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
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
• • G—PHYSICS
  • 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; CALCULATING OR COUNTING
  • G06F—ELECTRIC DIGITAL DATA PROCESSING
  • G06F3/00—Input arrangements for transferring data to be processed into a form capable of being handled by the computer; Output arrangements for transferring data from processing unit to output unit, e.g. interface arrangements
  • G06F3/01—Input arrangements or combined input and output arrangements for interaction between user and computer
  • G06F3/03—Arrangements for converting the position or the displacement of a member into a coded form
  • G06F3/041—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means
• • G—PHYSICS
  • G06—COMPUTING; CALCULATING OR COUNTING
  • G06F—ELECTRIC DIGITAL DATA PROCESSING
  • G06F3/00—Input arrangements for transferring data to be processed into a form capable of being handled by the computer; Output arrangements for transferring data from processing unit to output unit, e.g. interface arrangements
  • G06F3/01—Input arrangements or combined input and output arrangements for interaction between user and computer
  • G06F3/03—Arrangements for converting the position or the displacement of a member into a coded form
  • G06F3/041—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means
  • G06F3/044—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means by capacitive means
• • H—ELECTRICITY
  • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
  • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
  • H05K3/00—Apparatus or processes for manufacturing printed circuits
  • H05K3/02—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding
  • H05K3/06—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding the conductive material being removed chemically or electrolytically, e.g. by photo-etch process

Definitions

• the present invention relates to a method for manufacturing a transfer film, a laminate, a touch sensor, and a method for manufacturing a printed wiring substrate.
• Patent Document 1 a photosensitive transfer material (transfer) having a photosensitive layer, an adhesive layer, and a temporary support in this order on a cover film, the photosensitive layer containing particles, and having a predetermined configuration. Film) is disclosed.
• a conductive thin wire thin wire-shaped conductive layer
• a transfer film having a photosensitive composition layer it is required that poor formation of the conductive fine wire is unlikely to occur.
• a pattern resist pattern
• the conductive thin wire is not defective (for example, a chip called a mouth bite), the conductive thin wire is broken (open), and the conductive thin wire is short-circuited (short circuit). Has been done.
• Transfer film [2] The transfer film according to [1], wherein the thickness of the photosensitive composition layer is 20 ⁇ m or less. [3] The transfer film according to [1] or [2], wherein the number of foreign substances having a diameter of 1 ⁇ m or more in the temporary support is 10 pieces / mm 2 or less. [4] The transfer film according to any one of [1] to [3], wherein the temporary support has a thickness of 30 ⁇ m or less.
• the photosensitive composition layer contains a polymerizable compound, and the content of the polymerizable compound is 10.00 to 50.00% by mass with respect to the total mass of the photosensitive composition layer. [1] ] To [4].
• the transfer film according to any one of. [6] The photosensitive composition layer contains a polymerization initiator, and the content of the polymerization initiator is 0.10 to 10.00% by mass with respect to the total mass of the photosensitive composition layer. [1] ] To [5].
• the ratio of the mass of the component having a molecular weight of 100,000 or more contained in the photosensitive composition layer to the mass of the component having a molecular weight of 10,000 or less in the photosensitive composition layer is 0.10 or less [1].
• the photosensitive composition layer contains a polymerization inhibitor, and the content of the polymerization inhibitor is 0.10 to 5.00% by mass with respect to the total mass of the photosensitive composition layer.
• [1] ] To [7].
• 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 contains a residual solvent and the content of the residual solvent is 2 to 15 mg / m 2.
• the photosensitive composition layer on the temporary support of the transfer film according to any one of [1] to [9] is brought into contact with a substrate having a conductive layer and bonded to the substrate, the conductive layer, and the like.
• 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.
• a touch sensor comprising a laminate produced by the production method according to [10] or [11].
• a protective layer forming process for forming a protective layer on the metal plating layer The pattern removal process to remove the pattern and It has a seed layer removing step of removing the exposed seed layer to obtain a conductive thin wire.
• the manufacture of a printed wiring substrate having a peeling 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 developing step.
• a transfer film capable of suppressing the occurrence of poor formation of conductive thin wires when used for forming conductive thin wires having a narrow line width. Further, according to the present invention, it is possible to provide a method for manufacturing a laminate using the transfer film, a method for manufacturing a printed wiring substrate using the transfer film, and a touch sensor.
• the numerical range represented by using “-" means a range including the numerical values before and after "-" as the lower limit value and the upper limit value.
• the upper limit value or the lower limit value described in 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 is included in this term as long as the intended purpose of the process is achieved, not only in an independent process but also in the case where it cannot be clearly distinguished from other processes. ..
• transparent means that the average transmittance of visible light having a wavelength of 400 to 700 nm is 80% or more, and is preferably 90% or more.
• the average transmittance of visible light is a value measured by using a spectrophotometer, and can be measured by, for example, a spectrophotometer U-3310 manufactured by Hitachi, Ltd.
• the 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) are TSKgel GMHxL, TSKgel G4000HxL, or TSKgel G2000HxL (both are trade names manufactured by Toso Co., Ltd.) as columns. ), THF (tetrahydrofuran) as the eluent, a differential refractometer as the detector, and polystyrene as the standard substance, and the values converted using the standard substance polystyrene measured by a gel permeation chromatography (GPC) analyzer.
• GPC gel permeation chromatography
• the molecular weight of a compound having a molecular weight distribution is the weight average molecular weight (Mw).
• the content of the metal element is a value measured using an inductively coupled plasma (ICP) spectroscopic analyzer.
• the content of the residual solvent is a value measured using a GC / MS (Gas Chromatography Mass Spectrometry) analyzer.
• the refractive index is a value measured using an ellipsometer at a wavelength of 550 nm.
• the hue is a value measured using a color difference meter (CR-221, manufactured by Minolta Co., Ltd.).
• (meth) acrylic is a concept that includes both acrylic and methacrylic
• (meth) acryloxy group is a concept that includes both an acryloxy group and a metaacryloxy group.
• a feature of the transfer film of the present invention is that the number of foreign substances having a diameter of 1 ⁇ m or more in the photosensitive composition layer described later is 10 pieces / mm 2 or less.
• the present inventor has found that when a conventional transfer film is used to manufacture a conductive thin wire having a large line width, poor formation of the conductive thin wire is unlikely to occur. It has been found that when a conductive thin wire having a narrow line width is manufactured, poor formation of the conductive thin wire is likely to occur. As a result of investigating the reason, the present inventor has found that the above problem is caused by a foreign substance having a predetermined size contained in the photosensitive composition layer.
• the exposed area of the photosensitive composition layer is large with respect to foreign matter, so that the formation of the conductive thin wire is hardly affected.
• the exposure area itself of the photosensitive composition layer becomes narrow, and the ratio of the size of the foreign matter to the size of the exposure area becomes large, and the foreign matter becomes large. The proportion of the region where the exposure of the photosensitive composition layer is hindered by the above increases.
• the present inventors have found that a desired effect can be obtained by controlling the number of foreign substances having a predetermined size in order to prevent exposure damage due to foreign substances.
• the transfer film of the present invention has a temporary support and a photosensitive composition layer arranged on the temporary support.
• a photosensitive composition layer arranged on the temporary support.
• the transfer film has a temporary support.
• the temporary support is a member that supports the photosensitive composition layer described later, and is finally removed by a peeling treatment.
• the number of foreign substances having a diameter of 1 ⁇ m or more (hereinafter, also simply referred to as “first foreign matter”) in the temporary support is not particularly limited, but is preferably 10 pieces / mm 2 or less, more preferably 5 pieces / mm 2 or less. More preferably less than 1 piece / mm 2.
• the lower limit is not particularly limited, but 0 pieces / mm 2 can be mentioned.
• the first foreign matter is a portion (lump) that can be recognized as being optically different from other parts of the temporary support when the temporary support is observed using an optical microscope.
• the first foreign substance may be either an organic substance or an inorganic substance.
• the first foreign substance may be a component derived from a component constituting the temporary support, or may be a component derived from a component other than the component constituting the temporary support.
• the first foreign matter does not contain air bubbles.
• Examples of the first foreign substance include agglomerates, unmelted substances, inorganic substances, gelled substances, adhered foreign substances, and colored foreign substances. More specifically, poorly synthesized components or agglomerates generated during the production of the temporary support, foreign substances derived from additives, impurities such as additives, dust, metal particles, and metal pieces mixed in the manufacturing process. Can be mentioned.
• the size of the first foreign matter may be 1 ⁇ m or more in diameter.
• the upper limit is not particularly limited, but is preferably 10,000 ⁇ m or less.
• the longest side is defined as the diameter.
• the temporary support may contain foreign matter having a diameter of less than 1 ⁇ m, and preferably does not contain it.
• Examples of the method for measuring the number of first foreign substances in the temporary support include a method of visually observing the temporary support using an optical microscope. Specifically, from the normal direction of the surface of the temporary support, any five regions (1 mm ⁇ 1 mm) on the surface of the temporary support are visually observed using an optical microscope, and each of them is observed. The number of first foreign substances in the region is measured, and they are arithmetically averaged to calculate the number of first foreign substances.
• a method for reducing the first foreign matter in the temporary support for example, when the temporary support is made of resin, a method of producing the temporary support using the resin from which the foreign matter has been removed can be mentioned. ..
• the temporary support may have a single-layer structure or a multi-layer structure.
• the temporary support is preferably a film, more preferably a resin film.
• a film that is flexible and does not significantly deform, shrink, or stretch under pressure, or under pressure and heating can be used.
• the 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 is free from deformation such as wrinkles and 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.
• the temporary support preferably has high transparency, and the transmittance at 365 nm is preferably 60% or more, more preferably 70% or more.
• the thickness of the temporary support is not particularly limited, but is preferably 150 ⁇ m or less, preferably 50 ⁇ m or less, in that poor formation of conductive thin wires is further suppressed (hereinafter, also simply referred to as “the point where the effect of the present invention is more excellent”). Is more preferable, 30 ⁇ m or less is further preferable, and 16 ⁇ m or less is particularly preferable.
• the lower limit is not particularly limited, but 5 ⁇ m or more is preferable from the viewpoint of handleability.
• the thickness of the temporary support is calculated as an average value of 5 arbitrary points measured by cross-sectional observation with an SEM (Scanning Electron Microscope).
• Preferred forms of the temporary support include, for example, paragraphs [0017] to [0018] of JP2014-085643, paragraphs [0019] to [0026] of JP2016-0273363, and International Publication No. 2012 /.
• the contents of these publications are incorporated herein by reference to paragraphs 081680 [0041]-[0057] and paragraphs [0029]-[0040] of WO 2018/179370.
• the transfer film has a photosensitive composition layer.
• a pattern can be formed on the transferred body by transferring the photosensitive composition layer onto the transferred body and then exposing and developing the photosensitive composition layer.
• the photosensitive composition layer a known photosensitive composition layer can be used, and a negative type is preferable.
• the negative photosensitive composition layer is a photosensitive composition layer in which the exposed portion is less soluble in a developing solution due to exposure.
• the photosensitive composition layer is a negative photosensitive composition layer, the formed pattern corresponds to a cured layer.
• the number of foreign substances having a diameter of 1 ⁇ m or more (hereinafter, also simply referred to as “second foreign matter”) in the photosensitive composition layer is 10 pieces / mm 2 or less. Further, less than 5 pieces / mm 2 is more preferable because the effect of the present invention is more excellent.
• the lower limit is not particularly limited, but 0 pieces / mm 2 can be mentioned.
• the second foreign substance is a portion (lump) that can be recognized as being optically different from other portions of the photosensitive composition layer when the photosensitive composition layer is observed with an optical microscope.
• the second foreign substance may be either an organic substance or an inorganic substance.
• the second foreign substance may be a component derived from a component constituting the photosensitive composition layer, or may be a component derived from a component other than the component constituting the photosensitive composition layer.
• the second foreign matter does not contain air bubbles.
• Examples of the second foreign substance include agglomerates, unmelted substances, inorganic substances, gelled substances, adhered foreign substances, and colored foreign substances. More specifically, poorly synthesized components or aggregates generated during the production of the photosensitive composition layer, foreign substances derived from additives, impurities such as additives, dust mixed in the production process, metal particles, and metals. A piece can be mentioned.
• the size of the second foreign matter may be 1 ⁇ m or more in diameter.
• the upper limit is not particularly limited, but is preferably 10,000 ⁇ m or less.
• the longest side is defined as the diameter.
• the photosensitive composition layer may contain foreign substances having a diameter of less than 1 ⁇ m, and preferably does not contain them.
• Examples of the method for measuring the number of second foreign substances in the photosensitive composition layer include a method of visually observing the photosensitive composition layer using an optical microscope. Specifically, from the normal direction of the surface of the photosensitive composition layer, any five regions (1 mm ⁇ 1 mm) on the surface of the photosensitive composition layer are visually observed using an optical microscope. Then, the number of second foreign substances in each region is measured, and they are arithmetically averaged to calculate the number of second foreign substances.
• the first foreign matter in the temporary support together with the second foreign matter in the photosensitive composition layer May be observed at the same time.
• the transfer film itself including the temporary support and the photosensitive composition layer is observed with an optical microscope, and the number of observed foreign substances having a diameter of 1 ⁇ m or more is calculated by the above method.
• the number of first foreign substances in the remaining temporary support is calculated by the above method.
• the number of the second foreign matter in the photosensitive composition layer can be calculated by subtracting the number of the first foreign matter in the temporary support from the number of foreign matter calculated when observing the transfer film. ..
• the components contained in the photosensitive composition layer (particularly, the negative type photosensitive composition layer) will be described in detail.
• the photosensitive composition layer may contain 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, ethoxylated bisphenol A dimethacrylate [trade name: NK ester BPE-200, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.], ethoxylated bisphenol A dimethacrylate [trade name].
• NK Ester BPE-500 manufactured by Shin-Nakamura Chemical Industry Co., Ltd.
• Polypropylene glycol diacrylate Polypropylene glycol diacrylate [Product name: NK Ester M-270, manufactured by Toa Synthetic Co., Ltd.]
• Tricyclodecanedimethanol diacrylate Product name: NK ester A-DCP, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.] tricyclodecanedimethanol dimethacrylate [trade name: NK ester DCP, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.]
• 1,9-nonanediol diacrylate trade name: NK Ester A-NOD-N, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.]
• 1,10-decanediol diacrylate [trade name: NK ester A-DOD-N, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.]
• 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. Further, "(tri / tetra) (meth) acrylate” is a concept including tri (meth) acrylate and tetra (meth) acrylate.
• the upper limit of the number of functional groups is not particularly limited, but for example, 20 functional or less is preferable, and 15 functional or less is more preferable.
• trimetyl propanetriacrylate [trade name: A-TMPT, Shin-Nakamura Chemical Industry Co., Ltd.]
• trimetyl propane EO-added triacrylate [trade name: SR 454, ARKEMA Co., Ltd.]
• Trimethylol Propane EO-added triacrylate [Product name: SR 502, ARKEMA Co., Ltd.]
• ⁇ -caprolactone-modified tris- (2-acryloxyethyl) isocyanurate [Product name: A-9300 -1CL, Shin-Nakamura Chemical Industry Co., Ltd.] and Dipentaerythritol Hexaacrylate [Product name: KAYARAD DPHA, 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.
• Examples of the ethylenically unsaturated compound include caprolactone-modified compounds of (meth) acrylate compounds [trade name: KAYARAD (registered trademark) DPCA-20, manufactured by Nippon Kayaku Co., Ltd., and trade name: A-9300-1CL, etc.
• 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.
• the trifunctional or higher functional urethane (meth) acrylate compound include 8UX-015A [manufactured by Taisei Fine Chemical Co., Ltd.], NK ester UA-32P [manufactured by Shin-Nakamura Chemical Industry Co., Ltd.], and NK ester UA-1100H [new]. Nakamura Chemical Industry Co., Ltd.] can be mentioned.
• the ethylenically unsaturated compound preferably contains an ethylenically unsaturated compound having an acid group from the viewpoint of improving developability.
• Examples of the acid group include a phosphoric acid group, a sulfonic acid group, and a carboxy group. Among them, a carboxy group is preferable as the acid group because the effect of the present invention is more excellent.
• 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 in which a carboxy group is introduced into a tetraacrylate (PETA) skeleton (acid value:: 80-120 mgKOH / g)] and compounds with 5-6 functional ethylenically unsaturated compounds (dipentaerythritol penta and hexaacrylate (DPHA)) having acid groups introduced with carboxy groups [acid value: 25-70 mgKOH] / G]).
• PETA tetraacrylate
• DPHA dipentaerythritol penta and hexaacrylate
• 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 is selected from the group consisting of a bifunctional or higher functional ethylenically unsaturated compound having a carboxy group and its carboxylic acid anhydride in that the developability and film strength are further enhanced. At least one compound is preferred.
• Examples of the bifunctional or higher functional ethylenically unsaturated compound having a carboxy group include Aronix (registered trademark) TO-2349 [manufactured by Toagosei Co., Ltd.], Aronix (registered trademark) M-520 [manufactured by Toagosei Co., Ltd.], and the like. And, Aronix (registered trademark) M-510 [manufactured by 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 polymerizable 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. preferable.
• the content of the polymerizable compound having a molecular weight of 300 or less is 35. With respect to the content of all the polymerizable compounds contained in the photosensitive composition layer. It is preferably 00% by mass or less, more preferably 30.00% by mass or less, still more preferably 25.00% by mass or less.
• the photosensitive composition layer may contain one kind of polymerizable compound alone, or may contain two or more kinds of polymerizable compounds.
• the content of the polymerizable compound is preferably 1.00 to 70.00% by mass and 10.00 to 70.00% by mass with respect to the total mass of the photosensitive composition layer. % Is more preferable, 10.00 to 60.00% by mass is further preferable, and 10.00 to 50.00% 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 is preferably 10.00 to 100.00% by mass, more preferably 20.00 to 100.00% by mass, still more preferably 40.00 to 100.00% by mass.
• 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 1.00 to 70.00% by mass, more preferably 10.00 to 70.00% by mass, and 10.00 to 60.% With respect to the total mass of the photosensitive composition layer. 00% by mass is more preferable, and 10.00 to 50.00% by mass is particularly preferable.
• the photosensitive composition layer may contain a polymerization initiator.
• a photopolymerization initiator is preferable.
• the photopolymerization initiator include a photopolymerization initiator having an imidazole structure (hereinafter, also referred to as “imidazole-based photopolymerization initiator”) and a photopolymerization initiator having an oxime ester structure (hereinafter, “oxym-based photopolymerization”).
• photopolymerization initiator having an ⁇ -aminoalkylphenone structure (hereinafter, also referred to as “ ⁇ -aminoalkylphenone-based photopolymerization initiator”), photopolymerization having an ⁇ -hydroxyalkylphenone structure.
• Initiator (hereinafter, also referred to as “ ⁇ -hydroxyalkylphenone-based polymerization initiator”), photopolymerization initiator having an acylphosphine oxide structure (hereinafter, also referred to as “acylphosphine oxide-based photopolymerization initiator”).
• acylphosphine oxide-based photopolymerization initiator acylphosphine oxide-based photopolymerization initiator
• N-phenylglycine-based photopolymerization initiator a photopolymerization initiator having an N-phenylglycine structure
• the photopolymerization initiators are imidazole-based photopolymerization initiators, oxime-based photopolymerization initiators, ⁇ -aminoalkylphenone-based photopolymerization initiators, ⁇ -hydroxyalkylphenone-based polymerization initiators, and N-phenylglycine-based photopolymerization. It preferably contains at least one selected from the group consisting of initiators, imidazole-based photopolymerization initiators, oxime-based photopolymerization initiators, ⁇ -aminoalkylphenone-based photopolymerization initiators, and N-phenylglycine-based photoinitiators. It is more preferable to contain at least one selected from the group consisting of the polymerization initiator, and further preferably to contain an imidazole-based photopolymerization initiator.
• Examples of the imidazole-based photopolymerization initiator include 2,2'-bis (o-chlorophenyl) -4,5,4', 5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis. (O-Methoxyphenyl) -4,4', 5,5'-tetraphenylbiimidazole, and 2,2'-bis (o-chlorophenyl) -4,4', 5,5'-tetra (p-) Methylphenyl) biimidazole can be mentioned. Of these, 2,2'-bis (o-chlorophenyl) -4,5,4', 5'-tetraphenyl-1,2'-biimidazole is preferable because the effect of the present invention is more excellent.
• photopolymerization initiator for example, it is described in paragraphs [0031] to [0042] of JP-A-2011-095716 and paragraphs [0064]-[0081] of JP-A-2015-014783.
• a polymerization initiator may be used.
• photopolymerization initiators include, for example, 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetraphenylbiimidazole [trade name: B-CIM, Kurogane Kasei Co., Ltd.] ], 1- [4- (Phenylthio)] Phenyl-1,2-octanedione-2- (O-benzoyloxime) [Product name: 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]
• the photosensitive composition layer may contain one kind of photopolymerization initiator alone, or may contain two or more kinds of photopolymerization initiators.
• the content of the polymerization initiator is preferably 0.10 to 50.00% by mass, more preferably 0.10 to 30.00% by mass, and 0.10 to 10% by mass, based on the total mass of the photosensitive composition layer. .00% by mass is more preferable.
• the photosensitive composition layer may contain an alkali-soluble resin.
• the solubility of the photosensitive composition layer (non-exposed portion) in the developing solution is improved.
• alkali-soluble means that the dissolution rate determined 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
• an alkali-soluble acrylic resin is preferable.
• the alkali-soluble acrylic resin will be described in detail.
• the content of the alkali-soluble resin is preferably 10.00 to 100.00% by mass, more preferably 30.00 to 100.00% by mass, and 40.00 to 100% based on the total mass of the photosensitive composition layer. .00% by mass is more preferable, and 50.00 to 90.00% by mass is particularly preferable.
• 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 30.0 mol% or more, more preferably 50.0 mol% or more. ..
• the upper limit is not particularly limited, but is preferably 100.0 mol% or less, more preferably 80.0 mol% or less.
• 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 constituent 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 10.0 to 100.0 mol%, more preferably 30.0 to 100.0 mol%, and 50.0 to 50.0 to the total amount of the alkali-soluble acrylic resin. 100.0 mol% is more preferable.
• 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. Among them, styrene or ⁇ -methylstyrene is preferable as the monomer, and styrene is more preferable, because the effect of the present invention is more excellent.
• the constituent 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 10.0 to 100.0 mol% with respect to the total amount of the alkali-soluble acrylic resin. 0 to 90.0 mol% is more preferable, and 30.0 to 90.0 mol% is further preferable.
• the alkali-soluble acrylic resin may contain a structural unit having an aliphatic cyclic skeleton from the viewpoint of tackiness and strength after curing.
• the structural unit having a aliphatic cyclic skeleton may be monocyclic or 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 5.0 to 90.0 mol with respect to the total amount of the alkali-soluble acrylic resin.
• 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” refers to an atomic group branched from the main chain. show.
• a (meth) acrylic group or a (meth) acryloyl group is preferable, and a (meth) acryloyl group is more preferable.
• the constituent 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 10.0 to 100.0 mol with respect to the total amount of the alkali-soluble acrylic resin. % Is preferred, 20.0-90.0 mol% is more preferred, and 30-90 mol% is even more preferred.
• Examples of means for introducing a reactive group into an alkali-soluble acrylic resin include a hydroxyl group, a carboxy group, a primary amino group, a secondary amino group, an acetoacetyl group, a sulfonic acid, an epoxy compound, and a blocked isocyanate.
• Examples thereof include a method of reacting a compound, an isocyanate compound, a vinyl sulfone 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, for example, a part of the carboxy group of the alkali-soluble acrylic resin by a polymer reaction after synthesizing an alkali-soluble acrylic resin having a carboxy group by a polymerization reaction.
• a means of introducing a (meth) acryloxy group into an alkali-soluble acrylic resin by reacting with glycidyl (meth) acrylate can be mentioned.
• an alkali-soluble acrylic resin having a (meth) acryloxy group in the side chain can be obtained.
• 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, and even more preferably 15,000 to 70,000.
• 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.
• the content of the residual monomer of each structural unit of the alkali-soluble resin in the photosensitive composition layer is preferably 1000 mass ppm or less, preferably 500 mass by mass, based on the total mass of the alkali-soluble resin from the viewpoint of patterning property and reliability. It is more preferably ppm or less, and further preferably 100 mass ppm or less.
• the lower limit is not particularly limited, and is preferably 0.1 mass ppm or more, and more preferably 1 mass ppm or more.
• 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.
• 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 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 number of R A1a may be the same or different
• n 1a represents an integer of 0 or more.
• 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 residual monomer of each structural unit of the polymer B in the photosensitive composition layer is preferably 1000 mass ppm or less, preferably 500 mass by mass, based on the total mass of the polymer B from the viewpoint of patterning property and reliability. It is more preferably ppm or less, and further preferably 100 mass ppm or less.
• 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 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 may contain 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 film tends to decrease, and the function as a protective film tends to be strengthened.
• the blocked isocyanate compound means "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 the blocked isocyanate compound” is the heat absorption peak associated with the deprotection reaction of the blocked isocyanate compound when measured by DSC (Differential scanning calorimetry) analysis using a differential scanning calorimeter. Means temperature.
• a differential scanning calorimeter for example, a differential scanning calorimeter (model: DSC6200) manufactured by Seiko Instruments Co., Ltd. can be preferably used.
• the differential scanning calorimetry is not limited to the differential scanning calorimetry described above.
• 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 or 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.
• an oxime structure using an oxime compound as a blocking agent is used because it is easier to set the dissociation temperature in a preferable range and to reduce the development residue as compared with a compound having no oxime structure.
• the compound having is preferable.
• 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 polymerization inhibitor.
• the polymerization inhibitor means a compound having a function of delaying or prohibiting a polymerization reaction.
• a known compound used as a polymerization inhibitor can be used.
• the content of the polymerization inhibitor is preferably 0.01 to 10.00% by mass, preferably 0.05 to 5% by mass, based on the total mass of the photosensitive composition layer. .00% by mass is more preferable, and 0.10 to 3.00% by mass is further preferable.
• polymerization inhibitor examples include phenothiazine compounds such as phenothiazine, bis- (1-dimethylbenzyl) phenothiazine, and 3,7-dioctylphenothiazine; bis [3- (3-tert-butyl-4-hydroxy-5-.
• Methylphenyl) propionic acid [ethylenebis (oxyethylene)] 2,4-bis [(laurylthio) methyl] -o-cresol, 1,3,5-tris (3,5-di-t-butyl-4-) Hydroxybenzyl), 1,3,5-tris (4-t-butyl-3-hydroxy-2,6-dimethylbenzyl), 2,4-bis- (n-octylthio) -6- (4-hydroxy-3) , 5-Di-t-butylanilino) -1,3,5-triazine, and hindered phenolic compounds such as pentaerythritol tetrakis 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate; 4 Nitroso compounds such as -nitrosophenol, N-nitrosodiphenylamine, N-nitrosocyclohexylhydroxylamine, and N-nitrosophenylhydroxylamine or salts thereof;
• the polymerization inhibitor preferably contains at least one selected from the group consisting of a phenylothiazine compound, a nitroso compound or a salt thereof, and a hindered phenol compound, and phenothiazine.
• a phenylothiazine compound a nitroso compound or a salt thereof, and a hindered phenol compound, and phenothiazine.
• the photosensitive composition layer may contain one type of polymerization inhibitor alone, or may contain two or more types of polymerization inhibitors.
• the photosensitive composition layer may contain 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 hydrogen donating compounds include amines and amino acid compounds.
• Examples of amines include 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 thereof include dimethylaniline and p-methylthiodimethylaniline.
• at least one selected from the group consisting of 4,4'-bis (diethylamino) benzophenone and tris (4-dimethylaminophenyl) methane is selected as amines in that the effect of the present invention is more excellent. preferable.
• amino acid compound examples include N-phenylglycine, N-methyl-N-phenylglycine, and N-ethyl-N-phenylglycine.
• N-phenylglycine is preferable as the amino acid compound in that the effect of the present invention is more excellent.
• Examples of the hydrogen-donating compound include an organometallic compound (tributyltin acetate, etc.) described in JP-A-48-042465, a hydrogen donor described in JP-A-55-034414, and JP-A-6. Sulfur compounds (Trithian and the like) described in JP-A-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 10.00% by mass is preferable, 0.03 to 8.00% by mass is more preferable, and 0.10 to 5.00% by mass is further preferable.
• the photosensitive composition layer may contain 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 thiadiazol 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 at least one selected from the group consisting of a triazole compound, a benzotriazole compound, a tetrazole compound, a thiadiazol compound, a triazine compound, a rhonin compound, a thiazole compound, a benzoimidazole compound, and a benzoxazole compound.
• 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 20.00% by mass, preferably 0.10 to 10% by mass, based on the total mass of the photosensitive composition layer. .00% by mass is more preferable, 0.30 to 8.00% by mass is further preferable, and 0.50 to 5.00% by mass is particularly preferable.
• the photosensitive composition layer may contain 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 a polyfunctional aliphatic thiol compound is preferable from the viewpoint of the adhesion of the formed pattern (particularly, the adhesion after exposure).
• 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-mercaptobutyryloxy) butane, and 1,3,5-tris. At least one compound selected from the group consisting of (3-mercaptobutyryloxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione is preferred.
• 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 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 fluorine-based surfactant or a silicon-based surfactant is preferable, and a fluorine-based surfactant is more preferable.
• fluorine-based surfactants include Megafvck (registered trademark) F552 (manufactured by DIC Corporation) and Megafuck (registered trademark) F551A (manufactured by DIC Corporation).
• silicon-based surfactants include DOWNSIL (registered trademark) 8032 Adaptive.
• fluorine-based surfactants include, for example, Megafuck F-171, F-172, F-173, F-176, F-177, F-141, F-142, F-143, F-144. , F-437, F-475, F-477, F-479, F-482, F-554, F-555-A, F-556, F-557, F-558, F-559, F-560.
• a fluorine-based surfactant an acrylic compound having a molecular structure having a functional group containing a fluorine atom, and when heat is applied, a portion of the functional group containing a fluorine atom is cut and the fluorine atom volatilizes.
• fluorine-based surfactants include Megafuck DS series manufactured by DIC Corporation (The Chemical Daily (February 22, 2016), Nikkei Sangyo Shimbun (February 23, 2016)), for example, Mega. Fuck 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 as the fluorine-based surfactant.
• the fluorine-based surfactant has a structural 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).
• a fluorine-containing polymer compound containing a structural unit derived from a (meth) acrylate compound can also be preferably used.
• 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.
• fluorine-based surfactant compounds having a linear perfluoroalkyl group having 7 or more carbon atoms, such as perfluorooctanoic acid (PFOA) and perfluorooctanesulfonic acid (PFOS), are used. It is preferably a surfactant derived from an alternative material.
• Nonionic surfactants include glycerol, trimethylolpropane, trimethylolethane and their ethoxylates and propoxylates (eg, glycerol propoxylate, glycerol ethoxylate, etc.), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, etc.
• silicone-based surfactant examples 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 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 Dow Corning).
• the photosensitive composition layer may contain one type of surfactant alone, or may contain two or more types of surfactants.
• the content of the surfactant is preferably 0.01 to 3.00% by mass, preferably 0.05 to 1% by mass, based on the total mass of the photosensitive composition layer. .00% by mass is more preferable, and 0.10 to 0.80% by mass is further preferable.
• the photosensitive composition layer may contain metal ions.
• the photosensitive composition layer preferably contains metal ions from the viewpoint of adhesion between the photosensitive composition layer and the support.
• the metal element constituting the metal ion may be a metal element or a metalloid element. Further, the metal ion may be a peroxide ion.
• the valence of the metal ion is not particularly limited, but may be monovalent or divalent or higher.
• the content of the metal ions in the photosensitive composition layer is preferably 500 mass ppm or less, preferably 0.01 to 200 mass ppm, based on the total mass of the photosensitive composition layer.
• the mass ppm is more preferable, and 0.01 to 100 mass ppm is further preferable.
• the metal ion examples include an alkali metal ion, an alkaline earth metal ion, a typical metal ion, and a transition metal ion.
• an alkali metal ion an alkaline earth metal ion, a typical metal ion, and a transition metal ion.
• Ions, zinc ions, and tin ions can be mentioned. Among them, it is preferable to set the content of sodium ion and potassium ion to the above contents because the effect of the present invention is more excellent.
• metalloid element ion examples include silicon acid ion, silicon ion, boron ion, germanium ion, arsenic ion, antimony ion, and tellurium ion.
• the metal ion content can be quantified by, for example, a known method of ICP emission spectroscopy.
• the photosensitive composition layer may contain one kind of metal ion alone, or may contain two or more kinds of metal ions.
• the photosensitive composition layer may contain a residual solvent.
• the residual solvent means a solvent contained in the photosensitive composition layer.
• the solvent may be a solvent derived from the photosensitive composition, or may be a solvent derived from other solvents.
• the content of the residual solvent in the photosensitive composition layer is preferably 50 mg / m 2 or less, preferably 1 to 50 mg / m, in that the effect of the present invention is more excellent. 2 is preferable, 1 to 20 mg / m 2 is more preferable, and 2 to 15 mg / m 2 is further preferable.
• the method for measuring the residual solvent is as follows. First, a 1 cm ⁇ 1 cm sample piece is punched out from a transfer film having a temporary support and a photosensitive composition layer. The sample piece is then placed in a vial with 1 mL of tetrahydrofuran and shaken for 1 hour to extract the residual solvent in the photosensitive composition layer. GC-MS (Gas Chromatography-Mass spectrometry) measurement is performed on the obtained solution to measure the amount of residual solvent.
• Examples of the residual solvent include organic solvents contained in the photosensitive composition described later. Examples thereof include benzene, formaldehyde, trichlorethylene, 1,3-butadiene, carbon tetrachloride, chloroform, N, N-dimethylformamide, N, N-dimethylacetamide, and hexane.
• 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, colorants, antioxidants, and particles (eg, metal oxide particles).
• other additives described in paragraphs [0058] to [0071] of JP-A-2000-310706 can also be mentioned.
• colorant examples include brilliant green, eosin, ethyl violet, erythrosin B, methyl green, crystal violet, basic fuchsin, phenolphthalein, 1,3-diphenyltriazine, alizarin red S, timol phthalein, methyl violet 2B, and the like.
• the content of the colorant is preferably 0.01% by mass or more, preferably 0.01 to 5.00% by mass, based on the total mass of the photosensitive composition layer. More preferably, 0.01 to 1.00% by mass is further preferable.
• antioxidants examples include 1-phenyl-3-pyrazolidone (also known as phenidone), 1-phenyl-4,4-dimethyl-3-pyrazolidone, and 1-phenyl-4-methyl-4-hydroxymethyl-.
• 3-Pyrazoridones such as 3-pyrazolidone; polyhydroxybenzenes such as hydroquinone, catechol, pyrogallol, methylhydroquinone, and chlorhydroquinone; paramethylaminophenol, paraaminophenol, parahydroxyphenylglycine, and paraphenylenediamine. Be done.
• 3-pyrazolidones are preferable, and 1-phenyl-3-pyrazolidone is more preferable as the antioxidant in that the effect of the present invention is more excellent.
• the content of the antioxidant is preferably 0.001% by mass or more, more preferably 0.005% by mass or more, based on the total mass of the photosensitive composition layer. It is preferable, and 0.01% by mass or more is more preferable.
• the upper limit is not particularly limited, but is preferably 1% by mass or less.
• the thickness of the photosensitive composition layer is not particularly limited, but is often 30 ⁇ m or less, and is preferably 20 ⁇ m or less, more preferably 15 ⁇ m or less, further preferably 10 ⁇ m or less, and further preferably 5 ⁇ m or less in that the effect of the present invention is more excellent. Especially preferable.
• the lower limit is not particularly limited, but is preferably 0.05 ⁇ m or more.
• the thickness of the photosensitive composition layer can be calculated as, for example, the average value of any five points measured by cross-sectional observation with a scanning electron microscope (SEM).
• the refractive index of the photosensitive composition layer is preferably 1.47 to 1.56, more preferably 1.49 to 1.54.
• the photosensitive composition layer is preferably achromatic.
• the a * value of the photosensitive composition layer is preferably ⁇ 1.0 to 1.0
• the b * value of the photosensitive composition layer is -1. It is preferably 0 to 1.0.
• the ratio of the mass of the component having a molecular weight of 100,000 or more to the mass of the component having a molecular weight of 10,000 or less contained in the photosensitive composition layer (the mass / molecular weight of the component having a molecular weight of 100,000 or more is 50,000 or less).
• the mass of the component of the above is not particularly limited, but is preferably 0.10 or less in that the effect of the present invention is more excellent.
• the lower limit of the above ratio is not particularly limited, but 0 may be mentioned.
• a sample in which the photosensitive composition layer is dissolved is prepared, GPC measurement is performed, and the area of the region having a molecular weight of 10,000 or less and the area of the region having a molecular weight of 100,000 or more are determined from the obtained GPC chart. It can be calculated by comparing.
• the transfer film may include other layers other than the temporary support and the photosensitive composition layer described above. Examples of other layers include a protective film and an antistatic layer.
• 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.
• the protective film include polyolefin films such as polypropylene film and polyethylene film.
• a resin film made of the same material as the above-mentioned temporary support may be used.
• 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.
• the transfer film may include an antistatic layer. Since the transfer film has an antistatic layer, it is possible to suppress the generation of static electricity when peeling the film or the like arranged on the antistatic layer, and also suppress the generation of static electricity due to rubbing against equipment or other films or the like. Therefore, for example, the occurrence of a defect in an electronic device can be suppressed.
• the antistatic layer is preferably arranged between the temporary support and the photosensitive composition layer.
• the antistatic layer is a layer having antistatic properties and contains at least an antistatic agent.
• the antistatic agent is not particularly limited, and a known antistatic agent can be applied.
• the method for producing the transfer film of the present invention is not particularly limited, and a known method can be used. Among them, in terms of excellent productivity, a method of applying a photosensitive composition on a temporary support and, if necessary, performing a drying treatment to form a photosensitive composition layer (hereinafter, this method is referred to as "coating method"). ”) Is preferable.
• coating method in order to reduce the number of foreign substances in the photosensitive composition layer, a method of filtering the photosensitive composition used for forming the photosensitive composition layer can be mentioned. In the following, first, the filtration process will be described in detail.
• a method for adjusting the number of foreign substances in the photosensitive composition layer a method of filtering the photosensitive composition used for forming the photosensitive composition layer can be mentioned. More specifically, a method of filtering the photosensitive composition can be mentioned.
• filtering the photosensitive composition it is preferable to carry out filter filtration (hereinafter, also referred to as "multi-step filtration") twice or more.
• the number of times of filter filtration in the multi-step filtration is preferably 2 times or more, more preferably 3 times or more, and further preferably 4 times or more.
• the upper limit is not particularly limited, but from the viewpoint of economy, 10 times or less is preferable.
• the same type or various types of filters may be connected in series or in parallel.
• the step of multi-step filtration may be a circulation filtration step. When various types of filters are used, filters having different pore diameters and / or materials may be used in combination.
• the filter pore diameter is preferably 10 ⁇ m or less, more preferably 5 ⁇ m or less, further preferably 1 ⁇ m or less, particularly preferably 0.2 ⁇ m or less, and most preferably 0.1 ⁇ m or less.
• the lower limit is not particularly limited, but is preferably 0.01 ⁇ m or more. In the case of multi-step filtration using various types of filters, it is preferable to use a filter having a smaller pore size as the number of times of filter filtration is increased.
• a filter made of polytetrafluoroethylene, a filter made of polyethylene, or a filter made of nylon is preferable.
• a filter made of polytetrafluoroethylene is preferable.
• the filter for example, one in which the eluate disclosed in JP-A-2016-201426 is reduced is preferable.
• the adsorbent for example, a known adsorbent can be used, and for example, an inorganic adsorbent such as silica gel or zeolite, or an organic adsorbent such as activated carbon can be used.
• an inorganic adsorbent such as silica gel or zeolite
• an organic adsorbent such as activated carbon
• the metal adsorbent include those disclosed in JP-A-2016-206500.
• a raw material having a low metal content is selected as a raw material constituting various materials, a filter filter is performed on the raw material constituting various materials, or Teflon (registered trademark) is inside the apparatus. ), Etc., and distillation is performed under conditions in which contamination is suppressed as much as possible.
• the preferred conditions for filter filtration performed on the raw materials constituting the various materials are the same as those for the above-mentioned filter filtration.
• the photosensitive composition used in the coating method may contain components (for example, a polymerizable compound, an alkali-soluble resin, a photopolymerization initiator, etc.) constituting the above-mentioned photosensitive composition layer, 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 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 transferred body.
• the transfer film of the present invention is preferably used for producing a laminate having conductive thin wires.
• the photosensitive composition layer on the temporary support of the transfer film is brought into contact with a substrate having a conductive layer and bonded to the substrate, the conductive layer, and the photosensitive composition layer. , And a bonding step of obtaining a substrate with a photosensitive composition layer having a temporary support in this order.
• manufacturing method A the procedure of the above step will be described in detail.
• the bonding step the photosensitive composition layer on the temporary support of the transfer film is brought into contact with the substrate having the conductive layer and bonded, and the substrate, the conductive layer, the photosensitive composition layer, and the temporary support are bonded.
• This is a step of obtaining a substrate with a photosensitive composition layer which is sequentially provided.
• the exposed photosensitive composition layer on the temporary support of the transfer film is brought into contact with the substrate having the conductive layer and bonded.
• the photosensitive composition layer and the temporary support are arranged on the substrate having the conductive layer.
• the conductive layer and the surface of the photosensitive composition layer are pressure-bonded so as to be in contact with each other.
• the 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 exposure step is a step of pattern-exposing the photosensitive composition layer.
• the "pattern exposure” refers to an exposure in a pattern of exposure, that is, a form in which an exposed portion and a non-exposed portion are present.
• the positional relationship between the exposed region and the unexposed region in the pattern exposure is not particularly limited, and is appropriately adjusted so as to obtain a conductive thin line described later.
• any light source in a wavelength range capable of curing the photosensitive composition layer (for example, 365 nm or 405 nm) can be appropriately selected and used.
• the main wavelength of the exposure light for pattern exposure is preferably 365 nm.
• the main wavelength is the wavelength having the highest intensity.
• Exposure is preferably 5 ⁇ 200mJ / cm 2, more preferably 10 ⁇ 200mJ / cm 2.
• the peeling step is a step of peeling the temporary support from the substrate with the photosensitive composition layer between the bonding step and the exposure step, or between the exposure step and the development step described later.
• the peeling method is not particularly limited, and a mechanism similar to the cover film peeling mechanism described in paragraphs [0161] to [0162] of 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 hydrogencarbonate, potassium hydrogencarbonate, tetramethylammonium hydroxide, tetraethylammonium hydroxide, and tetrapropylammonium hydroxy.
• Examples of the development method include paddle development, shower development, spin development, and dip development.
• Examples of the developer preferably used in the present disclosure include the developer described in paragraph [0194] of International Publication No. 2015/093271, and 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 detailed arrangement and specific size of the pattern to be formed are not particularly limited, but a pattern is formed in which conductive thin lines described later can be obtained.
• the pattern interval is preferably 8 ⁇ m or less, more preferably 6 ⁇ m or less.
• the lower limit is not particularly limited, but is often 2 ⁇ m or more.
• 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 etching step is a step of obtaining a conductive thin wire by etching a conductive layer in a region where a pattern is not arranged in the obtained laminate.
• the pattern formed from the photosensitive composition layer by the developing step is used as an etching resist, and the conductive layer is etched.
• the etching treatment method include the methods described in paragraphs [0209] to [0210] of JP-A-2017-120435, the methods described in paragraphs [0048]-[0054] of JP-A-2010-152155, and the like.
• a known method such as a known dry etching method such as plasma etching can be applied.
• the line width of the formed conductive thin wire is preferably 8 ⁇ m or less, more preferably 6 ⁇ m or less.
• the lower limit is not particularly limited, but is often 2 ⁇ m or more.
• the removal step is a step of removing the pattern.
• 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 component is 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 component is 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 a laminate of the present invention may include any steps (other steps) other than those described above.
• the method for producing the laminate may include a step of exposing the pattern obtained by the development step (post-exposure step) and / or a step of heating (post-baking step).
• post-exposure step a step of exposing the pattern obtained by the development step
• post-baking step a step of heating
• Examples of the steps other than the above include the step of reducing the visible light reflectance described in paragraph [0172] of International Publication No. 2019/022089 and the step described in paragraph [0172] of International Publication No. 2019/022089. Examples thereof include a step of forming a new conductive layer on the insulating film.
• the laminate produced by the method for producing a laminate of the present invention can be applied to various uses.
• the laminate can be applied to a touch sensor.
• 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 conductive thin wire produced above is preferably applied to the sensor electrode or the lead-out wiring of the touch sensor, and more preferably to the lead-out wiring.
• the transfer film of the present invention is preferably used in a method for manufacturing a printed wiring board.
• the manufacturing method of the printed wiring board is A seed layer forming process for forming a seed layer on a substrate,
• the photosensitive composition layer on the temporary support of the transfer film of the present invention is brought into contact with a substrate having a seed layer and bonded to each other, and the substrate, the seed layer, the photosensitive composition layer, and the temporary support are provided in this order.
• the bonding process to obtain a substrate with a photosensitive composition layer An exposure process for pattern exposure of the photosensitive composition layer, and A developing step of developing the exposed photosensitive composition layer to form a pattern, A metal plating layer forming step of forming a metal plating layer by a plating process on a seed layer in a region where a pattern is not arranged, A protective layer forming process for forming a protective layer on the metal plating layer, The pattern removal process to remove the pattern and It has a seed layer removing step of removing the exposed seed layer to obtain a conductive thin wire. Further, there is a peeling 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 developing step.
• the procedure of the above step will be described in detail.
• the seed layer forming step is a step of forming a seed layer on the substrate.
• the substrate used in this step include the substrate used in the above-mentioned ⁇ method for manufacturing a laminated body>.
• the metal contained in the seed layer is not particularly limited, and known metals can be used.
• Examples of the main component (so-called main metal) contained in the seed layer include copper, chromium, lead, nickel, gold, silver, tin, and zinc.
• the main component is intended to be the metal having the highest content among the metals contained in the seed layer.
• the thickness of the seed layer is not particularly limited, and is preferably 50 nm or more, more preferably 100 nm or more.
• the upper limit is not particularly limited, but is preferably 2 ⁇ m or less.
• the method for forming the seed layer is not particularly limited, and examples thereof include a method of applying a dispersion liquid in which metal fine particles are dispersed and sintering a coating film, a sputtering method, and a vapor deposition method.
• Examples of the procedures of the bonding step, the exposure step, and the developing step in the above-mentioned manufacturing method of the printed wiring substrate include the procedures described in the steps carried out in the above-mentioned ⁇ Manufacturing method of laminated body>.
• the metal plating layer forming step is a step of forming a metal plating layer by a plating process on a seed layer in a region where a pattern is not arranged.
• Examples of the plating treatment include an electrolytic plating method and an electroless plating method, and the electrolytic plating method is preferable from the viewpoint of productivity.
• the metal contained in the metal plating layer is not particularly limited, and a known metal can be used.
• the metal plating layer may contain metals such as copper, chromium, lead, nickel, gold, silver, tin, and zinc, and alloys of these metals.
• the metal plating layer preferably contains copper or an alloy thereof in that the conductive thin wire is more excellent in conductivity.
• the main component of the metal plating layer is preferably copper in that the conductive thin wire is more excellent in conductivity.
• the thickness of the metal plating layer is not particularly limited, but is preferably 0.1 to 1 ⁇ m, more preferably 0.3 to 1 ⁇ m.
• the protective layer laminating step is a step of forming a protective layer on the metal plating layer.
• a material having resistance to the removing liquid or the etching liquid in the removing step or the conductive portion forming step is preferable. Examples thereof include metals such as nickel, chromium, tin, zinc, magnesium, gold and silver, alloys thereof, and resins. Among them, nickel or chromium is preferable as the material of the protective layer.
• Examples of the method for forming the protective layer include an electroless plating method, an electroplating method, and the like, and the electroplating method is preferable.
• the thickness of the protective layer is not particularly limited, but is preferably 0.3 ⁇ m or more, and more preferably 0.5 ⁇ m or more.
• the upper limit is not particularly limited, but is preferably 3.0 ⁇ m or less, and more preferably 2.0 ⁇ m or less.
• Examples of the procedure of the pattern removing step in the manufacturing method of the printed wiring board include the procedures described in the removing step carried out in the above-mentioned ⁇ Manufacturing method of laminated body>.
• the seed layer removing step is a step of removing the exposed seed layer to obtain a conductive thin wire.
• the method for removing a part of the seed layer is not particularly limited, but a known etching solution can be used. Examples of known etching solutions include ferric chloride solution, cupric chloride solution, ammonia alkali solution, sulfuric acid-hydrogen hydrogen mixture, and phosphoric acid-hydrogen mixture.
• the line width of the formed conductive thin wire is preferably 8 ⁇ m or less, more preferably 6 ⁇ m or less.
• the lower limit is not particularly limited, but is often 2 ⁇ m or more.
• Examples of the procedure of the peeling step in the manufacturing method of the printed wiring board include the procedure described in the step carried out in the above-mentioned ⁇ Manufacturing method of laminated body>.
• ⁇ Preparation of Photosensitive Composition 1> According to Tables 2 and 3, a photosensitive composition of each component and a mixed solvent of methyl ethyl ketone (manufactured by Sankyo Chemical Co., Ltd.) (60 parts) and propylene glycol monomethyl ether acetate (manufactured by Showa Denko KK) (40 parts). A mixed solvent was added so that the solid content concentration of the product 1 was 13% by mass to obtain a mixed solution.
• methyl ethyl ketone manufactured by Sankyo Chemical Co., Ltd.
• propylene glycol monomethyl ether acetate manufactured by Showa Denko KK
• the obtained mixed solution was subjected to a polytetrafluoroethylene filter having a pore size of 5.0 ⁇ m, a polytetrafluoroethylene filter having a pore size of 3.0 ⁇ m, a polytetrafluoroethylene filter having a pore size of 1.0 ⁇ m, and a pore diameter of 0.2 ⁇ m.
• the photosensitive composition 1 was prepared by multi-step filtration using a polytetrafluoroethylene filter and a polytetrafluoroethylene filter having a pore size of 0.1 ⁇ m in this order.
• Photosensitive composition 1 is applied onto a polyethylene terephthalate (PET) film having a thickness of 16 ⁇ m, which is a temporary support, using a slit-shaped nozzle, and is passed through a drying zone at 80 ° C. for 40 seconds to have a photosensitivity of 5 ⁇ m.
• the sex composition layer 1 was formed.
• a PET film having a thickness of 16 ⁇ m was laminated as a protective film on the photosensitive composition layer to obtain a transfer film of Example 1.
• Examples 2 to 19 Transfer films of Examples 2 to 19 were obtained in the same procedure as in Example 1 except that the types and amounts of various components used were changed according to Tables 1 to 3.
• ⁇ Test evaluation> [Residual solvent]
• the protective film was peeled off from the transfer films obtained in Examples and Comparative Examples to prepare a laminate composed of a photosensitive composition layer and a temporary support.
• a 1 cm ⁇ 1 m sample piece was punched from the obtained laminate, the obtained sample piece was placed in a vial, 1 mL of tetrahydrofuran was added to the vial, and the mixture was shaken for 1 hour to form a photosensitive composition layer.
• the residual solvent was extracted. Using the obtained solution, GC-MS measurement was carried out to measure the amount of residual solvent.
• Component B / Component A The mass ratio of the component B to the component A is defined as a component A having a molecular weight of 10,000 or less contained in each photosensitive composition layer and a component having a molecular weight of 100,000 or more contained in each photosensitive composition layer as a component B. (Mass of component B / mass of component A) was calculated. For the above ratio (component B / component A), a solution in which each photosensitive composition layer was dissolved was prepared, GPC measurement was performed under the following conditions, and the obtained GPC chart was used with respect to the area of a region having a molecular weight of 10,000 or less. The ratio of the area of the region having a molecular weight of 1,000,000 or more was calculated as the above mass ratio.
• the GPC measurement is a value obtained in terms of polystyrene under the following conditions.
• THF tetrahydrofuran
• For the calibration curve prepare a THF solution of standard polystyrene (standard polystyrene manufactured by Tosoh Corporation below), use the solution filtered through a 0.5 ⁇ m membrane filter, and inject it into a separation column under the following conditions, and elute time. And the relationship of molecular weight were obtained.
• the number of foreign substances having a diameter of 1 ⁇ m or more in the photosensitive composition layer was calculated by subtracting the number of foreign substances in the temporary support from the number of foreign substances in the transfer film obtained above.
• the calculated number of foreign substances having a diameter of 1 ⁇ m or more in the photosensitive composition layer was evaluated according to the following criteria.
• B: The number of foreign substances in the temporary support is 1 piece / mm 2 or more and 10 pieces / mm 2 or less
• Foreign substances in the temporary support The number of pieces exceeds 10 pieces / mm 2.
• a copper layer having a thickness of 200 nm was provided on a PET substrate having a thickness of 0.1 mm by a vapor deposition method, and a glass substrate with a copper layer was prepared. After peeling off the protective film of the produced transfer film, the copper layer is brought into contact with the photosensitive composition layer under laminating conditions of a roll temperature of 100 ° C., a linear pressure of 1.0 MPa, and a linear velocity of 4.0 m / min. Laminated on a layered glass substrate.
• Pattern shape chipping is less than 10 pieces / mm 2 and breakage and short circuit are 0 pieces / mm 2
• PET films having different thicknesses were used as the temporary support. As shown in the above table, the number of foreign substances having a diameter of 1 ⁇ m or more in each PET film was less than 1 piece / mm 2.
• Example 1 and Example 9 From the comparison between Example 1 and Example 9, the content of the polymerization initiator in the photosensitive composition layer was 0.10 to 10.00% by mass with respect to the total mass of the photosensitive composition layer. In some cases, it was confirmed that the effect was better. again, From the comparison between Example 1 and Example 7, the ratio of the mass of the component having a molecular weight of 100,000 or more contained in the photosensitive composition layer to the mass of the component having a molecular weight of 10,000 or less contained in the photosensitive composition layer is When it was 0.10 or less, it was confirmed that the effect was more excellent. From the comparison between Example 1 and Example 10, the content of the polymerization inhibitor in the photosensitive composition layer was 0.10 to 5.00% by mass with respect to the total mass of the photosensitive composition layer.
• Example 1 it was confirmed that the photosensitive composition layer contains a residual solvent and the content of the residual solvent is 2 to 15 mg / m 2 , the effect is more excellent. rice field.
• Example 20 The photosensitive composition 10 is applied onto a PET film (16QS71, manufactured by Toray Industries, Inc.) having a thickness of 16 ⁇ m using a slit-shaped nozzle, and is passed through a drying zone at 80 ° C. for 40 seconds to have a photosensitive composition having a thickness of 15 ⁇ m.
• the material layer 20 was formed.
• a PP film having a thickness of 12 ⁇ m (Trefan, manufactured by Toray Industries, Inc.) was laminated on the photosensitive composition layer as a protective film to obtain a transfer film of Example 20.

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