Classifications

• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
  • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
  • G03F7/029—Inorganic compounds; Onium compounds; Organic compounds having hetero atoms other than oxygen, nitrogen or sulfur
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
  • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
  • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
  • G03F7/031—Organic compounds not covered by group G03F7/029
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
  • G03F7/095—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having more than one photosensitive layer
• • 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
  • G03F7/16—Coating processes; Apparatus therefor
  • G03F7/161—Coating processes; Apparatus therefor using a previously coated surface, e.g. by stamping or by transfer lamination
• • 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
  • G03F7/2002—Exposure; Apparatus therefor with visible light or UV light, through an original having an opaque pattern on a transparent support, e.g. film printing, projection printing; by reflection of visible or UV light from an original such as a printed image
  • G03F7/2004—Exposure; Apparatus therefor with visible light or UV light, through an original having an opaque pattern on a transparent support, e.g. film printing, projection printing; by reflection of visible or UV light from an original such as a printed image characterised by the use of a particular light source, e.g. fluorescent lamps or deep UV light
• • 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
  • G03F7/26—Processing photosensitive materials; Apparatus therefor
  • G03F7/40—Treatment after imagewise removal, e.g. baking
• • G—PHYSICS
  • G06—COMPUTING OR CALCULATING; COUNTING
  • G06F—ELECTRIC DIGITAL DATA PROCESSING
  • G06F3/00—Input arrangements for transferring data to be processed into a form capable of being handled by the computer; Output arrangements for transferring data from processing unit to output unit, e.g. interface arrangements
  • G06F3/01—Input arrangements or combined input and output arrangements for interaction between user and computer
  • G06F3/03—Arrangements for converting the position or the displacement of a member into a coded form
  • G06F3/041—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means
  • G06F3/0416—Control or interface arrangements specially adapted for digitisers
• • G—PHYSICS
  • G06—COMPUTING OR CALCULATING; COUNTING
  • G06F—ELECTRIC DIGITAL DATA PROCESSING
  • G06F3/00—Input arrangements for transferring data to be processed into a form capable of being handled by the computer; Output arrangements for transferring data from processing unit to output unit, e.g. interface arrangements
  • G06F3/01—Input arrangements or combined input and output arrangements for interaction between user and computer
  • G06F3/03—Arrangements for converting the position or the displacement of a member into a coded form
  • G06F3/041—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means
  • G06F3/044—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means by capacitive means
• • G—PHYSICS
  • G06—COMPUTING OR CALCULATING; COUNTING
  • G06F—ELECTRIC DIGITAL DATA PROCESSING
  • G06F2203/00—Indexing scheme relating to G06F3/00 - G06F3/048
  • G06F2203/041—Indexing scheme relating to G06F3/041 - G06F3/045
  • G06F2203/04103—Manufacturing, i.e. details related to manufacturing processes specially suited for touch sensitive devices
• • G—PHYSICS
  • G06—COMPUTING OR CALCULATING; COUNTING
  • G06F—ELECTRIC DIGITAL DATA PROCESSING
  • G06F3/00—Input arrangements for transferring data to be processed into a form capable of being handled by the computer; Output arrangements for transferring data from processing unit to output unit, e.g. interface arrangements
  • G06F3/01—Input arrangements or combined input and output arrangements for interaction between user and computer
  • G06F3/03—Arrangements for converting the position or the displacement of a member into a coded form
  • G06F3/041—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means
  • G06F3/0416—Control or interface arrangements specially adapted for digitisers
  • G06F3/04164—Connections between sensors and controllers, e.g. routing lines between electrodes and connection pads

Definitions

• the present invention relates to a method for producing a transfer film and a laminate.
• Patent Document 1 describes a film (transfer film) including a photosensitive resin layer (photosensitive composition layer) containing an alkali-soluble binder polymer, a photopolymerizable compound, and a photopolymerization initiator. It is disclosed.
• the edge portion of the formed pattern is linear when the pattern on the substrate is visually recognized from the normal direction of the substrate without causing unevenness.
• the edge shape is excellent when the edge portion of the pattern has no unevenness and is linear as described above.
• the pattern formed from the photosensitive composition layer is also required to have excellent scratch resistance.
• the photosensitive composition layer contains a photopolymerization initiator, an alkali-soluble resin, and a polymerizable compound.
• the photopolymerization initiator comprises a first photopolymerization initiator and a second photopolymerization initiator.
• the molar extinction coefficient ⁇ 1 of the first photopolymerization initiator at a wavelength of 365 nm is 500 L / mol ⁇ cm or more.
• a transfer film in which the ratio of the molar extinction coefficient ⁇ 2 of the second photopolymerization initiator at a wavelength of 365 nm to the molar extinction coefficient ⁇ 3 of the second photopolymerization initiator at a wavelength of 313 nm is 0.200 or less.
• the transfer film according to (1) or (2), wherein the maximum absorption wavelength of the second photopolymerization initiator is 320 nm or less.
• the second photopolymerization initiator contains at least one selected from the group consisting of an aminobenzoate-based photopolymerization initiator, an alkylphenone-based photopolymerization initiator, and an acylphosphine oxide-based photopolymerization initiator. , (1) to (4).
• the transfer film according to any one of. (9) The transfer film according to any one of (1) to (8), wherein the photosensitive composition layer is used for forming an electrode protective film. (10) Further, a refractive index adjusting layer is included. The refractive index adjusting layer is arranged in contact with the photosensitive composition layer, The transfer film according to any one of (1) to (9), wherein the refractive index of the refractive index adjusting layer is 1.60 or more. (11) The transfer film is attached to the substrate so that the photosensitive composition layer side of the transfer film according to any one of (1) to (10) faces the substrate having the conductive layer, and the photosensitive composition layer is attached.
• the pattern has a post-exposure step of irradiating the pattern with light exposed to the second photopolymerization initiator.
• a method for producing a laminate which comprises a peeling step of peeling a temporary support from a substrate with a photosensitive composition layer between a bonding step and an exposure step, or between an exposure step and a developing step. .. (12) The method for manufacturing a laminate according to (11), wherein the substrate having a conductive layer is a substrate having a sensor electrode portion for a touch panel and a lead-out wiring portion conducting with the sensor electrode for a touch panel.
• a transfer film having a photosensitive composition layer capable of forming a pattern having excellent scratch resistance and an excellent edge shape. Further, according to the present invention, it is also possible to provide a method for producing a laminate using the transfer film.
• the numerical range represented by using "-" in the present specification means a range including the numerical values before and after "-" as the lower limit value and the upper limit value.
• the upper limit value or the lower limit value described in a certain numerical range may be replaced with the upper limit value or the lower limit value of another numerical range described stepwise.
• the upper limit value or the lower limit value described in a certain numerical range may be replaced with the value shown in the examples.
• process in the present specification is not limited to an independent process, and even if it cannot be clearly distinguished from other processes, the term “process” will be used as long as the intended purpose of the process is achieved. included.
• transparent means that the average transmittance of visible light having a wavelength of 400 to 700 nm is 80% or more, and is preferably 90% or more.
• the average transmittance of visible light is a value measured using a spectrophotometer, and can be measured using, for example, a spectrophotometer U-3310 manufactured by Hitachi, Ltd.
• the content ratio of each structural unit of the polymer is a molar ratio.
• the weight average molecular weight (Mw) and the number average molecular weight (Mn) in the present disclosure use columns of TSKgel GMHxL, TSKgel G4000HxL, and TSKgel G2000HxL (all trade names manufactured by Toso Co., Ltd.).
• the molecular weight is detected by THF (tetrahydrofuran) and a differential refractometer by a gel permeation chromatography (GPC) analyzer, and is converted using polystyrene as a standard substance.
• the molecular weight of a compound having a molecular weight distribution is the weight average molecular weight (Mw).
• Mw weight average molecular weight
• the refractive index is a value measured by an ellipsometer at a wavelength of 550 nm unless otherwise specified.
• (meth) acrylic is a concept that includes both acrylic and methacryl
• (meth) acryloxy group is a concept that includes both an acryloxy group and a metaacryloxy group.
• the transfer film of the present invention is characterized in that the photosensitive composition layer contains a first photopolymerization initiator and a second photopolymerization initiator that satisfy predetermined characteristics.
• the present inventors have examined the problems of the prior art. In the prior art in which only one type of photopolymerization initiator is used, when the exposure amount is increased in order to improve the scratch resistance of the formed pattern, the edge is formed. It has been found that the shape deteriorates and that the scratch resistance deteriorates when the exposure amount is reduced in order to improve the edge shape.
• the first photopolymerization initiator and the pattern which easily absorb the light at the time of pattern exposure using light having a wavelength of 365 nm as the main wavelength and sufficiently cause the polymerization reaction of the polymerizable compound, and the pattern.
• a second photopolymerization initiator is used. It is known that the desired effect can be obtained.
• the transfer film of the present invention has at least a temporary support and a photosensitive composition layer.
• a temporary support and a photosensitive composition layer.
• the transfer film has a temporary support.
• the temporary support is a member that supports a photosensitive composition layer or the like, which will be described later, and is finally removed by a peeling treatment.
• the temporary support is preferably a film, more preferably a resin film.
• a film that is flexible and does not significantly deform, shrink, or stretch under pressure, or under pressure and heating can be used. Examples of such a film include a polyethylene terephthalate film (for example, a biaxially stretched polyethylene terephthalate film), a cellulose triacetate film, a polystyrene film, a polyimide film, and a polycarbonate film.
• a biaxially stretched polyethylene terephthalate film is preferable as the temporary support.
• the film used as the temporary support has no deformation such as wrinkles or scratches.
• the temporary support preferably has high transparency from the viewpoint that pattern exposure can be performed through the temporary support, and the transmittance at 365 nm is preferably 60% or more, more preferably 70% or more. From the viewpoint of pattern formation during pattern exposure via the temporary support and transparency of the temporary support, it is preferable that the haze of the temporary support is small. Specifically, the haze value of the temporary support is preferably 2% or less, more preferably 0.5% or less, still more preferably 0.1% or less. From the viewpoint of pattern formation during pattern exposure via the temporary support and transparency of the temporary support, it is preferable that the number of fine particles, foreign substances and defects contained in the temporary support is small. Diameter 1 ⁇ m or more particles, the number of foreign matter and defects, preferably 50/10 mm 2 or less, more preferably 10/10 mm 2 or less, more preferably 3/10 mm 2 or less, particularly preferably 0/10 mm 2 ..
• the thickness of the temporary support is not particularly limited, but is preferably 5 to 200 ⁇ m, more preferably 10 to 150 ⁇ m, and further preferably 10 to 50 ⁇ m from the viewpoint of ease of handling and versatility.
• a layer (lubricant layer) containing fine particles may be provided on the surface of the temporary support in terms of imparting handleability.
• the lubricant layer may be provided on one side of the temporary support or on both sides.
• the diameter of the particles contained in the lubricant layer can be 0.05 to 0.8 ⁇ m.
• the film thickness of the lubricant layer can be 0.05 to 1.0 ⁇ m.
• the side of the temporary support in contact with the photosensitive composition layer may be surface-modified by UV irradiation, corona discharge, plasma, or the like. ..
• the exposure amount is preferably 10 mJ / cm 2 to 2000 mJ / cm 2 , and more preferably 50 to 1000 mJ / cm 2 .
• Light sources for UV irradiation include low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, carbon arc lamps, metal halide lamps, xenon lamps, chemical lamps, electrodeless discharge lamps, and light-emitting diodes that emit light in the wavelength band of 150 to 450 nm. (LED) and the like can be mentioned. As long as the light irradiation amount can be within this range, the lamp output and the illuminance are not particularly limited.
• Examples of the temporary support include a biaxially stretched polyethylene terephthalate film having a film thickness of 16 ⁇ m, a biaxially stretched polyethylene terephthalate film having a film thickness of 12 ⁇ m, and a biaxially stretched polyethylene terephthalate film having a film thickness of 9 ⁇ m.
• Preferred forms of the temporary support include, for example, paragraphs [0017] to [0018] of JP2014-085643, paragraphs [0019] to [0026] of JP2016-0273363, and WO2012 / 08168A1.
• Paragraphs [0041] to [0057] and paragraphs [0029] to [0040] of WO2018 / 179370A1 gazettes are described, and the contents of these gazettes are incorporated in the present specification.
• the transfer film has a photosensitive composition layer.
• a pattern can be formed on the transferred object by transferring the photosensitive composition layer onto the transferred object and then exposing and developing the photosensitive composition layer.
• the photosensitive composition layer contains a photopolymerization initiator, an alkali-soluble resin, and a polymerizable compound. When the photosensitive composition layer is irradiated with light, polymerization proceeds and the exposed portion is cured. That is, the photosensitive composition layer is a layer that is exposed to light and cured, and is a so-called negative type photosensitive composition layer (curable photosensitive composition layer).
• curable photosensitive composition layer curable photosensitive composition layer
• the photosensitive composition layer contains a first photopolymerization initiator and a second photopolymerization initiator.
• the photopolymerization initiator means one that initiates the polymerization of a polymerizable compound by receiving active light such as ultraviolet rays and visible light.
• the molar extinction coefficient and the value of the maximum absorption wavelength are calculated from the absorption spectrum obtained as follows. Specifically, first, an acetonitrile solution of a photopolymerization initiator having a concentration of 0.001% by mass was prepared, and the absorbance of the obtained solution was prepared using a spectrophotometer U-3310 manufactured by Hitachi, Ltd. (Measurement range 200 to 500 nm) is measured, and the molar extinction coefficient and the maximum absorption wavelength are calculated from the obtained absorption spectrum.
• the first photopolymerization initiator is not particularly limited as long as it is a photopolymerization initiator having a molar extinction coefficient ⁇ 1 of 500 L / mol ⁇ cm or more at a wavelength of 365 nm.
• the molar extinction coefficient ⁇ 1 is preferably 1000 L / mol ⁇ cm or more, and more preferably 1200 L / mol ⁇ cm or more.
• the upper limit is not particularly limited, but it is often 30,000 L / mol ⁇ cm or less, and more often 20,000 L / mol ⁇ cm or less.
• the maximum absorption wavelength of the first photopolymerization initiator is not particularly limited, but is preferably 300 nm or more, and more preferably 320 nm or more.
• the upper limit is not particularly limited, but 400 nm or less is preferable because the effect of the present invention is more excellent.
• the maximum absorption wavelength on the longest wavelength side is adopted.
• the first photopolymerization initiator examples include a photopolymerization initiator containing an oxime ester structure (hereinafter, also referred to as “oxym ester-based photopolymerization initiator”), an ⁇ -aminoalkylphenone structure, or an ⁇ -hydroxyalkylphenone structure.
• Photopolymerization initiator containing hereinafter, also referred to as “alkylphenone-based photopolymerization initiator”
• photopolymerization initiator containing an acylphosphine oxide structure hereinafter, also referred to as "acylphosphine oxide-based photopolymerization initiator”
• a photopolymerization initiator containing an aminobenzoic acid alkyl ester structure (hereinafter, also referred to as “aminobenzoate-based photopolymerization initiator”), and a photopolymerization initiator containing an N-phenylglycine structure (hereinafter, “N”. -Also referred to as "phenylglycine-based photopolymerization initiator”).
• aminobenzoate-based photopolymerization initiator examples include 2-ethylhexyl-4-dimethylaminobenzoate (2-ethylhexyl 4- (dimethylamino) benzoate) and ethyl-4-dimethylaminobenzoate (4- (dimethylamino)). ) Ethyl benzoate).
• the first photopolymerization initiator preferably contains at least one selected from the group consisting of an oxime ester-based photopolymerization initiator and an alkylphenone-based photopolymerization initiator.
• the content of the first photopolymerization initiator is preferably 0.01 to 10% by mass, more preferably 0.1 to 5% by mass, and 0.2 to 5% by mass with respect to the total mass of the photosensitive composition layer. % Is more preferable.
• the second photopolymerization initiator is a compound different from the first photopolymerization initiator, and is molar to the molar absorption coefficient ⁇ 3 of the second photopolymerization initiator at a wavelength of 313 nm and the molar absorption coefficient of the second photopolymerization initiator at a wavelength of 365 nm. If the photopolymerization initiator has a ratio of absorption coefficient ⁇ 2 (molar absorption coefficient ⁇ 2 at a wavelength of 365 nm of the second photopolymerization initiator / molar absorption coefficient ⁇ 3 at a wavelength of 313 nm of the second photopolymerization initiator) of 0.200 or less. , There are no particular restrictions. Among them, the ratio is preferably 0.100 or less, more preferably 0.050 or less, in that the effect of the present invention is more excellent. The lower limit is not particularly limited, but 0 can be mentioned.
• the molar extinction coefficient ⁇ 2 of the second photopolymerization initiator at a wavelength of 365 nm is not particularly limited, but 1500 L / mol ⁇ cm or less is preferable, 500 L / mol ⁇ cm or less is more preferable, and 200 L is more preferable in that the effect of the present invention is more excellent. It is more preferably / mol ⁇ cm or less.
• the lower limit is not particularly limited, but it is often 0 L / mol ⁇ cm or more, and more often 10 L / mol ⁇ cm or more.
• the molar extinction coefficient ⁇ 3 of the second photopolymerization initiator at a wavelength of 313 nm is not particularly limited, but is preferably 2000 L / mol ⁇ cm or more, more preferably 5000 L / mol ⁇ cm or more, and 10000 L in that the effect of the present invention is more excellent.
• / Mol ⁇ cm or more is more preferable.
• the upper limit is not particularly limited, but in many cases it is 200,000 L / mol ⁇ cm or less, more often it is 30,000 L / mol ⁇ cm or less, and more often it is 25,000 L / mol ⁇ cm or less.
• the maximum absorption wavelength of the second photopolymerization initiator is not particularly limited, but 320 nm or less is preferable, and 300 nm or less is more preferable, because the effect of the present invention is more excellent.
• the lower limit is not particularly limited, but 200 nm or more is preferable because the effect of the present invention is more excellent.
• the maximum absorption wavelength on the longest wavelength side is adopted.
• the second photopolymerization initiator examples include compounds similar to those of the first photopolymerization initiator described above.
• the second photopolymerization initiator is composed of an aminobenzoate-based photopolymerization initiator, an alkylphenone-based photopolymerization initiator, and an acylphosphine oxide-based photopolymerization initiator in that the effect of the present invention is more excellent. It preferably contains at least one selected from the group, and more preferably contains an aminobenzoate-based photopolymerization initiator.
• the content of the second photopolymerization initiator is preferably 0.01 to 10% by mass, more preferably 0.1 to 5% by mass, and 0.2 to 5% by mass with respect to the total mass of the photosensitive composition layer. % Is more preferable.
• Examples of the first photopolymerization initiator and the second photopolymerization initiator include paragraphs [0031] to [0042] of JP2011-0957116 and paragraphs [0064] to [0042] of JP2015-014783. ] To [0081], the photopolymerization initiator described in [0081] may be used.
• IRGACURE (registered trademark) OXE-01, manufactured by BASF] 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-3-yl] etanone-1- (O-acetyloxime)
• Product name: IRGACURE (registered trademark) OXE-02, manufactured by BASF] [8- [5- (2,4,6-trimethylphenyl) -11- (2-ethylhexyl) -11H-benzo [a] carbazoyl] ] [2- (2,2,3,3-tetrafluoropropoxy) phenyl] Metanon- (O-acetyloxime)
• IRGACURE (registered trademark) OXE-03, manufactured by BASF] 1- [4- [4- (2-Benzoflanylcarbonyl) phenyl] Phenyl] Phenyl-4-methyl-1-pentanone-1- (O-acetyloxime) [
• the ratio of the molar extinction coefficient ⁇ 1 of the first photopolymerization initiator at a wavelength of 365 nm to the molar extinction coefficient ⁇ 2 of the second photopolymerization initiator at a wavelength of 365 nm is not particularly limited. It is preferably 500 or less, more preferably 0.200 or less. The lower limit is not particularly limited, but is often 0.01 or more.
• the absorbance of the second photopolymerization initiator at a wavelength of 313 nm is larger than the absorbance of the first photopolymerization initiator at a wavelength of 313 nm.
• the photosensitive composition layer may contain at least two types of photopolymerization initiators, a first photopolymerization initiator and a second photopolymerization initiator, and may contain three or more types of photopolymerization initiators.
• the total content of the photopolymerization initiator is preferably 0.10% by mass or more, more preferably 0.50% by mass or more, based on the total mass of the photosensitive composition layer.
• the upper limit of the content of the photopolymerization initiator is preferably 10% by mass or less, more preferably 5.0% by mass or less, based on the total mass of the photosensitive composition layer.
• the total content of the photopolymerization initiator means the total content of all the photopolymerization initiators including the first photopolymerization initiator and the second photopolymerization initiator.
• the content of the second photopolymerization initiator is preferably 1.2 times or more, more preferably 1.5 times or more, with respect to the content of the first photopolymerization initiator.
• the upper limit is not particularly limited, but in many cases it is 5 times or less.
• the photosensitive composition layer contains an alkali-soluble resin.
• the solubility of the photosensitive composition layer (non-exposed portion) in the developing solution is improved.
• an alkali-soluble acrylic resin is preferable.
• the alkali-soluble acrylic resin will be described in detail.
• alkali-soluble means that the dissolution rate required by the following method is 0.01 ⁇ m / sec or more.
• a propylene glycol monomethyl ether acetate solution having a concentration of the target compound (for example, resin) of 25% by mass is applied onto a glass substrate, and then heated in an oven at 100 ° C. for 3 minutes to obtain a coating film of the target compound (for example, resin). A thickness of 2.0 ⁇ m) is formed.
• the dissolution rate ( ⁇ m / sec) of the coating film is determined by immersing the coating film in a 1% by mass aqueous solution of sodium carbonate (liquid temperature 30 ° C.).
• the target compound When the target compound is not soluble in propylene glycol monomethyl ether acetate, the target compound is dissolved in an organic solvent (for example, tetrahydrofuran, toluene, or ethanol) having a boiling point of less than 200 ° C. other than propylene glycol monomethyl ether acetate.
• an organic solvent for example, tetrahydrofuran, toluene, or ethanol
• the alkali-soluble acrylic resin is not limited as long as it is the alkali-soluble acrylic resin described above.
• the "acrylic resin” means a resin containing at least one of a structural unit derived from (meth) acrylic acid and a structural unit derived from (meth) acrylic acid ester.
• the total ratio of the structural unit derived from (meth) acrylic acid and the structural unit derived from (meth) acrylic acid ester in the alkali-soluble acrylic resin is preferably 30 mol% or more, more preferably 50 mol% or more.
• the content of "constituent unit” when the content of "constituent unit” is specified by mole fraction (molar ratio), the above “constituent unit” shall be synonymous with “monomer unit” unless otherwise specified. Further, in the present disclosure, when the resin or polymer has two or more specific structural units, the content of the specific structural units is the total of the two or more specific structural units unless otherwise specified. It shall represent the content.
• the alkali-soluble acrylic resin preferably has a carboxy group from the viewpoint of developability.
• Examples of the method for introducing a carboxy group into an alkali-soluble acrylic resin include a method for synthesizing an alkali-soluble acrylic resin using a monomer having a carboxy group. By the above method, the monomer having a carboxy group is introduced into the alkali-soluble acrylic resin as a structural unit having a carboxy group.
• the monomer having a carboxy group include acrylic acid and methacrylic acid.
• the alkali-soluble acrylic resin may have one carboxy group or two or more carboxy groups. Further, the structural unit having a carboxy group in the alkali-soluble acrylic resin may be one kind alone or two or more kinds.
• the content of the structural unit having a carboxy group is preferably 5 to 50 mol%, more preferably 5 to 40 mol%, still more preferably 10 to 30 mol%, based on the total amount of the alkali-soluble acrylic resin.
• the content of the structural unit having a carboxy group is preferably 3 to 40% by mass, more preferably 3 to 30% by mass, and further preferably 5 to 20% by mass, based on the total amount of the alkali-soluble acrylic resin. preferable.
• Examples of the (meth) acrylic compound for forming an acrylic resin include (meth) acrylic acid, (meth) acrylic acid ester, (meth) acrylamide, and (meth) acrylonitrile.
• Examples of the (meth) acrylic acid ester include (meth) acrylic acid alkyl ester, (meth) acrylic acid tetrahydrofurfuryl ester, (meth) acrylic acid dimethylaminoethyl ester, (meth) acrylic acid diethylaminoethyl ester, and (meth) acrylic acid ester. ) Acrylic acid glycidyl ester, (meth) acrylic acid benzyl ester, 2,2,2-trifluoroethyl (meth) acrylate, and 2,2,3,3-tetrafluoropropyl (meth) acrylate. Meta) Acrylic acid alkyl esters are preferred.
• Examples of (meth) acrylamide include acrylamide such as diacetone acrylamide.
• the alkyl group of the (meth) acrylic acid alkyl ester may be linear or branched. Specific examples include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, ( Heptyl acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, undecyl (meth) acrylate, and (meth) acrylate.
• Examples thereof include (meth) acrylic acid alkyl esters having an alkyl group having 1 to 12 carbon atoms such as dodecyl.
• As the (meth) acrylic acid ester a (meth) acrylic acid alkyl ester having an alkyl group having 1 to 4 carbon atoms is preferable, and methyl (meth) acrylate or ethyl (meth) acrylate is more preferable.
• the acrylic resin may have a structural unit other than the structural unit derived from the (meth) acrylic compound.
• the alkali-soluble acrylic resin preferably has a structural unit having an aromatic ring from the viewpoint of moisture permeability and strength after curing.
• the structural unit having an aromatic ring is preferably a structural unit derived from a styrene compound.
• Examples of the monomer forming the structural unit having an aromatic ring include a monomer forming a structural unit derived from a styrene compound and benzyl (meth) acrylate.
• Examples of the monomer forming the structural unit derived from the styrene compound include styrene, p-methylstyrene, ⁇ -methylstyrene, ⁇ , p-dimethylstyrene, p-ethylstyrene, pt-butylstyrene, and t-butoxy. Examples thereof include styrene and 1,1-diphenylethylene, preferably styrene or ⁇ -methylstyrene, and more preferably styrene.
• the structural unit having an aromatic ring in the alkali-soluble acrylic resin may be one kind alone or two or more kinds.
• the content of the structural unit having an aromatic ring is preferably 5 to 90 mol%, preferably 10 to 80 mol%, based on the total amount of the alkali-soluble acrylic resin. More preferably, 15 to 70 mol% is further preferable.
• the alkali-soluble acrylic resin preferably contains a structural unit having an aliphatic cyclic skeleton from the viewpoint of tackiness and strength after curing.
• Examples of the aliphatic cyclic skeleton include monocyclic and polycyclic.
• Examples of the aliphatic ring in the aliphatic cyclic skeleton include a dicyclopentane ring, a cyclohexane ring, an isoborone ring, and a tricyclodecane ring.
• the tricyclodecane ring is preferable as the aliphatic ring in the aliphatic cyclic skeleton.
• Examples of the monomer forming a structural unit having an aliphatic cyclic skeleton include dicyclopentanyl (meth) acrylate, cyclohexyl (meth) acrylate, and isobornyl (meth) acrylate.
• the constituent unit having an aliphatic cyclic skeleton in the alkali-soluble acrylic resin may be one kind alone or two or more kinds.
• the content of the structural unit having an aliphatic cyclic skeleton is preferably 5 to 90 mol% with respect to the total amount of the alkali-soluble acrylic resin. 10 to 80 mol% is more preferable, and 10 to 60 mol% is further preferable.
• the alkali-soluble acrylic resin preferably has a reactive group from the viewpoint of tackiness and strength after curing.
• the reactive group a radically polymerizable group is preferable, and an ethylenically unsaturated group is more preferable.
• the alkali-soluble acrylic resin has an ethylenically unsaturated group
• the alkali-soluble acrylic resin preferably has a structural unit having an ethylenically unsaturated group in the side chain.
• the "main chain” represents a relatively longest binding chain among the molecules of the polymer compound constituting the resin
• the "side chain” represents an atomic group branched from the main chain. ..
• a (meth) acrylic group or a (meth) acryloyl group is preferable, and a (meth) acryloyl group is more preferable.
• the structural unit having an ethylenically unsaturated group in the alkali-soluble acrylic resin may be one kind alone or two or more kinds.
• the content of the structural unit having an ethylenically unsaturated group is preferably 5 to 70 mol% with respect to the total amount of the alkali-soluble acrylic resin. 10 to 50 mol% is more preferable, and 15 to 40 mol% is further preferable.
• the structural unit having a reactive group include, but are not limited to, those shown below.
• a reactive group into an alkali-soluble acrylic resin, a hydroxyl group, a carboxy group, a primary amino group, a secondary amino group, an acetoacetyl group, a sulfonic acid or the like, an epoxy compound, a blocked isocyanate compound, etc.
• examples thereof include a method of reacting an isocyanate compound, a vinyl sulfonic compound, an aldehyde compound, a methylol compound, a carboxylic acid anhydride and the like.
• a preferable example of the means for introducing a reactive group into an alkali-soluble acrylic resin is that an alkali-soluble acrylic resin having a carboxy group is synthesized by a polymerization reaction and then glycidyl is added to a part of the carboxy groups of the alkali-soluble acrylic resin by a polymer reaction.
• Examples thereof include means for introducing a (meth) acryloxy group into an alkali-soluble acrylic resin by reacting the (meth) acrylate.
• the above polymerization reaction is preferably carried out under a temperature condition of 70 to 100 ° C., and more preferably carried out under a temperature condition of 80 to 90 ° C.
• an azo-based initiator is preferable, and for example, V-601 (trade name) or V-65 (trade name) manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. is more preferable.
• the polymer reaction is preferably carried out under temperature conditions of 80 to 110 ° C. In the above polymer reaction, it is preferable to use a catalyst such as an ammonium salt.
• the weight average molecular weight (Mw) of the alkali-soluble acrylic resin is preferably 10,000 or more, more preferably 10,000 to 100,000, further preferably 15,000 to 70,000, and preferably 15,000 to 30,000. Most preferred.
• the acid value of the alkali-soluble acrylic resin is preferably 50 mgKOH / g or more, more preferably 60 mgKOH / g or more, further preferably 70 mgKOH / g or more, and particularly preferably 80 mgKOH / g or more.
• the acid value of the alkali-soluble acrylic resin is a value measured according to the method described in JIS K0070: 1992.
• the upper limit of the acid value of the alkali-soluble acrylic resin is preferably 200 mgKOH / g or less, more preferably 150 mgKOH / g or less, from the viewpoint of suppressing dissolution in the developing solution.
• alkali-soluble acrylic resin Specific examples of the alkali-soluble acrylic resin are shown below.
• the content ratio (molar ratio) of each structural unit in the following alkali-soluble acrylic resin can be appropriately set according to the purpose.
• a 20 wt% to 60 wt%
• b 10 wt% to 50 wt%
• c 5.0 wt% to 25 wt%
• d 10 wt% to 50 wt% are preferable.
• a 30 wt% to 65 wt%
• b 1.0 wt% to 20 wt%
• c 5.0 wt% to 25 wt%
• d 10 wt% to 50 wt% are preferable.
• the photosensitive composition layer may contain one kind of alkali-soluble resin alone, or may contain two or more kinds of alkali-soluble resins.
• the content of the residual monomer of each structural unit of the alkali-soluble resin is preferably 2,000 mass ppm or less, preferably 1,000 mass ppm or less, based on the total mass of the alkali-soluble resin from the viewpoint of patterning property and reliability. Is more preferable, and 500 mass ppm or less is further preferable.
• the lower limit is not particularly limited, but 1 mass ppm or more is preferable, and 10 mass ppm or more is more preferable.
• the residual monomer of each structural unit of the alkali-soluble resin is preferably 1,000 mass ppm or less, more preferably 200 mass ppm or less, based on the total mass of the photosensitive composition layer from the viewpoint of patterning property and reliability. , 100 mass ppm or less is more preferable.
• the lower limit is not particularly limited, but is preferably 0.1 mass ppm or more, and more preferably 1 mass ppm or more.
• the content of the alkali-soluble resin is preferably 10 to 90% by mass, more preferably 20 to 80% by mass, further preferably 25 to 70% by mass, based on the total mass of the photosensitive composition layer from the viewpoint of developability. preferable.
• the photosensitive composition layer contains a polymerizable compound.
• a polymerizable compound is a compound having a polymerizable group. Examples of the polymerizable group include a radically polymerizable group and a cationically polymerizable group, and a radically polymerizable group is preferable.
• the polymerizable compound preferably contains a radically polymerizable compound having an ethylenically unsaturated group (hereinafter, also simply referred to as “ethylenically unsaturated compound”).
• ethylenically unsaturated compound a (meth) acryloxy group is preferable.
• the ethylenically unsaturated compound preferably contains a bifunctional or higher functional ethylenically unsaturated compound.
• the "bifunctional or higher functional ethylenically unsaturated compound” means a compound having two or more ethylenically unsaturated groups in one molecule.
• a (meth) acrylate compound is preferable.
• the ethylenically unsaturated compound include a bifunctional ethylenically unsaturated compound (preferably a bifunctional (meth) acrylate compound) and a trifunctional or higher functional ethylenically unsaturated compound in terms of film strength after curing. It preferably contains a compound (preferably a trifunctional or higher functional (meth) acrylate compound).
• bifunctional ethylenically unsaturated compound examples include tricyclodecanedimethanol di (meth) acrylate, tricyclodecanedimethanol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, and 1,10. -Decandiol di (meth) acrylate and 1,6-hexanediol di (meth) acrylate can be mentioned.
• bifunctional ethylenically unsaturated compounds include, for example, tricyclodecanedimethanol diacrylate [trade name: NK ester A-DCP, Shin-Nakamura Chemical Industry Co., Ltd.], tricyclodecanedimethanol dimethacrylate [commodity].
• NK Ester DCP Shin-Nakamura Chemical Industry Co., Ltd.
• 1,9-Nonandiol Diacrylate Product Name: NK Ester A-NOD-N, Shin-Nakamura Chemical Industry Co., Ltd.] 1,10-Decandiol Diacrylate
• NK ester A-DOD-N Shin-Nakamura Chemical Industry Co., Ltd.
• 1,6-hexanediol diacrylate Product name: NK ester A-HD-N, Shin-Nakamura Chemical Industry Co., Ltd.] Can be mentioned.
• Examples of the trifunctional or higher functional ethylenically unsaturated compound include dipentaerythritol (tri / tetra / penta / hexa) (meth) acrylate, pentaerythritol (tri / tetra) (meth) acrylate, and trimethylolpropane tri (meth).
• Examples thereof include acrylate, ditrimethylolpropane tetra (meth) acrylate, isocyanuric acid (meth) acrylate, and glycerin tri (meth) acrylate.
• (tri / tetra / penta / hexa) (meth) acrylate is a concept including tri (meth) acrylate, tetra (meth) acrylate, penta (meth) acrylate, and hexa (meth) acrylate. is there.
• (tri / tetra) (meth) acrylate” is a concept including tri (meth) acrylate and tetra (meth) acrylate.
• the trifunctional or higher functional ethylenically unsaturated compound is not particularly limited in the upper limit of the number of functional groups, but may be, for example, 20 functional or less, or 15 functional or less.
• Examples of commercially available products of trifunctional or higher functional ethylenically unsaturated compounds include dipentaerythritol hexaacrylate [trade name: A-DPH, Shin Nakamura Chemical Industry Co., Ltd.].
• Ethylene unsaturated compounds include 1,9-nonanediol di (meth) acrylate or 1,10-decanediol di (meth) acrylate and dipentaerythritol (tri / tetra / penta / hexa) (meth) acrylate. It is more preferable to include it.
• caprolactone-modified compounds of (meth) acrylate compounds [KAYARAD (registered trademark) DPCA-20 of Nippon Kayaku Co., Ltd., A-9300-1CL of Shin-Nakamura Chemical Industry Co., Ltd., etc.]
• (Meta ) Acrylate alkylene oxide-modified compound [KAYARAD (registered trademark) RP-1040 of Nippon Kayaku Co., Ltd., ATM-35E, A-9300 of Shin-Nakamura Chemical Industry Co., Ltd., EBECRYL (registered trademark) of Daicel Ornex Co., Ltd. 135 Etc.]
• ethoxylated glycerin triacrylate [NK ester A-GLY-9E, etc. of Shin-Nakamura Chemical Industry Co., Ltd.]
• Examples of the ethylenically unsaturated compound include urethane (meth) acrylate compounds.
• urethane (meth) acrylate compound a trifunctional or higher functional urethane (meth) acrylate compound is preferable.
• trifunctional or higher functional urethane (meth) acrylate compounds include 8UX-015A [Taisei Fine Chemical Co., Ltd.], NK ester UA-32P [Shin Nakamura Chemical Industry Co., Ltd.], and NK ester UA-1100H [New Nakamura Chemical Industry Co., Ltd.]. Co., Ltd.].
• the ethylenically unsaturated compound preferably contains an ethylenically unsaturated compound having an acid group from the viewpoint of improving developability.
• the acid group examples include a phosphoric acid group, a sulfonic acid group, and a carboxy group.
• the carboxy group is preferable as the acid group.
• Examples of the ethylenically unsaturated compound having an acid group include a 3- to 4-functional ethylenically unsaturated compound having an acid group [pentaerythritol tri and a compound having a carboxy group introduced into the tetraacrylate (PETA) skeleton (acid value: 80 to 80 to). 120 mgKOH / g)] and a 5- to 6-functional ethylenically unsaturated compound having an acid group (dipentaerythritol penta and hexaacrylate (DPHA)) with a carboxy group introduced into the skeleton [acid value: 25 to 70 mgKOH / g] )].
• the trifunctional or higher functional ethylenically unsaturated compound having an acid group may be used in combination with a bifunctional ethylenically unsaturated compound having an acid group, if necessary.
• the ethylenically unsaturated compound having an acid group at least one compound selected from the group consisting of a bifunctional or higher functional ethylenically unsaturated compound having a carboxy group and a carboxylic acid anhydride thereof is preferable.
• the ethylenically unsaturated compound having an acid group is at least one compound selected from the group consisting of a bifunctional or higher functional ethylenically unsaturated compound having a carboxy group and a carboxylic acid anhydride thereof, the developability and developability and The film strength is further increased.
• Bifunctional or higher functional unsaturated compounds having a carboxy group include Aronix (registered trademark) TO-2349 [Toagosei Co., Ltd.], Aronix (registered trademark) M-520 [Toagosei Co., Ltd.], and Aronix (registered trademark). Registered trademark) M-510 [Toagosei Co., Ltd.] can be mentioned.
• the polymerizable compound having an acid group described in paragraphs [0025] to [0030] of JP-A-2004-239942 can be preferably used, and is described in this publication. The contents are incorporated herein by reference.
• the molecular weight of the ethylenically unsaturated compound is preferably 200 to 3,000, more preferably 250 to 2,600, further preferably 280 to 2,200, and particularly preferably 300 to 2,200.
• the content of the ethylenically unsaturated compound having a molecular weight of 300 or less is preferably 30% by mass or less with respect to the content of all the ethylenically unsaturated compounds contained in the photosensitive composition layer. , 25% by mass or less, more preferably 20% by mass or less.
• the photosensitive composition layer may contain one kind of ethylenically unsaturated compound alone, or may contain two or more kinds of ethylenically unsaturated compounds.
• the content of the ethylenically unsaturated compound is preferably 1 to 70% by mass, more preferably 10 to 70% by mass, further preferably 20 to 60% by mass, and 20 to 20 to 70% by mass with respect to the total mass of the photosensitive composition layer. 50% by mass is particularly preferable.
• the photosensitive composition layer contains a bifunctional or higher functional ethylenically unsaturated compound, it may further contain a monofunctional ethylenically unsaturated compound.
• the bifunctional or higher functional ethylenically unsaturated compound may be the main component of the ethylenically unsaturated compound contained in the photosensitive composition layer. preferable.
• the content of the bifunctional or higher functional ethylenically unsaturated compound is the content of all the ethylenically unsaturated compounds contained in the photosensitive composition layer.
• the amount 60 to 100% by mass is preferable, 80 to 100% by mass is more preferable, and 90 to 100% by mass is further preferable.
• the photosensitive composition layer contains an ethylenically unsaturated compound having an acid group (preferably a bifunctional or higher functional ethylenically unsaturated compound having a carboxy group or a carboxylic acid anhydride thereof), the ethylenically unsaturated compound having an acid group.
• the content of the saturated compound is preferably 1 to 50% by mass, more preferably 1 to 20% by mass, still more preferably 1 to 10% by mass, based on the total mass of the photosensitive composition layer.
• the photosensitive composition layer may further contain a polymer containing a structural unit having a carboxylic acid anhydride structure (hereinafter, also referred to as “polymer B”) as a binder.
• polymer B a polymer containing a structural unit having a carboxylic acid anhydride structure
• the carboxylic acid anhydride structure may be either a chain carboxylic acid anhydride structure or a cyclic carboxylic acid anhydride structure, but a cyclic carboxylic acid anhydride structure is preferable.
• a cyclic carboxylic acid anhydride structure As the ring having a cyclic carboxylic acid anhydride structure, a 5- to 7-membered ring is preferable, a 5-membered ring or a 6-membered ring is more preferable, and a 5-membered ring is further preferable.
• the structural unit having a carboxylic acid anhydride structure is a structural unit containing a divalent group obtained by removing two hydrogen atoms from the compound represented by the following formula P-1 in the main chain, or the following formula P-1. It is preferable that the monovalent group obtained by removing one hydrogen atom from the represented compound is a structural unit bonded to the main chain directly or via a divalent linking group.
• R A1a represents a substituent
• n 1a R A1a may be the same or different
• Examples of the substituent represented by RA1a include an alkyl group.
• an alkylene group having 2 to 4 carbon atoms is preferable, an alkylene group having 2 or 3 carbon atoms is more preferable, and an alkylene group having 2 carbon atoms is further preferable.
• n 1a represents an integer of 0 or more.
• Z 1a represents an alkylene group having 2 to 4 carbon atoms
• n 1a is preferably an integer of 0 to 4, more preferably an integer of 0 to 2, and even more preferably 0.
• a plurality of RA1a may be the same or different. Further, the plurality of RA1a may be bonded to each other to form a ring, but it is preferable that they are not bonded to each other to form a ring.
• a structural unit derived from an unsaturated carboxylic acid anhydride is preferable, a structural unit derived from an unsaturated cyclic carboxylic acid anhydride is more preferable, and an unsaturated aliphatic cyclic carboxylic acid is preferable.
• a structural unit derived from an acid anhydride is more preferable, a structural unit derived from maleic anhydride or itaconic anhydride is particularly preferable, and a structural unit derived from maleic anhydride is most preferable.
• the structural unit having the carboxylic acid anhydride structure in the polymer B may be one kind alone or two or more kinds.
• the content of the structural unit having a carboxylic acid anhydride structure is preferably 0 to 60 mol%, more preferably 5 to 40 mol%, still more preferably 10 to 35 mol%, based on the total amount of the polymer B.
• the photosensitive composition layer may contain one type of polymer B alone, or may contain two or more types of polymer B.
• the content of the polymer B is 0.1 to 30 mass with respect to the total mass of the photosensitive composition layer in terms of developability and strength after curing. % Is preferable, 0.2 to 20% by mass is more preferable, 0.5 to 20% by mass is further preferable, and 1 to 20% by mass is particularly preferable.
• the photosensitive composition layer preferably contains a heterocyclic compound.
• the heterocycle contained in the heterocyclic compound may be either a monocyclic or polycyclic heterocycle.
• Examples of the hetero atom contained in the heterocyclic compound include a nitrogen atom, an oxygen atom, and a sulfur atom.
• the heterocyclic compound preferably has at least one atom selected from the group consisting of a nitrogen atom, an oxygen atom, and a sulfur atom, and more preferably has a nitrogen atom.
• heterocyclic compound examples include a triazole compound, a benzotriazole compound, a tetrazole compound, a thiazazole compound, a triazine compound, a rhonin compound, a thiazole compound, a benzothiazole compound, a benzoimidazole compound, a benzoxazole compound, and a pyrimidine compound.
• the heterocyclic compound is at least one selected from the group consisting of a triazole compound, a benzotriazole compound, a tetrazole compound, a thiazizol compound, a triazine compound, a rhonin compound, a thiazole compound, a benzoimidazole compound, and a benzoxazole compound.
• Species compounds are preferred, and at least one compound selected from the group consisting of triazole compounds, benzotriazole compounds, tetrazole compounds, thiazazole compounds, thiazole compounds, benzothiazole compounds, benzoimidazole compounds, and benzoxazole compounds is more preferred. ..
• heterocyclic compound A preferable specific example of the heterocyclic compound is shown below.
• examples of the triazole compound and the benzotriazole compound include the following compounds.
• Examples of the tetrazole compound include the following compounds.
• thiadiazole compounds include the following compounds.
• Examples of the triazine compound include the following compounds.
• Examples of the loadonine compound include the following compounds.
• Examples of the thiazole compound include the following compounds.
• benzothiazole compound examples include the following compounds.
• Examples of the benzimidazole compound include the following compounds.
• benzoxazole compound examples include the following compounds.
• the photosensitive composition layer may contain one kind of heterocyclic compound alone, or may contain two or more kinds of heterocyclic compounds.
• the content of the heterocyclic compound is preferably 0.01 to 20% by mass, preferably 0.01 to 5% by mass, based on the total mass of the photosensitive composition layer. Is more preferable.
• the photosensitive composition layer preferably contains an aliphatic thiol compound.
• the photosensitive composition layer contains an aliphatic thiol compound
• the aliphatic thiol compound undergoes an en-thiol reaction with a radically polymerizable compound having an ethylenically unsaturated group, thereby curing and shrinking the formed film. Is suppressed and the stress is relieved.
• aliphatic thiol compound a monofunctional aliphatic thiol compound or a polyfunctional aliphatic thiol compound (that is, a bifunctional or higher functional aliphatic thiol compound) is preferable.
• aliphatic thiol compound for example, a polyfunctional aliphatic thiol compound is preferable from the viewpoint of adhesion (particularly, adhesion after exposure) of the formed pattern.
• polyfunctional aliphatic thiol compound means an aliphatic compound having two or more thiol groups (also referred to as “mercapto groups”) in the molecule.
• the polyfunctional aliphatic thiol compound a low molecular weight compound having a molecular weight of 100 or more is preferable. Specifically, the molecular weight of the polyfunctional aliphatic thiol compound is more preferably 100 to 1,500, and even more preferably 150 to 1,000.
• the number of functional groups of the polyfunctional aliphatic thiol compound for example, 2 to 10 functionals are preferable, 2 to 8 functionals are more preferable, and 2 to 6 functionals are further preferable from the viewpoint of adhesion of the formed pattern.
• polyfunctional aliphatic thiol compound examples include trimethylolpropanthris (3-mercaptobutylate), 1,4-bis (3-mercaptobutylyloxy) butane, pentaerythritol tetrakis (3-mercaptobutyrate), and the like.
• the polyfunctional aliphatic thiol compounds include trimethylolpropane tris (3-mercaptobutyrate), 1,4-bis (3-mercaptobutylyloxy) butane, and 1,3,5-tris. At least one compound selected from the group consisting of (3-mercaptobutylyloxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione is preferable.
• Examples of the monofunctional aliphatic thiol compound include 1-octanethiol, 1-dodecanethiol, ⁇ -mercaptopropionic acid, methyl-3-mercaptopropionate, 2-ethylhexyl-3-mercaptopropionate, and n-. Examples thereof include octyl-3-mercaptopropionate, methoxybutyl-3-mercaptopropionate, and stearyl-3-mercaptopropionate.
• the photosensitive composition layer may contain one type of aliphatic thiol compound alone, or may contain two or more types of aliphatic thiol compounds.
• the content of the aliphatic thiol compound is preferably 5% by mass or more, more preferably 5 to 50% by mass, based on the total mass of the photosensitive composition layer. 5 to 30% by mass is more preferable, and 8 to 20% by mass is particularly preferable.
• the photosensitive composition layer preferably contains a blocked isocyanate compound.
• the blocked isocyanate compound contributes to the improvement of the strength of the formed pattern. Since the blocked isocyanate compound reacts with a hydroxyl group and a carboxy group, it is formed, for example, when at least one of the binder polymer and the radically polymerizable compound having an ethylenically unsaturated group has at least one of the hydroxyl group and the carboxy group. The hydrophilicity of the polymer tends to decrease, and the function as a protective film tends to be strengthened.
• the blocked isocyanate compound refers to "a compound having a structure in which the isocyanate group of isocyanate is protected (so-called masked) with a blocking agent".
• the dissociation temperature of the blocked isocyanate compound is preferably 100 to 160 ° C, more preferably 110 to 150 ° C.
• the "dissociation temperature of a blocked isocyanate compound” is the temperature of the endothermic peak associated with the deprotection reaction of the blocked isocyanate compound when measured by DSC (Differential scanning calorimetry) analysis using a differential scanning calorimeter. Means.
• a differential scanning calorimeter for example, a differential scanning calorimeter (model: DSC6200) manufactured by Seiko Instruments Inc. can be preferably used.
• the differential scanning calorimetry is not limited to the differential scanning calorimetry described above.
• Examples of the blocking agent having a dissociation temperature of 100 to 160 ° C. include active methylene compounds [(dimethyl malonate, diethyl malonate, din-butyl malonate, di2-ethylhexyl malonate, etc.)], etc.
• an oxime compound is preferable from the viewpoint of storage stability.
• the blocked isocyanate compound preferably has an isocyanurate structure from the viewpoint of improving the brittleness of the membrane and improving the adhesion to the transferred material.
• the blocked isocyanate compound having an isocyanurate structure can be obtained, for example, by isocyanurate-forming and protecting hexamethylene diisocyanate.
• a compound having an oxime structure using an oxime compound as a blocking agent is easier to set the dissociation temperature in a preferable range than a compound having no oxime structure, and reduces the development residue. It is preferable because it is easy.
• the blocked isocyanate compound preferably has a polymerizable group, and more preferably has a radically polymerizable group, from the viewpoint of the strength of the formed pattern.
• the polymerizable group examples include an ethylenically unsaturated group such as a (meth) acryloxy group, a (meth) acrylamide group and a styryl group, and a group having an epoxy group such as a glycidyl group.
• an ethylenically unsaturated group is preferable, and a (meth) acryloxy group is more preferable, from the viewpoint of surface surface condition, development speed, and reactivity in the obtained pattern.
• blocked isocyanate compound a commercially available product can be used.
• examples of commercially available blocked isocyanate compounds include, for example, Karenz (registered trademark) AOI-BM, Karenz (registered trademark) MOI-BM, Karenz (registered trademark) AOI-BP, Karenz (registered trademark) MOI-BP, etc.
• Showa Denko Co., Ltd.] and the block type Duranate series [for example, Duranate (registered trademark) TPA-B80E, manufactured by Asahi Kasei Chemicals Co., Ltd.] can be mentioned.
• the photosensitive composition layer may contain one type of blocked isocyanate compound alone, or may contain two or more types of blocked isocyanate compounds.
• the content of the blocked isocyanate compound is preferably 1 to 50% by mass, more preferably 5 to 30% by mass, based on the total mass of the photosensitive composition layer.
• the photosensitive composition layer may contain a surfactant.
• the surfactant include the surfactants described in paragraphs [0017] of Japanese Patent No. 4502784 and paragraphs [0060] to [0071] of JP2009-237362A.
• a nonionic surfactant a fluorine-based surfactant or a silicone-based surfactant is preferable.
• fluorine-based surfactants include, for example, Megafuck F-171, F-172, F-173, F-176, F-177, F-141, F-142, F-143, F-144.
• the fluorine-based surfactant has a molecular structure having a functional group containing a fluorine atom, and an acrylic compound in which a portion of the functional group containing a fluorine atom is cut off and the fluorine atom volatilizes when heat is applied.
• fluorine-based surfactants include the Megafuck DS series manufactured by DIC Corporation (The Chemical Daily (February 22, 2016), Nikkei Sangyo Shimbun (February 23, 2016)), for example, Megafuck. DS-21 can be mentioned.
• the fluorine-based surfactant it is also preferable to use a polymer of a fluorine atom-containing vinyl ether compound having a fluorinated alkyl group or a fluorinated alkylene ether group and a hydrophilic vinyl ether compound.
• a block polymer can also be used.
• the fluorine-based surfactant has a repeating unit derived from a (meth) acrylate compound having a fluorine atom and 2 or more (preferably 5 or more) alkyleneoxy groups (preferably ethyleneoxy groups and propyleneoxy groups) (meth).
• a fluorine-containing polymer compound containing a repeating unit derived from an acrylate compound can also be preferably used.
• a fluorine-based surfactant a fluorine-containing polymer having an ethylenically unsaturated bond-containing group in the side chain can also be used. Megafvck RS-101, RS-102, RS-718K, RS-72-K (all manufactured by DIC Corporation) and the like can be mentioned.
• the fluorine-based surfactant has a linear perfluoroalkyl group having 7 or more carbon atoms, such as perfluorooctanoic acid (PFOA) and perfluorooctanesulfonic acid (PFOS), from the viewpoint of improving environmental suitability.
• PFOA perfluorooctanoic acid
• PFOS perfluorooctanesulfonic acid
• a surfactant derived from a substitute material for the compound.
• the silicone-based surfactant include a linear polymer composed of a siloxane bond and a modified siloxane polymer in which an organic group is introduced into a side chain or a terminal.
• silicone-based surfactants include DOWNSIL 8032 ADDITIVE, Torre Silicone DC3PA, Torre Silicone SH7PA, Torre Silicone DC11PA, Torre Silicone SH21PA, Torre Silicone SH28PA, Torre Silicone SH29PA, Torre Silicone SH30PA, Torre Silicone SH8400 (above, Toray). ⁇ Made by Dow Corning Co., Ltd .; X-22-4952, X-22-2272, X-22-6266, KF-351A, K354L, KF-355A, KF-945, KF-640, KF-642, KF-643, X-22-6191, X-22-4515, KF-6004, KP-341, KF-6001, KF-6002 (all manufactured by Shin-Etsu Silicone Co., Ltd.); F-4440, TSF-4300, TSF-4445, TSF-4460, TSF-4452 (all manufactured by Momentive Performance Materials); BYK307, BYK32
• Nonionic surfactants include glycerol, trimethylolpropane, trimethylolethane and their ethoxylates and propoxylates (eg, glycerol propoxylate, glycerol ethoxylate, etc.), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, etc. Examples thereof include polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, and sorbitan fatty acid ester.
• nonionic surfactants include Pluronic® L10, L31, L61, L62, 10R5, 17R2, 25R2 (above, manufactured by BASF); Tetronic 304, 701, 704, 901, 904, 150R1 (above, manufactured by BASF); Solspers 20000 (manufactured by Nippon Lubrizol Co., Ltd.); NCW-101, NCW-1001, NCW-1002 (all manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.); Pionin D-6112, D-6112-W, D-6315 (all manufactured by Takemoto Oil & Fat Co., Ltd.); Orphine E1010, Surfinol 104, 400, 440 (all manufactured by Nisshin Kagaku Kogyo Co., Ltd.) and the like can be mentioned.
• the surfactant may be used alone or in combination of two or more.
• the content of the surfactant is preferably 0.01 to 3.0% by mass, preferably 0.05 to 1.% by mass, based on the total mass of the photosensitive composition layer. 0% by mass is more preferable, and 0.10 to 0.80% by mass is further preferable.
• the photosensitive composition layer preferably contains a hydrogen donating compound.
• the hydrogen-donating compound has actions such as further improving the sensitivity of the photopolymerization initiator to active light and suppressing the polymerization inhibition of the polymerizable compound by oxygen.
• Examples of the hydrogen donating compound include amines, for example, M.I. R. "Journal of Polymer Society" by Sander et al., Vol. 10, p. 3173 (1972), JP-A-44-02018, JP-A-51-081022, JP-A-52-134692, JP-A-59-138205. Examples thereof include compounds described in Japanese Patent Application Laid-Open No. 60-084305, Japanese Patent Application Laid-Open No. 62-018537, Japanese Patent Application Laid-Open No. 64-033104, Research Disclosure No. 33825, and the like.
• Examples of the hydrogen donating compound include triethanolamine, p-dimethylaminobenzoic acid ethyl ester, p-formyldimethylaniline, and p-methylthiodimethylaniline.
• Examples of the hydrogen donating compound include an amino acid compound (N-phenylglycine, etc.), an organometallic compound (tributyltin acetate, etc.) described in Japanese Patent Publication No. 48-042965, and hydrogen described in Japanese Patent Publication No. 55-034414. Donors and sulfur compounds (Tritian and the like) described in JP-A-6-308727 are also mentioned.
• the photosensitive composition layer may contain one kind of hydrogen donating compound alone, or may contain two or more kinds of hydrogen donating compounds.
• the content of the hydrogen donating compound is adjusted to the total mass of the photosensitive composition layer in terms of improving the curing rate due to the balance between the polymerization growth rate and the chain transfer.
• 0.01 to 10% by mass is preferable, 0.03 to 5% by mass is more preferable, and 0.05 to 3% by mass is further preferable.
• the photosensitive composition layer may contain components other than the components described above (hereinafter, also referred to as “other components”).
• Other components include, for example, particles (eg, metal oxide particles), sensitizers, and colorants.
• examples of other components include the thermal polymerization inhibitor described in paragraph [0018] of Japanese Patent No. 4502784, and other components described in paragraphs [0058] to [0071] of Japanese Patent Application Laid-Open No. 2000-310706. Additives can also be mentioned.
• the photosensitive composition layer may contain particles for the purpose of adjusting the refractive index, light transmittance, and the like.
• the particles include metal oxide particles.
• the metal in the metal oxide particles also includes metalloids such as B, Si, Ge, As, Sb, and Te.
• the average primary particle size of the particles is preferably 1 to 200 nm, more preferably 3 to 80 nm, for example, from the viewpoint of pattern transparency.
• the average primary particle size of the particles is calculated by measuring the particle size of 200 arbitrary particles using an electron microscope and arithmetically averaging the measurement results. When the shape of the particle is not spherical, the longest side is the particle diameter.
• the photosensitive composition layer may contain particles of one type alone, or may contain particles of two or more types. When the photosensitive composition layer contains particles, it may contain only one type of particles having different metal types, sizes, etc., or may contain two or more types of particles.
• the photosensitive composition layer does not contain particles, or the content of the particles is preferably more than 0% by mass and 35% by mass or less with respect to the total mass of the photosensitive composition layer, and contains particles. It is more preferable that there is no particle or the content of the particles is more than 0% by mass and 10% by mass or less based on the total mass of the photosensitive composition layer, and the content of the particles is not contained or the content of the particles is not contained. Is more preferably more than 0% by mass and 5% by mass or less with respect to the total mass of the photosensitive composition layer, and either does not contain particles or the content of particles is the total mass of the photosensitive composition layer. It is particularly preferable that it exceeds 0% by mass and 1% by mass or less, and it is most preferable that it does not contain particles.
• the photosensitive composition layer may contain a trace amount of a colorant (for example, a pigment and a dye), but for example, from the viewpoint of transparency, it is preferable that the photosensitive composition layer contains substantially no colorant.
• a colorant for example, a pigment and a dye
• the content of the colorant is preferably less than 1% by mass, more preferably less than 0.1% by mass, based on the total mass of the photosensitive composition layer.
• the photosensitive composition layer may contain a predetermined amount of impurities.
• impurities include sodium, potassium, magnesium, calcium, iron, manganese, copper, aluminum, titanium, chromium, cobalt, nickel, zinc, tin, halogen and ions thereof.
• halide ions, sodium ions, and potassium ions are likely to be mixed as impurities, so the content is preferably as follows.
• the content of impurities in the photosensitive composition layer is preferably 80 ppm or less, more preferably 10 ppm or less, still more preferably 2 ppm or less on a mass basis.
• the content of impurities in the photosensitive composition layer can be 1 ppb or more or 0.1 ppm or more on a mass basis.
• a material having a low content of impurities is selected as a raw material of the photosensitive composition layer, and the mixing of impurities is prevented during the formation of the photosensitive composition layer, and cleaning is performed. Removal is mentioned.
• the amount of impurities can be kept within the above range.
• the impurities can be quantified by known methods such as ICP (Inductively Coupled Plasma) emission spectroscopy, atomic absorption spectroscopy, and ion chromatography.
• ICP Inductively Coupled Plasma
• the content of compounds such as benzene, formaldehyde, trichlorethylene, 1,3-butadiene, carbon tetrachloride, chloroform, N, N-dimethylformamide, N, N-dimethylacetamide, and hexane in the photosensitive composition layer is Less is preferable.
• the content of these compounds in the photosensitive composition layer is preferably 100 ppm or less, more preferably 20 ppm or less, still more preferably 4 ppm or less on a mass basis.
• the lower limit is based on mass and can be 10 ppb or more, and can be 100 ppb or more.
• the content of these compounds can be suppressed in the same manner as the above-mentioned metal impurities. Moreover, it can be quantified by a known measurement method.
• the water content in the photosensitive composition layer is preferably 0.01 to 1.0% by mass, more preferably 0.05 to 0.5% by mass, from the viewpoint of improving reliability and laminateability.
• the thickness of the photosensitive composition layer is not particularly limited, but is preferably 10.0 ⁇ m or less, more preferably 8.0 ⁇ m or less.
• the lower limit of the thickness of the photosensitive composition layer is not limited. The smaller the thickness of the photosensitive composition layer, the better the bending resistance.
• the lower limit of the thickness of the photosensitive composition layer is preferably 0.05 ⁇ m or more from the viewpoint of manufacturing suitability.
• the lower limit of the thickness of the photosensitive composition layer is preferably 0.5 ⁇ m or more, more preferably 1.1 ⁇ m or more, from the viewpoint of improving the protective property of the transparent resin layer.
• the thickness of the photosensitive composition layer is calculated as an average value of 5 arbitrary points measured by cross-sectional observation with a scanning electron microscope (SEM).
• the refractive index of the photosensitive composition layer is preferably 1.47 to 1.56, more preferably 1.49 to 1.54.
• the photosensitive composition layer is preferably achromatic.
• the a * value of the photosensitive composition layer is preferably ⁇ 1.0 to 1.0
• the b * value of the photosensitive composition layer is -1. It is preferably 0 to 1.0.
• [Humidity permeability of photosensitive composition layer] Moisture permeability of a film thickness 40 ⁇ m pattern obtained by curing the photosensitive composition layer (cured film of the photosensitive composition layer), from the viewpoint of corrosion resistance, not more than 500g / m 2 / 24hr preferably, more preferably not more than 300g / m 2 / 24hr, more preferably not more than 100g / m 2 / 24hr.
• the photosensitive composition layer was cured by exposing the photosensitive composition layer with an i-ray at an exposure amount of 300 mJ / cm 2 and then performing post-baking at 145 ° C. for 30 minutes. Measure with a cured film.
• the transfer film may include layers other than the temporary support and the photosensitive composition layer described above.
• the transfer film may have a protective film for protecting the photosensitive composition layer on the surface opposite to the temporary support.
• the protective film is preferably a resin film, and a resin film having heat resistance and solvent resistance can be used.
• a polyolefin film such as a polypropylene film and a polyethylene film
• a polyester film such as a polyethylene terephthalate film
• a polycarbonate film and the like.
• polystyrene film can be mentioned.
• a resin film made of the same material as the above-mentioned temporary support may be used as the above-mentioned temporary support.
• the thickness of the protective film is preferably 1 to 100 ⁇ m, more preferably 5 to 50 ⁇ m, further preferably 5 to 40 ⁇ m, and particularly preferably 15 to 30 ⁇ m.
• the thickness of the protective film is preferably 1 ⁇ m or more in terms of excellent mechanical strength, and preferably 100 ⁇ m or less in that it is relatively inexpensive. Further, in the protective film, it is preferable that the number of fish eyes having a diameter of 80 ⁇ m or more contained in the protective film is 5 / m 2 or less. “Fisheye” refers to foreign substances, undissolved substances, oxidatively deteriorated substances, etc.
• the number of diameter 3 ⁇ m or more of the particles contained in the protective film is preferably 30 / mm 2 or less, more preferably 10 / mm 2 or less, more preferably 5 / mm 2 or less.
• the arithmetic mean roughness Ra of the surface of the protective film opposite to the photosensitive composition layer is preferably 0.01 ⁇ m or more, more preferably 0.02 ⁇ m or more, and 0.03 ⁇ m or more, from the viewpoint of imparting winding property. Is more preferable. On the other hand, less than 0.50 ⁇ m is preferable, 0.40 ⁇ m or less is more preferable, and 0.30 ⁇ m or less is further preferable. From the viewpoint of suppressing defects during transfer, the protective film preferably has a surface roughness Ra of the surface on the photosensitive composition layer side of 0.01 ⁇ m or more, more preferably 0.02 ⁇ m or more, and even more preferably 0.03 ⁇ m or more. On the other hand, less than 0.50 ⁇ m is preferable, 0.40 ⁇ m or less is more preferable, and 0.30 ⁇ m or less is further preferable.
• the transfer film may have a refractive index adjusting layer.
• the position of the refractive index adjusting layer is not particularly limited, but it is preferably arranged in contact with the photosensitive composition layer.
• the transfer film preferably has a temporary support, a photosensitive composition layer, and a refractive index adjusting layer in this order.
• the temporary support, the photosensitive composition layer, the refractive index adjusting layer, and the protective film it is preferable to have the temporary support, the photosensitive composition layer, the refractive index adjusting layer, and the protective film in this order.
• the refractive index adjusting layer As the refractive index adjusting layer, a known refractive index adjusting layer can be applied. Examples of the material contained in the refractive index adjusting layer include a binder and particles.
• binder examples include the alkali-soluble resin described in the above section "Photosensitive composition layer”.
• the particles include zirconium oxide particles (ZrO 2 particles), niobium oxide particles (Nb 2 O 5 particles), titanium oxide particles (TiO 2 particles), and silicon dioxide particles (SiO 2 particles).
• the refractive index adjusting layer preferably contains a metal oxidation inhibitor.
• a metal oxidation inhibitor for example, a compound having an aromatic ring containing a nitrogen atom in the molecule is preferable.
• the metal oxidation inhibitor include imidazole, benzimidazole, tetrazole, mercaptothiadiazole, and benzotriazole.
• the refractive index of the refractive index adjusting layer is preferably 1.60 or more, more preferably 1.63 or more.
• the upper limit of the refractive index of the refractive index adjusting layer is preferably 2.10 or less, and more preferably 1.85 or less.
• the thickness of the refractive index adjusting layer is preferably 500 nm or less, more preferably 110 nm or less, and even more preferably 100 nm or less.
• the thickness of the refractive index adjusting layer is preferably 20 nm or more, more preferably 50 nm or more.
• the thickness of the refractive index adjusting layer is calculated as an average value of 5 arbitrary points measured by cross-sectional observation with a scanning electron microscope (SEM).
• the method for producing the transfer film of the present invention is not particularly limited, and a known method can be used. Among them, a method of applying a photosensitive composition on a temporary support and, if necessary, performing a drying treatment to form a photosensitive composition layer is preferable from the viewpoint of excellent productivity. Hereinafter, the above method will be described in detail.
• the photosensitive composition preferably contains the components constituting the above-mentioned photosensitive composition layer (for example, a polymerizable compound, an alkali-soluble resin, a photopolymerization initiator, etc.), and a solvent.
• a solvent an organic solvent is preferable.
• the organic solvent include methyl ethyl ketone, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate (also known as 1-methoxy-2-propyl acetate), diethylene glycol ethyl methyl ether, cyclohexanone, methyl isobutyl ketone, ethyl lactate, methyl lactate, and caprolactam.
• a mixed solvent of methyl ethyl ketone and propylene glycol monomethyl ether acetate or a mixed solvent of diethylene glycol ethyl methyl ether and propylene glycol monomethyl ether acetate is preferable.
• the photosensitive composition may contain one kind of solvent alone, or may contain two or more kinds of solvents.
• the total solid content of the photosensitive composition is preferably 5 to 80% by mass, more preferably 5 to 40% by mass, or 5 to 40% by mass, based on the total mass of the photosensitive composition. 30% by mass is more preferable.
• the viscosity of the photosensitive composition at 25 ° C. is preferably 1 to 50 mPa ⁇ s, more preferably 2 to 40 mPa ⁇ s, and 3 to 30 mPa ⁇ s, for example, from the viewpoint of coatability. s is more preferable. Viscosity is measured using a viscometer.
• a viscometer manufactured by Toki Sangyo Co., Ltd. (trade name: VISCOMETER TV-22) can be preferably used.
• the viscometer is not limited to the above-mentioned viscometer.
• the surface tension of the photosensitive composition at 25 ° C. is, for example, preferably 5 to 100 mN / m, more preferably 10 to 80 mN / m, and 15 to 40 mN from the viewpoint of coatability. / M Is more preferable.
• Surface tension is measured using a tensiometer.
• a surface tension meter for example, a surface tension meter (trade name: Automatic Surface Tensiometer CBVP-Z) manufactured by Kyowa Interface Science Co., Ltd. can be preferably used.
• the tensiometer is not limited to the above-mentioned tensiometer.
• Examples of the method for applying the photosensitive composition include a printing method, a spray method, a roll coating method, a bar coating method, a curtain coating method, a spin coating method, and a die coating method (that is, a slit coating method).
• drying examples include natural drying, heat drying, and vacuum drying.
• drying means removing at least a portion of the solvent contained in the composition.
• the transfer film has a refractive index adjusting layer on the photosensitive composition layer
• the composition for forming the refractive index adjusting layer is applied on the photosensitive composition layer, and if necessary, it is refracted by drying.
• a rate adjustment layer can be formed.
• the transfer film When the transfer film has a protective film, the transfer film can be produced by adhering the protective film to the photosensitive composition layer.
• the method of attaching the protective film to the photosensitive composition layer is not particularly limited, and known methods can be mentioned.
• Examples of the device for adhering the protective film to the photosensitive composition layer include a vacuum laminator and a known laminator such as an auto-cut laminator. It is preferable that the laminator is provided with an arbitrary heatable roller such as a rubber roller and can be pressurized and heated.
• the photosensitive composition layer can be transferred to the object to be transferred.
• the transfer material is not particularly limited, but a substrate having a conductive layer is preferable.
• the method for producing the laminate includes a bonding step of bonding the transfer film to the substrate so that the photosensitive composition layer side of the transfer film faces the substrate having the conductive layer to obtain a substrate with the photosensitive composition layer.
• the second photopolymerization initiator has a post-exposure step of irradiating light to be exposed, and further, a photosensitive composition is provided between the bonding step and the exposure step, or between the exposure step and the developing step.
• a method for producing a laminate having a peeling step of peeling the temporary support from the substrate with a material layer is preferable.
• the pattern is arranged on the substrate having the conductive layer.
• the procedure of each step of the laminated body will be described in detail.
• the bonding step is a step of bonding the transfer film to the substrate so that the photosensitive composition layer side of the transfer film faces the substrate having the conductive layer to obtain a substrate with the photosensitive composition layer. That is, the transfer film and the substrate are bonded together with the photosensitive composition layer facing the substrate side rather than the support in the transfer film. By this bonding, the photosensitive composition layer and the temporary support are arranged on the substrate having the conductive layer. In the bonding, it is preferable that the conductive layer and the surface of the photosensitive composition layer are pressure-bonded so as to be in contact with each other. In the above aspect, the pattern obtained after exposure and development can be suitably used as an etching resist when etching the conductive layer.
• the crimping method is not particularly limited, and a known transfer method and laminating method can be used. Above all, it is preferable to superimpose the surface of the photosensitive composition layer on a substrate having a conductive layer, pressurize and heat with a roll or the like.
• a known laminator such as a vacuum laminator and an auto-cut laminator can be used for bonding.
• the substrate having a conductive layer has a conductive layer on the substrate, and an arbitrary layer may be formed if necessary. That is, the substrate having the conductive layer is a conductive substrate having at least a substrate and a conductive layer arranged on the substrate. Examples of the substrate include a resin substrate, a glass substrate, and a semiconductor substrate. Preferred embodiments of the substrate are described, for example, in paragraph 0140 of WO 2018/155193, the contents of which are incorporated herein.
• the conductive layer includes at least one layer selected from the group consisting of a metal layer, a conductive metal oxide layer, a graphene layer, a carbon nanotube layer, and a conductive polymer layer from the viewpoint of conductivity and fine wire forming property. preferable. Further, only one conductive layer may be arranged on the substrate, or two or more conductive layers may be arranged. When two or more conductive layers are arranged, it is preferable to have conductive layers made of different materials. Preferred embodiments of the conductive layer are described, for example, in paragraph 0141 of WO 2018/155193, the contents of which are incorporated herein.
• the conductive layer has a sensor electrode portion for the touch panel and a lead-out wiring portion that conducts with the sensor electrode for the touch panel. That is, the substrate having the conductive layer is preferably a substrate having a touch panel sensor electrode portion and a lead-out wiring portion conducting with the touch panel sensor electrode.
• the exposure step is a step of pattern-exposing the photosensitive composition layer with light having a wavelength of 365 nm as a main wavelength.
• the first photopolymerization initiator having high photosensitivity at a wavelength of 365 nm is exposed to light, and the polymerizable compound is polymerized.
• the "pattern exposure” refers to an exposure in a form of exposing in a pattern, that is, a form in which an exposed portion and a non-exposed portion are present.
• the detailed arrangement and specific size of the pattern in the pattern exposure are not particularly limited.
• the pattern formed by the developing step described later preferably includes thin lines having a width of 20 ⁇ m or less, and more preferably contains thin lines having a width of 10 ⁇ m or less.
• any light source having a wavelength of at least 365 nm as a main wavelength (exposure light) can be appropriately selected and used.
• the main wavelength is the wavelength having the highest intensity in the exposure light.
• Exposure is preferably 5 ⁇ 200mJ / cm 2, more preferably 10 ⁇ 100mJ / cm 2.
• the exposure step is carried out before the peeling step described later is carried out, the exposure is carried out with the temporary support remaining on the photosensitive composition layer.
• the temporary support side When exposure is performed from the temporary support side, a part of the light of the exposure (particularly the light on the short wavelength side) is easily absorbed by the temporary support, and as a result, the light on the long wavelength side of the light emitted from the light source is emitted. Easy to reach the photosensitive composition. That is, by carrying out the peeling step between the exposure step and the development step described later, it is easy to realize the exposure conditions in which the second photopolymerization initiator is hard to be exposed and the first photopolymerization initiator is easily exposed to light.
• the peeling step is a step of peeling the temporary support from the substrate with the photosensitive composition layer between the bonding step and the exposure step, or between the exposure step and the development step described later.
• the peeling method is not particularly limited, and a mechanism similar to the cover film peeling mechanism described in paragraphs [0161] to [0162] of JP-A-2010-072589 can be used.
• the developing step is a step of developing the exposed photosensitive composition layer to form a pattern.
• the development of the photosensitive composition layer can be carried out using a developing solution.
• An alkaline aqueous solution is preferable as the developing solution.
• the alkaline compound that can be contained in the alkaline aqueous solution include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, tetramethylammonium hydroxide, tetraethylammonium hydroxide, and tetrapropylammonium hydroxide. Do, tetrabutylammonium hydroxide, and choline (2-hydroxyethyltrimethylammonium hydroxide).
• Examples of the development method include paddle development, shower development, spin development, and dip development.
• Examples of the developing solution preferably used in the present disclosure include the developing solution described in paragraph [0194] of International Publication No. 2015/093271.
• Examples of the developing method preferably used include International Publication No. 2015. The developing method described in paragraph [0195] of No. 093271 can be mentioned.
• the post-exposure step is a step of irradiating the pattern obtained by the above-mentioned developing step with light exposed by the second photopolymerization initiator. By carrying out this step, it is difficult to be exposed to light in the exposure step, the remaining second photopolymerization initiator is exposed to light, and the polymerizable compound is further polymerized to form a pattern having excellent scratch resistance.
• any light (exposure light) exposed to the second photopolymerization initiator can be appropriately selected and used. Above all, it is preferable to irradiate light (exposure light) containing the above-mentioned maximum absorption wavelength light of the second photopolymerization initiator.
• the light irradiated in this step preferably contains light of 313 nm.
• the light source examples include various lasers, light emitting diodes (LEDs), ultra-high pressure mercury lamps, high pressure mercury lamps, and metal halide lamps.
• the exposure amount is not particularly limited, but it is preferably larger than the exposure amount in the above exposure step. Specifically, preferably 100 ⁇ 600mJ / cm 2, more preferably 300 ⁇ 500mJ / cm 2.
• the pattern (cured film of the photosensitive composition layer) formed by the above procedure is preferably achromatic.
• the a * value of the pattern is preferably -1.0 to 1.0
• the b * value of the pattern is -1.0 to 1 It is preferably 0.0.
• the method for producing a laminate of the present invention may include any steps (other steps) other than those described above.
• the transfer film has a protective film
• the method of peeling the protective film is not particularly limited, and a known method can be adopted.
• the cover film peeling mechanism described in paragraphs [0161] to [0162] of JP-A-2010-072589 can be used.
• the method for producing a laminate of the present invention may include a step of heating the obtained pattern (post-baking step).
• the heating temperature during the post-baking step is not particularly limited, but is preferably 110 to 180 ° C.
• the method for producing the laminated body may include an etching step of etching the conductive layer in the region where the pattern is not arranged in the obtained laminated body.
• the etching step the pattern formed from the photosensitive composition layer by the developing step is used as an etching resist, and the conductive layer is etched.
• Examples of the etching treatment method include the methods described in paragraphs [0209] to [0210] of JP-A-2017-120435, paragraphs [0048] to paragraph [0054] of JP-A-2010-152155, and the like.
• Known methods such as a method and a method by dry etching such as known plasma etching can be applied.
• the method for producing a laminated body may include a removing step of removing a pattern.
• the removal step can be performed as needed, but is preferably performed after the etching step.
• the method for removing the pattern is not particularly limited, but a method for removing the pattern by chemical treatment can be mentioned, and it is preferable to use a removing liquid.
• a method for removing the pattern a method of immersing the laminate having the pattern in the removing liquid being stirred at preferably 30 to 80 ° C., more preferably 50 to 80 ° C. for 1 to 30 minutes can be mentioned.
• the removing liquid examples include inorganic alkaline components such as sodium hydroxide and potassium hydroxide, or organic alkalis such as primary amine compounds, secondary amine compounds, tertiary amine compounds, and quaternary ammonium salt compounds. Examples thereof include a removal solution in which the components are dissolved in water, dimethylsulfoxide, N-methylpyrrolidone, or a mixed solution thereof. Further, the removing liquid may be used and removed by a spray method, a shower method, a paddle method or the like.
• inorganic alkaline components such as sodium hydroxide and potassium hydroxide
• organic alkalis such as primary amine compounds, secondary amine compounds, tertiary amine compounds, and quaternary ammonium salt compounds. Examples thereof include a removal solution in which the components are dissolved in water, dimethylsulfoxide, N-methylpyrrolidone, or a mixed solution thereof.
• the removing liquid may be used and removed by a spray method, a shower method, a
• the method for producing the laminate may include a step of reducing the visible light reflectance described in paragraph [0172] of International Publication No. 2019/022089. Further, the method for producing the laminate may include a step of forming a new conductive layer on the insulating film described in paragraph [0172] of International Publication No. 2019/022089.
• the laminate produced by the method for producing a laminate of the present invention can be applied to various devices.
• the device provided with the laminated body include an input device and the like, and a touch panel is preferable, and a capacitance type touch panel is more preferable.
• the input device can be applied to a display device such as an organic electroluminescence display device and a liquid crystal display device.
• the pattern formed from the photosensitive composition layer is preferably used as a protective film for the touch panel electrodes. That is, the photosensitive composition layer contained in the transfer film is preferably used for forming an electrode protective film (particularly, a touch panel electrode protective film).
• the present disclosure will be described in more detail with reference to Examples below.
• the materials, amounts used, proportions, treatment contents, treatment procedures, etc. shown in the following examples can be appropriately changed as long as they do not deviate from the gist of the present disclosure. Therefore, the scope of the present disclosure is not limited to the specific examples shown below.
• "parts" and "%" are based on mass.
• the weight average molecular weight of the resin is the weight average molecular weight determined by gel permeation chromatography (GPC) in terms of polystyrene.
• GPC gel permeation chromatography
• the theoretical acid value was used as the acid value.
• the photosensitive compositions A-1 to A-32 and A'-1 to A'-3 were prepared so as to have the compositions shown in Tables 1 to 5 below.
• the numerical values in the respective component columns in Tables 1 to 5 represent parts by mass.
• the dropping solution (1) As the preparation of the dropping solution (1), 107.1 g of methacrylic acid (manufactured by Mitsubishi Rayon, trade name Acryester M), methyl methacrylate (manufactured by Mitsubishi Gas Chemical Company, trade name MMA) (5.46 g), and cyclohexyl methacrylate (made by Mitsubishi Gas Chemical Company, trade name MMA) and cyclohexyl methacrylate (1).
• a dropping liquid (1) was obtained by mixing Mitsubishi Gas Chemical Co., Ltd., trade name CHMA) (231.42 g) and diluting with PGM-Ac (60 g).
• dimethyl 2,2'-azobis (2-methylpropionate) (manufactured by Wako Pure Chemical Industries, Ltd., trade name V-601) (9.637 g) was added to PGM-Ac (136.56 g). ) was dissolved to obtain a dropping liquid (2).
• the dropping liquid (1) and the dropping liquid (2) were simultaneously added dropwise to the above-mentioned 2000 mL flask (specifically, a 2000 mL flask containing a liquid heated to 90 ° C.) over 3 hours.
• the container of the dropping liquid (1) was washed with PGM-Ac (12 g), and the washing liquid was dropped into the above 2000 mL flask.
• the container of the dropping liquid (2) was washed with PGM-Ac (6 g), and the washing liquid was dropped into the above 2000 mL flask.
• the reaction solution in the 2000 mL flask was kept at 90 ° C. and stirred at a stirring speed of 250 rpm. Further, as a post-reaction, the mixture was stirred at 90 ° C. for 1 hour.
• V-601 (2.401 g) was added to the reaction solution after the post-reaction as the first additional addition of the initiator. Further, the container of V-601 was washed with PGM-Ac (6 g), and the washing liquid was introduced into the reaction liquid. Then, the mixture was stirred at 90 ° C. for 1 hour.
• V-601 (2.401 g) was added to the reaction solution as the second additional addition of the initiator. Further, the container of V-601 was washed with PGM-Ac (6 g), and the washing liquid was introduced into the reaction liquid. Then, the mixture was stirred at 90 ° C. for 1 hour. Next, V-601 (2.401 g) was added to the reaction solution as the third additional addition of the initiator. Further, the container of V-601 was washed with PGM-Ac (6 g), and the washing liquid was introduced into the reaction liquid. Then, the mixture was stirred at 90 ° C. for 3 hours. -Additional process- After stirring at 90 ° C.
• glycidyl methacrylate manufactured by NOF CORPORATION, trade name Blemmer G (76.03 g) was added dropwise to the reaction solution over 1 hour.
• the container of Blemmer G was washed with PGM-Ac (6 g), and the washing liquid was introduced into the reaction liquid. Then, as an addition reaction, the mixture was stirred at 100 ° C. for 6 hours.
• the reaction solution was cooled and filtered through a mesh filter (100 mesh) for removing dust to obtain a solution of polymer D (1158 g) (solid content concentration: 36.3% by mass).
• the obtained polymer P-1 had a weight average molecular weight of 27,000, a number average molecular weight of 15,000, and an acid value of 95 mgKOH / g. P-1 (Hereinafter, the molar ratio of the repeating unit in the formula was 51.5: 2: 26.5: 20 in order from the repeating unit on the left side.)
• V-601 was added three times every hour. After that, it was reacted for another 3 hours. Then, it was diluted with 160.7 g of propylene glycol monomethyl ether acetate and 233.3 g of propylene glycol monomethyl ether. The temperature of the reaction solution was raised to 100 ° C. under an air stream, and 1.8 g of tetraethylammonium bromide and 0.86 g of p-methoxyphenol were added. To this, 71.9 g of glycidyl methacrylate (NOF Corporation Blemmer G) was added dropwise over 20 minutes. This was reacted at 100 ° C. for 7 hours to obtain a solution of resin P-5.
• NOF Corporation Blemmer G glycidyl methacrylate
• the solid content concentration of the obtained solution was 36.2%.
• the weight average molecular weight in terms of standard polystyrene in GPC was 18,000, the dispersity was 2.3, and the acid value of the polymer was 124 mgKOH / g.
• the amount of residual monomer measured by gas chromatography was less than 0.1% by mass with respect to the polymer solid content in any of the monomers.
• P-5 (Hereinafter, the molar ratio of the repeating unit in the formula was 55.1: 26.5: 1.6: 16.9 in order from the repeating unit on the left side.)
• compositions B to B-4 for forming a refractive index adjusting layer were prepared with the compositions shown in Table 8 below.
• the numerical values in Table 6 represent "parts by mass”.
• Polymer A in Table 8 was synthesized as follows.
• 1-Methylenepropanol manufactured by Tokyo Kasei Co., Ltd.
• 270.0 g was introduced into a 1 L three-necked flask, and the temperature was raised to 70 ° C. under a nitrogen stream while stirring.
• allyl methacrylate (45.6 g) (manufactured by FFWK) and methacrylic acid (14.4 g) (manufactured by FFWK) were dissolved in 1-methoxypropanol (manufactured by Tokyo Kasei Co., Ltd.) (270.0 g), and further.
• a dropping solution was prepared by dissolving 3.94 g of V-65 (manufactured by FFWK), and the dropping solution was dropped into the flask over 2.5 hours. The reaction was carried out while maintaining the stirred state for 2.0 hours. Then, the temperature was returned to room temperature, the mixture was added dropwise to ion-exchanged water (2.7 L) in a stirred state, and reprecipitation was carried out to obtain a turbid solution. Filtration was carried out by introducing a turbid solution in Nutche with a filter paper, and the filtered material was further washed with ion-exchanged water to obtain a wet powder.
• Examples 33 to 52> Except that the photosensitive compositions A-33 to A-52 were used instead of the photosensitive composition A-1, and the coating amount was adjusted so that the thickness of the photosensitive composition layer after drying was 5.0 ⁇ m.
• Transfer films X33 to X52 were obtained according to the same procedure as in Example 1.
• a cycloolefin resin film having a film thickness of 38 ⁇ m and a refractive index of 1.53 is used as a wire electrode having an output voltage of 100% and an output of 250 W and a diameter of 1.2 mm using a high-frequency oscillator.
• a corona discharge treatment was carried out for 3 seconds under the condition of 5 mm, and the surface was modified to obtain a transparent substrate.
• the material-C shown in Table 9 below is applied to the corona discharge-treated surface of the transparent substrate using a slit-shaped nozzle, and then irradiated with ultraviolet rays (integrated light amount 300 mJ / cm 2 ) to about 110 ° C.
• a transparent film having a refractive index of 1.60 and a film thickness of 80 nm was formed by drying with.
• DC) Magnetron sputtering (conditions: transparent substrate temperature 150 ° C., argon pressure 0.13 Pa, oxygen pressure 0.01 Pa) formed an ITO thin film having a thickness of 40 nm and a refractive index of 1.82 on the transparent film.
• the surface resistance of the ITO thin film was 80 ⁇ / ⁇ (squares per ⁇ ).
• the ITO thin film was etched and patterned by a known chemical etching method to obtain a conductive substrate having a transparent film and a transparent electrode portion on a transparent substrate.
• the protective film of the transfer film 1 obtained above is peeled off, the surface of the exposed photosensitive composition layer is brought into contact with the forming surface of the transparent electrode portion of the conductive substrate, and the photosensitive composition layer is formed into the transparent electrode portion.
• laminating (bonding) so as to cover the above, a laminate in which the photosensitive composition layer and the temporary support were arranged was formed on the conductive substrate.
• the laminating was carried out using a vacuum laminator manufactured by MCK under the conditions of a transparent substrate temperature of 40 ° C., a rubber roller temperature of 100 ° C., a linear pressure of 3 N / cm, and a transport speed of 2 m / min.
• the surface of the exposure mask (quartz exposure mask including the pattern for forming an overcoat) surface and the temporary support were brought into close contact with each other.
• a pattern exposure was performed with an exposure amount of 60 mJ / cm 2 (i-line) via the temporary support.
• the main wavelength of the exposure light at the time of irradiation was light having a wavelength of 365 nm.
• the exposed photosensitive composition layer was developed for 60 seconds using a 1% by mass aqueous solution of sodium carbonate at a temperature of 32 ° C. Then, the residue was removed by injecting ultrapure water from the ultrapure water cleaning nozzle onto the laminate after the development treatment. Subsequently, air was blown onto the surface of the laminated chia to remove water. Next, the obtained pattern was exposed to an exposure amount of 400 mJ / cm 2 (i-line) using a post-exposure machine (manufactured by Ushio, Inc.) including a high-pressure mercury lamp (post-exposure). Then, a post-baking treatment at 145 ° C. for 30 minutes was performed to form a laminated body LX1 having a transparent film, a transparent electrode portion, and a pattern (a cured film of a photosensitive composition layer) on a transparent substrate in this order. ..
• Laminates LX2-52 and LC1-4 were formed according to the above procedure, except that transfer films X2-52 and C1-C4 were used instead of the transfer film X1, respectively.
• ⁇ 1 represents the molar extinction coefficient of the first photopolymerization initiator at a wavelength of 365 nm
• ⁇ 2 represents the molar extinction coefficient of the second photopolymerization initiator at a wavelength of 365 nm
• ⁇ 3 is It represents the molar extinction coefficient of the second photopolymerization initiator at a wavelength of 313 nm.
• Examples 101 to 152 In the production of the transfer film of Example 1, a composition for forming a refractive index adjusting layer is used on the photosensitive composition layer so that the thickness of the refractive index adjusting layer after drying is 70 nm. The coating amount of the substance B was adjusted, and the composition B for forming the refractive index adjusting layer was applied. Next, the obtained coating film was dried at a drying temperature of 80 ° C. to form a refractive index adjusting layer on the photosensitive composition layer. The refractive index of the refractive index adjusting layer was 1.68.
• a protective film (Lumirror 16KS40 (manufactured by Toray Industries, Inc.) was pressure-bonded to the surface of the refractive index adjusting layer to prepare a transfer film Y1.
• the same procedure as described above was carried out to prepare the transfer films Y2 to Y52 including the refractive index adjusting layer corresponding to Examples 101 to 152.
• the same procedure as above was carried out except that the composition B for forming the refractive index adjusting layer was changed to B-2 to B-4, and the transfer films Y34-2 to Y34- 4 was prepared.
• these transfer films Y34-2 to Y34-4 were used in the same manner as ⁇ edge shape evaluation (pattern linearity)> and ⁇ scratch resistance evaluation (surface scratch evaluation)>, each transfer film was evaluated. A result similar to the result of the transfer film of Example 34 corresponding to the embodiment not including the refractive index adjusting layer was obtained.
• the thickness of the photosensitive resin layer was adjusted in the same manner as in Example 1 except that the coating amount was adjusted in Example 1 to adjust the thickness of the photosensitive resin layer to 1.0 ⁇ m, 2.0 ⁇ m, and 4.0 ⁇ m, respectively.
• the coating amount was adjusted in Example 1 to adjust the thickness of the photosensitive resin layer to 1.0 ⁇ m, 2.0 ⁇ m, and 4.0 ⁇ m, respectively.
• Photosensitivity was performed in the same manner as in Example 1 except that the coating amount was adjusted in Example 34 to adjust the thickness of the photosensitive resin layer to 1.0 ⁇ m, 2.0 ⁇ m, 4.0 ⁇ m, and 8.0 ⁇ m, respectively.
• Transfer films having different thicknesses of the sex resin layers were prepared and evaluated in the same manner as ⁇ edge shape evaluation (pattern linearity)> and ⁇ scratch resistance evaluation (surface scratch evaluation)>. Results were obtained.
• transfer films having different refractive index adjustment layer thicknesses were produced in the same manner as Y34 except that the thickness of the refractive index adjustment layer was adjusted to 40 nm, 100 nm, and 150 nm, respectively.

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