Transfer film, method for producing laminate, and blocked isocyanate compound

Abstract

The present invention aims to provide a transfer film capable of suppressing corrosion of wiring and electrodes. Furthermore, the present invention aims to provide a method for producing a laminate using the transfer film. Furthermore, the present invention aims to provide a novel blocked isocyanate compound. The transfer film of the present invention comprises a temporary support and a photosensitive composition layer disposed on the temporary support. The photosensitive composition layer comprises an alkali-soluble resin, a polymerizable compound, a polymerization initiator, and a blocked isocyanate compound having an NCO value of 4.5 mmol / g or greater.

Description

Technical Field

[0001] The present invention relates to a transfer film, a method for producing a laminate, and a blocked isocyanate compound. Background Art

[0002] Since the number of steps for obtaining a predetermined pattern is small, a method of exposing a photosensitive composition layer provided on an arbitrary substrate using a transfer film through a mask and then developing the layer is widely used.

[0003] Transfer films having a photosensitive composition layer are sometimes used to form a protective film (touch panel electrode protective film) for protecting sensor electrodes and lead wiring in touch panels. For example, Patent Document 1 discloses a photosensitive resin film (photosensitive composition layer) comprising an alkali-soluble resin, a polymerizable compound having unsaturated double bonds, a photopolymerization initiator, a colorant, and a blocked isocyanate compound as a thermal crosslinking agent.

[0004] Previous technical literature

[0005] Patent Literature

[0006] Patent Document 1: Japanese Patent Application Publication No. 2020-071372 Summary of the Invention

[0007] Technical issues to be solved by the invention

[0008] In recent years, there has been a demand for further improvement in the performance of touch panel electrode protection films. Specifically, there has been a demand for touch panel electrode protection films that can suppress corrosion of sensor electrodes and lead wiring in a touch panel.

[0009] The present inventors formed a touch panel electrode protective film using a transfer film having a photosensitive composition layer described in Patent Document 1. However, they discovered that, depending on the type of blocked isocyanate compound contained in the photosensitive composition layer, corrosion of wiring and electrodes may not be suppressed, indicating that there is room for improvement.

[0010] Therefore, the present invention aims to provide a transfer film that can suppress corrosion of wiring and electrodes. Furthermore, the present invention aims to provide a method for producing a laminate using the transfer film. Furthermore, the present invention aims to provide a novel blocked isocyanate compound.

[0011] Means for solving technical problems

[0012] The present inventors have conducted intensive studies on the above-mentioned problems and have found that the above-mentioned problems can be solved by the following configuration. [1]

[0014] A transfer film comprising a temporary support and a photosensitive composition layer disposed on the temporary support.

[0015] The photosensitive composition layer includes an alkali-soluble resin, a polymerizable compound, a polymerization initiator, and a blocked isocyanate compound having an NCO value of 4.5 mmol / g or more. [2]

[0017] The transfer film according to [1], wherein

[0018] The NCO value of the blocked isocyanate compound is greater than 5.0 mmol / g. [3]

[0020] The transfer film according to [1] or [2], wherein

[0021] The blocked isocyanate compound has a ring structure. [4]

[0023] The transfer film according to any one of [1] to [3], wherein

[0024] The above-mentioned blocked isocyanate compound is a blocked isocyanate compound represented by Formula Q.

[0025] B 1 -A 1 -L 1 -A 2 -B 2 Formula Q

[0026] In formula Q, B 1 and B 2 Each independently represents a blocked isocyanate group, A 1 and A 2 Each independently represents a single bond or an alkylene group having 1 to 10 carbon atoms, L 1 represents a divalent linking group. [5]

[0028] The transfer film according to any one of [1] to [4], wherein

[0029] The above-mentioned blocked isocyanate compound is a blocked isocyanate compound represented by formula QA.

[0030] B 1a -A 1a -L 1a -A 2a -B 2a Formula QA

[0031] In formula QA, B 1a and B 2aEach independently represents a blocked isocyanate group, A 1a and A 2a Each independently represents a divalent linking group, L 1a represents a cyclic divalent saturated hydrocarbon group or a divalent aromatic hydrocarbon group. [6]

[0033] The transfer film according to any one of [1] to [5], wherein

[0034] The photosensitive composition layer further includes a blocked isocyanate compound having an NCO value of less than 4.5 mmol / g. [7]

[0036] The transfer film according to any one of [1] to [6], wherein

[0037] The alkali-soluble resin comprises a structural unit derived from a vinylbenzene derivative, a structural unit having a radical polymerizable group, and a structural unit having an acid group.

[0038] The content of the structural unit derived from the vinylbenzene derivative is 35% by mass or more based on the total amount of all structural units contained in the alkali-soluble resin. [8]

[0040] The transfer film according to [7], wherein

[0041] The content of the structural unit derived from the vinylbenzene derivative is 45% by mass or more based on the total amount of all structural units contained in the alkali-soluble resin. [9]

[0043] The transfer film according to any one of claims 1 to 8, further comprising a refractive index adjusting layer,

[0044] The refractive index adjusting layer is arranged in contact with the photosensitive composition layer.

[0045] The refractive index adjusting layer has a refractive index of 1.60 or greater.

[10]

[0047] The transfer film according to any one of [1] to [9], wherein

[0048] The photosensitive composition layer is used to form a touch panel electrode protection film.

[11]

[0050] A method for manufacturing a laminated body, comprising:

[0051] a laminating step of bringing the photosensitive composition layer on the temporary support of the transfer film according to any one of [1] to

[10] into contact with and laminating a substrate having a conductive layer, thereby obtaining a substrate with a photosensitive composition layer having the substrate, the conductive layer, the photosensitive composition layer, and the temporary support in this order;

[0052] an exposure step of pattern-exposing the photosensitive composition layer; and

[0053] a developing step of developing the exposed photosensitive composition layer to form a pattern,

[0054] The method for producing a laminate further comprises a peeling step of peeling the temporary support from the substrate with the photosensitive composition layer between the laminating step and the exposure step or between the exposure step and the development step.

[12]

[0056] A transfer film comprising a temporary support and a photosensitive composition layer disposed on the temporary support.

[0057] The photosensitive composition layer comprises an alkali-soluble resin, a polymerizable compound, a polymerization initiator and a blocked isocyanate compound.

[0058] The NCO value of the photosensitive composition layer is greater than 0.50 mmol / g.

[13]

[0060] A blocked isocyanate compound represented by the formula QA,

[0061] B 1a -A 1a -L 1a -A 2a -B 2a Formula QA

[0062] In formula QA, B 1a and B 2a Each independently represents a blocked isocyanate group, A 1a and A 2a Each independently represents a divalent linking group, L 1a represents a cyclic divalent saturated hydrocarbon group or a divalent aromatic hydrocarbon group.

[14]

[0064] The blocked isocyanate compound according to

[13] , which is represented by the formula Q-1 described below.

[15]

[0066] The blocked isocyanate compound according to

[14] , wherein

[0067] The mass ratio of cis body to trans body is cis body / trans body = 10 / 90 to 90 / 10.

[0068] Effects of the Invention

[0069] The present invention provides a transfer film that can suppress corrosion of wiring and electrodes. Furthermore, the present invention provides a method for producing a laminate using the transfer film. Furthermore, the present invention provides a novel blocked isocyanate compound. BRIEF DESCRIPTION OF THE DRAWINGS

[0070] Figure 1 This is a schematic cross-sectional view showing a specific example of a touch panel to which the transfer film of the present invention can be applied.

[0071] Figure 2 This is a schematic cross-sectional view showing a specific example of a touch panel to which the transfer film of the present invention can be applied.

[0072] Figure 3 This is a schematic plan view showing a specific example of a touch panel to which the transfer film of the present invention can be applied.

[0073] Figure 4 It is along Figure 3 Cross-sectional view taken along line AA. DETAILED DESCRIPTION

[0074] Hereinafter, the present invention will be described in detail.

[0075] In addition, in this specification, the numerical range expressed using "to" means a range including the numerical values ​​described before and after "to" as the lower limit and the upper limit.

[0076] Furthermore, in the numerical ranges described in this specification, the upper limit or lower limit described in a certain numerical range may be replaced by the upper limit or lower limit of another numerical range described in another stage. Furthermore, in the numerical ranges described in this specification, the upper limit or lower limit described in a certain numerical range may be replaced by the values ​​shown in the Examples.

[0077] Furthermore, the term "process" in this specification includes not only independent processes but also processes that cannot be clearly distinguished from other processes as long as the intended purpose of the process can be achieved.

[0078] In this specification, "transparent" means that the average transmittance of visible light with a wavelength of 400 to 700 nm is 80% or more, preferably 90% or more.

[0079] The average transmittance of visible light is a value measured using a spectrophotometer, and can be measured using, for example, a spectrophotometer U-3310 manufactured by Hitachi, Ltd.

[0080] Unless otherwise specified, the weight average molecular weight (Mw) and number average molecular weight (Mn) in the present invention are molecular weights obtained by measuring with THF (tetrahydrofuran) and a differential refractometer using a gel permeation chromatography (GPC) analyzer using TSKgel GMHxL, TSKgel G4000HxL, or TSKgel G2000HxL (all trade names manufactured by TOSOH CORPORATION) columns, and converting the results using polystyrene as a standard substance.

[0081] In the present invention, unless otherwise specified, the molecular weight of a compound having a molecular weight distribution is a weight average molecular weight.

[0082] In this specification, unless otherwise specified, the refractive index is a value measured by an ellipsometer at a wavelength of 550 nm.

[0083] In this specification, “(meth)acrylic acid” is a concept including both acrylic acid and methacrylic acid, “(meth)acrylate” is a concept including both acrylate and methacrylate, and “(meth)acryloyloxy” is a concept including both acryloyloxy and methacryloyloxy.

[0084] [First embodiment of transfer film]

[0085] The transfer film in the first embodiment of the present invention (hereinafter also referred to as the "first transfer film") comprises a temporary support and a photosensitive composition layer disposed on the temporary support. The photosensitive composition layer comprises an alkali-soluble resin, a polymerizable compound, a polymerization initiator, and a blocked isocyanate compound having an NCO value of 4.5 mmol / g or greater. Hereinafter, the blocked isocyanate compound having an NCO value of 4.5 mmol / g or greater is also referred to as the "first blocked isocyanate compound."

[0086] As a feature of the first transfer film, the point that the photosensitive composition layer included in the first transfer film contains the first blocked isocyanate compound can be mentioned.

[0087] Here, as a method for forming a protective film using the first transfer film, the following method can be cited: after the first transfer film is brought into contact with and bonded to a substrate having a conductive layer (sensor electrodes and lead wiring, etc.), a patterned protective film is formed through processes such as pattern exposure, development, and post-baking of the photosensitive composition layer possessed by the first transfer film.

[0088] The present inventors have found that an alkali-soluble resin contained in a photosensitive composition layer is essential for the developability of the photosensitive composition layer, but that acid groups such as carboxyl groups in the alkali-soluble resin may cause corrosion of the conductive layer.

[0089] In order to solve this problem, the present inventors have discovered that the use of a first blocked isocyanate compound can suppress corrosion of the conductive layer.

[0090] This is presumably because, in the post-baking step, a sufficient amount of isocyanate groups required for reacting with acid groups of the alkali-soluble resin is generated from the blocked isocyanate compound, thereby suppressing corrosion of the conductive layer.

[0091] Hereinafter, each member constituting the first transfer film will be described.

[0092] <Temporary Support Body>

[0093] The first 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.

[0094] The temporary support is preferably a film, more preferably a resin film. As the temporary support, a film that is flexible and does not significantly deform, shrink, or stretch under pressure or under pressure and heating can be used.

[0095] Examples of such a film include a polyethylene terephthalate film (for example, a biaxially stretched polyethylene terephthalate film), a cellulose triacetate film, a polystyrene film, a polyimide film, and a polycarbonate film.

[0096] Among these, a biaxially stretched polyethylene terephthalate film is preferable as the temporary support.

[0097] Furthermore, the film used as a temporary support preferably has no deformation such as wrinkles or scratches.

[0098] From the viewpoint of enabling pattern exposure via the temporary support, the temporary support preferably has high transparency, and the transmittance at 365 nm is preferably 60% or more, more preferably 70% or more.

[0099] From the viewpoint of pattern formation during pattern exposure via a temporary support and transparency of the temporary support, the temporary support preferably has a low haze value. Specifically, the temporary support preferably has a haze value of 2% or less, more preferably 0.5% or less, and even more preferably 0.1% or less.

[0100] From the viewpoint of pattern formation during pattern exposure through a temporary support and the transparency of the temporary support, it is preferred that the number of particles, foreign matter, and defects contained in the temporary support be small. The number of particles, foreign matter, and defects with a diameter of 1 μm or more is preferably 50 / 10 mm. 2 Less than 10 / 10mm, more preferably 10 / 10mm 2 Below, more preferably 3 / 10mm 2 Below, particularly preferably 0 / 10mm 2 .

[0101] The thickness of the temporary support is not particularly limited, but is preferably 5 to 200 μm, more preferably 10 to 150 μm, and even more preferably 10 to 50 μm from the viewpoint of ease of handling and versatility.

[0102] From the perspective of improving handling properties, a layer containing fine particles (lubricant layer) can be provided on the surface of the temporary support. The lubricant layer can be provided on one side of the temporary support or on both sides. The diameter of the particles contained in the lubricant layer can be set to 0.05 to 0.8 μm. Furthermore, the film thickness of the lubricant layer can be set to 0.05 to 1.0 μm.

[0103] Examples of the temporary support include a biaxially stretched polyethylene terephthalate film having a film thickness of 16 μm, a biaxially stretched polyethylene terephthalate film having a film thickness of 12 μm, and a biaxially stretched polyethylene terephthalate film having a film thickness of 9 μm.

[0104] Preferred forms of temporary supports are described, for example, in paragraphs

[0017] to

[0018] of Japanese Patent Publication No. 2014-085643, paragraphs

[0019] to

[0026] of Japanese Patent Publication No. 2016-027363, paragraphs

[0041] to

[0057] of International Publication No. 2012 / 081680, and paragraphs

[0029] to

[0040] of International Publication No. 2018 / 179370, and the contents of these publications are incorporated into this specification.

[0105] <Photosensitive Composition Layer>

[0106] The first transfer film has a photosensitive composition layer. After the photosensitive composition layer is transferred onto a transfer target, exposure and development are performed, thereby forming a pattern on the transfer target.

[0107] The photosensitive composition layer contains an alkali-soluble resin, a polymerizable compound, a polymerization initiator, and a first blocked isocyanate compound.

[0108] The photosensitive composition layer may be positive-type or negative-type.

[0109] The positive-working photosensitive composition layer is a photosensitive composition layer whose solubility in a developer is increased by exposure to light, and the negative-working photosensitive composition layer is a photosensitive composition layer whose solubility in a developer is decreased by exposure to light.

[0110] Among them, a negative-type photosensitive composition layer is preferably used. When the photosensitive composition layer is a negative-type photosensitive composition layer, the pattern formed corresponds to a cured film.

[0111] Hereinafter, the components contained in the negative photosensitive composition layer will be described in detail.

[0112] [Polymerizable compound]

[0113] The photosensitive composition layer contains a polymerizable compound.

[0114] The polymerizable compound is a compound having a polymerizable group. Examples of the polymerizable group include radical polymerizable groups and cationic polymerizable groups, with radical polymerizable groups being preferred.

[0115] The polymerizable compound preferably contains a radical polymerizable compound having an ethylenically unsaturated group (hereinafter, also simply referred to as an "ethylenically unsaturated compound").

[0116] As the ethylenically unsaturated group, a (meth)acryloyloxy group is preferred.

[0117] The ethylenically unsaturated compound preferably contains a difunctional or higher-functional ethylenically unsaturated compound. Here, the "difunctional or higher-functional ethylenically unsaturated compound" refers to a compound having two or more ethylenically unsaturated groups in one molecule.

[0118] As the ethylenically unsaturated compound, a (meth)acrylate compound is preferred.

[0119] As the ethylenically unsaturated compound, for example, from the viewpoint of film strength after curing, it is preferred to include a difunctional ethylenically unsaturated compound (preferably a difunctional (meth)acrylate compound) and a trifunctional or higher ethylenically unsaturated compound (preferably a trifunctional or higher (meth)acrylate compound).

[0120] Examples of the bifunctional ethylenically unsaturated compound include tricyclodecanedimethanol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, and 1,6-hexanediol di(meth)acrylate.

[0121] Examples of commercially available bifunctional ethylenically unsaturated compounds include tricyclodecane dimethanol diacrylate [trade name: NK ESTER A-DCP, Shin Nakamura Chemical Co., Ltd.], tricyclodecane dimethanol dimethacrylate [trade name: NK ESTER DCP, Shin Nakamura Chemical Co., Ltd.], 1,9-nonanediol diacrylate [trade name: NK ESTER A-NOD-N, Shin Nakamura Chemical Co., Ltd.], 1,10-decanediol diacrylate [trade name: NK ESTER A-DOD-N, Shin Nakamura Chemical Co., Ltd.], and 1,6-hexanediol diacrylate [trade name: NK ESTER A-HD-N, Shin Nakamura Chemical Co., Ltd.].

[0122] Examples of trifunctional or higher-functional ethylenically unsaturated compounds include dipentaerythritol (tri / tetra / penta / hexa) (meth)acrylate, pentaerythritol (tri / tetra) (meth)acrylate, trimethylolpropane tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, isocyanuric acid (meth)acrylate, and glycerol tri(meth)acrylate.

[0123] Here, "(tri / tetra / penta / hexa) (meth)acrylate" is a concept including tri(meth)acrylate, tetra(meth)acrylate, penta(meth)acrylate, and hexa(meth)acrylate. Furthermore, "(tri / tetra) (meth)acrylate" is a concept including tri(meth)acrylate and tetra(meth)acrylate.

[0124] The upper limit of the number of functional groups of the trifunctional or higher ethylenically unsaturated compound is not particularly limited, and the number of functional groups may be, for example, 20 or less, or 15 or less.

[0125] Examples of commercially available trifunctional or higher ethylenically unsaturated compounds include dipentaerythritol hexaacrylate (trade name: KAYARAD DPHA, SHIN-NAKAMURA CHEMICAL CO., LTD.).

[0126] The ethylenically unsaturated compound more preferably includes 1,9-nonanediol di(meth)acrylate or 1,10-decanediol di(meth)acrylate and dipentaerythritol (tri / tetra / penta / hexa) (meth)acrylate.

[0127] Examples of the ethylenically unsaturated compound include caprolactone-modified compounds of (meth)acrylate compounds [such as KAYARAD (registered trademark) DPCA-20 from Nippon Kayaku Co., Ltd. and A-9300-1CL from Shin Nakamura Chemical Co., Ltd.], alkylene oxide-modified compounds of (meth)acrylate compounds [such as KAYARAD (registered trademark) RP-1040 from Nippon Kayaku Co., Ltd. and ATM-35E and A-9300 from Shin Nakamura Chemical Co., Ltd. and EBECRYL (registered trademark) 135 from DAICEL-ALLNEX LTD.], and ethoxylated glycerol triacrylate [such as NK ESTER A-GLY-9E from Shin Nakamura Chemical Co., Ltd.].

[0128] Examples of ethylenically unsaturated compounds include urethane (meth)acrylate compounds. Urethane (meth)acrylate compounds that are trifunctional or higher are preferred. Examples of trifunctional or higher urethane (meth)acrylate compounds include 8UX-015A (Taisei Fine Chemical Co., Ltd.), NK ESTER UA-32P (Shin Nakamura Chemical Co., Ltd.), and NK ESTER UA-1100H (Shin Nakamura Chemical Co., Ltd.).

[0129] From the viewpoint of improving developability, the ethylenically unsaturated compound preferably contains an ethylenically unsaturated compound having an acid group.

[0130] Examples of the acid group include a phosphoric acid group, a sulfonic acid group, and a carboxyl group. Among the above, the carboxyl group is preferred as the acid group.

[0131] Examples of ethylenically unsaturated compounds having an acid group include tri- to tetra-functional ethylenically unsaturated compounds having an acid group (compounds obtained by introducing carboxyl groups into the backbone of pentaerythritol tri- and tetraacrylates (PETA) (acid value: 80 to 120 mgKOH / g)) and penta- to hexa-functional ethylenically unsaturated compounds having an acid group (compounds obtained by introducing carboxyl groups into the backbone of dipentaerythritol penta- and hexaacrylates (DPHA) (acid value: 25 to 70 mgKOH / g)). Tri- or higher-functional ethylenically unsaturated compounds having an acid group may be used in combination with difunctional ethylenically unsaturated compounds having an acid group, as needed.

[0132] The ethylenically unsaturated compound having an acid group is preferably at least one compound selected from difunctional or higher ethylenically unsaturated compounds having a carboxyl group and their carboxylic anhydrides. If the ethylenically unsaturated compound having an acid group is at least one compound selected from difunctional or higher ethylenically unsaturated compounds having a carboxyl group and their carboxylic anhydrides, developability and film strength are further improved.

[0133] Examples of the difunctional or higher functional ethylenically unsaturated compound having a carboxyl group include ARONIX (registered trademark) TO-2349 [TOAGOSEI CO., LTD.], ARONIX (registered trademark) M-520 [TOAGOSEI CO., LTD.], and ARONIX (registered trademark) M-510 [TOAGOSEI CO., LTD.].

[0134] As the ethylenically unsaturated compound having an acid group, the polymerizable compound having an acid group described in paragraphs

[0025] to

[0030] of JP-A-2004-239942 can be preferably used, and the contents described in this publication are incorporated herein by reference.

[0135] The molecular weight of the ethylenically unsaturated compound is preferably 200 to 3,000, more preferably 250 to 2,600, further preferably 280 to 2,200, and particularly preferably 300 to 2,200.

[0136] The content of ethylenically unsaturated compounds having a molecular weight of 300 or less among the ethylenically unsaturated compounds is preferably 30% by mass or less, more preferably 25% by mass or less, and further preferably 20% by mass or less, based on the content of all ethylenically unsaturated compounds contained in the photosensitive composition layer.

[0137] The photosensitive composition layer may contain a single polymerizable compound, or may contain two or more polymerizable compounds.

[0138] The content of the polymerizable compound (preferably an ethylenically unsaturated compound) is preferably 1 to 70 mass %, more preferably 10 to 70 mass %, further preferably 20 to 60 mass %, and particularly preferably 20 to 50 mass % based on the total mass of the photosensitive composition layer.

[0139] When the photosensitive composition layer contains a difunctional or higher-functional ethylenically unsaturated compound, it may further contain a monofunctional ethylenically unsaturated compound.

[0140] When the photosensitive composition layer contains a difunctional or higher-functional ethylenically unsaturated compound, the difunctional or higher-functional ethylenically unsaturated compound is preferably a main component of the ethylenically unsaturated compounds contained in the photosensitive composition layer.

[0141] When the photosensitive composition layer contains a difunctional or higher-functional ethylenically unsaturated compound, the content of the difunctional or higher-functional ethylenically unsaturated compound is preferably 60 to 100% by mass, more preferably 80 to 100% by mass, and even more preferably 90 to 100% by mass relative to the content of all ethylenically unsaturated compounds contained in the photosensitive composition layer.

[0142] When the photosensitive composition layer contains an ethylenically unsaturated compound having an acid group (preferably, a difunctional or higher-functional ethylenically unsaturated compound having a carboxyl group or a carboxylic anhydride thereof), the content of the ethylenically unsaturated compound having an acid group is preferably 1 to 50% by mass, more preferably 1 to 20% by mass, and even more preferably 1 to 10% by mass, relative to the total mass of the photosensitive composition layer.

[0143] [Polymerization initiator]

[0144] The photosensitive composition layer contains a polymerization initiator.

[0145] As the polymerization initiator, a photopolymerization initiator is preferred.

[0146] Examples of the photopolymerization initiator include a photopolymerization initiator having an oxime ester structure (hereinafter also referred to as an "oxime-based photopolymerization initiator"), a photopolymerization initiator having an α-aminoalkylphenone structure (hereinafter also referred to as an "α-aminoalkylphenone-based photopolymerization initiator"), a photopolymerization initiator having an α-hydroxyalkylphenone structure (hereinafter also referred to as an "α-hydroxyalkylphenone-based polymerization initiator"), a photopolymerization initiator having an acylphosphine oxide structure (hereinafter also referred to as an "acylphosphine oxide-based photopolymerization initiator"), and a photopolymerization initiator having an N-phenylglycine structure (hereinafter also referred to as an "N-phenylglycine-based photopolymerization initiator").

[0147] The photopolymerization initiator preferably includes at least one selected from an oxime-based photopolymerization initiator, an α-aminoalkylphenone-based photopolymerization initiator, an α-hydroxyalkylphenone-based photopolymerization initiator, and an N-phenylglycine-based photopolymerization initiator, and more preferably includes at least one selected from an oxime-based photopolymerization initiator, an α-aminoalkylphenone-based photopolymerization initiator, and an N-phenylglycine-based photopolymerization initiator.

[0148] Furthermore, as the photopolymerization initiator, for example, polymerization initiators described in paragraphs

[0031] to

[0042] of JP-A-2011-095716 and paragraphs

[0064] to

[0081] of JP-A-2015-014783 can be used.

[0149] Examples of commercially available photopolymerization initiators include 1-[4-(phenylthio)]phenyl-1,2-octanedione-2-(O-benzoyl oxime) [trade name: IRGACURE (registered trademark) OXE-01, manufactured by BASF], 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone-1-(O-acetyl oxime) [trade name: IRGACURE (registered trademark) OXE-02, manufactured by BASF], and 8-[5-(2,4,6-trimethylphenyl)-11-(2-ethylhexane]-1-[1-(2-ethylhexane) ... [(4-(2-Benzofurylcarbonyl)phenyl]thio]phenyl]-4-methyl-1-pentanone-1-(O-acetoxime) [(4-(2-Benzofurylcarbonyl)phenyl)methyl)-1-[(4-(2-Benzofurylcarbonyl)phenyl)-1-[(4-(2-Benzofurylcarbonyl)phenyl)-1-[(4-(2-Benzofurylcarbonyl)phenyl)-1-[(4-(2-Benzofurylcarbonyl)phenyl)-1-[(4-(2-Benzofurylcarbonyl)phenyl)-1-[(4-(2-Benzofurylcarbonyl)phenyl)-1-[(4-(2-Benzofurylcarbonyl)phenyl)-1-[(4-(2-Benzofurylcarbonyl)phenyl)-1-[(4-(2-Benzofurylcarbonyl)phenyl)-1-[(4-(2-Benzofurylcarbonyl)phenyl)-1-[ 4-(4-morpholinyl)phenyl]-1-butanone [trade name: IRGACURE (registered trademark) 379EG, manufactured by BASF], 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one [trade name: IRGACURE (registered trademark) 907, manufactured by BASF], 2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propionyl)benzyl]phenyl}-2-methylpropan-1-one [trade name: IRGACURE (registered trademark) 127, manufactured by BASF], 2 Benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone [Trade name: IRGACURE (registered trademark) 369, manufactured by BASF], 2-hydroxy-2-methyl-1-phenyl-propan-1-one [Trade name: IRGACURE (registered trademark) 1173, manufactured by BASF], 1-hydroxycyclohexylphenyl ketone [Trade name: IRGACURE (registered trademark) 184, manufactured by BASF], 2,2-dimethoxy-1,2-diphenylethane-1-one [Trade name: IRGACURE 651, manufactured by BASF Corporation], Oxime ester compounds [Trade name: Lunar (registered trademark) 6, manufactured by DKSH Japan KK], 1-[4-(phenylthio)phenyl]-3-cyclopentylpropane-1,2-dione-2-(O-benzoyloxime) (Trade name: TR-PBG-305, Changzhou Tronly New Electronic Materials Co., Ltd.manufactured by Changzhou Tronly New Electronic Materials Co., Ltd.), 1,2-propanedione, 3-cyclohexyl-1-[9-ethyl-6-(2-furylcarboxyl)-9H-carbazol-3-yl]-, 2-(O-acetoxime) (trade name: TR-PBG-326, manufactured by Changzhou Tronly New Electronic Materials Co., Ltd.), 3-cyclohexyl-1-(6-(2-(benzoyloxyimino)hexanoyl)-9-ethyl-9H-carbazol-3-yl)-propane-1,2-dione-2-(O-benzoyloxime) (trade name: TR-PBG-391, manufactured by Changzhou Tronly New Electronic Materials Co., Ltd.), and API-307 (1-(biphenyl-4-yl)-2-methyl-2-morpholinopropane-1-one, manufactured by Shenzhen UV-ChemTech Ltd.).

[0150] The photosensitive composition layer may contain a single type of photopolymerization initiator, or may contain two or more types of photopolymerization initiators.

[0151] The content of the photopolymerization initiator is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, relative to the total mass of the photosensitive composition layer. Furthermore, the upper limit of the content of the photopolymerization initiator is preferably 10% by mass or less, more preferably 5% by mass or less, relative to the total mass of the photosensitive composition layer.

[0152] [Alkali-soluble resin]

[0153] The photosensitive composition layer contains an alkali-soluble resin. When the photosensitive composition layer contains an alkali-soluble resin, the solubility of the photosensitive composition layer (non-exposed portion) in the developer is improved.

[0154] In the present invention, "alkali-soluble" means that the dissolution rate determined by the following method is 0.01 μm / sec or more.

[0155] A 25% by mass solution of propylene glycol monomethyl ether acetate containing a target compound (e.g., a resin) was applied to a glass substrate and then heated in an oven at 100°C for 3 minutes to form a coating film (2.0 μm thick) of the target compound. The coating film was immersed in a 1% by mass aqueous solution of sodium carbonate (liquid temperature 30°C) to determine the dissolution rate (μm / second) of the coating film.

[0156] Alternatively, when the target compound is insoluble in propylene glycol monomethyl ether acetate, the target compound is dissolved in an organic solvent other than propylene glycol monomethyl ether acetate having a boiling point of less than 200° C. (eg, tetrahydrofuran, toluene, or ethanol).

[0157] The alkali-soluble resin preferably contains a structural unit derived from a vinylbenzene derivative, a structural unit having a radical polymerizable group, and a structural unit having an acid group.

[0158] (Structural unit derived from vinylbenzene derivative)

[0159] As the structural unit derived from a vinylbenzene derivative (hereinafter also referred to as a "vinylbenzene derivative unit"), a unit represented by the following formula (1) (hereinafter also referred to as "unit (1)") is preferred.

[0160] [Chemical Formula 1]

[0161]

[0162] In formula (1), n ​​represents an integer of 0 to 5. In formula (1), R 1 represents a substituent. When n is 2 or more, two R 1 They can be bonded to each other to form a condensed ring structure. When n is 2 or more, R 1 It can be the same or different.

[0163] As R 1 The substituent represented by is preferably a halogen atom, an alkyl group, an aryl group, an alkoxy group or a hydroxyl group.

[0164] As R 1 The halogen atom, which is one preferred embodiment of the present invention, is preferably a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, and more preferably a fluorine atom, a chlorine atom or a bromine atom.

[0165] As R 1 The number of carbon atoms in the alkyl group in one preferred embodiment is preferably 1 to 20, more preferably 1 to 12, more preferably 1 to 6, further preferably 1 to 3, particularly preferably 1 or 2, and most preferably 1.

[0166] As R 1 The number of carbon atoms in the aryl group in one preferred embodiment is preferably 6 to 20, more preferably 6 to 12, further preferably 6 to 10, and particularly preferably 6.

[0167] As R 1 The number of carbon atoms in the alkoxy group in one preferred embodiment is preferably 1 to 20, more preferably 1 to 12, more preferably 1 to 6, further preferably 1 to 3, particularly preferably 1 or 2, and most preferably 1.

[0168] R 11 represents a hydrogen atom or a methyl group.

[0169] In formula (1), n ​​is particularly preferably an integer of 0 to 2.

[0170] In formula (1), when n is 2, it is possible to 1The fused ring structure formed by bonding to each other is preferably a naphthalene ring structure or an anthracene ring structure.

[0171] Examples of the monomer for forming the vinylbenzene derivative unit include styrene, 1-vinylnaphthalene, 2-vinylnaphthalene, vinylbiphenyl, vinylanthracene, 4-hydroxystyrene, 4-bromostyrene, 4-methoxystyrene, and α-methylstyrene. Styrene is particularly preferred.

[0172] From the viewpoint of achieving more excellent effects of the present invention, the content of the vinylbenzene derivative unit is preferably 30% by mass or more, more preferably 40% by mass or more, and even more preferably 45% by mass or more, based on the total amount of all structural units contained in the alkali-soluble resin.

[0173] The upper limit of the content of the vinylbenzene derivative unit is preferably 70% by mass or less, more preferably 60% by mass or less, and further preferably 50% by mass or less.

[0174] The alkali-soluble resin may contain a single vinylbenzene derivative unit, or may contain two or more vinylbenzene derivative units.

[0175] In the present invention, when the content of a "structural unit" is specified in mass %, unless otherwise specified, the "structural unit" has the same meaning as the "monomer unit." Furthermore, in the present invention, when a resin or polymer has two or more specific structural units, the content of the specific structural units refers to the total content of the two or more specific structural units, unless otherwise specified.

[0176] (Structural unit having a radical polymerizable group)

[0177] In the structural unit having a radical polymerizable group (hereinafter also referred to as a "radical polymerizable group-containing unit"), the radical polymerizable group is preferably a group having an ethylenic double bond (hereinafter also referred to as an "ethylenically unsaturated group"), and more preferably a (meth)acryloyl group.

[0178] As the unit containing a radical polymerizable group, a unit represented by the following formula (2) (hereinafter also referred to as "unit (2)") is preferred.

[0179] [Chemical Formula 2]

[0180]

[0181] In formula (2), R 2 and R 3 Each independently represents a hydrogen atom or an alkyl group, and L represents a divalent linking group.

[0182] As R 2 and R 3The number of carbon atoms of the alkyl groups represented by is preferably 1 to 3, more preferably 1 or 2, and even more preferably 1.

[0183] The divalent linking group represented by L is preferably one group selected from the group consisting of a carbonyl group (i.e., a -C(=O)- group), an oxygen atom (i.e., a -O- group), an alkylene group, and an arylene group, or a group formed by linking two or more groups selected from the above group.

[0184] The alkylene group or the arylene group may be substituted with a substituent (for example, a hydroxyl group other than a primary hydroxyl group, a halogen atom, etc.).

[0185] The divalent linking group represented by L may have a branched structure.

[0186] The number of carbon atoms in the divalent linking group represented by L is preferably 1 to 30, more preferably 1 to 20, and even more preferably 2 to 10.

[0187] As the divalent linking group represented by L, the following groups are particularly preferred.

[0188] [Chemical Formula 3]

[0189]

[0190] In each of the above groups, *1 represents a bonding position to a carbon atom contained in the main chain in formula (2), and *2 represents a bonding position to a carbon atom forming a double bond in formula (2).

[0191] Furthermore, in (L-5), n and m each independently represent an integer of 1 to 6.

[0192] Examples of the radical polymerizable group-containing unit include a structural unit obtained by adding an epoxy group-containing monomer to a (meth)acrylic acid unit and a structural unit obtained by adding an isocyanate group-containing monomer to a hydroxyl group-containing monomer unit.

[0193] The epoxy group-containing monomer is preferably an epoxy group-containing (meth)acrylate having a total carbon number of 5 to 24, more preferably an epoxy group-containing (meth)acrylate having a total carbon number of 5 to 12, and still more preferably glycidyl (meth)acrylate or 3,4-epoxycyclohexylmethyl (meth)acrylate.

[0194] As the hydroxyl-containing monomer for forming the hydroxyl-containing monomer unit, hydroxyalkyl (meth)acrylates having a total carbon number of 4 to 24 are preferred, hydroxyalkyl (meth)acrylates having a total carbon number of 4 to 12 are more preferred, and hydroxyethyl (meth)acrylate is further preferred.

[0195] Here, the "(meth)acrylic acid unit" refers to a structural unit derived from (meth)acrylic acid.

[0196] Likewise, in this specification, a term with the word "unit" appended immediately after the name of a monomer (eg, "hydroxyl-containing monomer unit") refers to a structural unit derived from the monomer (eg, hydroxyl-containing monomer).

[0197] More specifically, the radical polymerizable group-containing unit includes:

[0198] A structural unit obtained by adding glycidyl (meth)acrylate to a (meth)acrylic acid unit;

[0199] A structural unit obtained by adding (meth)acrylic acid to a (meth)acrylic acid unit;

[0200] A structural unit obtained by adding 3,4-epoxycyclohexylmethyl(meth)acrylate to a (meth)acrylic acid unit;

[0201] A structural unit obtained by adding 2-isocyanatoethyl methacrylate to a hydroxyethyl (meth)acrylate unit;

[0202] A structural unit obtained by adding 2-isocyanatoethyl methacrylate to a hydroxybutyl (meth)acrylate unit;

[0203] A structural unit obtained by adding 2-isocyanatoethyl methacrylate to a p-hydroxystyrene unit, etc.

[0204] As a unit containing a radical polymerizable group,

[0205] More preferably, a structural unit obtained by adding glycidyl (meth)acrylate to a (meth)acrylic acid unit or a structural unit obtained by adding 3,4-epoxycyclohexylmethyl (meth)acrylate to a (meth)acrylic acid unit is used.

[0206] In particular, a structural unit obtained by adding glycidyl methacrylate to a methacrylic acid unit or a structural unit obtained by adding 3,4-epoxycyclohexylmethyl methacrylate to a methacrylic acid unit is preferred.

[0207] From the viewpoint of achieving more excellent effects of the present invention, the content of the radical polymerizable group-containing unit is preferably 20 to 50% by mass, more preferably 25 to 45% by mass, and even more preferably 30 to 40% by mass based on the total amount of all structural units contained in the alkali-soluble resin.

[0208] The alkali-soluble resin may contain a single type of radical polymerizable group-containing unit, or may contain two or more types of radical polymerizable group-containing units.

[0209] (Structural unit having an acid group)

[0210] When the alkali-soluble resin contains a structural unit having an acid group (hereinafter also referred to as “acid group-containing unit”), the photosensitive composition layer has alkali solubility.

[0211] Examples of the acid group in the acid group-containing unit include a carboxyl group, a sulfonic acid group, a sulfuric acid group, and a phosphoric acid group, and a carboxyl group is preferred.

[0212] As the acid group-containing unit, a unit represented by the following formula (3) (hereinafter also referred to as "unit (3)") is preferred.

[0213] [Chemical Formula 4]

[0214]

[0215] In formula (3), R 5 represents a hydrogen atom or an alkyl group.

[0216] As R 5 The number of carbon atoms in the alkyl group represented by is preferably 1 to 3, more preferably 1 or 2, and even more preferably 1.

[0217] As R 5 , preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, more preferably a hydrogen atom, a methyl group or an ethyl group, further preferably a hydrogen atom or a methyl group.

[0218] As the monomer for forming the acid group-containing unit, (meth)acrylic acid is particularly preferred.

[0219] From the viewpoint of achieving more excellent effects of the present invention, the content of the acid group-containing unit is preferably 5 to 30% by mass, more preferably 10 to 25% by mass, and even more preferably 15 to 20% by mass based on the total amount of all structural units contained in the alkali-soluble resin.

[0220] The alkali-soluble resin may contain a single type of acid group-containing unit, or may contain two or more types of acid group-containing units.

[0221] (Other structural units)

[0222] The alkali-soluble resin may contain other structural units in addition to the above-mentioned structural units.

[0223] Other structural units include (meth)acrylate structural units having a hydroxyl group and having neither a radical polymerizable group nor an acid group, and (meth)acrylate structural units having neither a hydroxyl group, a radical polymerizable group, nor an acid group.

[0224] Examples of the monomer that forms the (meth)acrylate structural unit having a hydroxyl group and having neither a radical polymerizable group nor an acid group include hydroxyethyl (meth)acrylate and 4-hydroxyethyl (meth)acrylate.

[0225] Examples of monomers forming the (meth)acrylate structural unit having no hydroxyl group, free radical polymerizable group, or acid group include alkyl (meth)acrylates having a monocyclic or polycyclic cyclic aliphatic hydrocarbon group (e.g., dicyclopentanyl (meth)acrylate, cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, 1-adamantyl (meth)acrylate, etc.) and alkyl (meth)acrylates having a linear or branched aliphatic hydrocarbon group (e.g., methyl (meth)acrylate, butyl (meth)acrylate, etc.).

[0226] The content of the (meth)acrylate structural unit having a hydroxyl group and having neither a radical polymerizable group nor an acid group is preferably 0 to 5% by mass, more preferably 1 to 3% by mass, based on the total amount of all structural units contained in the alkali-soluble resin.

[0227] The content of the alkyl (meth)acrylate structural unit having no hydroxyl group, radical polymerizable group, or acid group is preferably 0 to 5% by mass, more preferably 1 to 3% by mass, based on the total amount of all structural units contained in the alkali-soluble resin.

[0228] The alkali-soluble resin may contain a single type of other structural unit, or may contain two or more types of other structural units.

[0229] The weight average molecular weight (Mw) of the alkali-soluble resin is preferably 5,000 or more, more preferably 5,000 to 100,000, and even more preferably 7,000 to 50,000.

[0230] From the viewpoint of film strength, the dispersion degree (weight average molecular weight Mw / number average molecular weight Mn) of the alkali-soluble resin is preferably 1.0 to 3.0, more preferably 1 to 2.5.

[0231] From the viewpoint of developability, the acid value of the alkali-soluble 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.

[0232] From the viewpoint of suppressing dissolution in a developer, the upper limit of the acid value of the alkali-soluble resin is preferably 200 mgKOH / g or less, and more preferably 150 mgKOH / g or less.

[0233] As the acid value, a theoretical acid value calculated by the calculation method described in paragraph

[0063] of JP-A-2004-149806 or paragraph

[0070] of JP-A-2012-211228 can be used.

[0234] The photosensitive composition layer may contain a single alkali-soluble resin or may contain two or more alkali-soluble resins.

[0235] The photosensitive composition layer may contain residual monomers of each structural unit of the above-mentioned alkali-soluble resin.

[0236] From the perspective of patterning properties and reliability, the residual monomer content is preferably 5,000 ppm by mass or less, more preferably 2,000 ppm by mass or less, and even more preferably 500 ppm by mass or less, relative to the total mass of the alkali-soluble resin. The lower limit is not particularly limited, but is preferably 1 ppm by mass or more, and more preferably 10 ppm by mass or more.

[0237] From the perspective of patterning properties and reliability, the residual monomer content of each structural unit of the alkali-soluble resin is preferably 3,000 mass ppm or less, more preferably 600 mass ppm or less, and even more preferably 100 mass ppm or less, relative to the total mass of the photosensitive composition layer. The lower limit is not particularly limited, but is preferably 0.1 mass ppm or more, and more preferably 1 mass ppm or more.

[0238] The residual monomer content of monomers when synthesizing an alkali-soluble resin by polymer reaction is also preferably within the above range. For example, when synthesizing an alkali-soluble resin by reacting glycidyl acrylate with a carboxylic acid side chain, the glycidyl acrylate content is preferably within the above range.

[0239] The amount of residual monomers can be measured by known methods such as liquid chromatography and gas chromatography.

[0240] From the viewpoint of developability, the content of the alkali-soluble resin is preferably 10 to 90% by mass, more preferably 20 to 80% by mass, and even more preferably 25 to 70% by mass relative to the total mass of the photosensitive composition layer.

[0241] [First blocked isocyanate compound]

[0242] The photosensitive composition layer contains a first blocked isocyanate compound.

[0243] A blocked isocyanate compound refers to a compound having a structure in which the isocyanate group of an isocyanate is protected (so-called masked) by a blocking agent. In this specification, the term "blocked isocyanate compound" includes not only the "first blocked isocyanate compound" but also the "second blocked isocyanate compound" described below. Furthermore, a structure in which an isocyanate group is protected by a blocking agent may be referred to as a "blocked isocyanate group."

[0244] The NCO value of the first blocked isocyanate compound is 4.5 mmol / g or more, preferably 5.0 mmol / g or more, and more preferably 5.3 mmol / g or more, from the viewpoint of further improving the effects of the present invention.

[0245] From the viewpoint of further improving the effects of the present invention, the upper limit of the NCO value of the first blocked isocyanate compound is preferably 8.0 mmol / g or less, more preferably 6.0 mmol / g or less, further preferably less than 5.8 mmol / g, and particularly preferably 5.7 mmol / g or less.

[0246] The NCO value of the blocked isocyanate compound in the present invention refers to the number of moles of isocyanate groups contained per 1 g of the blocked isocyanate compound, and is a value calculated from the structural formula of the blocked isocyanate compound.

[0247] The dissociation temperature of the first blocked isocyanate compound is preferably 100 to 160°C, more preferably 110 to 150°C.

[0248] In this specification, the "dissociation temperature of the blocked isocyanate compound" refers to the temperature of the endothermic peak associated with the deprotection reaction of the blocked isocyanate compound, as measured by DSC (Differential Scanning Calorimetry) analysis using a differential scanning calorimeter. As a differential scanning calorimeter, for example, a differential scanning calorimeter (Model: DSC6200) manufactured by Seiko Instruments Inc. can be preferably used. However, the differential scanning calorimeter is not limited to the above differential scanning calorimeter.

[0249] Examples of end-capping agents having a dissociation temperature of 100 to 160°C include active methylene compounds [malonic acid diesters (such as dimethyl malonate, diethyl malonate, di-n-butyl malonate, and di-2-ethylhexyl malonate)] and oxime compounds (formaldehyde oxime, acetaldehyde oxime, acetone oxime, methyl ethyl ketone oxime, and cyclohexanone oxime, which have a structure represented by -C(=N-OH)- in the molecule). Among the above, oxime compounds are preferred as end-capping agents having a dissociation temperature of 100 to 160°C from the perspective of storage stability.

[0250] From the perspective of achieving a more excellent effect of the present invention, the first blocked isocyanate compound preferably has a ring structure. Examples of the ring structure include aliphatic hydrocarbon rings, aromatic hydrocarbon rings, and heterocyclic rings. From the perspective of achieving a more excellent effect of the present invention, aliphatic hydrocarbon rings and aromatic hydrocarbon rings are preferred, and aliphatic hydrocarbon rings are more preferred.

[0251] Specific examples of the aliphatic hydrocarbon ring include a cyclopentane ring and a cyclohexane ring, and among them, a cyclohexane ring is preferred.

[0252] Specific examples of the aromatic hydrocarbon ring include a benzene ring and a naphthalene ring, and among them, a benzene ring is preferred.

[0253] Specific examples of the heterocyclic ring include an isocyanurate ring.

[0254] When the first blocked isocyanate compound has a ring structure, from the viewpoint of achieving more excellent effects of the present invention, the number of rings is preferably 1 to 2, more preferably 1. Furthermore, when the first blocked isocyanate compound contains a fused ring, the number of rings constituting the fused ring is calculated; for example, the number of rings in the naphthalene ring is counted as 2.

[0255] The number of blocked isocyanate groups in the first blocked isocyanate compound is preferably 2 to 5, more preferably 2 to 3, and even more preferably 2, from the viewpoint of excellent strength of the formed pattern and further excellent effects of the present invention.

[0256] The first blocked isocyanate compound is preferably a blocked isocyanate compound represented by Formula Q from the viewpoint of achieving more excellent effects of the present invention.

[0257] B 1 -A 1 -L 1 -A 2 -B 2 Formula Q

[0258] In formula Q, B 1 and B 2 Each independently represents a blocked isocyanate group.

[0259] The blocked isocyanate group is not particularly limited. From the viewpoint of achieving the best effect of the present invention, a group in which the isocyanate group is blocked by an oxime compound is preferred, and a group in which the isocyanate group is blocked by methyl ethyl ketoxime is more preferred (specifically, a group represented by *-NH-C(=O)-ON=C(CH3)-C2H5. * represents the same as A 1 or A 2 bonding position. ).

[0260] B 1 and B 2 The same groups are preferred.

[0261] In formula Q, A 1 and A 2 Each independently represents a single bond or an alkylene group having 1 to 10 carbon atoms, and preferably an alkylene group having 1 to 10 carbon atoms.

[0262] The alkylene group may be linear, branched, or cyclic, and is preferably linear.

[0263] The number of carbon atoms in the alkylene group is 1 to 10, and preferably 1 to 5, more preferably 1 to 3, and even more preferably 1, from the viewpoint of further improving the effects of the present invention.

[0264] A 1 and A 2 The same groups are preferred.

[0265] In formula Q, L 1 represents a divalent linking group.

[0266] Specific examples of the divalent linking group include divalent hydrocarbon groups.

[0267] Specific examples of the divalent hydrocarbon group include a divalent saturated hydrocarbon group, a divalent aromatic hydrocarbon group, and a group in which two or more of these groups are linked together.

[0268] The divalent saturated hydrocarbon group may be linear, branched, or cyclic, but is preferably cyclic from the viewpoint of achieving the best effects of the present invention. From the viewpoint of achieving the best effects of the present invention, the divalent saturated hydrocarbon group preferably has 4 to 15 carbon atoms, more preferably 5 to 10, and even more preferably 5 to 8 carbon atoms.

[0269] The divalent aromatic hydrocarbon group preferably has 5 to 20 carbon atoms, and an example thereof is a phenylene group. The divalent aromatic hydrocarbon group may have a substituent (for example, an alkyl group).

[0270] Among them, the divalent linking group is preferably a linear, branched or cyclic divalent saturated hydrocarbon group having 5 to 10 carbon atoms, a group formed by linking a cyclic saturated hydrocarbon group having 5 to 10 carbon atoms and a linear alkylene group having 1 to 3 carbon atoms, a divalent aromatic hydrocarbon group which may have a substituent, or a group formed by linking a divalent aromatic hydrocarbon group and a linear alkylene group having 1 to 3 carbon atoms. A cyclic divalent saturated hydrocarbon group having 5 to 10 carbon atoms or a phenylene group which may have a substituent is more preferred. A cyclohexylene group or a phenylene group which may have a substituent is further preferred, and a cyclohexylene group is particularly preferred.

[0271] From the viewpoint of achieving more excellent effects of the present invention, the blocked isocyanate compound represented by Formula Q is particularly preferably a blocked isocyanate compound represented by Formula QA.

[0272] B 1a -A 1a -L 1a -A 2a -B 2a Formula QA

[0273] In formula QA, B 1a and B 2a Each independently represents a blocked isocyanate group. 1a and B 2aThe preferred embodiment is the same as B in formula Q 1 and B 2 same.

[0274] In formula QA, A 1a and A 2a Each independently represents a divalent linking group. 1a and A 2a The preferred embodiment of the divalent linking group in formula Q is the same as that of A 1 and A 2 same.

[0275] In formula QA, L 1a represents a cyclic divalent saturated hydrocarbon group or a divalent aromatic hydrocarbon group.

[0276] L 1a The number of carbon atoms in the cyclic divalent saturated hydrocarbon group is preferably 5 to 10, more preferably 5 to 8, further preferably 5 to 6, and particularly preferably 6.

[0277] L 1a The preferred embodiment of the divalent aromatic hydrocarbon group in formula Q is the same as L 1 same.

[0278] Among them, L 1a A cyclic divalent saturated hydrocarbon group is preferred, a cyclic divalent saturated hydrocarbon group having 5 to 10 carbon atoms is more preferred, a cyclic divalent saturated hydrocarbon group having 5 to 10 carbon atoms is further preferred, a cyclic divalent saturated hydrocarbon group having 5 to 6 carbon atoms is particularly preferred, and a cyclohexylene group is most preferred.

[0279] When L 1a In the case of a cyclohexylene group, the blocked isocyanate compound represented by the formula QA may be an isomer mixture of a cis isomer and a trans isomer (hereinafter also referred to as a "cis-trans isomer mixture").

[0280] The mass ratio of the cis phase to the trans phase is preferably cis phase / trans phase = 10 / 90 to 90 / 10, more preferably cis phase / trans phase = 40 / 60 to 60 / 40.

[0281] Although specific examples of the first blocked isocyanate compound are shown below, the first blocked isocyanate compound is not limited thereto.

[0282] [Chemical Formula 5]

[0283]

[0284] The photosensitive composition layer may contain a single type of the first blocked isocyanate compound, or may contain two or more types of the first blocked isocyanate compounds.

[0285] From the viewpoint of further improving the effects of the present invention, the content of the first blocked isocyanate compound is preferably 1 to 20% by mass, more preferably 2 to 15% by mass, and even more preferably 2.5 to 13% by mass relative to the total mass of the photosensitive composition layer.

[0286] The first blocked isocyanate compound is obtained by, for example, making a compound having an isocyanate group (for example, B in the above formula Q) 1 and B 2 isocyanate group of the compound) is obtained by reacting the isocyanate group with the above-mentioned blocking agent.

[0287] [Second blocked isocyanate compound]

[0288] The photosensitive composition layer preferably further contains a blocked isocyanate compound having an NCO value of less than 4.5 mmol / g (hereinafter also referred to as a "second blocked isocyanate compound"), thereby suppressing the generation of development residues after pattern exposure and development of the photosensitive composition layer.

[0289] The NCO value of the second blocked isocyanate compound is less than 4.5 mmol / g, preferably 3.0 to 4.5 mmol / g, more preferably 3.3 to 4.4 mmol / g, and even more preferably 3.5 to 4.3 mmol / g.

[0290] The dissociation temperature of the second blocked isocyanate compound is preferably 100 to 160°C, more preferably 110 to 150°C.

[0291] Specific examples of the blocking agent having a dissociation temperature of 100 to 160° C. are as described above.

[0292] The second blocked isocyanate compound preferably has an isocyanurate structure from the viewpoint of improving film brittleness or improving adhesion to the transfer body. The blocked isocyanate compound having an isocyanurate structure can be obtained, for example, by isocyanurating and blocking hexamethylene diisocyanate.

[0293] As the blocked isocyanate compound having an isocyanurate structure, a compound having an oxime structure using an oxime compound as a blocking agent is preferred because it is easier to set the dissociation temperature within a preferred range and to reduce development residues than a compound not having an oxime structure.

[0294] From the viewpoint of the strength of the formed pattern, the second blocked isocyanate compound may have a polymerizable group. As the polymerizable group, a radical polymerizable group is preferred.

[0295] Examples of the polymerizable group include ethylenically unsaturated groups such as (meth)acryloyloxy, (meth)acrylamide, and styryl, and groups having an epoxy group such as glycidyl. Among the above, the polymerizable group is preferably an ethylenically unsaturated group, and more preferably a (meth)acryloyloxy group, from the viewpoints of the surface shape of the obtained pattern, the development speed, and the reactivity.

[0296] Specific examples of the second blocked isocyanate compound are shown below, but the second blocked isocyanate compound is not limited thereto.

[0297] [Chemical Formula 6]

[0298]

[0299] As the second blocked isocyanate compound, a commercially available product can be used. Examples of commercially available blocked isocyanate compounds include Karenz (registered trademark) AOI-BM, Karenz (registered trademark) MOI-BM, Karenz (registered trademark) AOI-BP, and Karenz (registered trademark) MOI-BP (all manufactured by Showa Denko KK) and the blocked DURANATE series (for example, DURANATE (registered trademark) TPA-B80E, manufactured by Asahi Kasei Chemicals Corporation).

[0300] The photosensitive composition layer may contain a single type of the second blocked isocyanate compound, or may contain two or more types of the second blocked isocyanate compounds.

[0301] When the photosensitive composition layer contains the second blocked isocyanate compound, the content of the second blocked isocyanate compound is preferably 5 to 20% by mass, more preferably 7 to 17% by mass, and even more preferably 10 to 15% by mass relative to the total mass of the photosensitive composition layer, from the viewpoint of further reducing the generation of development residues.

[0302] When the photosensitive composition layer contains a second blocked isocyanate compound, from the viewpoint of bending resistance, the mass ratio of the content of the first blocked isocyanate compound to the content of the second blocked isocyanate compound (first blocked isocyanate compound / second blocked isocyanate compound) is preferably 0.1 to 1.5, more preferably 0.2 to 1.0, and even more preferably 0.2 to 0.8.

[0303] [Polymer containing a structural unit having a carboxylic acid anhydride structure]

[0304] The photosensitive composition layer may further contain a polymer containing a structural unit having a carboxylic anhydride structure (hereinafter also referred to as "polymer B") as a binder. The photosensitive composition layer contains polymer B to improve developability and strength after curing.

[0305] 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 preferred.

[0306] The ring of the cyclic carboxylic acid anhydride structure is preferably a 5- to 7-membered ring, more preferably a 5-membered ring or a 6-membered ring, and still more preferably a 5-membered ring.

[0307] The structural unit having a carboxylic acid anhydride structure is preferably a structural unit containing a divalent group obtained by removing two hydrogen atoms from a compound represented by the following formula P-1 in the main chain, or a structural unit in which a monovalent group obtained by removing one hydrogen atom from a compound represented by the following formula P-1 is bonded to the main chain directly or via a divalent linking group.

[0308] [Chemical Formula 7]

[0309]

[0310] In formula P-1, R A1a represents a substituent, n 1a R A1a Can be the same or different, Z 1a represents a divalent group forming a ring containing -C(=O)-O-C(=O)-, n 1a Indicates an integer greater than 0.

[0311] As R A1a Examples of the substituent represented by include an alkyl group.

[0312] As Z 1a , preferably an alkylene group having 2 to 4 carbon atoms, more preferably an alkylene group having 2 or 3 carbon atoms, and further preferably an alkylene group having 2 carbon atoms.

[0313] n 1a represents an integer greater than 0. Z 1a When it represents an alkylene group having 2 to 4 carbon atoms, n 1a It is preferably an integer of 0 to 4, more preferably an integer of 0 to 2, and even more preferably 0.

[0314] When n 1a When an integer greater than 2 is represented, there are multiple R A1a Can be the same or different. Also, there are multiple R A1a They may be bonded to each other to form a ring, but preferably are not bonded to each other to form a ring.

[0315] The structural unit having a carboxylic acid anhydride structure is preferably a structural unit derived from an unsaturated carboxylic acid anhydride, more preferably a structural unit derived from an unsaturated cyclic carboxylic acid anhydride, further preferably a structural unit derived from an unsaturated aliphatic cyclic carboxylic acid anhydride, particularly preferably a structural unit derived from maleic anhydride or itaconic anhydride, and most preferably a structural unit derived from maleic anhydride.

[0316] The structural unit having a carboxylic acid anhydride structure in the polymer B may be of a single type or of two or more types.

[0317] The content of the structural unit having a carboxylic acid anhydride structure is preferably 0 to 60 mol %, more preferably 5 to 40 mol %, and further preferably 10 to 35 mol % based on the total amount of the polymer B.

[0318] The photosensitive composition layer may contain a single polymer B, or may contain two or more polymers B.

[0319] From the perspective of patterning properties and reliability, the content of residual monomers of each structural unit of polymer B in the photosensitive composition layer is preferably 1000 mass ppm or less, more preferably 500 mass ppm or less, and even more preferably 100 mass ppm or less, relative to the total mass of polymer B. The lower limit is not particularly limited, but is preferably 0.1 mass ppm or more, and more preferably 1 mass ppm or more.

[0320] When the photosensitive composition layer contains polymer B, the content of polymer B is preferably 0.1 to 30 mass %, more preferably 0.2 to 20 mass %, further preferably 0.5 to 20 mass %, and particularly preferably 1 to 20 mass % relative to the total mass of the photosensitive composition layer, from the viewpoint of developability and strength after curing.

[0321] [Heterocyclic compounds]

[0322] The photosensitive composition layer preferably contains a heterocyclic compound.

[0323] The heterocyclic ring of the heterocyclic compound may be either a monocyclic ring or a polycyclic ring.

[0324] Examples of the heteroatom possessed by 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 a nitrogen atom, an oxygen atom, and a sulfur atom, and more preferably has a nitrogen atom.

[0325] Examples of the heterocyclic compound include triazole compounds, benzotriazole compounds, tetrazole compounds, thiadiazole compounds, triazine compounds, rhodanine compounds, thiazole compounds, benzothiazole compounds, benzimidazole compounds, benzoxazole compounds, and pyrimidine compounds (eg, isonicotinamide).

[0326] Among the above, the heterocyclic compound is preferably at least one compound selected from triazole compounds, benzotriazole compounds, tetrazole compounds, thiadiazole compounds, triazine compounds, rhodanine compounds, thiazole compounds, benzimidazole compounds and benzoxazole compounds, and more preferably at least one compound selected from triazole compounds, benzotriazole compounds, tetrazole compounds, thiadiazole compounds, thiazole compounds, benzothiazole compounds, benzimidazole compounds and benzoxazole compounds.

[0327] Preferred specific examples of the heterocyclic compound are shown below. As the triazole compound and the benzotriazole compound, the following compounds can be exemplified.

[0328] [Chemical Formula 8]

[0329]

[0330] [Chemical Formula 9]

[0331]

[0332] Examples of the tetrazole compound include the following compounds.

[0333] [Chemical Formula 10]

[0334]

[0335] [Chemical Formula 11]

[0336]

[0337] Examples of the thiadiazole compound include the following compounds.

[0338] [Chemical Formula 12]

[0339]

[0340] Examples of the triazine compound include the following compounds.

[0341] [Chemical Formula 13]

[0342]

[0343] Examples of the rhodanine compound include the following compounds.

[0344] [Chemical Formula 14]

[0345]

[0346] As the thiazole compound, the following compounds can be exemplified.

[0347] [Chemical Formula 15]

[0348]

[0349] Examples of the benzothiazole compound include the following compounds.

[0350] [Chemical Formula 16]

[0351]

[0352] Examples of the benzimidazole compound include the following compounds.

[0353] [Chemical Formula 17]

[0354]

[0355] [Chemical Formula 18]

[0356]

[0357] Examples of the benzoxazole compound include the following compounds.

[0358] [Chemical Formula 19]

[0359]

[0360] The photosensitive composition layer may contain a single heterocyclic compound, or may contain two or more heterocyclic compounds.

[0361] When the photosensitive composition layer contains a heterocyclic compound, the content of the heterocyclic compound is preferably 0.01 to 20 mass %, more preferably 0.1 to 10 mass %, further preferably 0.3 to 8 mass %, and particularly preferably 0.5 to 5 mass % relative to the total mass of the photosensitive composition layer.

[0362] [Aliphatic thiol compounds]

[0363] The photosensitive composition layer preferably contains an aliphatic thiol compound.

[0364] When the photosensitive composition layer contains an aliphatic thiol compound, the aliphatic thiol compound and the radical polymerizable compound having an ethylenically unsaturated group undergo an ene-thiol reaction, whereby cure shrinkage of the formed film is suppressed and stress is relieved.

[0365] The aliphatic thiol compound is preferably a monofunctional aliphatic thiol compound or a polyfunctional aliphatic thiol compound (ie, a difunctional or higher-functional aliphatic thiol compound).

[0366] Among the above, as the aliphatic thiol compound, for example, from the viewpoint of the adhesion of the formed pattern (particularly, the adhesion after exposure), a polyfunctional aliphatic thiol compound is preferred.

[0367] In the present invention, the "polyfunctional aliphatic thiol compound" refers to an aliphatic compound having two or more thiol groups (also referred to as "mercapto groups") in the molecule.

[0368] The polyfunctional aliphatic thiol compound is preferably a low molecular weight compound having a molecular weight of not less than 100. 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.

[0369] The number of functional groups of the polyfunctional aliphatic thiol compound is preferably 2 to 10, more preferably 2 to 8, and even more preferably 2 to 6, from the viewpoint of adhesion of the formed pattern.

[0370] Examples of the polyfunctional aliphatic thiol compound include trimethylolpropane tris(3-mercaptobutyrate), 1,4-bis(3-mercaptobutyryloxy)butane, pentaerythritol tetrakis(3-mercaptobutyrate), 1,3,5-tris(3-mercaptobutyryloxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, trimethylolethane tris(3-mercaptobutyrate), tris[(3-mercaptopropionyloxy)ethyl]isocyanurate, trimethylolpropane tris(3-mercaptopropionate), pentaerythritol tetrakis(3-mercaptopropionate), tetraethylene glycol bis(3-mercaptopropionate), dipentaerythritol hexa(3-mercaptopropionate), ethylene glycol bismercaptopropionate, 1,4-bis(3-mercaptobutyryloxy)butane, 1,2-ethanedithiol, 1,3-propanedithiol, 1,6-hexamethylenedithiol, 2,2'-(ethylenedithio)diethanethiol, meso-2,3-dimercaptosuccinic acid and bis(mercaptoethyl) ether.

[0371] Among the above, the polyfunctional aliphatic thiol compound is preferably at least one compound selected from trimethylolpropane tris(3-mercaptobutyrate), 1,4-bis(3-mercaptobutyryloxy)butane and 1,3,5-tris(3-mercaptobutyryloxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione.

[0372] Examples of the monofunctional aliphatic thiol compound include 1-octanethiol, 1-dodecanethiol, β-mercaptopropionic acid, methyl-3-mercaptopropionate, 2-ethylhexyl-3-mercaptopropionate, n-octyl-3-mercaptopropionate, methoxybutyl-3-mercaptopropionate, and stearyl-3-mercaptopropionate.

[0373] The photosensitive composition layer may contain a single aliphatic thiol compound, or may contain two or more aliphatic thiol compounds.

[0374] When the photosensitive composition layer contains an aliphatic thiol compound, the content of the aliphatic thiol compound is preferably 5% by mass or more, more preferably 5 to 50% by mass, further preferably 5 to 30% by mass, and particularly preferably 8 to 20% by mass, based on the total mass of the photosensitive composition layer.

[0375] [Surfactant]

[0376] The photosensitive composition layer preferably contains a surfactant.

[0377] Examples of the surfactant include surfactants described in paragraph

[0017] of Japanese Patent No. 4502784 and paragraphs

[0060] to

[0071] of Japanese Patent Application Laid-Open No. 2009-237362.

[0378] As the surfactant, a nonionic surfactant, a fluorine-based surfactant, or a silicon-based surfactant is preferable.

[0379] Examples of commercially available fluorochemical surfactants include MEGAFACE F-171, F-172, F-173, F-176, F-177, F-141, F-142, F-143, F-144, F-437, F-475, F-477, F-479, F-482, F-551-A, F-552, F-554, F-555-A, F-556, F-557, F-558, F-559, F-560, F-561, F-562, F-563, F-564, F-565, F-566, F-567, F-568, F-569, F-570, F-571, F-572, F-573, F-574, F-575, F-576, F-577, F-578, F-579, F-580, F-581, F-582, F-583, F-584, F-585, F-586, F-587, F-588, F-589, F-590, F-591, F-592, F-593, F-594, F-595, F-596, F-597, F-598, F-599, F-591, F-597, F-598, F-599, F-591, F-599, F-591, F-591, F-592, F-593, F-594, F-595, F-596, F-597, F-598, F-599, F-599, F-591, F-591, F-599, -565, F-563, F-568, F-575, F-780, EXP, MFS-330, MFS-578, MFS-579, MFS-586, MFS-587, R-41, R-41-LM, R-01, R-40, R-40-LM, RS-43, TF-1956, RS-90, R-94, RS-72-K, DS-21 (all DIC Corporation), Fluorad FC430, FC431, FC171 (all manufactured by Sumitomo 3M Limited), Surflon S-382, SC-101, SC-103, SC-104, SC-105, SC-1068, SC-381, SC-383, S-393, KH-40 (all manufactured by AGC Inc.), PolyFox PF636, PF656, PF6320, PF6520, PF7002 (all manufactured by OMNOVA Solutions Inc.), Ftergent 710FL, 710FM, 610FM, 601AD, 601ADH2, 602A, 215M, 245F, 251, 212M, 250, 209F, 222F, 208G, 710LA, 710FS, 730LM, 650AC, 681, 683 (all manufactured by Neos Corporation), etc.

[0380] Furthermore, acrylic compounds can also be preferably used as fluorochemical surfactants. These acrylic compounds have a molecular structure containing a functional group containing a fluorine atom, and when heat is applied, the functional group containing a fluorine atom is partially cleaved, causing the fluorine atom to volatilize. Examples of such fluorochemical surfactants include the MAGAFACE DS series manufactured by DIC Corporation (Chemical Industry Daily (February 22, 2016), Nikkei Industry News (February 23, 2016)), such as MAGAFACE DS-21.

[0381] Furthermore, as the fluorine-based surfactant, 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 is also preferably used.

[0382] Furthermore, as the fluorine-based surfactant, a blocked polymer can also be used.

[0383] Furthermore, as a fluorine-based surfactant, a fluorine-containing polymer compound can also be preferably used, which contains: a structural unit derived from a (meth)acrylate compound having a fluorine atom; and a structural unit derived from a (meth)acrylate compound having two or more (preferably five or more) alkyleneoxy groups (preferably ethyleneoxy, propyleneoxy).

[0384] Furthermore, as fluorine-based surfactants, fluorine-containing polymers having a group containing an ethylenically unsaturated bond in a side chain can also be used, such as MEGAFAC RS-101, RS-102, RS-718K, and RS-72-K (all manufactured by DIC Corporation).

[0385] From the viewpoint of improving environmental adaptability, the fluorine-based surfactant is preferably a surfactant derived from an alternative material to compounds having a linear perfluoroalkyl group having 7 or more carbon atoms, such as perfluorooctane acid (PFOA) and perfluorooctane sulfonic acid (PFOS).

[0386] Examples of the nonionic surfactant include glycerin, trimethylolpropane, trimethylolethane, and ethoxylates and propoxylates thereof (e.g., glycerol propoxylate, glycerol ethoxylate, etc.), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid esters, PLURONIC L10, L31, L61, L62, 10R5, 17R2, and 25R2 (all manufactured by BASF), TETRONIC 304, 701, 704, 901, 904, and 150R1 (all manufactured by BASF), SOLSPERSE 20000 (manufactured by Lubrizol Japan Ltd.), NCW-101, NCW-1001, and NCW-1002 (all manufactured by FUJIFILM Wako Pure Chemical Corporation), PIONIN D-6112, D-6112-W, D-6315 (all manufactured by Takemoto Oil & Fat Co., Ltd.), OLFIN E1010, Surfynol 104, 400, 440 (all manufactured by NIssin Chemical Co., Ltd.), and the like.

[0387] Examples of commercially available silicone surfactants include DOWSIL 8032 ADDITIVE, Toray Silicone DC3PA, Toray Silicone SH7PA, Toray Silicone DC11PA, Toray Silicone SH21PA, Toray Silicone SH28PA, Toray Silicone SH29PA, Toray Silicone SH30PA, and Toray Silicone SH8400 (all manufactured by Dow Corning Toray). Co., Ltd.), and X-22-4952, X-22-4272, X-22-6266, KF-351A, K354L, KF-355A, KF-945, KF-640, KF-642, KF-643, X-22-6191, X-22-4515, KF-6004, KP-341, KF-6001, KF-6002 (all manufactured by Shin-Etsu Chemical Co., Ltd.), F-4440, TSF-4300, TSF-4445, TSF-4460, TSF-4452 (all manufactured by Momentive Performance Materials Inc.), BYK307, BYK323, BYK330 (all manufactured by BYK Chemie GmbH), etc.

[0388] The photosensitive composition layer may contain a single surfactant or two or more surfactants.

[0389] When the photosensitive composition layer contains a surfactant, the content of the surfactant is preferably 0.01 to 3 mass %, more preferably 0.05 to 1 mass %, and further preferably 0.1 to 0.8 mass % relative to the total mass of the photosensitive composition layer.

[0390] [Hydrogen-donating compound]

[0391] The photosensitive composition layer preferably contains a hydrogen-donating compound. The hydrogen-donating compound has the function of further increasing the sensitivity of the photopolymerization initiator to actinic rays and suppressing the polymerization inhibition of the polymerizable compound caused by oxygen.

[0392] Examples of hydrogen-donating compounds include amines, such as those described in "Journal of Polymer Society" by M.R. Sander et al., Vol. 10, p. 3173 (1972), Japanese Patent Publication No. 44-020189, Japanese Patent Application Publication No. 51-082102, Japanese Patent Application Publication No. 52-134692, Japanese Patent Application Publication No. 59-138205, Japanese Patent Application Publication No. 60-084305, Japanese Patent Application Publication No. 62-018537, Japanese Patent Application Publication No. 64-033104, and Research Disclosure No. 33825.

[0393] Examples of the hydrogen-donating compound include triethanolamine, ethyl p-dimethylaminobenzoate, p-formyldimethylaniline, and p-methylthiodimethylaniline.

[0394] In addition, examples of hydrogen-donating compounds include amino acid compounds (N-phenylglycine, etc.), organometallic compounds described in Japanese Patent Publication No. 48-042965 (tributyltin acetate, etc.), hydrogen donors described in Japanese Patent Publication No. 55-034414, and sulfur compounds (trithiane, etc.) described in Japanese Patent Application Laid-Open No. 6-308727.

[0395] The photosensitive composition layer may contain a single hydrogen-donating compound, or may contain two or more hydrogen-donating compounds.

[0396] When the photosensitive composition layer contains a hydrogen-donating compound, the content of the hydrogen-donating compound is preferably 0.01 to 10% by mass, more preferably 0.03 to 5% by mass, and even more preferably 0.05 to 3% by mass relative to the total mass of the photosensitive composition layer, from the viewpoint of improving the curing rate by balancing the polymerization growth rate and chain transfer.

[0397] [Other ingredients]

[0398] The photosensitive composition layer may contain components other than the above components (hereinafter also referred to as “other components”). Examples of other components include particles (for example, metal oxide particles) and colorants.

[0399] Furthermore, examples of other components include the thermal polymerization inhibitors described in paragraph

[0018] of Japanese Patent No. 4502784 and other additives described in paragraphs

[0058] to

[0071] of Japanese Patent Application Laid-Open No. 2000-310706.

[0400] The photosensitive composition layer may contain particles for the purpose of adjusting the refractive index, light transmittance, etc. Examples of the particles include metal oxide particles.

[0401] The metal in the metal oxide particles also includes metalloids such as B, Si, Ge, As, Sb, and Te.

[0402] The average primary particle size of the particles is preferably 1 to 200 nm, more preferably 3 to 80 nm, from the perspective of pattern transparency. The average primary particle size of the particles is calculated by measuring the particle size of 200 random particles using an electron microscope and taking the arithmetic average of the measurement results. In the case of non-spherical particles, the longest side is used as the particle size.

[0403] The photosensitive composition layer may contain a single type of particles or two or more types of particles. Furthermore, when the photosensitive composition layer contains particles, it may contain only one type of particles having different metal types, sizes, etc., or two or more types of particles.

[0404] The photosensitive composition layer preferably contains no particles or the content of particles exceeds 0 mass% and is 35 mass% or less relative to the total mass of the photosensitive composition layer. It is more preferred that the photosensitive composition layer contains no particles or the content of particles exceeds 0 mass% and is 10 mass% or less relative to the total mass of the photosensitive composition layer. It is further preferred that the photosensitive composition layer contains no particles or the content of particles exceeds 0 mass% and is 5 mass% or less relative to the total mass of the photosensitive composition layer. It is particularly preferred that the photosensitive composition layer contains no particles or the content of particles exceeds 0 mass% and is 1 mass% or less relative to the total mass of the photosensitive composition layer. It is most preferred that the photosensitive composition layer contains no particles.

[0405] The photosensitive composition layer may contain a small amount of a colorant (eg, a pigment and a dye), but preferably contains substantially no colorant from the viewpoint of transparency, for example.

[0406] When the photosensitive composition layer contains a colorant, the content of the colorant is preferably less than 1% by mass, more preferably less than 0.1% by mass, relative to the total mass of the photosensitive composition layer.

[0407] [Impurities, etc.]

[0408] The photosensitive composition layer may contain a predetermined amount of impurities.

[0409] Specific examples of impurities include sodium, potassium, magnesium, calcium, iron, manganese, copper, aluminum, titanium, chromium, cobalt, nickel, zinc, tin, halogen, and ions thereof. Among them, halide ions, sodium ions, and potassium ions are easily incorporated as impurities, and therefore are preferably set to the following contents.

[0410] The impurity content in the photosensitive composition layer is preferably 80 ppm or less, more preferably 10 ppm or less, and further preferably 2 ppm or less, based on mass. The impurity content in the photosensitive composition layer can be 1 ppb or more, and can be 0.1 ppm or more, based on mass.

[0411] Methods for keeping impurities within the above range include: selecting raw materials with low impurity content for the photosensitive composition layer; preventing impurities from entering the photosensitive composition layer during formation; and removing impurities through cleaning. These methods can keep the impurity content within the above range.

[0412] Impurities can be quantified by, for example, a known method such as ICP (Inductively Coupled Plasma) emission spectrometry, atomic absorption spectrometry, and ion chromatography.

[0413] The photosensitive composition layer preferably contains low levels of compounds such as benzene, formaldehyde, trichloroethylene, 1,3-butadiene, carbon tetrachloride, chloroform, N,N-dimethylformamide, N,N-dimethylacetamide, and hexane. The content of these compounds in the photosensitive composition layer is preferably 100 ppm by mass or less, more preferably 20 ppm by mass or less, and even more preferably 4 ppm by mass or less. The lower limit can be 10 ppb by mass or greater, or even 100 ppb by mass or greater. The content of these compounds can be suppressed using the same methods as for the metal impurities described above. Furthermore, their quantification can be achieved using known measurement methods.

[0414] From the viewpoint of improving reliability and laminating properties, the water content in the photosensitive composition layer is preferably 0.01 to 1.0% by mass, more preferably 0.05 to 0.5% by mass.

[0415] [Thickness of Photosensitive Composition Layer]

[0416] From the viewpoint of coating properties, the upper limit of the thickness of the photosensitive composition layer is preferably 20.0 μm or less, more preferably 15.0 μm or less, and further preferably 12.0 μm or less.

[0417] The lower limit of the thickness of the photosensitive composition is preferably 0.05 μm or more, more preferably 3.0 μm or more, further preferably 4.0 μm or more, and particularly preferably 5.0 μm or more from the viewpoint of further improving the effects of the present invention.

[0418] The thickness of the photosensitive composition layer was calculated as an average value of five arbitrary points measured by cross-sectional observation using a scanning electron microscope (SEM).

[0419] [Refractive Index of Photosensitive Composition Layer]

[0420] The refractive index of the photosensitive composition layer is preferably 1.47 to 1.56, more preferably 1.49 to 1.54.

[0421] [Color of the photosensitive composition layer]

[0422] The photosensitive composition layer is preferably achromatic. * The value is preferably -1.0 to 1.0, and the b value of the photosensitive composition layer is preferably -1.0 to 1.0. * The value is preferably -1.0 to 1.0.

[0423] The hue of the photosensitive composition layer can be measured using a colorimeter (CR-221, manufactured by Minolta Co., Ltd.).

[0424] [NCO value of photosensitive composition layer]

[0425] From the viewpoint of further improving the effects of the present invention, the NCO value of the photosensitive composition layer is preferably greater than 0.50 mmol / g, more preferably 0.55 mmol / g or more, and even more preferably 0.60 mmol / g or more.

[0426] From the viewpoint of further improving the effects of the present invention, the upper limit of the NCO value of the photosensitive composition layer is preferably 1.0 mmol / g or less, more preferably less than 0.80 mmol / g, and still more preferably 0.70 mmol / g or less.

[0427] The NCO value of the photosensitive composition layer in the present invention refers to the number of moles of isocyanate groups contained per 1 g of the photosensitive composition layer, and is a value calculated from the structural formula of the blocked isocyanate compound.

[0428] [Transmittance of Photosensitive Composition Layer]

[0429] The visible light transmittance of the photosensitive composition layer per 1.0 μm of film thickness is preferably 80% or more, more preferably 90% or more, and most preferably 95% or more.

[0430] As for the transmittance of visible light, it is preferred that the average transmittance at a wavelength of 400 nm to 800 nm, the minimum value of the transmittance at a wavelength of 400 nm to 800 nm, and the transmittance at a wavelength of 400 nm all satisfy the above.

[0431] Preferred values ​​of the transmittance include, for example, 87%, 92%, and 98%.

[0432] The same also applies to the transmittance per 1.0 μm film thickness of the cured film of the photosensitive composition layer.

[0433] [Moisture Permeability of Photosensitive Composition Layer]

[0434] From the viewpoint of rust prevention of electrodes or wiring and the reliability of the device, the moisture permeability of the pattern obtained by curing the photosensitive composition layer (cured film of the photosensitive composition layer) is preferably 500 g / m at a film thickness of 40 μm. 2 / 24hr or less, more preferably 300g / m 2 / 24hr or less, more preferably 100g / m 2 / 24hr or less

[0435] Regarding the moisture permeability, the photosensitive composition layer was exposed to i-rays at an exposure dose of 300 mJ / cm 2 After exposure, the photosensitive composition layer was post-baked at 145° C. for 30 minutes to obtain a cured film for measurement.

[0436] The moisture permeability is measured according to the cup method of JIS Z 0208. It is preferable that the moisture permeability be the same as above under any of the test conditions of temperature 40°C / humidity 90%, temperature 65°C / humidity 90%, and temperature 80°C / humidity 95%.

[0437] As a specific preferred value, for example, 80 g / m 2 / 24hr、150g / m 2 / 24hr、220g / m 2 / 24hr, etc.

[0438] [Dissolution rate of photosensitive composition layer]

[0439] From the viewpoint of suppressing residue during development, the dissolution rate of the photosensitive composition layer in a 1.0 mass % sodium carbonate aqueous solution is preferably 0.01 μm / s or more, more preferably 0.10 μm / s or more, and even more preferably 0.20 μm / s or more.

[0440] From the viewpoint of the edge shape of the pattern, it is preferably 5.0 μm / second or less, more preferably 4.0 μm / second or less, and still more preferably 3.0 μm / second or less.

[0441] Specific preferred numerical values ​​include, for example, 1.8 μm / second, 1.0 μm / second, and 0.7 μm / second.

[0442] The dissolution rate per unit time of the photosensitive composition layer in a 1.0 mass % sodium carbonate aqueous solution was measured as follows.

[0443] The photosensitive composition layer (film thickness in the range of 1.0 to 10 μm) formed on the glass substrate from which the solvent was fully removed was subjected to shower development at 25° C. using a 1.0 mass % sodium carbonate aqueous solution until the photosensitive composition layer was completely dissolved (for a maximum of 2 minutes).

[0444] The dissolution rate of the photosensitive composition layer was calculated by dividing the thickness of the photosensitive composition layer by the time required for the photosensitive composition layer to completely dissolve. If complete dissolution was not achieved within 2 minutes, the same calculation was performed based on the change in thickness up to that point.

[0445] The dissolution rate of the cured film of the photosensitive composition layer (film thickness within the range of 1.0 to 10 μm) in a 1.0 mass % aqueous solution of sodium carbonate is preferably 3.0 μm / second or less, more preferably 2.0 μm / second or less, further preferably 1.0 μm / second or less, and most preferably 0.2 μm / second or less. The cured film of the photosensitive composition layer is exposed to 300 mJ / cm by i-ray. 2 A film obtained by exposing a photosensitive composition layer.

[0446] Specific preferred numerical values ​​include, for example, 0.8 μm / second, 0.2 μm / second, and 0.001 μm / second.

[0447] For development, a 1 / 4 MINJJX030PP shower nozzle manufactured by H. IKEUCHI Co., Ltd. was used, and the shower pressure was set to 0.08 MPa. Under the above conditions, the shower flow rate per unit time was set to 1,800 mL / min.

[0448] [Swelling Ratio of Photosensitive Composition Layer]

[0449] From the viewpoint of improving pattern formability, the swelling ratio of the photosensitive composition layer after exposure to a 1.0 mass % sodium carbonate aqueous solution is preferably 100% or less, more preferably 50% or less, and even more preferably 30% or less.

[0450] The swelling ratio of the photosensitive resin layer after exposure to light with respect to a 1.0% by mass sodium carbonate aqueous solution was measured as follows.

[0451] A photosensitive resin layer (with a thickness of 1.0 to 10 μm) formed on a glass substrate from which the solvent was fully removed was subjected to a high pressure mercury lamp at 500 mJ / cm 2 (i-ray measurement) Exposure was performed. Each glass substrate was immersed in a 1.0 mass % sodium carbonate aqueous solution at 25°C, and the film thickness was measured after 30 seconds. The ratio of the increase in film thickness after immersion to the film thickness before immersion was then calculated.

[0452] Specific preferred numerical values ​​include, for example, 4%, 13%, and 25%.

[0453] [Foreign Matter in Photosensitive Composition Layer]

[0454] From the viewpoint of pattern formation, the number of foreign particles having a diameter of 1.0 μm or more in the photosensitive composition layer is preferably 10 pieces / mm. 2 Below, more preferably 5 / mm 2 the following.

[0455] The number of foreign matter was measured as follows.

[0456] Using an optical microscope, five random areas (1 mm × 1 mm) on the surface of the photosensitive composition layer were visually observed from the normal direction of the surface of the photosensitive composition layer, the number of foreign matter with a diameter of 1.0 μm or more in each area was measured, and the arithmetic average of these was taken to calculate the number of foreign matter.

[0457] As a specific preferred numerical value, for example, 0 pieces / mm can be cited. 2 , 1 piece / mm 2 , 4 pieces / mm 2 , 8 pieces / mm 2 wait.

[0458] [Haze of Dissolved Matter in Photosensitive Composition Layer]

[0459] From the viewpoint of suppressing the generation of aggregates during development, 1.0 cm 3 The haze of a solution obtained by dissolving the photosensitive resin layer in 1.0 L of a 1.0 mass % sodium carbonate aqueous solution at 30° C. is preferably 60% or less, more preferably 30% or less, further preferably 10% or less, and most preferably 1% or less.

[0460] The haze is measured as follows.

[0461] First, a 1.0 mass % sodium carbonate aqueous solution was prepared and the liquid temperature was adjusted to 30° C. 1.0 cm 3 The photosensitive resin layer was stirred at 30°C for 4 hours while being careful to prevent the incorporation of air bubbles. After stirring, the haze of the solution in which the photosensitive resin layer had dissolved was measured. The haze was measured using a haze meter (product name "NDH4000", manufactured by NIPPON DENSHOKU INDUSTRIES CO., LTD.) using a liquid measurement cell and a dedicated liquid measurement cell with an optical path length of 20 mm.

[0462] Specific preferred numerical values ​​include, for example, 0.4%, 1.0%, 9%, and 24%.

[0463] <Refractive Index Adjustment Layer>

[0464] The first transfer film may include a refractive index adjusting layer. The position of the refractive index adjusting layer is not particularly limited, but is preferably disposed in contact with the photosensitive composition layer. The first transfer film preferably includes a temporary support, a photosensitive composition layer, and a refractive index adjusting layer in this order.

[0465] When the first transfer film further includes a protective film described later, it preferably includes a temporary support, a photosensitive composition layer, a refractive index adjusting layer, and a protective film in this order.

[0466] As the refractive index adjusting layer, a known refractive index adjusting layer can be applied. Examples of materials contained in the refractive index adjusting layer include a binder and particles.

[0467] Examples of the binder include the alkali-soluble resins described in the section "photosensitive composition layer".

[0468] Examples of the particles include zirconium oxide particles (ZrO 2 particles), niobium oxide particles (Nb 2 O 5 particles), titanium oxide particles (TiO 2 particles), and silicon dioxide particles (SiO 2 particles).

[0469] Furthermore, the refractive index adjusting layer preferably contains a metal oxidation inhibitor. The refractive index adjusting layer contains a metal oxidation inhibitor, thereby being able to suppress oxidation of metal in contact with the refractive index adjusting layer.

[0470] As the metal oxidation inhibitor, for example, a compound having an aromatic ring containing a nitrogen atom in the molecule is preferable. Examples of the metal oxidation inhibitor include imidazole, benzimidazole, tetrazole, mercaptothiadiazole, and benzotriazole.

[0471] The refractive index of the refractive index adjusting layer is preferably 1.60 or greater, more preferably 1.63 or greater.

[0472] The upper limit of the refractive index of the refractive index adjusting layer is preferably 2.10 or less, and more preferably 1.85 or less.

[0473] The thickness of the refractive index adjusting layer is preferably 500 nm or less, more preferably 110 nm or less, and further preferably 100 nm or less.

[0474] The thickness of the refractive index adjusting layer is preferably 20 nm or more, more preferably 50 nm or more.

[0475] The thickness of the refractive index adjusting layer was calculated as the average value of five arbitrary points measured by cross-sectional observation using a scanning electron microscope (SEM).

[0476] <Other layers>

[0477] The first transfer film may include other layers in addition to the temporary support, the photosensitive composition layer, and the refractive index adjusting layer.

[0478] Examples of other layers include a protective film and an antistatic layer.

[0479] The first transfer film may have a protective film for protecting the photosensitive composition layer on the surface opposite to the temporary support.

[0480] The protective film is preferably a resin film, and a resin film having heat resistance and solvent resistance can be used.

[0481] Examples of the protective film include polyolefin films such as polypropylene films and polyethylene films. Alternatively, a resin film made of the same material as the temporary support may be used as the protective film.

[0482] The thickness of the protective film is preferably 1 to 100 μm, more preferably 5 to 50 μm, further preferably 5 to 40 μm, and particularly preferably 15 to 30 μm. For excellent mechanical strength, the thickness of the protective film is preferably 1 μm or greater, and for relative low cost, preferably 100 μm or less.

[0483] The first transfer film may include an antistatic layer.

[0484] Since the first transfer film has an antistatic layer, the generation of static electricity when peeling off a film arranged on the antistatic layer can be suppressed, and the generation of static electricity caused by friction with equipment or other films can also be suppressed. Therefore, for example, the occurrence of malfunctions in electronic devices can be suppressed.

[0485] The antistatic layer is preferably disposed between the temporary support and the photosensitive composition layer.

[0486] 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 used.

[0487] [Second embodiment of transfer film]

[0488] The transfer film in the second embodiment of the present invention (hereinafter also referred to as the "second transfer film") has a temporary support body and a photosensitive composition layer arranged on the temporary support body, the above-mentioned photosensitive composition layer contains an alkali-soluble resin, a polymerizable compound, a polymerization initiator and a blocked isocyanate compound, and the NCO value of the above-mentioned photosensitive composition layer is greater than 0.50 mmol / g.

[0489] As a characteristic feature of the second transfer film, the NCO value of the photosensitive composition layer is larger than 0.50 mmol / g.

[0490] Here, as a method for forming a protective film using a second transfer film, the following method can be cited: after the second transfer film is brought into contact with and bonded to a substrate having a conductive layer (sensor electrodes and lead wiring), a patterned protective film is formed by processes such as pattern exposure, development, and post-baking of the photosensitive composition layer possessed by the second transfer film.

[0491] The alkali-soluble resin contained in the photosensitive composition layer is essential for the developability of the photosensitive composition layer. However, the present inventors have discovered that acid groups such as carboxyl groups in the alkali-soluble resin may cause corrosion of the conductive layer.

[0492] To address this problem, the present inventors have discovered that the corrosion of the conductive layer can be suppressed by using a photosensitive composition layer having an NCO value of more than 0.50 mmol / g.

[0493] This is presumably because, in the post-baking step, a sufficient amount of isocyanate groups required for reacting with acid groups of the alkali-soluble resin is generated from the blocked isocyanate compound, thereby suppressing corrosion of the conductive layer.

[0494] The second transfer film differs from the first transfer film in that the NCO value of the photosensitive composition layer must be greater than 0.50 mmol / g and the NCO value of the blocked isocyanate compound contained in the photosensitive composition layer is not specified.

[0495] The NCO value of the photosensitive composition layer in the second transfer film is greater than 0.50 mmol / g. From the viewpoint of further improving the effects of the present invention, it is preferably 0.55 mmol / g or greater, and more preferably 0.60 mmol / g or greater.

[0496] From the viewpoint of further improving the effects of the present invention, the upper limit of the NCO value of the photosensitive composition layer in the second transfer film is preferably 1.0 mmol / g or less, more preferably less than 0.80 mmol / g, and still more preferably 0.70 mmol / g or less.

[0497] The method for measuring the NCO value of the photosensitive composition layer is as described above, and therefore description thereof is omitted.

[0498] Here, as a method for setting the NCO value of the photosensitive composition layer within the above range, there is a method of using the first blocked isocyanate compound described in the section of the first transfer film as the blocked isocyanate compound contained in the photosensitive composition layer. As another method, there is a method of adjusting the content of the blocked isocyanate compound in the photosensitive composition.

[0499] Components contained in and components that may be contained in the photosensitive composition layer in the second transfer film are the same as those in the photosensitive composition layer in the first transfer film, and therefore, description thereof will be omitted.

[0500] The physical properties such as thickness, refractive index, and color of the photosensitive composition layer in the second transfer film are the same as those of the photosensitive composition layer in the first transfer film, and therefore, description thereof will be omitted.

[0501] The temporary support included in the second transfer film is the same as the temporary support included in the first transfer film, and therefore, description thereof will be omitted.

[0502] The second transfer film may include the same refractive index adjustment layer as the first transfer film. Furthermore, the second transfer film may include the same other layers as the first transfer film.

[0503] [Method for manufacturing transfer film]

[0504] The manufacturing method of the transfer film (the first transfer film and the second transfer film) of the present invention is not particularly limited, and a known method can be used. In addition, in the following description, when simply referred to as "transfer film", it refers to both the first transfer film and the second transfer film.

[0505] Among these, a method of forming a photosensitive composition layer by coating a photosensitive composition on a temporary support and, if necessary, drying the composition (hereinafter also referred to as a "coating method") is preferred from the viewpoint of excellent productivity.

[0506] The photosensitive composition used in the coating method preferably contains components constituting the photosensitive composition layer (for example, a polymerizable compound, an alkali-soluble resin, a polymerization initiator, a blocked isocyanate compound, etc.) and a solvent.

[0507] The solvent is preferably an organic solvent. Examples of 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, caprolactam, n-propanol, and 2-propanol. Preferred solvents include 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.

[0508] Furthermore, as the solvent, an organic solvent (high boiling point solvent) having a boiling point of 180 to 250° C. may be used as needed.

[0509] The photosensitive composition may contain a single solvent or two or more solvents.

[0510] When the photosensitive composition contains a solvent, the total solid content of the photosensitive composition is preferably 5 to 80% by mass, more preferably 5 to 40% by mass, and even more preferably 5 to 30% by mass, relative to the total mass of the photosensitive composition.

[0511] When the photosensitive composition contains a solvent, the viscosity of the photosensitive composition at 25°C is preferably 1 to 50 mPa·s, more preferably 2 to 40 mPa·s, and even more preferably 3 to 30 mPa·s, from the perspective of coating properties. The viscosity is measured using a viscometer. For example, a viscometer manufactured by TOKI SANGYO CO., LTD. (trade name: VISCOMETER TV-22) can be preferably used. However, the viscometer is not limited to the above-mentioned viscometer.

[0512] When the photosensitive composition contains a solvent, for example, from the perspective of coating properties, the surface tension of the photosensitive composition at 25°C is preferably 5 to 100 mN / m, more preferably 10 to 80 mN / m, and even more preferably 15 to 40 mN / m. The surface tension is measured using a surface tensiometer. As a surface tensiometer, for example, a surface tensiometer manufactured by Kyowa Interface Science Co., Ltd. (trade name: Automatic Surface Tensiometer CBVP-Z) can be preferably used. However, the surface tensiometer is not limited to the above surface tensiometer.

[0513] Examples of a method for applying the photosensitive composition include printing, spraying, roll coating, bar coating, curtain coating, spin coating, and die coating (ie, slit coating).

[0514] Examples of the drying method include natural drying, heat drying, and reduced-pressure drying. These methods can be used alone or in combination.

[0515] In the present invention, "drying" means removing at least a portion of the solvent contained in the composition.

[0516] Furthermore, when the transfer film has a protective film, the transfer film can be produced by bonding the protective film to the photosensitive composition layer.

[0517] The method of bonding the protective film to the photosensitive composition layer is not particularly limited, and a known method may be used.

[0518] As an apparatus for bonding the protective film to the photosensitive composition layer, well-known laminators such as a vacuum laminator and an automatic cutting laminator are mentioned.

[0519] The laminator preferably includes any heatable roller such as a rubber roller and is capable of applying pressure and heat.

[0520] The transfer film of the present invention can be used in various applications, such as electrode protection films, insulating films, planarization films, overcoat films, hard coat films, passivation films, partition walls, spacers, microlenses, optical filters, antireflection films, etching resists, and plated components.

[0521] As more specific examples, there can be cited protective films or insulating films for touch panel electrodes, protective films or insulating films for printed wiring boards, protective films or insulating films for TFT substrates, color filters, outer coating films for color filters, etching resists for forming wiring, and sacrificial layers in plating processes.

[0522] [Method for producing laminate]

[0523] By using the above transfer film, the photosensitive composition layer can be transferred to a transfer target.

[0524] Among them, a method for producing a laminated body is preferred, comprising: a laminating step of bringing the photosensitive composition layer on the temporary support of the transfer film into contact with and laminating the substrate having the conductive layer, thereby obtaining a substrate with a photosensitive composition layer having, in this order, a substrate, a conductive layer, a photosensitive composition layer, and a temporary support;

[0525] An exposure step of exposing the photosensitive composition layer in a pattern;

[0526] A development step of developing the exposed photosensitive composition layer to form a pattern.

[0527] The method for producing a laminate further includes a peeling step of peeling the temporary support from the substrate with the photosensitive composition layer between the laminating step and the exposure step or between the exposure step and the development step.

[0528] Hereinafter, the sequence of the above steps will be described in detail.

[0529] <Lamination process>

[0530] The laminating step is a step of bringing the photosensitive composition layer on the temporary support of the transfer film into contact with and laminating the substrate having the conductive layer to obtain a substrate with a photosensitive composition layer having, in this order, a substrate, a conductive layer, a photosensitive composition layer, and a temporary support.

[0531] The exposed photosensitive composition layer on the temporary support of the transfer film is brought into contact with and laminated to the substrate having the conductive layer. By laminating, the photosensitive composition layer and the temporary support are arranged on the substrate having the conductive layer.

[0532] In the lamination, the conductive layer and the surface of the photosensitive composition layer are pressed together so as to be in contact with each other. In this embodiment, the pattern obtained after exposure and development can be preferably used as an etching resist when etching the conductive layer.

[0533] The pressure-bonding method is not particularly limited, and known transfer methods and lamination methods can be used. Of these, it is preferred to overlap the surface of the photosensitive composition layer on the substrate having the conductive layer and apply pressure and heat with a roller or the like.

[0534] The lamination can be performed using a known laminator such as a vacuum laminator and an automatic cutting laminator.

[0535] The substrate with a conductive layer has a conductive layer on a substrate, and any layer can be formed as needed. That is, the substrate with a conductive layer is a conductive substrate having at least a substrate and a conductive layer arranged on the substrate.

[0536] Examples of the substrate include a resin substrate, a glass substrate, and a semiconductor substrate.

[0537] Preferred embodiments of the substrate are described in, for example, paragraph 0140 of International Publication No. 2018 / 155193, and the contents are incorporated into this specification.

[0538] From the viewpoint of electrical conductivity and thin line formability, the conductive layer is preferably at least one layer selected from a metal layer, a conductive metal oxide layer, a graphene layer, a carbon nanotube layer, and a conductive polymer layer.

[0539] Furthermore, 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, the conductive layers are preferably made of different materials.

[0540] Preferred embodiments of the conductive layer are described in, for example, paragraph 0141 of International Publication No. 2018 / 155193, and the contents are incorporated into this specification.

[0541] As the substrate having a conductive layer, a substrate having at least one of a transparent electrode and a routing wiring is preferable. Such a substrate can be preferably used as a substrate for a touch panel.

[0542] The transparent electrode can preferably function as a touch panel electrode and is preferably composed of a metal oxide film such as ITO (indium tin oxide) and IZO (indium zinc oxide), and a metal mesh or metal fine wires such as silver nanowires.

[0543] Examples of the metal thin wires include thin wires of silver, copper, etc. Among them, silver conductive materials such as silver mesh and silver nanowires are preferred.

[0544] As a material for the routing wiring, metal is preferable.

[0545] Examples of metals used as materials for the lead-out wiring include gold, silver, copper, molybdenum, aluminum, titanium, chromium, zinc, and manganese, as well as alloys composed of two or more of these metal elements. Preferred materials for the lead-out wiring are copper, molybdenum, aluminum, and titanium, with copper being particularly preferred.

[0546] <Exposure Process>

[0547] The exposure step is a step of pattern-exposing the photosensitive composition layer.

[0548] In addition, here, "pattern exposure" means exposure in a patterned manner, that is, exposure in which exposed areas and non-exposed areas exist.

[0549] The detailed arrangement and specific size of the pattern in the pattern exposure are not particularly limited. In addition, the pattern formed by the development step described later preferably includes thin lines with a width of 20 μm or less, and more preferably includes thin lines with a width of 10 μm or less.

[0550] As a light source for pattern exposure, any light source capable of irradiating at least a wavelength within a range capable of curing the photosensitive composition layer (e.g., 365 nm or 405 nm) can be appropriately selected and used. The dominant wavelength of the exposure light for pattern exposure is preferably 365 nm. The dominant wavelength is the wavelength with the highest intensity.

[0551] Examples of the light source include various lasers, light emitting diodes (LEDs), ultrahigh-pressure mercury lamps, high-pressure mercury lamps, and metal halide lamps.

[0552] The exposure dose is preferably 5 to 200 mJ / cm 2 , more preferably 10 to 200 mJ / cm 2 .

[0553] Preferred aspects of the light source, exposure amount, and exposure method used for exposure are described, for example, in paragraphs

[0146] to

[0147] of International Publication No. 2018 / 155193, and these contents are incorporated into this specification.

[0554] <Peeling process>

[0555] The peeling step is a step of peeling the temporary support from the substrate with the photosensitive composition layer between the laminating step and the exposure step or between the exposure step and the development step described later.

[0556] The peeling method is not particularly limited, and the same mechanism as the cover film peeling mechanism described in paragraphs

[0161] and

[0162] of Japanese Patent Application Laid-Open No. 2010-072589 can be used.

[0557] <Development Process>

[0558] The development step is a step of developing the exposed photosensitive composition layer to form a pattern.

[0559] The development of the photosensitive composition layer can be performed using a developer.

[0560] As a developer, an alkaline aqueous solution is preferred. Examples of alkaline compounds that can be contained in the alkaline aqueous solution include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, and choline (2-hydroxyethyltrimethylammonium hydroxide).

[0561] Examples of the development method include spin immersion development, shower development, spin development, and immersion development.

[0562] Examples of preferably used developing solutions in the present invention include those described in paragraph

[0194] of International Publication No. 2015 / 093271, and examples of preferably used developing methods include those described in paragraph

[0195] of International Publication No. 2015 / 093271.

[0563] The detailed arrangement and specific dimensions of the pattern formed are not particularly limited, but a pattern that produces the conductive fine lines described below is formed. Furthermore, the spacing between the patterns is preferably 8 μm or less, more preferably 6 μm or less. While the lower limit is not particularly limited, it is often 2 μm or greater.

[0564] The pattern (cured film of the photosensitive composition layer) formed by the above-mentioned procedure is preferably achromatic. * a * b * In the color system, the pattern's a * The value is preferably -1.0 to 1.0, and the b * The value is preferably -1.0 to 1.0.

[0565] <Post-exposure process and post-baking process>

[0566] The method for producing the laminate may include a step of exposing the pattern obtained in the development step (post-exposure step) and / or a step of heating (post-baking step).

[0567] When both the post-exposure step and the post-bake step are included, it is preferred to perform the post-bake after the post-exposure step.

[0568] <Other Processes>

[0569] The method for producing a laminate of the present invention may include any steps (other steps) other than those described above.

[0570] For example, the process of reducing the visible light reflectivity described in paragraph

[0172] of International Publication No. 2019 / 022089, the process of forming a new conductive layer on the insulating film described in paragraph

[0172] of International Publication No. 2019 / 022089, etc. can be cited, but it is not limited to these processes.

[0571] The laminate produced by the method for producing a laminate of the present invention can be applied to various devices. Examples of devices including the laminate include display devices, printed wiring boards, semiconductor packages, and input devices, preferably touch panels, more preferably capacitive touch panels. Furthermore, the input device can be applied to display devices such as organic electroluminescent displays and liquid crystal displays.

[0572] When the laminate is used in a touch panel, the pattern formed by the photosensitive composition layer is preferably used as a protective film for the touch panel electrodes. That is, the photosensitive composition layer included in the transfer film is preferably used to form a touch panel electrode protective film. Furthermore, touch panel electrodes include not only the sensor electrodes of the touch sensor but also lead-out wiring.

[0573] [Blocked isocyanate compound represented by formula QA]

[0574] The blocked isocyanate compound of the present invention is a blocked isocyanate compound represented by the following formula QA, and is a blocked isocyanate compound having a novel structure.

[0575] B 1a -A 1a -L 1a -A 2a -B 2a Formula QA

[0576] B in formula QA 1a 、A 1a 、L 1a 、A 2a and B 2a The definition and preferred embodiment of are as described above, so their description is omitted.

[0577] The compound represented by the formula QA is prepared by, for example, reacting a compound having an isocyanate group (for example, B in the above formula Q) with a 1a and B 2a isocyanate group of the compound) is obtained by reacting the isocyanate group with the above-mentioned blocking agent.

[0578] The reaction conditions of the compound having an isocyanate group and the blocking agent are not particularly limited, and the same reaction conditions as those for known blocked isocyanate compounds can be employed.

[0579] The blocked isocyanate compound represented by Formula QA is preferably a blocked isocyanate compound represented by Formula Q-1.

[0580] [Chemical Formula 20]

[0581]

[0582] Formula Q-1

[0583] The blocked isocyanate compound represented by Formula Q-1 may be an isomer mixture of a cis isomer and a trans isomer (hereinafter also referred to as a "cis-trans isomer mixture").

[0584] When the blocked isocyanate compound represented by formula Q-1 is a cis-trans isomer mixture, the mass ratio of the cis isomer to the trans isomer is preferably cis / trans = 10 / 90 to 90 / 10, more preferably cis / trans = 40 / 60 to 60 / 40.

[0585] The use of the compound represented by Formula QA is not particularly limited, but it is particularly preferably used as a component for forming the photosensitive composition layer in the transfer film.

[0586] [Specific example of a touch panel]

[0587] Figure 1 This is a schematic cross-sectional view of a touch panel 90 as a first specific example of a touch panel to which the transfer film of the present invention can be applied.

[0588] like Figure 1 As shown, the touch panel 90 includes an image display area 74 and an image non-display area 75 (ie, a frame portion).

[0589] Furthermore, the touch panel 90 includes touch panel electrodes on both surfaces of the substrate 32. Specifically, the touch panel 90 includes the first metal conductive material 70 on one surface of the substrate 32 and the second metal conductive material 72 on the other surface.

[0590] In the touch panel 90, the routing wiring 56 is connected to each of the first metal conductive material 70 and the second metal conductive material 72. Examples of the routing wiring 56 include copper wiring and silver wiring.

[0591] In the touch panel 90 , a metal conductive material protective film 18 is formed on one surface of the substrate 32 to cover the first transparent electrode pattern 70 and the bypass wiring 56 , and a metal conductive material protective film 18 is formed on the other surface of the substrate 32 to cover the second metal conductive material 72 and the bypass wiring 56 .

[0592] A refractive index adjusting layer may be formed on one surface of the substrate 32 .

[0593] and, Figure 2 1 is a schematic cross-sectional view of a touch panel 90 as a second example of a touch panel to which the transfer film of the present invention can be applied.

[0594] like Figure 2 As shown, the touch panel 90 includes an image display area 74 and an image non-display area 75 (ie, a frame portion).

[0595] Furthermore, the touch panel 90 includes touch panel electrodes on both surfaces of the substrate 32. Specifically, the touch panel 90 includes the first metal conductive material 70 on one surface of the substrate 32 and the second metal conductive material 72 on the other surface.

[0596] In touch panel 90, bypass wiring 56 is connected to first metal conductive material 70 and second metal conductive material 72. Examples of bypass wiring 56 include copper wiring or silver wiring. Furthermore, bypass wiring 56 is formed within the interior surrounded by metal conductive material protective film 18 and first metal conductive material 70 or second metal conductive material 72.

[0597] In the touch panel 90 , a metal conductive material protective film 18 is formed on one surface of the substrate 32 to cover the first transparent electrode pattern 70 and the bypass wiring 56 , and a metal conductive material protective film 18 is formed on the other surface of the substrate 32 to cover the second metal conductive material 72 and the bypass wiring 56 .

[0598] A refractive index adjusting layer may be formed on one surface of the substrate 32 .

[0599] The metal conductive material protection film 18 is preferably a photosensitive composition layer or a cured film of a photosensitive composition layer in the present invention.

[0600] refer to Figure 3 and Figure 4 Still another embodiment of the touch panel will be described.

[0601] Figure 3 is a schematic plan view showing another specific example of a touch panel. Figure 4 It is along Figure 3 Cross-sectional view taken along line AA.

[0602] Figure 3 and Figure 4 , a transparent laminate 200 is shown having a transparent electrode pattern (including a first island-shaped electrode portion, a first wiring portion 116 , a second island-shaped electrode portion, and a bridge wiring 118 ), a protective layer 130 , and an overcoat layer 132 in this order on a transparent film substrate 124 .

[0603] At least one of the protective layer 130 and the overcoat layer 132 is preferably the photosensitive composition layer or the cured film of the photosensitive composition layer in the present invention.

[0604] And, as Figure 3 and Figure 4 As shown, the protective layer 130 arranged on the second island-shaped electrode portion 114 in the transparent electrode pattern on the transparent film substrate 124 is formed with a through hole 120 for connecting the second island-shaped electrode portion 114 and the bridging wiring (second wiring portion) 118, and the bridging wiring (second wiring portion) 118 is used to bridge between two adjacent second island-shaped electrode portions 114 to electrically connect the second island-shaped electrode portions 114 to each other.

[0605] The transparent laminate 200 includes a first electrode pattern 134 and a second electrode pattern 136 on a transparent substrate 124 , each extending in the arrow P direction or the arrow Q direction intersecting with each other.

[0606] exist Figure 3 and Figure 4 Only a portion of the touch panel is shown in the figure, but on the transparent substrate, a first electrode pattern 134 is arranged in one direction (first direction) over a wide range of the transparent substrate, and a second electrode pattern 136 is arranged in a direction (second direction) different from the first direction over a wide range of the transparent substrate.

[0607] exist Figure 3 In the embodiment, the first electrode pattern 134 is formed on the transparent substrate 124, and a plurality of square electrode portions (first island-shaped electrode portions) 112 are arranged in an island shape at equal intervals along the direction of arrow P. Adjacent first island-shaped electrode portions 112 are connected and interconnected by first wiring portions 116. Thus, a long strip of electrodes is formed along one direction on the surface of the transparent substrate.

[0608] The first wiring portion is preferably formed of the same material as the first island-shaped electrode portion.

[0609] And, in Figure 3 In the figure, the second electrode pattern 136 is on the transparent substrate 124, and the square electrode portion (second island electrode portion) 114 which is substantially the same as the first island electrode portion is arranged in an island shape at equal intervals along the arrow Q direction which is substantially orthogonal to the arrow P direction, and the second island electrode portions 114 adjacent to each other are connected and connected via the second wiring portion (bridge wiring) 118.

[0610] Thus, the long-strip electrodes are formed along a direction different from the first electrode pattern on the surface of the transparent substrate.

[0611] like Figure 3 and Figure 4As shown, the first electrode pattern 134 and the second electrode pattern 136 form a bridge structure at the intersection portion so that one of the intersecting electrodes passes over the other electrode to prevent them from being electrically connected to each other.

[0612] exist Figure 4 In the touch panel shown, the protective layer 130 is provided so as to cover the first electrode pattern 34 and the second electrode pattern 136 .

[0613] Example

[0614] The present invention will be further described below with reference to the following examples. The materials, usage amounts, ratios, treatment contents, and treatment sequences shown in the following examples may be appropriately modified without departing from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. In addition, unless otherwise specified, "parts" and "%" are by mass.

[0615] In the following examples, the weight average molecular weight of the resin is the weight average molecular weight determined in terms of polystyrene by gel permeation chromatography (GPC), and the acid value is the theoretical acid value.

[0616] <Synthesis of Alkali-Soluble Resin P-1>

[0617] 82.4 g of propylene glycol monomethyl ether was placed in a flask and heated to 90° C. under a nitrogen stream. A solution obtained by dissolving 38.4 g of styrene, 30.1 g of dicyclopentanyl methacrylate, and 34.0 g of methacrylic acid in 20 g of propylene glycol monomethyl ether and a solution obtained by dissolving 5.4 g of polymerization initiator V-601 (manufactured by FUJIFILM Wako Pure Chemical Corporation) in 43.6 g of propylene glycol monomethyl ether acetate were simultaneously added dropwise to this solution over 3 hours. After the dropwise addition was completed, 0.75 g of V-601 was added three times every hour. Then, the mixture was allowed to react for a further 3 hours. Thereafter, it was diluted with 58.4 g of propylene glycol monomethyl ether acetate and 11.7 g of propylene glycol monomethyl ether. Under an air stream, the reaction solution was heated to 100° C., and 0.53 g of tetraethylammonium bromide and 0.26 g of p-methoxyphenol were added. 25.5 g of glycidyl methacrylate (Brenmar GH, manufactured by NOFCORPORATION) was added dropwise thereto over 20 minutes. The mixture was reacted at 100° C. for 7 hours to obtain a solution of alkali-soluble resin P-1. The solid content concentration of the obtained solution was 36.5%. The weight average molecular weight of alkali-soluble resin P-1 as converted to standard polystyrene in GPC was 17,000, the dispersity was 2.4, and the acid value was 94.5 mgKOH / g. The amount of residual monomers measured by gas chromatography was less than 0.1% by mass relative to the polymer solid content in any monomer.

[0618] <Synthesis of Alkali-Soluble Resins P-2 to P-19>

[0619] Alkali-soluble resins P-2 to P-19 were synthesized in the same manner as for the synthesis of alkali-soluble resin P-1, except that the types of monomers used to obtain the structural units contained in the alkali-soluble resins and the contents of the structural units were changed as shown in Table 1. All alkali-soluble resins were synthesized as polymer solutions, and the amount of diluent (propylene glycol monomethyl ether acetate (PGMEA)) was adjusted so that the concentration (solids content) of the alkali-soluble resin in the polymer solution was 36.3% by mass.

[0620] In Table 1, structural units other than the structural unit having a radical polymerizable group are represented by the abbreviations of the monomers used to form each structural unit.

[0621] The structural unit having a radical polymerizable group is represented as an addition structure of monomers. For example, MAA-GMA refers to a structural unit obtained by adding glycidyl methacrylate to a structural unit derived from methacrylic acid.

[0622] In Table 1, the abbreviations have the following meanings.

[0623] St: Styrene (manufactured by Wako Pure Chemical Industries, Ltd.)

[0624] VN: Vinylnaphthalene (manufactured by Wako Pure Chemical Industries, Ltd.)

[0625] AMS: α-methylstyrene (manufactured by Tokyo Chemical Industry Co., Ltd.)

[0626] DCPMA: dicyclopentanyl methacrylate (Tg: 175° C., FANCRYL FA-513M, manufactured by Hitachi Chemical Company, Ltd.)

[0627] IBXMA: Isobornyl methacrylate (Tg: 173° C., Light Ester IB-X, manufactured by KYOEISHA CHEMICAL Co., LTD.)

[0628] ADMA: 1-adamantyl methacrylate (Tg: 250° C., Adamantate AM (manufactured by Idemitsu Kosan Co., Ltd.)

[0629] CHMA; Cyclohexyl methacrylate (Tg = 66°C, CHMA, manufactured by MITSUBISHI GAS CHEMICAL COMPANY, INC.)

[0630] MAA-GMA: A structural unit obtained by adding glycidyl methacrylate to a structural unit derived from methacrylic acid

[0631] MAA-M100: A structural unit obtained by adding CYM-M100 (manufactured by Daicel Corporation; 3,4-epoxycyclohexylmethyl methacrylate) to a structural unit derived from methacrylic acid

[0632] MAA: Methacrylic acid (manufactured by Wako Pure Chemical Industries, Ltd.)

[0633] AA: Acrylic acid (manufactured by Wako Pure Chemical Industries, Ltd.)

[0634] MMA: Methyl methacrylate (manufactured by Wako Pure Chemical Industries, Ltd.)

[0635] nBMA: n-butyl methacrylate (manufactured by Wako Pure Chemical Industries, Ltd.)

[0636] HEMA: Hydroxyethyl methacrylate (manufactured by Wako Pure Chemical Industries, Ltd.)

[0637] 4HBA: 4-Hydroxybutyl acrylate (manufactured by Wako Pure Chemical Industries, Ltd.)

[0638]

[0639] <Synthesis of Blocked Isocyanate Compound Q-1>

[0640] Under nitrogen flow, 453 g of butanone oxime (manufactured by Idem Kitasu Kosan Co., Ltd.) was dissolved in 700 g of methyl ethyl ketone. Under ice cooling, 500 g of 1,3-bis(isocyanatomethyl)cyclohexane (cis, trans isomer mixture, manufactured by Mitsui Chemicals, Inc., Takenate 600) was added dropwise over 1 hour, and the mixture was allowed to react for another 1 hour. Then, the temperature was raised to 40°C and the mixture was allowed to react for 1 hour. 1The completion of the reaction was confirmed by H-NMR (Nuclear Magnetic Resonance) and HPLC (High Performance Liquid Chromatography), and a methyl ethyl ketone solution of the blocked isocyanate compound Q-1 (see the following formula) was obtained.

[0641] <Synthesis of Blocked Isocyanate Compound Q-1-A>

[0642] A methyl ethyl ketone solution of blocked isocyanate compound Q-1-A was obtained by referring to the synthesis of blocked isocyanate compound Q-1. The amount of butanone oxime in the solution was 0.3 parts by mass per 100 parts by mass of Q-1-A.

[0643] <Synthesis of Blocked Isocyanate Compound Q-1-B>

[0644] A methyl ethyl ketone solution of blocked isocyanate compound Q-1-B was obtained by referring to the synthesis of blocked isocyanate compound Q-1-A. The amount of butanone oxime in the solution was 1.2 parts by mass per 100 parts by mass of Q-1-B.

[0645] <Synthesis of Blocked Isocyanate Compounds Q-2 to Q-8>

[0646] By referring to the synthesis method of blocked isocyanate compound Q-1, methyl ethyl ketone solutions of blocked isocyanate compounds Q-2 to Q-8 (see the following formula) were obtained. Blocked isocyanate compound Q-6 was a 1:1 (mass ratio) mixture of isomers.

[0647] [Chemical Formula 21]

[0648]

[0649] The NCO values ​​of the blocked isocyanate compounds Q-1 to Q-8 were measured according to the above method.

[0650] <Preparation of Photosensitive Composition>

[0651] Photosensitive compositions A-1 to A-38 and A'-1 having the compositions shown in Table 2 below were prepared. In Table 2, the numerical values ​​of the components represent the content (solid content mass) of each component. Methyl ethyl ketone and 1-methoxy-2-propyl acetate were appropriately added to prepare coating solutions of the photosensitive compositions so that the methyl ethyl ketone content in the solvent was 60% by mass, the solid content concentration in A-1 to A-31 was 25% by mass, and the solid content concentration in A-32 to A-38 was 20% by mass.

[0652] [Table 2]

[0653]

[0654] [Table 3]

[0655]

[0656] [Table 4]

[0657]

[0658] [Table 5]

[0659]

[0660] [Table 6]

[0661]

[0662] [Table 7]

[0663]

[0664] <Preparation of Coating Liquid for Forming Refractive Index Adjusting Layer>

[0665] Next, a coating liquid B-1 for forming a refractive index adjusting layer was prepared with the composition described in the following Table 3. The numerical values ​​in Table 3 represent "parts by mass".

[0666] [Table 8]

[0667]

[0668] <Preparation of Transfer Films of Examples 1 to 45 and Comparative Example 1>

[0669] Any of the photosensitive compositions A-1 to A-38, and A'-1 was applied to a temporary support, Lumirror 16KS40 (16 μm thick, manufactured by Toray Industries, Inc., polyethylene terephthalate film), using a slit nozzle. The solvent was then evaporated in a drying zone at 100°C to form a photosensitive composition layer on the temporary support. The amount of photosensitive composition applied was adjusted to achieve the thickness of the photosensitive composition layer listed in Table 4. A protective film (Lumirror 16KS40 (manufactured by Toray Industries, Inc.)) was then pressure-bonded to the photosensitive composition layer to produce transfer films according to Examples 1 to 45 and Comparative Example 1.

[0670] <Manufacturing of Laminated Body>

[0671] A cycloolefin resin film with a thickness of 38 μm and a refractive index of 1.53 was surface-modified by corona discharge treatment for 3 seconds using a high-frequency oscillator at an output voltage of 100% and an output power of 250 W, using a wire electrode with a diameter of 1.2 mm, an electrode length of 240 mm, and a working electrode distance of 1.5 mm. The resulting film was used as a transparent substrate.

[0672] Next, the material C shown in Table 4 below was applied onto the transparent substrate using a slit nozzle, and then irradiated with ultraviolet light (cumulative light dose 300 mJ / cm 2 ) and dried at about 110° C., thereby forming a transparent film with a refractive index of 1.60 and a film thickness of 80 nm.

[0673] [Table 9]

[0674]

[0675] [Chemical Formula 22]

[0676]

[0677] A film having a transparent film formed on a transparent substrate was introduced into a vacuum chamber. Using an ITO (indium tin oxide) target (indium:tin = 95:5 (molar ratio)) with a SnO2 content of 10% by mass, direct current (DC) magnetron sputtering (conditions: transparent substrate temperature 150°C, argon pressure 0.13 Pa, oxygen pressure 0.01 Pa), a 40nm thick ITO film with a refractive index of 1.82 was formed on the transparent film. The surface resistivity of the ITO film was 80Ω / □ (Ω per square).

[0678] Next, the ITO film was etched and patterned by a known chemical etching method, thereby obtaining a conductive substrate having a transparent film and a transparent electrode portion on a transparent substrate.

[0679] The protective film of each transfer film of the embodiment and comparative example was peeled off, and the surface of the exposed photosensitive composition was brought into contact with the transparent electrode portion of the conductive substrate. The layers were laminated (bonded) so that the photosensitive composition layer covered the transparent electrode portion, thereby forming a laminate having a photosensitive composition layer and a temporary support body arranged on the conductive substrate.

[0680] The lamination was performed using a vacuum laminator manufactured by MCK Corporation under the conditions of a transparent substrate temperature of 40° C., a rubber roller temperature of 100° C., a linear pressure of 3 N / cm, and a conveying speed of 2 m / min.

[0681] Then, using a proximity exposure machine equipped with an ultra-high pressure mercury lamp (manufactured by Hitachi High-Tech Electronics Engineering Co., Ltd.), an exposure mask (a quartz exposure mask having a pattern for forming an overcoat layer) was brought into close contact with the temporary support, and an exposure dose of 120 mJ / cm was applied through the temporary support. 2 (Measurement value based on i-ray) Pattern exposure was performed. In addition, the exposure light during irradiation had a wavelength of 365 nm as the main wavelength.

[0682] After the exposed sample was allowed to stand for 48 hours at 23°C and 55% humidity, the temporary support was removed and the sample was then developed in a 1% sodium carbonate aqueous solution at 32°C for 60 seconds. Ultrapure water was then sprayed onto the developed transparent substrate from an ultrahigh-pressure cleaning nozzle to remove any residue. Subsequently, air was blown to remove moisture from the transparent substrate.

[0683] Next, a post-exposure machine equipped with a high-pressure mercury lamp (manufactured by Ushio Inc.) was used to expose the sample at an exposure dose of 400 mJ / cm 2 The obtained pattern was exposed (based on the measured values ​​of the i-ray) (post-exposure).

[0684] Then, a post-baking treatment was performed at 145° C. for 30 minutes to form a laminate having a transparent film, a transparent electrode portion, and a pattern (cured film of the photosensitive composition layer) in this order on the transparent substrate.

[0685] <Corrosiveness Evaluation>

[0686] Using the transfer films of each embodiment and comparative example with the protective film peeled off, a PET (polyethylene terephthalate) film (manufactured by GEOMATEC Co., Ltd.) laminated with copper foil (a substitute for electrodes in electrostatic capacitive input devices) was prepared by the same method as for transferring the transfer film to a film having a transparent film and a transparent electrode portion formed on a transparent substrate. The exposed surface of the photosensitive composition was brought into contact with the copper foil on the PET film, and the two films were laminated (laminated) so that the copper foil was covered by the photosensitive composition layer. Post-processing (peeling off the temporary support, exposure, development, post-baking, etc.) was then performed to obtain a sample (laminated body) having the copper foil and a pattern (cured film of the photosensitive composition layer) in this order on the PET film.

[0687] Add 50g / L salt water to the surface of the sample pattern for 5cm 3 , at 50cm 2After spreading evenly inside, the water was evaporated at room temperature and the HAST tester EHS-221MD (manufactured by ESPEC Corp.) was used at 110°C 85% for 32 hours. The salt water was then wiped off, and the surface condition of the sample was observed and evaluated according to the following ratings.

[0688] AA, A, B, and C are necessary levels for practical applications, with AA being preferred.

[0689] (Evaluation Criteria)

[0690] AA: The copper has no discoloration at all.

[0691] A: Some copper discoloration is visible in some areas.

[0692] B: Slight copper discoloration was observed in part.

[0693] C: Slight discoloration of copper was seen on the entire surface.

[0694] D: Discoloration of copper was clearly seen over the entire surface.

[0695] <Evaluation of Development Residue>

[0696] The development-removed portion of the laminate was observed visually and with an optical microscope (20x objective lens).

[0697] A and B are the actual usage levels, with A being the preferred level.

[0698] (Evaluation Criteria)

[0699] A: The residue cannot be visually identified even under an optical microscope.

[0700] B: Through optical microscope observation, a very small amount of residue can be observed.

[0701] C: Even with visual observation, generation of residue was clearly observed over the entire surface.

[0702] The evaluation results are summarized in Table 5 below.

[0703]

[0704]

[0705] As shown in Table 5, it is shown that the use of a photosensitive composition layer containing an alkali-soluble resin, a polymerizable compound, a polymerization initiator, and a first blocked isocyanate compound can suppress corrosion of wiring (electrodes) (Examples 1 to 45).

[0706] The comparison between Examples 1 to 4 and 6 shows that when the first blocked isocyanate compound has a ring structure (Examples 1, 3, and 4), the corrosion of the wiring (electrode) can be further suppressed.

[0707] Comparison of Examples 1, 3 to 5, and 7 shows that when the NCO value of the first blocked isocyanate compound is 5.0 mmol / g or more (Examples 1, 3, and 4), corrosion of wiring (electrodes) can be further suppressed.

[0708] Comparison of Examples 8 to 10 and 15 to 31 shows that when the content of the structural units derived from the vinylbenzene derivative is 35% by mass or more relative to the total amount of all structural units contained in the alkali-soluble resin (Examples 15 to 31), corrosion of the wiring (electrode) can be further suppressed. In particular, it was shown that when the content of the structural units derived from the vinylbenzene derivative is 45% by mass or more relative to the total amount of all structural units contained in the alkali-soluble resin (Examples 17 to 31), corrosion of the wiring (electrode) can be further suppressed.

[0709] Comparison between Examples 22 to 25 and 32 to 35 shows that when the thickness of the photosensitive composition layer is 3 μm or more (Examples 22 to 25 and 33 to 35), corrosion of the wiring (electrode) can be further suppressed.

[0710] On the other hand, it was shown that when a photosensitive composition layer not containing the first blocked isocyanate compound was used, corrosion of the wiring (electrode) became significant (Comparative Example 1).

[0711] In the preparation of the transfer films of the above-mentioned embodiments and comparative examples, a refractive index adjusting layer (refractive index: 1.60 or more) having a thickness of 80 nm was provided by coating the refractive index adjusting layer-forming coating liquid B-1 on the photosensitive composition layer. In addition, transfer films having a refractive index adjusting layer corresponding to each embodiment and comparative example were obtained in the same order as the preparation of the transfer films of the above-mentioned embodiments and comparative examples.

[0712] The above-mentioned evaluations were performed using the transfer film having the refractive index adjusting layer obtained in this manner. The results showed the same evaluation results as those obtained when the transfer films of Examples and Comparative Examples were used.

[0713] Explanation of symbols

[0714] 18-Metal conductive material protective film, 32-Substrate, 56-Detour wiring, 70-First metal conductive material, 72-Second metal conductive material, 74-Image display area, 75-Image non-display area, 90-Touch panel, 112-First island-shaped electrode portion, 114-Second island-shaped electrode portion, 116-First wiring portion, 118-Second wiring portion (bridge wiring), 120-Through hole, 124-Transparent substrate (transparent film substrate), 130-Protective layer, 132-Overcoat layer, 134-First electrode pattern, 136-Second electrode pattern, 200-Transparent laminate, P-Extension direction of the first electrode pattern, Q-Extension direction of the second electrode pattern.

Claims

1. A transfer film comprising a temporary support and a photosensitive composition layer disposed on the temporary support. The photosensitive composition layer comprises an alkali-soluble resin, a polymerizable compound, a polymerization initiator, and a blocked isocyanate compound having an NCO value of 4.5 mmol / g or more. The blocked isocyanate compound is a blocked isocyanate compound represented by formula Q, or the blocked isocyanate compound is a blocked isocyanate compound represented by formula QA, B 1 -A 1 -L 1 -A 2 -B 2 Formula Q In formula Q, B 1 and B 2 Each independently represents a blocked isocyanate group, A 1 and A 2 Each independently represents a single bond or an alkylene group having 1 to 10 carbon atoms, L 1 represents a divalent linking group, B 1a -A 1a -L 1a -A 2a -B 2a Formula QA In formula QA, B 1a and B 2a Each independently represents a blocked isocyanate group, A 1a and A 2a Each independently represents a divalent linking group, L 1a represents a cyclic divalent saturated hydrocarbon group or a divalent aromatic hydrocarbon group.

2. The transfer film according to claim 1, wherein The NCO value of the blocked isocyanate compound is greater than 5.0 mmol / g.

3. The transfer film according to claim 1 or 2, wherein The blocked isocyanate compound has a ring structure.

4. The transfer film according to claim 1 or 2, wherein The photosensitive composition layer further includes a blocked isocyanate compound having an NCO value of less than 4.5 mmol / g.

5. The transfer film according to claim 1 or 2, wherein The alkali-soluble resin comprises a structural unit derived from a vinylbenzene derivative, a structural unit having a free radical polymerizable group, and a structural unit having an acid group. The content of the structural unit derived from the vinylbenzene derivative is 35% by mass or more relative to the total amount of all structural units contained in the alkali-soluble resin. The transfer film according to claim 5 , wherein: The content of the structural unit derived from the vinylbenzene derivative is 45% by mass or more relative to the total amount of all structural units contained in the alkali-soluble resin.

7. The transfer film according to claim 1 or 2, further comprising a refractive index adjusting layer, wherein the refractive index adjusting layer is arranged in contact with the photosensitive composition layer. The refractive index adjusting layer has a refractive index of 1.60 or greater.

8. The transfer film according to claim 1 or 2, wherein The photosensitive composition layer is used to form a touch panel electrode protection film.

9. A method for producing a laminate, comprising: a laminating step of bringing the photosensitive composition layer on the temporary support of the transfer film according to any one of claims 1 to 8 into contact with and laminating a substrate having a conductive layer, thereby obtaining a substrate with a photosensitive composition layer having, in this order, the substrate, the conductive layer, the photosensitive composition layer, and the temporary support; An exposure step of pattern-exposing the photosensitive composition layer; and a developing step of developing the exposed photosensitive composition layer to form a pattern, The method for producing a laminate further includes a peeling step of peeling the temporary support from the substrate having the photosensitive composition layer between the laminating step and the exposure step or between the exposure step and the development step.

10. A transfer film comprising a temporary support and a photosensitive composition layer disposed on the temporary support. The photosensitive composition layer comprises an alkali-soluble resin, a polymerizable compound, a polymerization initiator, and a blocked isocyanate compound having an NCO value of 4.5 mmol / g or more. The blocked isocyanate compound is a blocked isocyanate compound represented by formula Q, or the blocked isocyanate compound is a blocked isocyanate compound represented by formula QA, B 1 -A 1 -L 1 -A 2 -B 2 Formula Q In formula Q, B 1 and B 2 Each independently represents a blocked isocyanate group, A 1 and A 2 Each independently represents a single bond or an alkylene group having 1 to 10 carbon atoms, L 1 represents a divalent linking group, B 1a -A 1a -L 1a -A 2a -B 2a Formula QA In formula QA, B 1a and B 2a Each independently represents a blocked isocyanate group, A 1a and A 2a Each independently represents a divalent linking group, L 1a represents a cyclic divalent saturated hydrocarbon group or a divalent aromatic hydrocarbon group, The NCO value of the photosensitive composition layer is greater than 0.50 mmol / g.

11. A blocked isocyanate compound represented by formula QA, B 1a -A 1a -L 1a -A 2a -B 2a Formula QA In formula QA, B 1a and B 2a Each independently represents a blocked isocyanate group, A 1a and A 2a Each independently represents a divalent linking group, L 1a represents a cyclic divalent saturated hydrocarbon group or a divalent aromatic hydrocarbon group, The blocked isocyanate compound has an NCO value of 4.5 mmol / g or more.

12. The blocked isocyanate compound according to claim 11, which is represented by formula Q-1, Formula Q-1.

13. The blocked isocyanate compound according to claim 12, wherein The mass ratio of cis body to trans body is cis body / trans body = 10 / 90~90 / 10.

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