の質量に対する上記重合性化合物の質量の比が、0.5以上である、<6>に記載の転写フィルム。
<8> 上記中間層の厚さが、10μm以下である、<6>又は<7>に記載の転写フィルム。
<9> 上記中間層が、熱可塑性樹脂層及び水溶性樹脂層を含む、<6>~<8>のいずれか1つに記載の転写フィルム。
<10> 上記感光層が、アルカリ可溶性樹脂及び重合性化合物を含み、上記感光層における上記アルカリ可溶性樹脂の質量に対する上記重合性化合物の質量の比が、0.6以上である、<5>~<9>のいずれか1つに記載の転写フィルム。
<11> 上記感光層の厚さが、10μm以下である、<5>~<10>のいずれか1つに記載の転写フィルム。
<12> <1>~<11>のいずれか1つに記載の転写フィルムの保護フィルムを剥離することと、上記転写フィルムと、金属層を含む基板とを貼り合わせて、上記基板の上記金属層の上に、上記転写層及び上記仮支持体をこの順に配置することと、上記転写層を露光することと、上記転写層を現像し、レジストパターンを形成することと、上記レジストパターンに覆われていない上記金属層に対してエッチング又はめっきを行うことと、上記レジストパターンを剥離することと、をこの順に含む、導体パターンの製造方法。
<13> <1>~<11>のいずれか1つに記載の転写フィルムの保護フィルムを剥離することと、上記転写フィルムと、金属層を含む基板とを貼り合わせて、上記基板の上記金属層の上に、上記転写層及び上記仮支持体をこの順に配置することと、上記仮支持体を剥離することと、上記転写層を露光することと、上記転写層を現像し、レジストパターンを形成することと、上記レジストパターンに覆われていない上記金属層に対してエッチング又はめっきを行うことと、上記レジストパターンを剥離することと、をこの順に含む、導体パターンの製造方法。
<14> 上記仮支持体の剥離における上記仮支持体の剥離強度が、0.3mN/mm~2.0mN/mmである、<13>に記載の導体パターンの製造方法。
本開示において「~」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。
本開示において、「(メタ)アクリル」はアクリル及びメタクリルの双方、又は、いずれかを表し、「(メタ)アクリレート」はアクリレート及びメタクリレートの双方、又は、いずれかを表し、「(メタ)アクリロイル」はアクリロイル及びメタクリロイルの双方、又は、いずれかを表す。
本開示において組成物中の各成分の量は、組成物中に各成分に該当する物質が複数存在する場合、特に断らない限り、組成物中に存在する該当する複数の物質の合計量を意味する。
本開示において「工程」との語は、独立した工程だけでなく、他の工程と明確に区別できない場合であっても工程の所期の目的が達成されれば、本用語に含まれる。
本開示における基(原子団)の表記において、置換及び無置換を記していない表記は、置換基を有さないものと共に置換基を有するものをも包含するものである。例えば「アルキル基」とは、置換基を有さないアルキル基(無置換アルキル基)のみならず、置換基を有するアルキル基(置換アルキル基)をも包含するものである。
本開示において「露光」とは、特に断らない限り、光を用いた露光のみならず、電子線、イオンビーム等の粒子線を用いた描画も含む。また、露光に用いられる光としては、一般的に、水銀灯の輝線スペクトル、エキシマレーザに代表される遠紫外線、極紫外線(EUV光)、X線、電子線等の活性光線(活性エネルギー線)が挙げられる。
本開示における化学構造式は、水素原子を省略した簡略構造式で記載する場合もある。
本開示において、「質量%」と「重量%」とは同義であり、「質量部」と「重量部」とは同義である。
本開示において、2以上の好ましい態様の組み合わせは、より好ましい態様である。
本開示において、「透明」とは、波長400nm~700nmの可視光の平均透過率が、80%以上であることを意味し、90%以上であることが好ましい。
本開示において、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、株式会社日立製作所製の分光光度計U-3310を用いて測定できる。
本開示における重量平均分子量(Mw)及び数平均分子量(Mn)は、特に断りのない限り、TSKgel GMHxL、TSKgel G4000HxL、TSKgel G2000HxL(何れも東ソー株式会社製の商品名)のカラムを使用したゲルパーミエーションクロマトグラフィ(GPC)分析装置により、溶剤THF(テトラヒドロフラン)、示差屈折計により検出し、標準物質としてポリスチレンを用いて換算した分子量である。
本開示において、特段の断りがない限り、金属元素の含有量は、誘導結合プラズマ(ICP:Inductively Coupled Plasma)分光分析装置を用いて測定した値である。
本開示において、特段の断りがない限り、屈折率は、波長550nmでエリプソメーターを用いて測定した値である。
本開示において、特段の断りがない限り、色相は、色差計(CR-221、ミノルタ株式会社製)を用いて測定した値である。
本開示において、「アルカリ可溶性」とは、液温が22℃である炭酸ナトリウムの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。
本開示において「水溶性」とは、液温が22℃であるpH7.0の水100gへの溶解度が0.1g以上であることを意味する。したがって、例えば、水溶性樹脂とは、上述の溶解度条件を満たす樹脂を意図する。
本開示において、「固形分」とは、溶剤を除いたすべての成分を意味する。
本開示において、転写フィルムが備える各層の厚さは、転写フィルムの主面に対し垂直な方向の断面を走査型電子顕微鏡(SEM)により観察し、得られた観察画像に基づいて各層の厚さを任意の5点以上計測し、その平均値を算出することにより、測定される。
本開示の一実施形態に係る転写フィルムは、仮支持体と、転写層と、保護フィルムと、をこの順に含み、25℃における上記転写層の上記保護フィルム側の貯蔵弾性率が、1.0×106Pa~3.0×108Paである。本開示において「転写層の保護フィルム側の貯蔵弾性率」は、転写層において保護フィルムに最も近い位置にある層の貯蔵弾性率によって規定される。例えば、転写層が複層構造を有する場合には、転写層に含まれる複数の層のうち保護フィルムに最も近い位置にある層の貯蔵弾性率を「転写層の保護フィルム側の貯蔵弾性率」といい、転写層が単層構造を有する場合には、単一の転写層の貯蔵弾性率を「転写層の保護フィルム側の貯蔵弾性率」という。25℃における転写層の保護フィルム側の貯蔵弾性率が1.0×106Pa以上であると、剥離された保護フィルムの表面への転写層の付着が抑制され、解像性の低下も抑制される。25℃における転写層の保護フィルム側の貯蔵弾性率が3.0×108Pa以下であると、対象物(例えば、基板)への転写層の転写において転写層と対象物との密着性が向上し、解像性も向上する。したがって、本開示の一実施形態によれば、優れた解像性を有する転写フィルムが提供される。
(2)「仮支持体/中間層/感光層/保護フィルム」
(3)「仮支持体/熱可塑性樹脂層/水溶性樹脂層/感光層/保護フィルム」
本開示の一実施形態に係る転写フィルムは、仮支持体を含む。仮支持体は、転写層を支持し、かつ、剥離可能な支持体である。
本開示の一実施形態に係る転写フィルムは、転写層を含む。25℃における転写層の保護フィルム側の貯蔵弾性率は、1.0×106Pa~3.0×108Paである。25℃における転写層の保護フィルム側の貯蔵弾性率が1.0×106Pa以上であると、剥離された保護フィルムの表面への転写層の付着が抑制され、解像性の低下も抑制される。25℃における転写層の保護フィルム側の貯蔵弾性率が3.0×108Pa以下であると、対象物(例えば、基板)への転写層の転写において転写層と対象物との密着性が向上し、解像性も向上する。解像性の観点から、25℃における転写層の保護フィルム側の貯蔵弾性率は、1.0×106Pa~2.0×108Paであることが好ましく、1.0×107Pa~1.0×108Paであることがより好ましい。
感光層は、例えば、基板の上に転写された後、露光及び現像によってパターンを形成できる。感光層は、ネガ型感光層又はポジ型感光層であってもよい。感光層は、ネガ型感光層であることが好ましい。感光層がネガ型感光層である場合、形成されるパターンは硬化層に該当する。感光層がネガ型感光層である場合、ネガ型感光層は、樹脂、重合性化合物及び重合開始剤を含むことが好ましい。また、感光層がネガ型感光層である場合、樹脂の一部又は全部としてアルカリ可溶性樹脂が含まれることも好ましい。つまり、一態様において、感光層は、アルカリ可溶性樹脂を含む樹脂、重合性化合物及び重合開始剤を含むことが好ましい。感光層は、感光層の全質量に対し、10質量%~90質量%のアルカリ可溶性樹脂、5質量%~70質量%のエチレン性不飽和化合物及び0.01質量%~20質量%の光重合開始剤を含むことが好ましい。
感光層は、アルカリ可溶性樹脂を含むことが好ましい。アルカリ可溶性樹脂としては、例えば、エッチングレジストに用いられる公知のアルカリ可溶性樹脂が好適に挙げられる。また、アルカリ可溶性樹脂は、バインダーポリマーであることが好ましい。アルカリ可溶性樹脂は、酸基を有するアルカリ可溶性樹脂であることが好ましい。アルカリ可溶性樹脂としては、後述する重合体Aが好ましい。
アルカリ可溶性樹脂の、感光層の全質量に対する割合は、好ましくは10質量%~90質量%であり、より好ましくは30質量%~70質量%であり、更に好ましくは40質量%~60質量%である。感光層に対するアルカリ可溶性樹脂の割合を90質量%以下にすることは、現像時間を制御する観点から好ましい。一方で、感光層に対するアルカリ可溶性樹脂の割合を10質量%以上にすることは、耐エッジフューズ性を向上させる観点から好ましい。
感光層がネガ型感光層である場合、ネガ型感光層は、重合性基を有する重合性化合物を含むことが好ましい。本開示において、「重合性化合物」とは、重合開始剤の作用を受けて重合する化合物であって、上述したアルカリ可溶性樹脂とは異なる化合物を意味する。重合性化合物の分子量は、1,500以下であることが好ましい。重合性化合物の分子量は、150以上であることが好ましい。
感光層がネガ型感光層である場合、ネガ型感光層は、重合開始剤を含むことが好ましい。重合開始剤は重合反応の形式に応じて選択され、例えば、熱重合開始剤、及び、光重合開始剤が挙げられる。また、重合開始剤としては、ラジカル重合開始剤、及び、カチオン重合開始剤が挙げられる。
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。
感光層は、露光部及び非露光部の視認性、現像後のパターン視認性、及び、解像性の観点から、色素を含有することが好ましく、発色時の波長範囲400nm~780nmにおける極大吸収波長が450nm以上であり、かつ、酸、塩基、又はラジカルにより極大吸収波長が変化する色素(単に「色素N」ともいう。)を含有することがより好ましい。色素Nを含有すると、詳細なメカニズムは不明であるが、隣接する層(例えば仮支持体及び中間層)との密着性が向上し、解像性により優れる。
感光層は、露光部及び非露光部の視認性並びに解像性の観点から、色素Nとしてラジカルにより極大吸収波長が変化する色素、及び、光ラジカル重合開始剤の両者を含有することが好ましい。
また、露光部及び非露光部の視認性の観点から、色素Nは、酸、塩基、又はラジカルにより発色する色素であることが好ましい。
感光層は、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観点から、熱架橋性化合物を含むことが好ましい。なお、本開示においては、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。熱架橋性化合物としては、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。中でも、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観点から、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、アルカリ可溶性樹脂及び/又はエチレン性不飽和化合物等が、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、感光層を硬化した膜を保護膜として使用する場合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。
感光層は、上述した成分以外の他の成分を含有してもよい。他の成分としては、例えば、ラジカル重合禁止剤、界面活性剤、増感剤、各種添加剤等が挙げられる。他の成分は、1種単独で使用してもよく、2種以上使用してもよい。
可塑剤及びヘテロ環状化合物としては、国際公開第2018/179640号の段落0097~0103及び0111~0118に記載された化合物が挙げられる。
感光層は、所定量の不純物を含んでいてもよい。不純物の具体例としては、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。中でも、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。
感光層は、上述したアルカリ可溶性樹脂の各構成単位に対応する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、アルカリ可溶性樹脂全質量に対して、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、1質量ppm以上が好ましく、10質量ppm以上がより好ましい。アルカリ可溶性樹脂の各構成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、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。
感光層の厚さは、現像性、及び、解像性の観点から、20μm以下であることが好ましく、10μm以下であることがより好ましく、8μm以下であることが更に好ましく、5μm以下であることが特に好ましく、1μm以上5μm以下であることが最も好ましい。
感光層の形成方法は、上記の成分を含有する層を形成可能な方法であれば特に制限されない。感光層の形成方法としては、例えば、アルカリ可溶性樹脂、エチレン性不飽和化合物、光重合開始剤及び溶剤等を含有する感光性樹脂組成物を調製し、中間層等の表面に感光性樹脂組成物を塗布し、感光性樹脂組成物の塗膜を乾燥することにより形成する方法が挙げられる。感光性樹脂組成物の塗膜の乾燥方法としては、加熱乾燥及び減圧乾燥が好ましい。なお、本開示において、「乾燥」とは、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。乾燥方法としては、例えば、自然乾燥、加熱乾燥、及び、減圧乾燥が挙げられる。上記した方法を単独で又は複数組み合わせて適用することができる。乾燥温度としては、80℃以上が好ましく、90℃以上がより好ましい。また、その上限値としては130℃以下が好ましく、120℃以下がより好ましい。温度を連続的に変化させて乾燥させることもできる。乾燥時間としては、20秒以上が好ましく、40秒以上がより好ましく、60秒以上が更に好ましい。また、その上限値としては特に制限されないが、600秒以下が好ましく、300秒以下がより好ましい。
中間層は、アルカリ可溶性樹脂及び重合性化合物を含むことが好ましい。アルカリ可溶性樹脂としては、例えば、既述した感光層の成分であるアルカリ可溶性樹脂及び後述する熱可塑性樹脂層の成分であるアルカリ可溶性樹脂が挙げられる。重合性化合物としては、例えば、既述した感光層の成分である重合性化合物が挙げられる。
熱可塑性樹脂層は、例えば、転写フィルムと基板との貼り合わせにおける基板への追従性を向上させ、基板と転写フィルムとの間の気泡の混入を抑制し、基板と転写フィルムとの密着性を向上させる。
熱可塑性樹脂層は、熱可塑性樹脂として、アルカリ可溶性樹脂を含有することが好ましい。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。
熱可塑性樹脂層は、発色時の波長範囲400nm~780nmにおける極大吸収波長が450nm以上であり、酸、塩基、又はラジカルにより極大吸収波長が変化する色素(単に「色素B」ともいう。)を含有することが好ましい。色素Bの好ましい態様は、後述する点以外は、色素Nの好ましい態様と同様である。
熱可塑性樹脂層は、光により酸、塩基又はラジカルを発生する化合物(単に「化合物C」ともいう。)を含有してもよい。化合物Cとしては、紫外線及び可視光線等の活性光線を受けて、酸、塩基、又はラジカルを発生する化合物が好ましい。化合物Cとしては、公知の、光酸発生剤、光塩基発生剤、及び、光ラジカル重合開始剤(すなわち、光ラジカル発生剤)を用いることができる。中でも、光酸発生剤が好ましい。
熱可塑性樹脂層は、解像性、隣接する層との密着性及び現像性の観点から、可塑剤を含有することが好ましい。
熱可塑性樹脂層は、厚さ均一性の観点から、界面活性剤を含有することが好ましい。界面活性剤としては、上述した感光層が含有してもよい界面活性剤が挙げられ、好ましい態様も同じである。
熱可塑性樹脂層は、増感剤を含有してもよい。増感剤としては、特に制限されず、上述した感光層が含有してもよい増感剤が挙げられる。
熱可塑性樹脂層は、上記成分以外に、必要に応じて公知の添加剤を含有してもよい。また、熱可塑性樹脂層については、特開2014-85643号公報の段落0189~0193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。
熱可塑性樹脂層の層厚は、特に制限されないが、隣接する層との密着性の観点から、1μm以上が好ましく、2μm以上がより好ましい。上限は特に制限されないが、現像性及び解像性の観点から、20μm以下が好ましく、10μm以下がより好ましく、5μm以下が更に好ましい。
熱可塑性樹脂層の形成方法は、上記の成分を含有する層を形成可能な方法であれば特に制限されない。熱可塑性樹脂層の形成方法としては、例えば、上記の成分と溶剤とを含有する熱可塑性樹脂組成物を調製し、仮支持体等の表面に熱可塑性樹脂組成物を塗布し、熱可塑性樹脂組成物の塗膜を乾燥することにより形成する方法が挙げられる。
熱可塑性樹脂組成物は、熱可塑性樹脂組成物の粘度を調節し、熱可塑性樹脂層の形成を容易にするため、溶剤を含有することが好ましい。
熱可塑性樹脂組成物に含有される溶剤としては、上述した感光性樹脂組成物が含有してもよい溶剤が挙げられ、好ましい態様も同じである。
熱可塑性樹脂組成物を塗布する際における溶剤の含有量は、熱可塑性樹脂組成物中の全固形分100質量部に対し、50質量部~1,900質量部が好ましく、100質量部~900質量部がより好ましい。
例えば、熱可塑性樹脂層に含有される各成分を上記溶剤に溶解させた溶液を予め調製し、得られた溶液を所定の割合で混合することにより、熱可塑性樹脂組成物が調製した後、
得られた熱可塑性樹脂組成物を仮支持体の表面に塗布し、熱可塑性樹脂組成物の塗膜を乾燥させることにより、熱可塑性樹脂層が形成される。
また、後述する保護フィルム上に、感光層及び中間層を形成した後、中間層の表面に熱可塑性樹脂層を形成してもよい。
水溶性樹脂層は、水溶性樹脂を含有することが好ましい。水溶性樹脂としては、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。水溶性樹脂層に含有される樹脂は、複数層間の成分の混合を抑制する観点から、感光層に含有される重合体A、及び、熱可塑性樹脂層に含有される熱可塑性樹脂(例えば、アルカリ可溶性樹脂)のいずれとも異なる樹脂であることが好ましい。
水溶性樹脂層の厚みが上記の範囲内であると、酸素遮断性を低下させることがなく、複数層を塗布する際及び塗布後の保存の際における成分の混合を抑制でき、また、現像時の水溶性樹脂層除去時間の増大を抑制できるためである。
水混和性の有機溶剤としては、例えば、炭素数1~3のアルコール、アセトン、エチレングリコール及びグリセリンが挙げられ、炭素数1~3のアルコールが好ましく、メタノール又はエタノールがより好ましい。
本開示の一実施形態に係る転写フィルムは、保護フィルムを含む。保護フィルムを構成する材料としては、樹脂フィルム及び紙が挙げられ、強度及び可撓性の観点から、樹脂フィルムが好ましい。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、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。中でも、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い。
本開示の一実施形態に係る転写フィルムにおいて、感光層を硬化した硬化膜の120℃における破断伸びが15%以上であり、仮支持体の感光層側の表面の算術平均粗さRaが50nm以下であり、保護フィルムの感光層側の表面の算術平均粗さRaが150nm以下であることが好ましい。
X×Y<1,500 式(R1)
ここで、上記式(R1)中、Xは、感光層を硬化した硬化膜の120℃における破断伸びの値(%)を表し、Yは、仮支持体の感光層側の表面の算術平均粗さRaの値(nm)を表す。X×Yは、750以下がより好ましい。
Y≦Z 式(R2)
ここで、上記式(R2)中、Yは、仮支持体の感光層側の表面の算術平均粗さRaの値(nm)を表し、Zは、保護フィルムの感光層側の表面の算術平均粗さRaの値(nm)を表す。
本開示に係る転写フィルムの製造方法は、特に制限されず、公知の製造方法、例えば、公知の各層の形成方法を用いることができる。以下、図1を参照しながら、本開示に係る転写フィルムの製造方法について説明する。ただし、本開示に係る転写フィルムは、図1に示す構成を有するものに制限されない。
本開示の一実施形態に係る導体パターンの製造方法は、本開示の一実施形態に係る転写フィルムの保護フィルムを剥離すること(以下、「保護フィルムの剥離工程」という場合がある。)と、上記転写フィルムと、金属層を含む基板とを貼り合わせて、上記基板の上記金属層の上に、上記転写層及び上記仮支持体をこの順に配置すること(以下、「貼り合わせ工程」という場合がある。)と、上記転写層を露光すること(以下、「露光工程」という場合がある。)と、上記転写層を現像し、レジストパターンを形成すること(以下、「レジストパターン形成工程」という場合がある。)と、上記レジストパターンに覆われていない上記金属層に対してエッチング又はめっきを行うこと(以下、「エッチング又はめっき工程」という場合がある。)と、上記レジストパターンを剥離すること(以下、「レジストパターンの剥離工程」という場合がある。)と、をこの順に含む。上記した導体パターンの製造方法は、貼り合わせ工程と露光工程との間に、仮支持体を剥離すること(以下、「仮支持体の剥離工程」という場合がある。)を含んでもよい。上記した導体パターンの製造方法は、露光工程の前に、仮支持体の剥離工程を含んでもよい。
保護フィルムの剥離工程では、転写フィルムの保護フィルムを剥離する。保護フィルムの剥離方法としては、公知の方法が適用される。保護フィルムの剥離工程では、例えば、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使用できる。
貼り合わせ工程では、転写フィルムと、金属層を含む基板とを貼り合わせて、基板の金属層の上に、転写層及び仮支持体をこの順に配置する。転写フィルムと基板との貼り合わせは、転写フィルムと基板とを圧着させることを含むことが好ましい。
仮支持体の剥離工程では、仮支持体を剥離する。具体的に、貼り合わせ工程によって得られた積層体の仮支持体を剥離する。仮支持体の剥離によって、通常、転写層が露出する。仮支持体の剥離方法としては、公知の方法が適用される。仮支持体の剥離工程では、例えば、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使用できる。
露光工程では、転写層を露光する。露光工程では、転写層をパターン露光することが好ましい。「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露光部と未露光部との位置関係は特に制限されず、適宜調整される。露光は、基板から転写層に向かう方向に沿って実施されてもよく、転写層から基板に向かう方向に沿って実施されてもよい。
レジストパターン形成工程では、転写層を現像し、レジストパターンを形成する。現像は、現像液を用いて行うことができる。
エッチング又はめっき工程では、レジストパターンに覆われていない金属層に対してエッチング又はめっきを行う。レジストパターンに覆われていない金属層に対してエッチングを行うと、レジストパターンに覆われていない金属層が除去され、導体パターンが形成される。レジストパターンに覆われていない金属層に対してめっきを行うと、レジストパターンに覆われていない金属層の上に導体パターンが形成される。後者の方法は、セミアディティブ法と称されることがある。ある実施形態では、レジストパターンに覆われていない金属層に対してエッチングを行うことが好ましい。ある実施形態では、レジストパターンに覆われていない金属層に対してめっきを行うことが好ましい。
レジストパターンの剥離工程では、レジストパターンを剥離する。レジストパターンの剥離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。ジストパターンの剥離方法としては、液温が好ましくは30℃~80℃、より好ましくは50℃~80℃である撹拌中の除去液に、レジストパターンを有する基板を、1分間~30分間浸漬する方法が挙げられる。
ある実施形態に係る導体パターンの製造方法は、レジストパターン形成工程によって得られたレジストパターンを、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。導体パターンの製造方法が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。
導体パターンの製造方法に適用可能な工程としては、例えば、特開2006-23696号公報の段落0035~段落0051に記載の工程も挙げられる。導体パターンの製造方法に適用可能な工程としては、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及び国際公開第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も挙げられるが、これらの工程に制限されない。
導体パターンは、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導体パターンを備えた装置としては、例えば、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。
本開示の一実施形態に係るタッチパネルの製造方法は、本開示の一実施形態に係る転写フィルムの保護フィルムを剥離すること(すなわち、「保護フィルムの剥離工程」)と、上記転写フィルムと、金属層を含む基板とを貼り合わせて、上記基板の上記金属層の上に、転写層及び仮支持体をこの順に配置すること(すなわち、「貼り合わせ工程」)と、上記転写層を露光すること(すなわち、「露光工程」)と、上記転写層を現像し、レジストパターンを形成すること(すなわち、「レジストパターン形成工程」)と、上記レジストパターンに覆われていない上記金属層に対してエッチング又はめっきを行うこと(すなわち、「エッチング又はめっき工程」)と、上記レジストパターンを剥離すること(すなわち、「レジストパターンの剥離工程」)と、をこの順に含む。上記したタッチパネルの製造方法は、貼り合わせ工程と露光工程との間に、仮支持体を剥離すること(すなわち、「仮支持体の剥離工程」)を含んでもよい。上記したタッチパネルの製造方法は、露光工程の前に、仮支持体の剥離工程を含んでもよい。
仮支持体1は、以下の方法により作製された。
下記に示す配合で、各成分を混合し、粒子含有層形成組成物1を得た。粒子含有層形成組成物1を調製後、6μmフィルター(F20、マーレフィルターシステムズ株式会社製)にてろ過し、続いて、2x6ラジアルフロースーパーフォビック(ポリポア株式会社製)を用いて、膜脱気した。
・ノニオン系界面活性剤(ナロアクティーCL95、三洋化成工業株式会社製、固形分100質量%)0.7部
・アニオン系界面活性剤(ラピゾールA-90、日油株式会社製、固形分1質量%に水で希釈)114.4部
・カルナバワックス分散物(セロゾール524、中京油脂株式会社製、固形分30質量%)7部
・カルボジイミド化合物(カルボジライトV-02-L2、日清紡ケミカル株式会社製、固形分10質量%に水で希釈)20.9部
・マット剤(スノーテックスXL、日産化学株式会社製、固形分40質量%、平均粒子径50nm):2.8部
・水:690.2部
特許第5575671号公報に記載のクエン酸キレート有機チタン錯体を重合触媒としたポリエチレンテレフタレートのペレットを、含水率50ppm以下に乾燥させた後、直径30mmの1軸混練押出し機のホッパーに投入し、280℃で溶融して押出した。この溶融体(メルト)を、濾過器(孔径2μm)を通した後、ダイから25℃の冷却ロールに押出し、未延伸フィルムを得た。なお、押出されたメルトは、静電印加法を用い冷却ロールに密着させた。
固化した未延伸フィルムに対し、以下の方法で逐次2軸延伸を施し、厚さ16μmのポリエステルフィルムと厚さ40nmの粒子含有層とを含む仮支持体を得た。
未延伸フィルムを周速の異なる2対のニップロールの間に通し、縦方向(搬送方向)に延伸した。なお、予熱温度を75℃、延伸温度を90℃、延伸倍率を3.4倍、延伸速度を1300%/秒として実施した。
縦延伸したフィルムの片面に、粒子含有層形成組成物1を、製膜後40nmの厚さとなるように、バーコーターで塗布した。
上記縦延伸と塗布を行ったフィルムに対し、テンターを用いて下記条件にて横延伸した。
予熱温度:110℃
延伸温度:120℃
延伸倍率:4.2倍
延伸速度:50%/秒
縦延伸及び横延伸を終えた後の二軸延伸フィルムを下記条件で熱固定した。
熱固定温度:227℃
熱固定時間:6秒
熱緩和温度:190℃
熱緩和率:4%
熱固定及び熱緩和の後、両端をトリミングし、端部に幅10mmで押出し加工(ナーリング)した後、張力40kg/mで巻き取った。なお、幅は1.5m、巻長は6300mであった。得られたフィルムロールを仮支持体1とした。仮支持体1のヘーズは0.2であった。なお、ヘーズはヘーズメーター(日本電色工業株式会社製、NDH2000)を用いて全光ヘーズとして測定した。また、150℃、30分加熱による熱収縮率は、MD(搬送方向、Machine Direction)側で1.0%であり、TD(フィルムの面上において搬送方向と直交する方向、Transverse Direction)側で0.2%であった。また、粒子含有層の膜厚は断面TEM写真から測定し、40nmであった。粒子含有層に含まれる粒子の平均粒子径を、株式会社日立ハイテクノロジーズ製HT-7700型透過型電子顕微鏡(TEM)を用いて、上述の方法で測定したところ、50nmであった。
以下の成分を混合し、水溶性樹脂層の材料1として使用される水溶性樹脂組成物を得た。
・イオン交換水:38.12部
・メタノール(三菱ガス化学株式会社製):57.17部
・クラレポバール 4-88LA(ポリビニルアルコール、株式会社クラレ製):3.22部
・ポリビニルピロリドンK-30(株式会社日本触媒製):1.49部
・メガファックF-444(フッ素系界面活性剤、DIC株式会社製):0.0035部
メチルエチルケトン(三協化学株式会社製、60部)及びプロピレングリコールモノメチルエーテルアセテート(昭和電工株式会社製、40部)を含む混合溶剤を準備した。表1に記載の各成分と、混合溶剤とを混合して、表1において、材料1~4及び5A~5Eで示される感光性樹脂組成物をそれぞれ調製した。なお、混合溶剤の添加量は、感光性組成物の固形分濃度が13質量%となるように調整した。
表2に記載された成分を混合し、熱可塑性樹脂層の材料として使用される熱可塑性樹脂組成物を得た。
・A-2:ベンジルメタクリレート/メタクリル酸/アクリル酸共重合体(75質量%/10質量%/15質量%、重量平均分子量:30,000、Tg:75℃、酸価:186mgKOH/g)
・B-1:下記に示す構造の化合物(酸により発色する色素)
・D-4:8UX-015A(多官能ウレタンアクリレート化合物、大成ファインケミカル株式会社)
・D-5:アロニックスTO-2349(カルボキシ基を有する多官能アクリレート化合物、東亞合成株式会社)
・E-1:メガファックF552(DIC株式会社)
・F-1:フェノチアジン(富士フイルム和光純薬株式会社)
・F-2:CBT-1(城北化学工業株式会社)
・MEK:メチルエチルケトン
・PGME:プロピレングリコールモノメチルエーテル
・PGMEA:プロピレングリコールモノメチルエーテルアセテート
表3の記載に従って、仮支持体の上に、必要に応じて熱可塑性樹脂層、必要に応じて水溶性樹脂層、そして、感光層をこの順に形成した。熱可塑性樹脂は、熱可塑性樹脂組成物の塗布及び乾燥によって形成された。水溶性樹脂層は、水溶性樹脂組成物の塗布及び乾燥によって形成された。感光層は、感光性樹脂組成物の塗布及び乾燥によって形成された。表3の記載に従って、感光層の上に保護フィルムを設け、転写フィルムを得た。
スパッタリングによってポリエチレンテレフタレートフィルムの上に200nmの厚さを有する銅層を形成し、銅基板を得た。得られた銅基板は、以下の評価に使用される。
粘弾性測定装置(ティー・エイ・インスツルメント社製レオメータDHR-2)、20mmφのパラレルプレート及びペルチェプレート(Gap:約0.5mm)を用いて、温度20℃~125℃、昇温速度5℃/分、周波数1Hz及び歪み0.5%の条件で、熱可塑性樹脂層及び感光層の貯蔵弾性率を測定した。具体的に、測定前にペルチェプレートの上で80℃~95℃で試料を溶融させ、降温速度5℃/分で20℃まで冷却した後、Gap一定モードで測定した。貯蔵弾性率については25℃での値を採用する。測定結果を表3に示す。
以下の方法によって、転写層に面する仮支持体の表面の粗さRa及び仮支持体に面する転写層の表面の粗さRaを測定した。転写フィルムから保護フィルムを剥離し、ラミネートロール温度100℃、線圧0.6MPa及び線速度(ラミネート速度)4.0m/分の条件で転写フィルムを銅基板に貼り付けた。3次元光学プロファイラー(New View7300、Zygo社)を用いて、対象面の表面プロファイルを得た。測定及び解析ソフトウェアとして、「MetroPro ver8.3.2」の「Microscope Application」を用いた。上記ソフトによって「Surface Map」画面を表示し、「Surface Map」画面中でヒストグラムデータを得た。得られたヒストグラムデータから、対象面の算術平均粗さRaを算出した。測定結果を表3に示す。
以下の方法によって、保護フィルムの剥離強度を測定した。転写フィルムの保護フィルムの表面にテープ(日東電工株式会社製PRINTACK)を貼りつけた後、70mm×10mmの大きさにカットして試料を作製した。試料の仮支持体を試料台の上に固定した。引張圧縮試験機(株式会社今田製作所製SV-55)を用いて、180度の方向に5.5mm/秒でテープを引っ張って、試料から保護フィルムを剥離して、保護フィルムの剥離強度を測定した。測定結果を表3に示す。
以下の方法によって、仮支持体の剥離強度を測定した。転写フィルムから保護フィルムを剥離し、ラミネートロール温度100℃、線圧0.6MPa及び線速度(ラミネート速度)4.0m/分の条件で転写フィルムを銅基板に貼り付けた。仮支持体の表面にテープ(NITTO製PRINTACK)を貼りつけた後、70mm×10mmにカットして試料を作製した。試料の銅基板を試料台の上に固定した。引張圧縮試験機(株式会社今田製作所製SV-55)を用いて、180度の方向に5.5mm/秒でテープを引っ張って、試料から仮支持体を剥離して、仮支持体の剥離強度を測定した。測定結果を表3に示す。
転写フィルムから保護フィルムを剥離し、ラミネートロール温度100℃、線圧0.6MPa及び線速度(ラミネート速度)4.0m/分の条件で転写フィルムを銅基板に貼り付けた。得られた積層体から仮支持体を剥離し、銅基板の上に配置された転写層と、ラインアンドスペースパターンを有するフォトマスクとを接触させて、超高圧水銀灯を用いて転写層を露光した。露光された転写層に対して、28℃の1.0質量%炭酸ナトリウム水溶液を用い、40秒間のシャワー現像を施した。上記した一連の手順をフォトマスクのラインアンドスペース(すなわち、L/S)を5/5~8/8の範囲で変更して実施し、以下の基準に従って、解像性を評価した。評価結果を表3に示す。
A:L/S=5/5~L/S=6/6の条件で樹脂パターン間に残渣なく解像できる。
B:L/S=7/7~L/S=8/8の条件でパターン間に残渣なく解像できる。
C:L/S=8/8の条件では解像できない。
転写フィルムから保護フィルムを剥離し、ラミネートロール温度100℃、線圧0.6MPa及び線速度(ラミネート速度)4.0m/分の条件で転写フィルムを銅基板に貼り付けた。光学顕微鏡を用いて、得られた積層体を観察した。幅1mm及び長さ1mmの領域における転写フィルムと銅基板との間にある泡を数えた。観察された泡の数に基づき、以下の基準に従って、ラミネート性を評価した。評価結果を表3に示す。
A:0個
B:1個以上10個未満
C:10個以上
転写フィルムから保護フィルムを剥離し、保護フィルムの表面における転写層の付着物の有無を目視で確認した。次に、ラミネートロール温度100℃、線圧0.6MPa及び線速度(ラミネート速度)4.0m/分の条件で転写フィルムを銅基板に貼り付けた。得られた積層体から仮支持体を剥離し、仮支持体の表面における転写層の付着物の有無を目視で確認した。平面視において、保護フィルムの表面における幅100mm及び長さ100mmの領域で観察された転写層の付着物の面積を求め、そして、仮支持体の表面における幅100mm及び長さ100mmの領域で観察された転写層の付着物の面積を求めた。観察対象の領域の面積(すなわち、20,000mm2)に占める転写層の付着物の面積の割合を求め、以下の基準に従って、剥離不良を評価した。評価結果を表3に示す。
A:0%
B:0%超0.1%未満
C:0.1%以上
表3に記載された「16FB40」は、東レ株式会社製ルミラー16FB40を意味する。
表3に記載された「FG201」は、王子エフテック株式会社製アルファンFG-201を意味する。
表3に記載された「M/B」は、アルカリ可溶性樹脂に対する重合性化合物の質量比を意味する。
表3に記載された「10^5」は、105を意味する。
表3に記載された「10^6」は、106を意味する。
表3に記載された「10^7」は、107を意味する。
表3に記載された「10^8」は、108を意味する。
表3において「仮支持体」の欄に記載された「表面の粗さRa」は、転写層に面する仮支持体の表面の粗さRaを意味する。
表3において「転写層」の欄に記載された「表面の粗さRa」は、仮支持体に面する転写層の表面の粗さRaを意味する。
10:仮支持体
20:中間層
30:感光層
40:保護フィルム
100:転写フィルム
GR:遮光部(非画像部)
EX:露光部(画像部)
DL:アライメント合せの枠
本明細書に記載された全ての文献、特許出願、及び、技術規格は、個々の文献、特許出願、及び、技術規格が参照により取り込まれることが具体的かつ個々に記された場合と同程度に、本明細書中に参照により取り込まれる。
Claims (14)
- 仮支持体と、転写層と、保護フィルムと、をこの順に含み、
25℃における前記転写層の前記保護フィルム側の貯蔵弾性率が、1.0×106Pa~3.0×108Paである、
転写フィルム。 - 25℃における前記転写層の前記仮支持体側の貯蔵弾性率が、1.0×106Pa以上である、請求項1に記載の転写フィルム。
- 前記仮支持体に面する前記転写層の表面の粗さRaが、0.1nm~15nmである、請求項1又は請求項2に記載の転写フィルム。
- 前記転写層に面する前記仮支持体の表面の粗さRaが、0.1nm~15nmである、請求項1~請求項3のいずれか1項に記載の転写フィルム。
- 前記転写層が、感光層である、請求項1~請求項4のいずれか1項に記載の転写フィルム。
- 前記転写層が、中間層及び感光層を含む、請求項1~請求項4のいずれか1項に記載の転写フィルム。
- 前記中間層が、アルカリ可溶性樹脂及び重合性化合物を含み、前記中間層における前記アルカリ可溶性樹脂の質量に対する前記重合性化合物の質量の比が、0.5以上である、請求項6に記載の転写フィルム。
- 前記中間層の厚さが、10μm以下である、請求項6又は請求項7に記載の転写フィルム。
- 前記中間層が、熱可塑性樹脂層及び水溶性樹脂層を含む、請求項6~請求項8のいずれか1項に記載の転写フィルム。
- 前記感光層が、アルカリ可溶性樹脂及び重合性化合物を含み、前記感光層における前記アルカリ可溶性樹脂の質量に対する前記重合性化合物の質量の比が、0.6以上である、請求項5~請求項9のいずれか1項に記載の転写フィルム。
- 前記感光層の厚さが、10μm以下である、請求項5~請求項10のいずれか1項に記載の転写フィルム。
- 請求項1~請求項11のいずれか1項に記載の転写フィルムの保護フィルムを剥離することと、
前記転写フィルムと、金属層を含む基板とを貼り合わせて、前記基板の前記金属層の上に、前記転写層及び前記仮支持体をこの順に配置することと、
前記転写層を露光することと、
前記転写層を現像し、レジストパターンを形成することと、
前記レジストパターンに覆われていない前記金属層に対してエッチング又はめっきを行うことと、
前記レジストパターンを剥離することと、をこの順に含む、
導体パターンの製造方法。 - 請求項1~請求項11のいずれか1項に記載の転写フィルムの保護フィルムを剥離することと、
前記転写フィルムと、金属層を含む基板とを貼り合わせて、前記基板の前記金属層の上に、前記転写層及び前記仮支持体をこの順に配置することと、
前記仮支持体を剥離することと、
前記転写層を露光することと、
前記転写層を現像し、レジストパターンを形成することと、
前記レジストパターンに覆われていない前記金属層に対してエッチング又はめっきを行うことと、
前記レジストパターンを剥離することと、をこの順に含む、
導体パターンの製造方法。 - 前記仮支持体の剥離における前記仮支持体の剥離強度が、0.3mN/mm~2.0mN/mmである、請求項13に記載の導体パターンの製造方法。
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