Transfer film and method for manufacturing laminate

Abstract

To provide a transfer film that has excellent laminate properties when transferred onto a transfer target member having a conductive pattern, and has a low reflective index of a laminate which includes a cured film obtained from a transferred photosensitive composition layer.SOLUTION: A transfer film includes a temporary support body and a photosensitive composition layer, where the photosensitive composition layer has a first photosensitive composition layer and a second photosensitive composition layer in this order from the temporary support body side; the first photosensitive composition layer contains a polymerization initiator; a refractive index of the first photosensitive composition layer is 1.45 or less, and smaller than a refractive index of the second photosensitive composition layer; and an average film thickness of the second photosensitive composition layer is more than 30 μm.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a method for manufacturing a transfer film and a laminate.

Background Art

[0002] Transfer films containing a photosensitive layer have been increasingly used in various fields in recent years. Since transfer films can contribute to cost reduction of products, it has been proposed to use them as films for etching resist, films for wiring protection films, and the like. For example, Patent Document 1 discloses a transfer film for wiring protection film applications.

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0004] Recently, when the present inventors examined the characteristics of a transfer film produced with reference to Patent Document 1, they found that when the photosensitive composition layer of the transfer film was transferred onto the surface on the conductive pattern side of a transfer member having a conductive pattern, at least one of the following occurred: bubbles were likely to enter between the transfer member and the photosensitive composition layer, and the reflectance of the laminate obtained by subjecting the photosensitive composition layer to exposure and development processes was high. Hereinafter, when the photosensitive composition layer of the transfer film is transferred onto a transfer member, the fact that bubbles are unlikely to enter between the transfer member and the photosensitive composition layer is also referred to as excellent "laminability".

[0005] Therefore, an object of the present invention is to provide a transfer film that has excellent laminability when transferred onto a transfer member having a conductive pattern and has a low reflectance of a laminate including a cured film obtained from the transferred photosensitive composition layer. Another object of the present invention is to provide a method for manufacturing a laminate.

Means for Solving the Problems

[0006] As a result of intensive studies to solve the above problems, the present inventors have found that the above problems can be solved by the following configuration.

[0007] [1] A transfer film including a temporary support and a photosensitive composition layer, wherein the photosensitive composition layer has, in this order from the temporary support side, a first photosensitive composition layer and a second photosensitive composition layer, the first photosensitive composition layer contains a polymerization initiator, the refractive index of the first photosensitive composition layer is 1.45 or less and is smaller than the refractive index of the second photosensitive composition layer, and the average film thickness of the second photosensitive composition layer is more than 30 μm. A transfer film. [2] The ratio of the complex viscosity B of the second photosensitive composition layer at 25° C. to the complex viscosity A of the second photosensitive composition layer at 90° C. is 4.0×10 3 or more. The transfer film according to [1]. [3] The transfer film according to [1] or [2], wherein the first photosensitive composition layer contains refractive index adjusting particles. [4] The transfer film according to any one of [1] to [3], wherein the average film thickness of the first photosensitive composition layer is 200 nm or less. [5] The transfer film according to any one of [1] to [4], wherein the average film thickness of the second photosensitive composition layer is 40 to 300 μm. [6] A laminating step of laminating the second photosensitive composition layer in the transfer film according to any one of [1] to [5] and the surface on the conductive layer side in a transfer member having a base material and a conductive layer disposed on the base material, An exposure step of exposing the photosensitive composition layer, A method for manufacturing a laminate, including a peeling step of peeling the temporary support between the bonding step and the exposure step, or after the exposure step.

Effects of the Invention

[0008] According to the present invention, it is possible to provide a transfer film that is excellent in laminating properties when transferred to a transfer member having a conductive pattern, and has a low reflectance of a laminate including a cured film obtained from the transferred photosensitive composition layer. Further, according to the present invention, it is also possible to provide a method for manufacturing a laminate.

Brief Description of the Drawings

[0009]

Figure 1

Embodiments for Carrying Out the Invention

[0010] Hereinafter, the present invention will be described in detail. The meanings of the terms in this specification are shown below. A numerical range represented by "~" means a range including the numerical values described before and after "~" as the lower limit value and the upper limit value. In a numerical range described step by step, the upper limit value or the lower limit value described in a certain numerical range may be replaced with the upper limit value or the lower limit value of the numerical range of other step-by-step descriptions. Also, in the numerical range described in this specification, the upper limit value or the lower limit value described in a certain numerical range may be replaced with the value shown in the examples.

[0011] The term "step" includes not only an independent step but also a case where it cannot be clearly distinguished from other steps, as long as the intended purpose of the step is achieved.

[0012] The weight average molecular weight (Mw) and the number average molecular weight (Mn) are values converted using polystyrene as a standard substance measured by a gel permeation chromatography (GPC) analyzer, with TSKgel GMHxL, TSKgel G4000HxL, or TSKgel G2000HxL (all are trade names of Tosoh Corporation) as columns, THF (tetrahydrofuran) as the eluent, a differential refractometer as the detector, and without special notice. Also, unless otherwise specified, the molecular weight of a compound with a molecular weight distribution is the weight average molecular weight (Mw). The content of the metal element is a value measured using an inductively coupled plasma (ICP) spectroscopic analyzer, unless otherwise specified. The hue is a value measured using a color difference meter (CR-221, manufactured by Minolta Co., Ltd.), unless otherwise specified.

[0013] “(Meth)acryl” is a concept encompassing both acrylic and methacrylic, “(meth)acryloyloxy group” is a concept encompassing both acryloyloxy group and methacryloyloxy group, “(meth)acrylamide group” is a concept encompassing both acrylamide group and methacrylamide group, and “(meth)acrylate” is a concept encompassing both acrylate and methacrylate.

[0014] “Alkali-soluble” means that the solubility in 100 g of a 1% by mass aqueous sodium carbonate solution at a liquid temperature of 22°C is 0.1 g or more. Therefore, for example, an alkali-soluble resin refers to a resin that satisfies the above solubility conditions.

[0015] “Water-soluble” means that the solubility in 100 g of water at pH 7.0 with a liquid temperature of 22°C is 0.1 g or more. Therefore, for example, a water-soluble resin refers to a resin that satisfies the above solubility conditions.

[0016] "Solid content" means, for example, the components that form a composition layer (e.g., a photosensitive composition layer, etc.) formed using a coating solution. When the coating solution contains a solvent (e.g., an organic solvent and water, etc.), it means all components excluding the solvent. Also, any component that forms the composition layer, even if it is in a liquid state, is regarded as a solid content.

[0017] "Transparent" means that the average transmittance of visible light with wavelengths of 400 to 700 nm is 80% or more, preferably 90% or more. Therefore, when referring to a "transparent layer", it means a layer with an average transmittance of visible light with wavelengths of 400 to 700 nm of 80% or more. The average transmittance is measured every 1 nm for the directly transmitted light. The average transmittance of visible light is a value measured at 25°C using a spectrophotometer. For example, it can be measured using a spectrophotometer U-3310 manufactured by Hitachi, Ltd.

[0018] Unless otherwise specified, the average film thickness of the first photosensitive composition layer and the second photosensitive composition layer is a value obtained by observing a cross-section cut by a microtome with an SEM (scanning electron microscope) or a TEM (transmission electron microscope) and using the average value of the film thickness measured at 10 points. However, when the film thickness is 1 μm or more, it is measured with an SEM, and when the film thickness is less than 1 μm, it is measured with a TEM.

[0019] Unless otherwise specified, the refractive index is the refractive index at a wavelength of 550 nm measured at 25°C based on a measuring device conforming to the ellipsometry method. In particular, the refractive indices of the first photosensitive composition layer and the second photosensitive composition layer are, unless otherwise specified, the refractive index at a wavelength of 550 nm obtained by measuring the reflection spectrum (wavelength: 400 to 1000 nm) at 25°C using a measuring device conforming to the ellipsometry method and fitting using the Cauchy model.

[0020] [Transfer film] The transfer film of the present invention is a transfer film including a temporary support and a photosensitive composition layer, The photosensitive composition layer has, from the temporary support side, a first photosensitive composition layer and a second photosensitive composition layer in this order. The first photosensitive composition layer contains a polymerization initiator. The refractive index of the first photosensitive composition layer is smaller than that of the second photosensitive composition layer and is 1.45 or less. The average film thickness of the second photosensitive composition layer is more than 30 μm.

[0021] Regarding the mechanism of action that when the transfer film of the present invention is used, the reflectance of the resulting laminate is low and the laminating property is excellent, the present inventor speculates as follows. A laminate including a cured film formed by transferring the transfer film of the present invention to a transfer member having a conductive pattern and performing an exposure treatment and a development treatment has, in this order, a layer derived from the first photosensitive composition layer (refractive index adjustment layer), a layer derived from the second photosensitive composition layer (resin layer), and the transfer member. In the above laminate, since the refractive index adjustment layer having a lower refractive index than the resin layer is disposed on the air interface side, reflection of light incident from the air interface side is less likely to occur compared to a laminate having no refractive index adjustment layer. Further, according to the studies of the present inventors this time, it has also been confirmed that when the refractive index of the first photosensitive composition layer in the transfer film is 1.45 or less and is lower than that of the second photosensitive composition layer, the antireflection performance is significantly excellent. Further, when the second photosensitive composition layer in the transfer film of the present invention is transferred to the conductive pattern side of a transfer member having a conductive pattern, if the average film thickness of the second photosensitive composition layer in the resulting laminate is more than 30 μm, the second photosensitive composition layer is transferred following the shape of the conductive pattern, so generation of bubbles and the like in the laminate is easily suppressed. On the other hand, when the average film thickness of the second photosensitive composition layer is thick as described above, development often becomes difficult unless the conditions of the subsequent image processing are made harsher than those for a thin film. However, when the development treatment is carried out under harsh conditions, the resulting conventional refractive index adjustment layer is likely to peel off, and the reflectance and patterning property of the laminate are inferior. In contrast, since the first photosensitive composition layer in the transfer film of the present invention contains a polymerization initiator, it is presumed that a desired refractive index adjustment layer can be formed even under the above harsh conditions.

[0022] Hereinafter, with reference to the drawings, the configuration of the transfer film of the present invention will be specifically described.

[0023] FIG. 1 is a schematic cross-sectional view showing an embodiment of the transfer film of the present invention. The transfer film 10 has a protective film 11, a second photosensitive composition layer 13, a first photosensitive composition layer 15, and a temporary support 17 in this order. The refractive index of the first photosensitive composition layer 15 is 1.45 or less and is lower than that of the second photosensitive composition layer 13. Note that the transfer film 10 shown in FIG. 1 has the protective film 11 disposed thereon, but the protective film 11 may not be disposed.

[0024] Hereinafter, each member constituting the transfer film of the present invention will be described in detail.

[0025] <Temporary support> The transfer film has a temporary support. The temporary support is a member that supports the photosensitive composition layer and is finally removed by a peeling process.

[0026] The temporary support may have a single-layer structure or a multilayer structure. The temporary support is preferably a film, more preferably a resin film. As the temporary support, a film having flexibility and not undergoing significant deformation, shrinkage, or elongation under pressure or under pressure and heat is preferred. Examples of the above film include a polyethylene terephthalate film (e.g., a biaxially stretched polyethylene terephthalate film), a polymethyl methacrylate film, a triacetate cellulose film, a polystyrene film, a polyimide film, and a polycarbonate film. Among them, a polyethylene terephthalate film is preferred as the temporary support. In addition, the film used as the temporary support preferably has no deformation such as wrinkles and no scratches.

[0027] The temporary support preferably has high transparency in terms of being able to perform pattern exposure through the temporary support. The transmittance at a wavelength of 365 nm is preferably 60% or more, more preferably 70% or more. In terms of pattern formability during pattern exposure through the temporary support and the transparency of the temporary support, the haze of the temporary support is preferably small. Specifically, the haze value of the temporary support is preferably 2% or less, more preferably 0.5% or less, and even more preferably 0.1% or less. In terms of pattern formability during pattern exposure through the temporary support and the transparency of the temporary support, the number of fine particles, foreign substances, and defects contained in the temporary support is preferably small. The number of fine particles, foreign substances, and defects with a diameter of 1 μm or more in the temporary support is 50 pieces / 10 mm 2 or less is preferred, 10 pieces / 10 mm 2 or less is more preferred, 3 pieces / 10 mm 2 or less is even more preferred, and 0 pieces / 10 mm 2 is particularly preferred.

[0028] The thickness of the temporary support is not particularly limited, but is preferably 5 to 200 μm, more preferably 5 to 150 μm, even more preferably 5 to 50 μm, and particularly preferably 5 to 25 μm from the viewpoints of ease of handling and versatility.

[0029] Also, from the viewpoint of improving the adhesion between the temporary support and the photosensitive composition layer formed on the temporary support, the surface of the temporary support on the side in contact with the photosensitive composition layer may be surface-modified by UV (ultraviolet) irradiation, corona discharge, plasma, or the like.

[0030] When the surface modification of the temporary support is carried out by UV irradiation, the exposure amount is preferably 10 to 2000 mJ / cm 2 and preferably 50 to 1000 mJ / cm 2It is more preferable. As the light source, for example, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high pressure mercury lamp, a carbon arc lamp, a metal halide lamp, a xenon lamp, a chemical lamp, an electrodeless discharge lamp, and a light-emitting diode (LED) that emit light in a wavelength band of 150 to 450 nm can be mentioned. If the light irradiation amount is within the above range, the lamp output and illuminance are not particularly limited.

[0031] Examples of the temporary support include a biaxially stretched polyethylene terephthalate film with a thickness of 16 μm, a biaxially stretched polyethylene terephthalate film with a thickness of 12 μm, and a biaxially stretched polyethylene terephthalate film with a thickness of 9 μm.

[0032] Preferable forms of the temporary support include, for example, the temporary supports described in paragraphs

[0017] to

[0018] of JP-A No. 2014-085643, paragraphs

[0019] to

[0026] of JP-A No. 2016-027363, paragraphs

[0041] to

[0057] of WO 2012 / 081680, and paragraphs

[0029] to

[0040] of WO 2018 / 179370. The contents of these publications are incorporated herein.

[0033] From the viewpoint of imparting handleability, a layer containing fine particles (lubricant layer) may be provided on the surface of the temporary support. The lubricant layer may be provided on one side or both sides of the temporary support. The diameter of the particles contained in the lubricant layer is preferably 0.05 to 0.8 μm. Also, the film thickness of the lubricant layer is preferably 0.05 to 1.0 μm. Examples of commercially available products of the temporary support include Lumirror 16KS40, Lumirror 16FB40 (both manufactured by Toray Industries, Inc.), Cosmo Shine A4100, Cosmo Shine A4300, and Cosmo Shine A8300 (all manufactured by Toyobo Co., Ltd.).

[0034] <Photosensitive composition layer> The transfer film has a photosensitive composition layer. The photosensitive composition layer has, in this order from the temporary support side, a first photosensitive composition layer described later and a second photosensitive composition layer described later. The photosensitive composition layer may have other layers other than the first photosensitive composition layer and the second photosensitive composition layer (for example, a photosensitive composition layer other than the first and second photosensitive composition layers, etc.). Further, after transferring the photosensitive composition layer onto the transfer body, by performing exposure and development, a pattern can be formed on the transfer body. In particular, the first photosensitive composition layer can form a resin layer (refractive index adjustment layer) having a predetermined refractive index adjustment. As the photosensitive composition layer, a negative photosensitive composition layer is preferable. The negative photosensitive composition layer is a photosensitive composition layer in which the solubility of the exposed portion in the developer decreases due to exposure. When the photosensitive composition layer is a negative photosensitive composition layer, the formed pattern corresponds to a cured film.

[0035] (The first photosensitive composition layer) The photosensitive composition layer has the first photosensitive composition layer. The first photosensitive composition layer contains a polymerization initiator and is a layer disposed between the temporary support and the second photosensitive composition layer. Further, the refractive index of the first photosensitive composition layer is smaller than the refractive index of the second photosensitive composition layer and is 1.45 or less.

[0036] The refractive index of the first photosensitive composition layer is 1.45 or less, preferably 1.10 to 1.45, more preferably 1.15 to 1.40, and still more preferably 1.20 to 1.30. The method for controlling the refractive index of the first photosensitive composition layer is not particularly limited, but examples include a method of using a resin or a polymerizable compound having a desired refractive index, a method of using particles having a desired refractive index (for example, hollow particles, metal particles, and metal oxide particles, etc.), and a method of using a composite of a metal salt and a polymer having a desired refractive index.

[0037] The upper limit of the average film thickness of the first photosensitive composition layer is preferably 300 nm or less, more preferably 200 nm or less, and still more preferably 120 nm or less. The lower limit is preferably 10 nm or more, more preferably 30 nm or more, and still more preferably 50 nm or more.

[0038] The first photosensitive composition layer preferably contains a polymerization initiator, and further preferably contains refractive index adjusting particles and a resin (preferably an alkali-soluble resin). When having the above configuration, with respect to the total mass of the first photosensitive composition layer, the polymerization initiator is preferably contained in an amount of 0.1 to 5.0% by mass, the refractive index adjusting particles are preferably contained in an amount of 30.0 to 95.0% by mass, and the resin is preferably contained in an amount of 1.0 to 60.0% by mass. Further, the first photosensitive composition layer preferably contains a polymerization initiator, and further preferably contains refractive index adjusting particles, a resin (preferably an alkali-soluble resin), and a polymerizable compound. When having the above configuration, with respect to the total mass of the first photosensitive composition layer, the polymerization initiator is preferably contained in an amount of 0.1 to 5.0% by mass, the refractive index adjusting particles are preferably contained in an amount of 30.0 to 95.0% by mass, the resin is preferably contained in an amount of 1.0 to 60.0% by mass, and the polymerizable compound is preferably contained in an amount of 1.0 to 60.0% by mass.

[0039] Hereinafter, the components that the first photosensitive composition layer may contain will be described in detail.

[0040] - Polymerization initiator - The first photosensitive composition layer contains a polymerization initiator. The polymerization initiator used in the first photosensitive composition layer is not particularly limited, and examples thereof include a polymerization initiator that the second photosensitive composition layer described later may contain, IRGACURE 2959, and a photopolymerization initiator of the following Structural Formula 3.

[0041]

Chemical formula

[0042] The polymerization initiator may be used alone or in combination of two or more. The content of the polymerization initiator is preferably 0.1 to 5.0% by mass, more preferably 0.1 to 3.0% by mass, with respect to the total mass of the first photosensitive composition layer.

[0043] - Resin - The first photosensitive composition layer preferably contains a resin. As the resin, an alkali-soluble resin is preferred. Examples of the alkali-soluble resin include the alkali-soluble resins that may be included in the second photosensitive composition layer described later.

[0044] As a preferred embodiment of the alkali-soluble resin, a (meth)acrylic resin having a structural unit derived from at least one of (meth)acrylic acid and (meth)acrylic acid ester can be mentioned. Among them, a (meth)acrylic resin having a structural unit derived from a structural unit derived from (meth)acrylic acid and a structural unit derived from allyl (meth)acrylate is preferably used. In the present specification, the (meth)acrylic resin means a resin having a structural unit derived from a (meth)acrylic compound. The content of the structural unit derived from the (meth)acrylic compound is preferably 50% by mass or more, more preferably 70% by mass or more, and still more preferably 90% by mass or more with respect to all the structural units of the (meth)acrylic resin. The (meth)acrylic resin may be composed only of a structural unit derived from a (meth)acrylic compound, or may have a structural unit derived from a polymerizable monomer other than the (meth)acrylic compound. That is, the upper limit of the content of the structural unit derived from the (meth)acrylic compound is 100% by mass or less with respect to all the structural units of the (meth)acrylic resin. Examples of the (meth)acrylic compound include the (meth)acrylic compounds in the binder polymer described later.

[0045] In addition, as another preferred embodiment of the alkali-soluble resin, a copolymer containing a structural unit derived from (meth)acrylic acid and a structural unit derived from styrene in the main chain can also be mentioned. Among them, a copolymer containing a structural unit derived from (meth)acrylic acid and a structural unit derived from styrene is preferable, and a copolymer containing a structural unit derived from (meth)acrylic acid, a structural unit derived from styrene, and a structural unit derived from a (meth)acrylic acid ester having an ethyleneoxy chain is preferably used.

[0046] As the alkali-soluble resin, commercially available products can also be used. Examples of commercially available products include ARUFON (registered trademark) UC3000, UC3510, UC3080, UC3920, UF5041 (above are product names) manufactured by Toagosei Co., Ltd., and JONCRYL (registered trademark) 67, JONCRYL611, JONCRYL678, JONCRYL690, and JONCRYL819 (above are product names) manufactured by BASF.

[0047] The resin may be used alone or in combination of two or more. In the first photosensitive composition layer, the content of the resin is preferably 1.0 to 60.0% by mass, more preferably 1.0 to 40.0% by mass, and still more preferably 1.0 to 30.0% by mass based on the total mass of the first photosensitive composition layer.

[0048] -Refractive index adjusting particles- The first layer preferably contains refractive index adjusting particles. The refractive index adjusting particles may be either inorganic particles or organic particles, and inorganic particles are preferred. Examples of the inorganic particles include metal oxide particles such as silica particles (SiO2 particles). The inorganic particles may be either solid particles or hollow particles. Examples of the hollow particles include silica hollow particles.

[0049] The hollow particles are intended to be particles containing air in a cavity covered by an outer shell. The air (refractive index 1.0) contained in the cavity of the particles can reduce the refractive index of the film when introduced into the film. The porosity of the hollow particles is preferably 10 to 80%, more preferably 20 to 60%, and still more preferably 30 to 60% from the viewpoint of being easily adjusted to a low refractive index.

[0050] In addition, the refractive index adjusting particles may be subjected to physical surface treatment such as plasma discharge treatment and corona discharge treatment, or chemical surface treatment with surfactants and coupling agents, etc.

[0051] The refractive index adjusting particles preferably contain silica particles because they can easily adjust the refractive index of the first photosensitive composition layer to 1.45 or less.

[0052] Examples of the silica particles include colloidal silica and fumed silica. Examples of commercially available products include Snowtex ST-N (colloidal silica: non-volatile content 20% by mass) and Snowtex ST-C (colloidal silica: non-volatile content 20% by mass) manufactured by Nissan Chemical Industries, Ltd. Examples of commercially available hollow silica particles include the Thruia series manufactured by JGC Catalysts and Chemicals Ltd.

[0053] The refractive index of the refractive index adjusting particles is preferably 1.45 or less, more preferably 1.0 to 1.45, and even more preferably 1.1 to 1.35. The refractive index of the refractive index adjusting particles is intended to be the refractive index at a wavelength of 550 nm at 25 °C and can be measured by methods such as the attenuation spectrum method, extrapolation method, Becke line method, and immersion method.

[0054] From the viewpoint of optical performance such as haze, the average primary particle diameter of the refractive index adjusting particles is preferably 100 nm or less, more preferably 60 nm or less, and even more preferably 20 nm or less. The lower limit is preferably 1 nm or more, and more preferably 10 nm or more. The average primary particle diameter of the refractive index adjusting particles is a value obtained by measuring the diameters of any 100 particles by observation with a transmission electron microscope (TEM) and calculating the arithmetic average of the 100 diameters.

[0055] The refractive index adjusting particles may be used alone or in combination of two or more. In the first photosensitive composition layer, the content of the refractive index adjusting particles is preferably 30.0 to 95.0% by mass, more preferably 55.0 to 95.0% by mass, and even more preferably 60.0 to 95.0% by mass based on the total mass of the first photosensitive composition layer.

[0056] - Metal Oxidation Inhibitor - When the first photosensitive composition layer contains inorganic particles as refractive index adjusting particles, the first photosensitive composition layer preferably further contains a metal oxidation inhibitor. The metal oxidation inhibitor is preferably a compound having an aromatic ring (nitrogen-containing aromatic ring) containing a nitrogen atom as a ring member atom. Examples of the nitrogen-containing aromatic ring include an imidazole ring, a triazole ring, a tetrazole ring, a thiadiazole ring; a condensed ring of at least one selected from the group consisting of an imidazole ring, a triazole ring, a tetrazole ring, and a thiadiazole ring and another aromatic ring. The other aromatic ring may be either an aromatic hydrocarbon ring or an aromatic heterocyclic ring, preferably an aromatic hydrocarbon ring, more preferably a benzene ring or a naphthalene ring, and still more preferably a benzene ring.

[0057] Among them, as the compound having a nitrogen-containing aromatic ring, triazole, imidazole, benzimidazole, tetrazole, mercaptothiadiazole, or benzotriazole is preferable, and triazole or benzotriazole is more preferable.

[0058] The metal oxidation inhibitor may be used alone or in combination of two or more. In the first photosensitive composition layer, the content of the metal oxidation inhibitor is preferably 0.01 to 8.0% by mass, more preferably 0.01 to 5.0% by mass, and still more preferably 0.01 to 3.0% by mass based on the total mass of the first photosensitive composition layer.

[0059] -Polymerizable compound- The first photosensitive composition layer preferably contains a polymerizable compound. The polymerizable compound is a compound having a polymerizable group. Examples of the polymerizable group include a radical polymerizable group and a cationic polymerizable group, and a radical polymerizable group is preferable. Note that the polymerizable compound that the first photosensitive composition layer can contain is a compound other than the above resin, and preferably has a molecular weight of less than 5,000.

[0060] The coincidence compound preferably contains a radically polymerizable compound having an ethylenically unsaturated group (hereinafter also simply referred to as "ethylenically unsaturated compound"). As the ethylenically unsaturated group, a (meth)acryloxy group or a (meth)acrylamide group is preferable, and a (meth)acryloxy group is more preferable.

[0061] Examples of the polymerizable compound include the polymerizable compound in the second photosensitive composition layer described later, and the polymerizable compounds described in paragraphs

[0023] to

[0024] of Japanese Patent No. 4098550. Among them, pentaerythritol tetraacrylate, pentaerythritol triacrylate, or tetraacrylate of a pentaerythritol ethylene oxide adduct is preferable.

[0062] Examples of the polymerizable compound include a polymerizable compound represented by the following structural formula 1, a polymerizable compound represented by the following structural formula 2, and an ethylenically unsaturated compound having three or more functional groups. Examples of the ethylenically unsaturated compound having three or more functional groups include dipentaerythritol (tri / tetra / penta / hexa)(meth)acrylate, pentaerythritol (tri / tetra)(meth)acrylate, tetraacrylate of a pentaerythritol ethylene oxide adduct, trimethylolpropane tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, isocyanuric acid (meth)acrylate, and (meth)acrylate compounds having a glycerin tri(meth)acrylate skeleton. Here, "(tri / tetra / penta / hexa)(meth)acrylate" is a concept including tri(meth)acrylate, tetra(meth)acrylate, penta(meth)acrylate, and hexa(meth)acrylate, and "(tri / tetra)(meth)acrylate" is a concept including tri(meth)acrylate and tetra(meth)acrylate. Examples of ethylenically unsaturated compounds having three or more functional groups include caprolactone-modified compounds of (meth)acrylate compounds (such as KAYARAD® DPCA-20 manufactured by Nippon Kayaku Co., Ltd., A-9300-1CL manufactured by Shin-Nakamura Chemical Co., Ltd., etc.), alkylene oxide-modified compounds of (meth)acrylate compounds (such as KAYARAD® RP-1040 manufactured by Nippon Kayaku Co., Ltd., ATM-35E, A-9300 manufactured by Shin-Nakamura Chemical Co., Ltd., EBECRYL® 135 manufactured by Daicel Ornex Co., Ltd., etc.), and ethoxylated glycerol triacrylate (such as NK Ester A-GLY-9E manufactured by Shin-Nakamura Chemical Co., Ltd.).

[0063] [Chemical formula] JPEG2025103326000003.jpg37103

[0064] Examples of commercially available polymerizable compounds include, for example, NK Ester A-TMMT, A-TMM3LM-N, A-TMM-3L, A-TMM3 (all manufactured by Shin-Nakamura Chemical Co., Ltd.), and Kayrad RP-1040 (manufactured by Nippon Kayaku Co., Ltd.).

[0065] As the polymerizable compound, an ethylenically unsaturated compound having an acid group is also preferable. Examples of the acid group include a phosphoric acid group, a sulfo group, and a carboxy group, and the carboxy group is preferable. Further, the carboxy group may be in the form of an acid anhydride.

[0066] Examples of the ethylenically unsaturated compound having an acid group include, for example, ethylenically unsaturated compounds having 3 to 4 functional groups having an acid group [those in which a carboxy group is introduced into the pentaerythritol tri and tetraacrylate (PETA) skeleton (acid value: 80 to 120 mgKOH / g)], and ethylenically unsaturated compounds having 5 to 6 functional groups having an acid group [those in which a carboxy group is introduced into the dipentaerythritol penta and hexaacrylate (DPHA) skeleton (acid value: 25 to 70 mgKOH / g)]. In addition, 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 is also preferable.

[0067] As the ethylenically unsaturated compound having an acid group, from the viewpoints of developability and film strength, at least one selected from the group consisting of a polyfunctional (two or more functional groups) ethylenically unsaturated compound having a carboxy group and a polyfunctional (two or more functional groups) ethylenically unsaturated compound having a carboxylic anhydride is preferable. The polyfunctional (two or more functional groups) ethylenically unsaturated compound having a carboxy group is not particularly limited and can be appropriately selected from known compounds. In the present specification, the "polyfunctional (two or more functional groups) ethylenically unsaturated compound" means a compound having two or more ethylenically unsaturated groups in one molecule. Examples of the polyfunctional (two or more functional groups) ethylenically unsaturated compound having a carboxy group include Aronix (registered trademark) TO-2349 (manufactured by Toagosei Co., Ltd.), Aronix (registered trademark) M-520 (manufactured by Toagosei Co., Ltd.), and Aronix (registered trademark) M-510 (manufactured by Toagosei Co., Ltd.).

[0068] The polymerizable compound may be used alone or in combination of two or more. In the first photosensitive composition layer, the content of the polymerizable compound is preferably 1.0 to 60.0% by mass, more preferably 1.0 to 20.0% by mass, based on the total mass of the first photosensitive composition layer.

[0069] - Other Components - The first photosensitive composition layer may contain components other than the above-described components (hereinafter also referred to as "other components"). Examples of the other components include surfactants. Examples of the surfactant include the surfactants described in paragraph

[0017] of Japanese Patent No. 4502784 and paragraphs

[0060] to

[0071] of JP-A-2009-237362.

[0070] As the surfactant, a fluorine-based surfactant or a silicone-based surfactant is preferable. Examples of commercially available fluorosurfactants include Megafac F-171, F-172, F-173, F-176, F-177, F-141, F-142, F-143, F-144, F-437, F-475, F-477, F-479, F-482, F-551-A, F-552, F-554, F-555-A, F-556, F-557, F-558, F-559, F-560, F-561, F-565, F-563, F-568, F-575, F-780, EXP, MFS-330, 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 (manufactured by DIC Corporation, Ltd. hereinafter), Fluorad FC430, FC431, FC171 (manufactured by Sumitomo 3M Limited hereinafter), Surflon S-382, SC-101, SC-103, SC-104, SC-105, SC-1068, SC-381, SC-383, S-393, KH-40 (manufactured by AGC Inc. hereinafter), PolyFox PF636, PF656, PF6320, PF6520, PF7002 (manufactured by OMNOVA Solutions Inc. hereinafter), Ftergent 710FM, 710FL, 610FM, 601AD, 601ADH2, 602A, 215M, 245F, 251, 212M, 250, 209F, 222F, 208G, 710LA, 710FS, 730LM, 650AC, and 681 (manufactured by NEOS Co., Ltd. hereinafter), etc. In addition, as the fluorosurfactant, an acrylic compound having a molecular structure with a functional group containing a fluorine atom and in which the portion of the functional group containing the fluorine atom is cleaved and the fluorine atom volatilizes when heated can also be preferably used. Examples of such fluorosurfactants include the Megafac DS series manufactured by DIC Corporation (Chemical Industry Daily (February 22, 2016), Nikkei Industrial Newspaper (February 23, 2016)), for example, Megafac DS-21. In addition, as the fluorosurfactant, it is also preferable to use a polymer of a fluorine atom-containing vinyl ether compound having a fluorinated alkyl group or a fluorinated alkylene ether group and a hydrophilic vinyl ether compound. In addition, block polymers can also be used as the fluorosurfactant. In addition, as the fluorosurfactant, a fluorine-containing polymer compound containing 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 an ethyleneoxy group or a propyleneoxy group) can also be preferably used. In addition, as the fluorosurfactant, a fluorine-containing polymer having an ethylenically unsaturated bond-containing group in the side chain can also be used. Examples include Megafac RS-101, RS-102, RS-718K, RS-72-K (manufactured by DIC Corporation). As the fluorosurfactant, from the viewpoint of improving environmental suitability, it is preferably a surfactant derived from a substitute material for compounds having a perfluoroalkyl group with 7 or more carbon atoms such as perfluorooctanoic acid (PFOA) and perfluorooctanesulfonic acid (PFOS). Examples of the nonionic surfactant include glycerol, trimethylolpropane, trimethylolethane, and their ethoxylates and propoxylates (e.g., glycerol propoxylate, glycerol ethoxylate, etc.), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester, Pluronic (registered trademark) L10, L31, L61, L62, 10R5, 17R2, 25R2 (manufactured by BASF), Tetronic 304, 701, 704, 901, 904, 150R1 (manufactured by BASF), Solsperse 20000 (manufactured by Lubrizol Japan), NCW-101, NCW-1001, NCW-1002 (manufactured by Fujifilm Wako Pure Chemical Corporation), Pyonin D-6112, D-6112-W, D-6315 (manufactured by Takemoto Yushi), Orfin E1010, Surfynol 104, 400, and 440 (manufactured by Nissin Chemical Industry Co., Ltd.).

[0071] Examples of silicone surfactants include linear polymers composed of siloxane bonds and modified siloxane polymers with organic groups introduced into the side chains or terminals.

[0072] Specific examples of the surfactant 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, Toray Silicone SH8400 (all manufactured by Toray Dow Corning), as well as 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 Silicone Co., Ltd.), F-4440, TSF-4300, TSF-4445, TSF-4460, TSF-4452 (all manufactured by Momentive Performance Materials), and BYK307, BYK323, BYK330 (all manufactured by BYK Chemie).

[0073] The surfactant may be used alone or in combination of two or more. In the first photosensitive composition layer, the content of the surfactant is preferably 0.01 to 3.0% by mass, more preferably 0.01 to 1.0% by mass, and still more preferably 0.05 to 0.80% by mass, based on the total mass of the first photosensitive composition layer.

[0074] (Second photosensitive composition layer) The photosensitive composition layer has a second photosensitive composition layer. The average film thickness of the second photosensitive composition layer is more than 30 μm, preferably more than 30 μm and 300 μm or less, more preferably 40 to 300 μm, still more preferably 40 to 100 μm, and particularly preferably 40 to 90 μm. When the average film thickness of the second photosensitive composition layer is less than 30 μm, when the surface of the second photosensitive composition layer of the transfer film is transferred to the surface on the conductive pattern side of the transfer member having the conductive pattern, bubbles are likely to be generated between the transfer member and the second photosensitive composition layer, and the laminating property is poor. Further, in the subsequent process after the development process, a failure may occur in which the photosensitive material at the bubble portion falls off. When the average film thickness of the second photosensitive composition layer is 300 μm or less, since the development time can be adjusted within an appropriate range, it is easy to suppress the peeling and dissolution due to overdevelopment of the first photosensitive composition layer, and it is preferable in that an increase in local reflectance can be suppressed.

[0075] The refractive index of the second photosensitive composition layer is not particularly limited as long as it is larger than the refractive index of the first photosensitive composition layer, but it is preferably more than 1.45, more preferably 1.47 to 1.56, and still more preferably 1.49 to 1.54.

[0076] The complex viscosity A of the second photosensitive composition layer at 90 °C is preferably 1.0×10 3 Pa·s or less, more preferably 7.0×10 2 Pa·s or less, and still more preferably 5.0×10 2 Pa·s or less. The lower limit is preferably 1.0×10 2 Pa·s or more. When the complex viscosity A is 1.0×10 3 Pa·s or less, when the transfer film is transferred, the adhesion between the second photosensitive composition layer and the transfer member is improved, and the temporary support after exposure can be peeled off from the temporary support without the photosensitive composition layer remaining, so it is preferable from the point of suppressing the occurrence of unexpected defects. The complex viscosity B of the second photosensitive composition layer at 25 °C is preferably 1.0×10 6 Pa·s or more, more preferably 2.0×10 6 Pa·s or more, and still more preferably 3.0×10 6 Pa·s or more. The upper limit is preferably 1.0×10 7 Pa·s or less. When the complex viscosity B is 1.0×10 6When it is above Pa·s, it is possible to prevent or reduce the peeling of the pattern (cured film) of the photosensitive composition layer (especially the second photosensitive composition layer) that forms a pattern in the development process. In addition, the ratio of the complex viscosity B at 25°C of the second photosensitive composition layer to the complex viscosity A at 90°C of the second photosensitive composition layer (complex viscosity B / complex viscosity A) is 2.0×10 3 or more, preferably 4.0×10 3 or more. The upper limit is preferably 1.0×10 4 or less. The complex viscosity A and the complex viscosity B are measured under the following conditions using a rheometer (for example, Rheometer MCR302 manufactured by Anton Paar) and a disposable parallel plate of 12 mmφ (Gap: about 0.7 mm). (1) Temperature: 20 to 100°C (2) Heating rate: 3°C / min (3) Frequency: 1 Hz (4) Strain: 0.02%

[0077] The second photosensitive composition layer is preferably achromatic. Specifically, for total reflection (incident angle 8°, light source: D-65 (2° field of view)), in the CIE1976 (L*, a*, b*) color space, the L * value is preferably 10 to 90, the a * value is preferably -1.0 to 1.0, and the b * value is preferably -1.0 to 1.0. Note that the pattern (cured film of the second photosensitive composition layer) obtained by curing the second photosensitive composition layer is preferably achromatic. Specifically, for total reflection (incident angle 8°, light source: D-65 (2° field of view)), in the CIE1976 (L*, a*, b*) color space, the L * value of the pattern is preferably 10 to 90, the a * value of the pattern is preferably -1.0 to 1.0, and the b * value of the pattern is preferably -1.0 to 1.0.

[0078] The moisture permeability of the pattern (cured film of the second photosensitive composition layer) obtained by curing the second photosensitive composition layer at a film thickness of 40 μm is preferably 500 g / m 2 / 24 hr or less, more preferably 300 g / m 2 / 24 hr or less, and even more preferably 100 g / m 2 / 24 hr or less from the viewpoint of rust prevention. The moisture permeability is measured on the cured film obtained by curing the second photosensitive composition layer by performing post-baking at 145°C for 30 minutes after exposing the second photosensitive composition layer to an exposure dose of 300 mJ / cm 2 with i-line.

[0079] The second photosensitive composition layer preferably contains at least a binder polymer, a polymerizable compound, and a polymerization initiator. As a suitable example of the content of each component in the second photosensitive composition layer, for example, with respect to the total mass of the second photosensitive composition layer, the binder polymer is 30.0 to 80.0% by mass, the polymerizable compound is 15.0 to 70.0% by mass, and the polymerization initiator is 0.01 to 10.0% by mass. The second photosensitive composition layer preferably contains a thermally crosslinkable compound or an ethylenically unsaturated compound having two or more functional groups having an aromatic ring, more preferably contains an ethylenically unsaturated compound having two or more functional groups not having an aromatic ring and contains a thermally crosslinkable compound or an ethylenically unsaturated compound having two or more functional groups having an aromatic ring. Hereinafter, the components that the second photosensitive composition layer may contain will be described in detail.

[0080] - Binder polymer - The photosensitive composition layer may contain a binder polymer. Examples of the binder polymer include (meth)acrylic resins, styrene resins, epoxy resins, amide resins, amide epoxy resins, alkyd resins, phenol resins, ester resins, urethane resins, epoxy acrylate resins obtained by the reaction of epoxy resins and (meth)acrylic acid, and acid-modified epoxy acrylate resins obtained by the reaction of epoxy acrylate resins and acid anhydrides.

[0081] As one of the preferred embodiments of the binder polymer, a (meth)acrylic resin can be mentioned because of its excellent alkali developability and film-forming properties. As described above, the (meth)acrylic resin is a resin having a structural unit derived from a (meth)acrylic compound.

[0082] Examples of the (meth)acrylic compound include (meth)acrylic acid, (meth)acrylic acid ester, (meth)acrylamide, and (meth)acrylonitrile. Examples of the (meth)acrylic acid ester include (meth)acrylic acid alkyl ester, (meth)acrylic acid tetrahydrofurfuryl ester, (meth)acrylic acid dimethylaminoethyl ester, (meth)acrylic acid diethylaminoethyl ester, (meth)acrylic acid glycidyl ester, (meth)acrylic acid benzyl ester, 2,2,2-trifluoroethyl (meth)acrylate, and 2,2,3,3-tetrafluoropropyl (meth)acrylate, and (meth)acrylic acid alkyl ester is preferred. Examples of the (meth)acrylamide include acrylamides such as diacetoneacrylamide.

[0083] The alkyl group of the (meth)acrylic acid alkyl ester may be either linear or branched. Specific examples include (meth)acrylic acid alkyl esters having an alkyl group with 1 to 12 carbon atoms such as methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate, octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, nonyl (meth)acrylate, decyl (meth)acrylate, undecyl (meth)acrylate, and dodecyl (meth)acrylate. As the (meth)acrylic acid ester, (meth)acrylic acid alkyl esters having an alkyl group with 1 to 4 carbon atoms are preferred, and methyl (meth)acrylate or ethyl (meth)acrylate is more preferred.

[0084] (Meth)acrylic resins may have structural units other than the structural units derived from (meth)acrylic compounds. The polymerizable monomer that forms the above structural unit is not particularly limited as long as it is a compound other than (meth)acrylic compounds copolymerizable with (meth)acrylic compounds. For example, styrene, vinyltoluene, and α-methylstyrene may have substituents at the α-position or on the aromatic ring. Styrene compounds, vinyl alcohol esters such as acrylonitrile and vinyl-n-butyl ether, maleic acid, maleic anhydride, maleic acid monomethyl, maleic acid monoethyl, and maleic acid monoisopropyl, maleic acid monoester, fumaric acid, cinnamic acid, α-cyanocinnamic acid, itaconic acid, and crotonic acid are mentioned.

[0085] In addition, from the viewpoint of improving the alkali developability, it is preferable for the (meth)acrylic resin to have a structural unit having an acid group. Examples of the acid group include a carboxy group, a sulfo group, a phosphoric acid group, and a phosphonic acid group. Among them, it is more preferable for the (meth)acrylic resin to have a structural unit having a carboxy group, and it is still more preferable to have a structural unit derived from the above (meth)acrylic acid.

[0086] The content of the structural unit having an acid group (preferably the structural unit derived from (meth)acrylic acid) in the (meth)acrylic resin is preferably 10% by mass or more based on the total mass of the (meth)acrylic resin from the viewpoint of excellent developability. Also, the upper limit value is preferably 50% by mass or less, more preferably 40% by mass or less, from the viewpoint of excellent alkali resistance.

[0087] In addition, it is more preferable for the (meth)acrylic resin to have a structural unit derived from the above-mentioned (meth)acrylic acid alkyl ester. The content of the structural unit derived from the (meth)acrylic acid alkyl ester in the (meth)acrylic resin is preferably 50 to 90% by mass, more preferably 60 to 90% by mass, and still more preferably 65 to 90% by mass with respect to all the structural units of the (meth)acrylic resin.

[0088] As the (meth)acrylic resin, a resin having both a structural unit derived from (meth)acrylic acid and a structural unit derived from (meth)acrylic acid alkyl ester is preferable, and a resin composed only of a structural unit derived from (meth)acrylic acid and a structural unit derived from (meth)acrylic acid alkyl ester is more preferable. Further, as the (meth)acrylic resin, an acrylic resin having a structural unit derived from methacrylic acid, a structural unit derived from methyl methacrylate, and a structural unit derived from ethyl acrylate is also preferable.

[0089] Further, the (meth)acrylic resin preferably has at least one selected from the group consisting of a structural unit derived from methacrylic acid and a structural unit derived from methacrylic acid alkyl ester, and preferably has both a structural unit derived from methacrylic acid and a structural unit derived from methacrylic acid alkyl ester. The total content of the structural unit derived from methacrylic acid and the structural unit derived from methacrylic acid alkyl ester in the (meth)acrylic resin is preferably 40% by mass or more, more preferably 60% by mass or more with respect to all the structural units of the (meth)acrylic resin. The upper limit is not particularly limited and may be 100% by mass or less, preferably 80% by mass or less.

[0090] Further, the (meth)acrylic resin preferably has at least one selected from the group consisting of a structural unit derived from methacrylic acid and a structural unit derived from methacrylic acid alkyl ester, and at least one selected from the group consisting of a structural unit derived from acrylic acid and a structural unit derived from acrylic acid alkyl ester. The total content of the structural units derived from methacrylic acid and the structural units derived from alkyl methacrylate is preferably 60 / 40 to 80 / 20 in terms of mass ratio with respect to the total content of the structural units derived from acrylic acid and the structural units derived from alkyl acrylate.

[0091] (Meth)acrylic resin preferably has an ester group at the terminal from the viewpoint of excellent developability of the photosensitive composition layer after transfer. Note that the terminal part of the (meth)acrylic resin is composed of a site derived from the polymerization initiator used in the synthesis. The (meth)acrylic resin having an ester group at the terminal can be synthesized by using a polymerization initiator that generates a radical having an ester group.

[0092] Another preferred embodiment of the binder polymer includes an alkali-soluble resin. The binder polymer is preferably a binder polymer having an acid value of 60 mgKOH / g or more from the viewpoint of developability, for example. Further, the binder polymer is more preferably a resin having a carboxyl group with an acid value of 60 mgKOH / g or more (so-called carboxyl group-containing resin) from the viewpoint of easily forming a strong film by thermally crosslinking with a crosslinking component by heating, for example, and still more preferably a (meth)acrylic resin having a carboxyl group with an acid value of 60 mgKOH / g or more (so-called carboxyl group-containing (meth)acrylic resin). When the binder polymer is a resin having a carboxyl group, for example, the three-dimensional crosslinking density can be increased by adding a thermally crosslinkable compound such as a blocked isocyanate compound and performing thermal crosslinking. Further, when the carboxyl group of the resin having a carboxyl group is anhydrified and hydrophobized, the wet heat resistance can be improved.

[0093] The carboxyl group-containing (meth)acrylic resin having an acid value of 60 mgKOH / g or more is not particularly limited as long as it satisfies the above acid value conditions, and can be appropriately selected from known (meth)acrylic resins. For example, among the polymers described in paragraph

[0025] of JP-A-2011-095716, carboxy group-containing acrylic resins having an acid value of 60 mgKOH / g or more, and among the polymers described in paragraphs

[0033] to

[0052] of JP-A-2010-237589, carboxy group-containing acrylic resins having an acid value of 60 mgKOH / g or more can be preferably used.

[0094] Another preferred embodiment of the binder polymer includes styrene-acrylic copolymers. In the present specification, the styrene-acrylic copolymer refers to a resin having a structural unit derived from a styrene compound and a structural unit derived from a (meth)acrylic compound. The total content of the structural unit derived from the styrene compound and the structural unit derived from the (meth)acrylic compound is preferably 30% by mass or more, more preferably 50% by mass or more, based on all the structural units of the copolymer. The upper limit is often 100% by mass or less. Also, the content of the structural unit derived from the styrene compound is preferably 1% by mass or more, more preferably 5% by mass or more, and still more preferably 5 to 80% by mass, based on all the structural units of the copolymer. Also, the content of the structural unit derived from the (meth)acrylic compound is preferably 5% by mass or more, more preferably 10% by mass or more, and still more preferably 20 to 95% by mass, based on all the structural units of the copolymer.

[0095] The binder polymer preferably has an aromatic ring structure, and more preferably has a structural unit having an aromatic ring structure. Examples of the monomer that forms a structural unit having an aromatic ring structure include monomers having an aralkyl group, styrene, and polymerizable styrene derivatives (for example, methylstyrene, vinyltoluene, tert-butoxystyrene, acetoxystyrene, 4-vinylbenzoic acid, styrene dimer, and styrene trimer, etc.). Among them, monomers having an aralkyl group or styrene are preferred. Examples of the aralkyl group include a substituted or unsubstituted phenylalkyl group (excluding benzyl group), a substituted or unsubstituted benzyl group, etc., and a substituted or unsubstituted benzyl group is preferred.

[0096] Examples of the monomer having a phenylalkyl group include phenylethyl (meth) acrylate.

[0097] Examples of the monomer having a benzyl group include (meth) acrylate having a benzyl group, such as benzyl (meth) acrylate and chlorobenzyl (meth) acrylate; vinyl monomers having a benzyl group, such as vinyl benzyl chloride and vinyl benzyl alcohol. Among them, benzyl (meth) acrylate is preferred.

[0098] Further, the binder polymer more preferably has a structural unit (structural unit derived from styrene) represented by the following formula (S).

[0099]

Chemical formula

[0100] When the binder polymer has a structural unit having an aromatic ring structure, the content of the structural unit having an aromatic ring structure is preferably 5 to 90% by mass, more preferably 10 to 70% by mass, and still more preferably 20 to 60% by mass based on all the structural units of the binder polymer.

[0101] The binder polymer preferably has an aliphatic hydrocarbon ring structure. That is, the binder polymer preferably has a structural unit having an aliphatic hydrocarbon ring structure. The aliphatic hydrocarbon ring structure may be a monocyclic or polycyclic ring. Among them, the binder polymer more preferably has a ring structure in which two or more aliphatic hydrocarbon rings are fused.

[0102] Examples of the ring constituting the aliphatic hydrocarbon ring structure in the structural unit having an aliphatic hydrocarbon ring structure include a tricyclodecane ring, a cyclohexane ring, a cyclopentane ring, a norbornane ring, and an isobornyl ring. Among them, a ring in which two or more aliphatic hydrocarbon rings are fused is preferable, and a tetrahydrodicyclopentadiene ring (tricyclo[5.2.1.0 2,6 decane ring) is more preferable. Examples of the monomer that forms the structural unit having an aliphatic hydrocarbon ring structure include dicyclopentanyl (meth)acrylate, cyclohexyl (meth)acrylate, and isobornyl (meth)acrylate.

[0103] The binder polymer may have one kind or two or more kinds of structural units having an aliphatic hydrocarbon ring structure. When the binder polymer has a structural unit having an aliphatic hydrocarbon ring structure, the content of the structural unit having an aliphatic hydrocarbon ring structure is preferably 5 to 90% by mass, more preferably 10 to 80% by mass, and still more preferably 20 to 70% by mass with respect to all the structural units of the binder polymer.

[0104] When the binder polymer has a structural unit having an aromatic ring structure and a structural unit having an aliphatic hydrocarbon ring structure, the total content of the structural unit having an aromatic ring structure and the structural unit having an aliphatic hydrocarbon ring structure is preferably 10 to 90% by mass, more preferably 20 to 80% by mass, and still more preferably 40 to 75% by mass with respect to all the structural units of the binder polymer.

[0105] The binder polymer preferably has a structural unit having an acid group. Examples of the acid group include a carboxy group, a sulfo group, a phosphonic acid group, and a phosphoric acid group, and a carboxy group is preferable. As the structural unit having the acid group, a structural unit derived from (meth)acrylic acid shown below is preferable, and a structural unit derived from methacrylic acid is more preferable.

[0106] [Chemical formula]

[0107] The binder polymer may have one kind or two or more kinds of structural units having an acid group. When the binder polymer has a structural unit having an acid group, the content of the structural unit having an acid group is preferably 5 to 50% by mass, more preferably 5 to 40% by mass, and still more preferably 10 to 30% by mass based on all the structural units of the binder polymer.

[0108] The binder polymer preferably has a reactive group, and more preferably has a structural unit having a reactive group. As the reactive group, a radically polymerizable group is preferable, and an ethylenically unsaturated group is more preferable. When the binder polymer has an ethylenically unsaturated group, the binder polymer preferably has a structural unit having an ethylenically unsaturated group in the side chain. In the present specification, the "main chain" represents the relatively longest bond chain in the molecule of the high molecular compound constituting the resin, and the "side chain" represents an atomic group branched from the main chain. As the ethylenically unsaturated group, an allyl group or a (meth)acryloxy group is more preferable. Examples of the structural unit having a reactive group include, but are not limited to, those shown below.

[0109] [Chemical formula]

[0110] The binder polymer may be used alone or in combination of two or more kinds of structural units having a reactive group. When the binder polymer has a structural unit having a reactive group, the content of the structural unit having a reactive group is preferably 5 to 70% by mass, more preferably 10 to 50% by mass, and still more preferably 20 to 40% by mass based on all the structural units of the binder polymer.

[0111] As a means for introducing a reactive group into a binder polymer, methods include reacting a functional group such as a hydroxy group, a carboxy group, a primary amino group, a secondary amino group, an acetoacetyl group, and a sulfo group with a compound such as an epoxy compound, a blocked isocyanate compound, an isocyanate compound, a vinyl sulfone compound, an aldehyde compound, a methylol compound, and a carboxylic anhydride. Preferable examples of the means for introducing a reactive group into a binder polymer include synthesizing a polymer having a carboxy group by a polymerization reaction and then reacting glycidyl (meth)acrylate with a part of the carboxy groups of the obtained polymer by a polymer reaction to introduce a (meth)acryloxy group into the polymer. By this means, a binder polymer having a (meth)acryloxy group in the side chain can be obtained. The above polymerization reaction is preferably carried out under temperature conditions of 70 to 100 °C, more preferably under temperature conditions of 80 to 90 °C. As the polymerization initiator used in the above polymerization reaction, an azo-based initiator is preferable, and for example, V-601 (trade name) or V-65 (trade name) manufactured by Fuji Film Wako Pure Chemical Corporation is more preferable. The above polymer reaction is preferably carried out under temperature conditions of 80 to 110 °C. In the above polymer reaction, it is preferable to use a catalyst such as an ammonium salt.

[0112] As the binder polymer, the following polymers X1 to X4 are preferable. The content ratios (a to d) of each constitutional unit shown below, the weight average molecular weight Mw, etc. can be appropriately changed according to the purpose, but among them, the following constitution is preferable. (Polymer X1) a: 20 to 60% by mass, b: 10 to 50% by mass, c: 5.0 to 25% by mass, d: 10 to 50% by mass. (Polymer X2) a: 20 to 60% by mass, b: 10 to 50% by mass, c: 5.0 to 25% by mass, d: 10 to 50% by mass. (Polymer X3) a: 30 to 65% by mass, b: 1.0 to 20% by mass, c: 5.0 to 30% by mass, d: 10 to 50% by mass. (Polymer X4) a: 1.0 to 20% by mass, b: 20 to 60% by mass, c: 5.0 to 230% by mass, d: 10 to 50% by mass.

[0113]

Chem.

[0114] Further, the binder polymer may contain a polymer having a structural unit having a carboxylic anhydride structure (hereinafter, also referred to as "polymer X"). The carboxylic anhydride structure may be either a chain carboxylic anhydride structure or a cyclic carboxylic anhydride structure, but a cyclic carboxylic anhydride structure is preferred. As the ring of the cyclic carboxylic anhydride structure, a 5- to 7-membered ring is preferred, a 5- or 6-membered ring is more preferred, and a 5-membered ring is even more preferred.

[0115] As the structural unit having a carboxylic anhydride structure, a structural unit derived from an unsaturated carboxylic anhydride is preferred, a structural unit derived from an unsaturated cyclic carboxylic anhydride is more preferred, a structural unit derived from an unsaturated aliphatic cyclic carboxylic anhydride is even more preferred, a structural unit derived from maleic anhydride or itaconic anhydride is particularly preferred, and a structural unit derived from maleic anhydride is most preferred.

[0116] Hereinafter, specific examples of the structural unit having a carboxylic anhydride structure will be given, but the structural unit having a carboxylic anhydride structure is not limited to these specific examples. In the following structural units, Rx represents a hydrogen atom, a methyl group, a CH2OH group, or a CF3 group, and Me represents a methyl group.

[0117]

Chem.

[0118] [Chemical formula]

[0119] The structural unit having a carboxylic anhydride structure in polymer X may be used alone or in combination of two or more.

[0120] The total content of the structural unit having a carboxylic anhydride structure is preferably 0 to 60 mol%, more preferably 5 to 40 mol%, still more preferably 10 to 35 mol% based on all the structural units of polymer X.

[0121] Polymer X may be used alone or in combination of two or more. The content of polymer X is preferably 0.1 to 30% by mass, more preferably 0.2 to 20% by mass, still more preferably 0.5 to 20% by mass, and still more preferably 1 to 20% by mass based on the total mass of the second photosensitive composition layer.

[0122] The weight average molecular weight (Mw) of the binder polymer is preferably 5,000 or more, more preferably 10,000 or more, still more preferably 10,000 to 50,000, and particularly preferably 20,000 to 30,000.

[0123] The acid value of the binder polymer is preferably 10 to 200 mgKOH / g, more preferably 60 mg to 200 mgKOH / g, still more preferably 60 to 150 mgKOH / g, and particularly preferably 70 to 125 mgKOH / g. Note that the acid value of the binder polymer is a value measured according to the method described in JIS K0070:1992. From the viewpoint of developability, the dispersity of the binder polymer is preferably 1.0 to 6.0, more preferably 1.0 to 5.0, still more preferably 1.0 to 4.0, and particularly preferably 1.0 to 3.0.

[0124] The binder polymer may be used alone or in combination of two or more. The content of the binder polymer is preferably 10.0 to 90.0% by mass, more preferably 20.0 to 80.0% by mass, still more preferably 30.0 to 80.0% by mass, and particularly preferably 30.0 to 70.0% by mass with respect to the total mass of the second photosensitive composition layer.

[0125] -Polymerizable compound- The photosensitive composition layer may contain a polymerizable compound. Examples of the polymerizable compound include the polymerizable compounds that the above-described first photosensitive composition layer may contain. The polymerizable compound that the second photosensitive composition layer may contain is a compound other than the above binder polymer, and preferably has a molecular weight of less than 5,000.

[0126] As one of the preferred embodiments of the polymerizable compound, a compound represented by the following formula (M) (simply referred to as "compound M") can be mentioned. Q 2 -R 1 -Q 1 Formula (M) In formula (M), Q 1 and Q 2 each independently represents a (meth)acryloyloxy group, and R 1 represents a divalent linking group having a chain structure.

[0127] Q in formula (M) 1 and Q 2 are preferably the same group from the viewpoint of ease of synthesis. 1 and Q 2 are preferably the same group. Also, Q in formula (M) 1 and Q 2 are preferably acryloyloxy groups from the viewpoint of reactivity. R in formula (M) 1 is, for example, an alkylene group, an alkyleneoxyalkylene group (-L 1 -O-L 1 -), or a polyalkyleneoxyalkylene group (-(L 1 -O) p -L 1-) is preferred, a hydrocarbon group having 2 to 20 carbon atoms, or a polyalkyleneoxyalkylene group is more preferred, an alkylene group having 4 to 20 carbon atoms is still more preferred, and a linear alkylene group having 6 to 18 carbon atoms is particularly preferred. The above hydrocarbon group only needs to have a chain structure in at least a part thereof, and there is no particular limitation on the part other than the chain structure. For example, it may be any of a branched chain, a cyclic, or a linear alkylene group having 1 to 5 carbon atoms, an arylene group, an ether bond, and combinations thereof. A group combining an alkylene group or two or more alkylene groups and one or more arylene groups is preferred, an alkylene group is more preferred, and a linear alkylene group is still more preferred. In addition, the above L 1 each independently represents an alkylene group, and an ethylene group, a propylene group, or a butylene group is preferred, and an ethylene group or a 1,2-propylene group is more preferred. p represents an integer of 2 or more, and is preferably an integer of 2 to 10.

[0128] In addition, the shortest number of atoms in the connecting chain connecting Q 1 and Q 2 in compound M is preferably 3 to 50, more preferably 4 to 40, still more preferably 6 to 20, and particularly preferably 8 to 12. In this specification, the "shortest number of atoms in the connecting chain connecting Q 1 and Q 2 " means the shortest number of atoms connecting from the atom in R 1 connected to Q 1 to the atom in R 2 connected to Q 1 .

[0129] One of the preferred embodiments of the polymerizable compound includes the following compound M. Examples of compound M include 1,3 - butanediol di(meth)acrylate, tetramethylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,6 - hexanediol di(meth)acrylate, 1,7 - heptanediol di(meth)acrylate, 1,8 - octanediol di(meth)acrylate, 1,9 - nonanediol di(meth)acrylate, 1,10 - decanediol di(meth)acrylate, di(meth)acrylate of hydrogenated bisphenol A, di(meth)acrylate of hydrogenated bisphenol F, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, poly(ethylene glycol / propylene glycol) di(meth)acrylate, and polybutylene glycol di(meth)acrylate. The above ester monomers can also be used as a mixture. Among them, compound M is preferably at least one compound selected from the group consisting of 1,6 - hexanediol di(meth)acrylate, 1,9 - nonanediol di(meth)acrylate, 1,10 - decanediol di(meth)acrylate, and neopentyl glycol di(meth)acrylate.

[0130] One of the preferred embodiments of the polymerizable compound includes ethylenically unsaturated compounds having two or more functional groups. As the ethylenically unsaturated group in the ethylenically unsaturated compound, the (meth)acryloyl group is preferred. As the ethylenically unsaturated compound having two or more functional groups, a (meth)acrylate compound having two or more functional groups is preferred.

[0131] Examples of the difunctional ethylenically unsaturated compound other than the above compound M include tricyclodecane dimethanol di(meth)acrylate and 1,4 - cyclohexanediol di(meth)acrylate. Examples of commercially available difunctional ethylenically unsaturated compounds include tricyclodecane dimethanol diacrylate (NK Ester A-DCP, manufactured by Shin-Nakamura Chemical Co., Ltd.), tricyclodecane dimethanol dimethacrylate (NK Ester DCP, manufactured by Shin-Nakamura Chemical Co., Ltd.), 1,9-nonanediol diacrylate (NK Ester A-NOD-N, manufactured by Shin-Nakamura Chemical Co., Ltd.), 1,6-hexanediol diacrylate (NK Ester A-HD-N, manufactured by Shin-Nakamura Chemical Co., Ltd.), and ethoxylated bisphenol A diacrylate (A-BPE-4, manufactured by Shin-Nakamura Chemical Co., Ltd.).

[0132] Examples of ethylenically unsaturated compounds having three or more functional groups include, for example, the ethylenically unsaturated compounds having three or more functional groups in the above-described first photosensitive composition layer.

[0133] One preferred embodiment of the polymerizable compound also includes a urethane (meth)acrylate compound. Examples of urethane (meth)acrylate include urethane di(meth)acrylate, such as propylene oxide-modified urethane di(meth)acrylate, and ethylene oxide and propylene oxide-modified urethane di(meth)acrylate. Examples of urethane (meth)acrylate include, for example, 8UX-015A (manufactured by Taisei Fine Chemical Co., Ltd.), UA-32P (manufactured by Shin-Nakamura Chemical Co., Ltd.), U-15HA (manufactured by Shin-Nakamura Chemical Co., Ltd.), UA-1100H (manufactured by Shin-Nakamura Chemical Co., Ltd.), AH-600 (trade name) manufactured by Kyoeisha Chemical Co., Ltd., and UA-306H, UA-306T, UA-306I, UA-510H, and UX-5000 (all manufactured by Nippon Kayaku Co., Ltd.).

[0134] Examples of the overlapping compound include compounds obtained by reacting a polyhydric alcohol with an α,β-unsaturated carboxylic acid, compounds obtained by reacting a glycidyl group-containing compound with an α,β-unsaturated carboxylic acid, urethane monomers such as (meth)acrylate compounds having a urethane bond, γ-chloro-β-hydroxypropyl-β'-(meth)acryloyloxyethyl-o-phthalate, β-hydroxyethyl-β'-(meth)acryloyloxyethyl-o-phthalate, and phthalic acid-based compounds such as β-hydroxypropyl-β'-(meth)acryloyloxyethyl-o-phthalate, and (meth)acrylic acid alkyl esters. These may be used alone or in combination of two or more.

[0135] Examples of the compound obtained by reacting a polyhydric alcohol with an α,β-unsaturated carboxylic acid include bisphenol A-based (meth)acrylate compounds such as 2,2-bis(4-((meth)acryloxypolyethoxy)phenyl)propane, 2,2-bis(4-((meth)acryloxypolypropoxy)phenyl)propane, and 2,2-bis(4-((meth)acryloxypolyethoxypolypropoxy)phenyl)propane; polyethylene glycol di(meth)acrylate having 2 to 14 ethylene oxide groups; polypropylene glycol di(meth)acrylate having 2 to 14 propylene oxide groups; polyethylene polypropylene glycol di(meth)acrylate having 2 to 14 ethylene oxide groups and 2 to 14 propylene oxide groups; trimethylolpropane di(meth)acrylate, trimethylolpropane tri(meth)acrylate, trimethylolpropane ethoxytri(meth)acrylate, trimethylolpropane diethoxytri(meth)acrylate, trimethylolpropane triethoxytri(meth)acrylate, trimethylolpropane tetraethoxytri(meth)acrylate, trimethylolpropane pentaethoxytri(meth)acrylate, di(trimethylolpropane) tetraacrylate, tetramethylolmethane tri(meth)acrylate, tetramethylolmethane tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, and dipentaerythritol hexa(meth)acrylate. Among them, an ethylenically unsaturated compound having a tetramethylolmethane structure or a trimethylolpropane structure is preferable, and tetramethylolmethane tri(meth)acrylate, tetramethylolmethane tetra(meth)acrylate, trimethylolpropane tri(meth)acrylate, or di(trimethylolpropane) tetraacrylate is more preferable.

[0136] Examples of the polymerizable compound include caprolactone-modified compounds of ethylenically unsaturated compounds (e.g., KAYARAD (registered trademark) DPCA-20 manufactured by Nippon Kayaku Co., Ltd., A-9300-1CL manufactured by Shin-Nakamura Chemical Co., Ltd., etc.), alkylene oxide-modified compounds of ethylenically unsaturated compounds (e.g., KAYARAD RP-1040 manufactured by Nippon Kayaku Co., Ltd., ATM-35E, A-9300 manufactured by Shin-Nakamura Chemical Co., Ltd., EBECRYL (registered trademark) 135 manufactured by Daicel Ornex Co., Ltd., etc.), and ethoxylated glycerol triacrylate (A-GLY-9E manufactured by Shin-Nakamura Chemical Co., Ltd., etc.). Examples of the polymerizable compound also include bisacrylic acid (2,2-dimethylethylene) (5-ethyl-1,3-dioxane-2,5-diyl)methylene (KAYARAD R-604 manufactured by Nippon Kayaku Co., Ltd.).

[0137] As the polymerizable compound (particularly, an ethylenically unsaturated compound), those containing an ester bond are particularly preferable in terms of excellent developability of the photosensitive composition layer after transfer. The ethylenically unsaturated compound containing an ester bond is not particularly limited as long as it contains an ester bond in the molecule, but an ethylenically unsaturated compound having a tetramethylolmethane structure or a trimethylolpropane structure is preferable in terms of excellent effects of the present invention, and tetramethylolmethane tri(meth)acrylate, tetramethylolmethane tetra(meth)acrylate, trimethylolpropane tri(meth)acrylate, or di(trimethylolpropane) tetraacrylate is more preferable. From the viewpoint of imparting reliability, the ethylenically unsaturated compound preferably includes an ethylenically unsaturated compound having an aliphatic group with 6 to 20 carbon atoms and an ethylenically unsaturated compound having the above tetramethylolmethane structure or trimethylolpropane structure. Examples of the ethylenically unsaturated compound having an aliphatic structure with 6 or more carbon atoms include 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, and tricyclodecane dimethanol di(meth)acrylate.

[0138] As one of the preferred embodiments of the polymerizable compound, a polymerizable compound having an aliphatic hydrocarbon ring structure (preferably a bifunctional ethylenically unsaturated compound) can be mentioned. As the above polymerizable compound, a polymerizable compound having a ring structure in which two or more aliphatic hydrocarbon rings are fused (preferably a structure selected from the group consisting of a tricyclodecane structure and a tricyclodecene structure) is preferable, a bifunctional ethylenically unsaturated compound having a ring structure in which two or more aliphatic hydrocarbon rings are fused is more preferable, and tricyclodecane dimethanol di(meth)acrylate is even more preferable. As the above aliphatic hydrocarbon ring structure, a cyclopentane structure, a cyclohexane structure, a tricyclodecane structure, a tricyclodecene structure, a norbornane structure, or an isophorone structure is preferable.

[0139] As one of the preferred embodiments of the polymerizable compound, it may include a bifunctional or higher-functional ethylenically unsaturated compound having no aromatic ring and a bifunctional or higher-functional ethylenically unsaturated compound having an aromatic ring. In the case of the above preferred embodiment, it can be excellent in the balance between the hardness and flexibility of the cured film derived from the second photosensitive composition layer. Further, as the bifunctional or higher-functional ethylenically unsaturated compound having no aromatic ring, it can be appropriately selected from the above-mentioned polymerizable compounds (preferably compound M).

[0140] The molecular weight of the polymerizable compound is often less than 5,000, preferably 200 to 3,000, more preferably 250 to 2,600, even more preferably 280 to 2,200, and particularly preferably 300 to 2,200.

[0141] As one of the preferred embodiments of the second photosensitive composition layer, the second photosensitive composition layer preferably contains a bifunctional or higher-functional ethylenically unsaturated compound, more preferably contains a trifunctional or higher-functional ethylenically unsaturated compound, and even more preferably contains a trifunctional or tetrafunctional ethylenically unsaturated compound. Further, the content of the trifunctional or higher-functional ethylenically unsaturated compound is preferably 1 to 50% by mass, more preferably 22 to 50% by mass, and even more preferably 22 to 40% by mass based on the total mass of the polymerizable compound.

[0142] As one of the preferred embodiments of the second photosensitive composition layer, the second photosensitive composition layer preferably contains a bifunctional ethylenically unsaturated compound having an aliphatic hydrocarbon ring structure and a binder polymer having a structural unit having an aliphatic hydrocarbon ring.

[0143] As one of the preferred embodiments of the second photosensitive composition layer, the second photosensitive composition layer preferably contains Compound M and an ethylenically unsaturated compound having an acid group, and more preferably contains 1,9-nonanediol diacrylate and a polyfunctional ethylenically unsaturated compound having a carboxylic acid group.

[0144] As one of the preferred embodiments of the second photosensitive composition layer, the second photosensitive composition layer preferably contains Compound M, an ethylenically unsaturated compound having an acid group, and a thermally crosslinkable compound described later, and more preferably contains Compound M, an ethylenically unsaturated compound having an acid group, and a melamine compound or a blocked isocyanate compound described later.

[0145] As one of the preferred embodiments of the second photosensitive composition layer, from the viewpoints of development residue suppression and rust prevention, the second photosensitive composition layer preferably contains a bifunctional ethylenically unsaturated compound (preferably a bifunctional (meth)acrylate compound) and a polyfunctional ethylenically unsaturated compound having three or more functional groups (preferably a polyfunctional (meth)acrylate compound having three or more functional groups). The mass ratio of the content of the bifunctional ethylenically unsaturated compound to the content of the polyfunctional ethylenically unsaturated compound having three or more functional groups (mass of the bifunctional ethylenically unsaturated compound / mass of the polyfunctional ethylenically unsaturated compound having three or more functional groups) is preferably 10 / 90 to 90 / 10, and more preferably 30 / 70 to 70 / 30. The content of the bifunctional ethylenically unsaturated compound with respect to the total amount of all ethylenically unsaturated compounds is preferably 20.0% by mass or more, more preferably 30.0% by mass or more, and still more preferably 40.0% by mass or more. The upper limit is not particularly limited, but for example, it is 100% by mass or less, preferably 90.0% by mass or less, and more preferably 80.0% by mass or less. In the second photosensitive composition layer, the content of the bifunctional ethylenically unsaturated compound is preferably 5.0 to 60.0% by mass, more preferably 5.0 to 40.0% by mass, and still more preferably 5.0 to 40.0% by mass.

[0146] As one of the preferred embodiments of the second photosensitive composition layer, from the viewpoint of rust prevention, the second photosensitive composition layer preferably contains Compound M and a bifunctional ethylenically unsaturated compound having an aliphatic hydrocarbon ring structure. As one of the preferred embodiments of the second photosensitive composition layer, from the viewpoints of substrate adhesion, development residue suppression, and rust prevention, the second photosensitive composition layer preferably contains Compound M and an ethylenically unsaturated compound having an acid group, more preferably contains Compound M, a bifunctional ethylenically unsaturated compound having an aliphatic hydrocarbon ring structure, and an ethylenically unsaturated compound having an acid group, and still more preferably contains Compound M, a bifunctional ethylenically unsaturated compound having an aliphatic hydrocarbon ring structure, an ethylenically unsaturated compound having three or more functional groups, and an ethylenically unsaturated compound having an acid group.

[0147] The second photosensitive composition layer may contain a monofunctional ethylenically unsaturated compound as the ethylenically unsaturated compound. The content of the ethylenically unsaturated compound having two or more functional groups is preferably 60 to 100% by mass based on the total content of all the ethylenically unsaturated compounds contained in the second photosensitive composition layer.

[0148] The polymerizable compound (particularly, the ethylenically unsaturated compound) may be used alone or in combination of two or more. In the second photosensitive composition layer, the content of the polymerizable compound (particularly, the ethylenically unsaturated compound) is preferably 15.0 to 70.0% by mass, more preferably 15.0 to 60.0% by mass, and still more preferably 15.0 to 50.0% by mass based on the total mass of the second photosensitive composition layer.

[0149] - Photoinitiator - The second photosensitive composition layer may contain a photoinitiator. As the photoinitiator, a photoinitiator is preferred. Examples of the photopolymerization initiator include known photopolymerization initiators. Specifically, photopolymerization initiators having an oxime ester structure (hereinafter also referred to as "oxime-based photopolymerization initiators"), photopolymerization initiators having an α-aminoalkylphenone structure (hereinafter also referred to as "α-aminoalkylphenone-based photopolymerization initiators"), photopolymerization initiators having an α-hydroxyalkylphenone structure (hereinafter also referred to as "α-hydroxyalkylphenone-based polymerization initiators"), photopolymerization initiators having an acylphosphine oxide structure (hereinafter also referred to as "acylphosphine oxide-based photopolymerization initiators"), and photopolymerization initiators having an N-phenylglycine structure (hereinafter also referred to as "N-phenylglycine-based photopolymerization initiators") can be mentioned.

[0150] The photopolymerization initiator preferably contains at least one selected from the group consisting of an oxime-based photopolymerization initiator, an α-aminoalkylphenone-based photopolymerization initiator, an α-hydroxyalkylphenone-based polymerization initiator, and an N-phenylglycine-based photopolymerization initiator.

[0151] In addition, examples of the photopolymerization initiator include the polymerization initiators described in paragraphs

[0031] to

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

[0064] to

[0081] of JP-A-2015-014783.

[0152] As commercially available photoinitiators, 1-[4-(phenylthio)phenyl]-1,2-octanedione 2-(O-benzoyloxime) [trade name: IRGACURE® OXE-01, manufactured by BASF], 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone 1-(O-acetoxime) [trade name: IRGACURE® OXE-02, manufactured by BASF], IRGACURE® OXE03 (manufactured by BASF), IRGACURE® OXE04 (manufactured by BASF), 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone [trade name: Omnirad® 379EG, manufactured by IGM Resins B.V.], 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one [trade name: Omnirad® 907, manufactured by IGM Resins B.V.], 2-hydroxy-1-{4-[4-(2-hydroxy-2-methylpropionyl)benzyl]phenyl}-2-methylpropan-1-one [trade name: Omnirad® 127, manufactured by IGM Resins B.V.], 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butanone-1 [trade name: Omnirad® 369, manufactured by IGM Resins B.V.], 2-hydroxy-2-methyl-1-phenylpropan-1-one [trade name: Omnirad® 1173, manufactured by IGM Resins B.V.], 1-hydroxycyclohexyl phenyl ketone [trade name: Omnirad® 184, manufactured by IGM Resins B.V.], 2,2-dimethoxy-1,2-diphenylethan-1-one [trade name: Omnirad® 651, manufactured by IGM Resins B.Examples include oxime ester - based products such as those manufactured by Valve (etc.), [trade name: Lunar (registered trademark) 6, manufactured by DKSH Japan], 1 - [4 - (phenylthio)phenyl] - 3 - cyclopentylpropane - 1,2 - dione - 2 - (O - benzoyloxime) (trade name: TR - PBG - 305, manufactured by Changzhou Qiangli Electronic New Materials Co., Ltd.), 1,2 - propanedione, 3 - cyclohexyl - 1 - [9 - ethyl - 6 - (2 - furanylcarbonyl) - 9H - carbazole - 3 - yl] -, 2 - (O - acetyloxime) (trade name: TR - PBG - 326, manufactured by Changzhou Qiangli Electronic New Materials Co., Ltd.), 3 - cyclohexyl - 1 - (6 - (2 - (benzoyloxyimino)hexanoyl) - 9 - ethyl - 9H - carbazole - 3 - yl) - propane - 1,2 - dione - 2 - (O - benzoyloxime) (trade name: TR - PBG - 391, manufactured by Changzhou Qiangli Electronic New Materials Co., Ltd.), APi - 307 (1 - (biphenyl - 4 - yl) - 2 - methyl - 2 - morpholinopropan - 1 - one, manufactured by Shenzhen UV - ChemTech Ltd.), and the like.

[0153] The polymerization initiator may be used alone or in combination of two or more. When using two or more in combination, it is preferable to use an oxime - based photoinitiator and at least one selected from the group consisting of an α - aminoalkylphenone - based photoinitiator and an α - hydroxyalkylphenone - based polymerization initiator. The content of the polymerization initiator is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, and still more preferably 0.5% by mass or more with respect to the total mass of the second photosensitive composition layer. The upper limit is preferably 10.0% by mass or less, more preferably 5.0% by mass or less with respect to the total mass of the second photosensitive composition layer.

[0154] - Heterocyclic compound - The photosensitive composition layer may contain a heterocyclic compound.

[0155] Examples of the heterocyclic ring compound include a triazole compound, a benzotriazole compound, a tetrazole compound, a thiadiazole compound, a triazine compound, a rhodanine compound, a thiazole compound, a benzothiazole compound, a benzimidazole compound, a benzoxazole compound, and a pyrimidine compound. Among them, as the heterocyclic ring compound, at least one compound selected from the group consisting of a triazole compound, a benzotriazole compound, a tetrazole compound, a thiadiazole compound, a triazine compound, a rhodanine compound, a thiazole compound, a benzimidazole compound, and a benzoxazole compound is preferable.

[0156] As the heterocyclic ring compound, the following compounds are preferable.

[0157]

Chemical formula

[0158]

Chemical formula

[0159] The heterocyclic ring compound may be used alone or in combination of two or more. The content of the heterocyclic ring compound is preferably 0.01 to 20.0% by mass, more preferably 0.10 to 10.0% by mass, still more preferably 0.30 to 8.0% by mass, and particularly preferably 0.50 to 5.0% by mass based on the total mass of the second photosensitive composition layer.

[0160] -Aliphatic thiol compound- The second photosensitive composition layer may contain an aliphatic thiol compound. When the second photosensitive composition layer contains an aliphatic thiol compound, the en-thiol reaction between the aliphatic thiol compound and a radically polymerizable compound having an ethylenically unsaturated group suppresses the curing shrinkage of the formed film and relaxes the stress.

[0161] As the aliphatic thiol compound, a monofunctional aliphatic thiol compound or a polyfunctional aliphatic thiol compound (that is, an aliphatic thiol compound having two or more functional groups) is preferable. In the present specification, the "polyfunctional aliphatic thiol compound" means an aliphatic compound having two or more thiol groups (also referred to as "mercapto groups") in the molecule. Among them, as the aliphatic thiol compound, a polyfunctional aliphatic thiol compound is preferable from the viewpoint of the adhesion of the formed pattern (particularly, the adhesion after exposure). As the polyfunctional aliphatic thiol compound, a low molecular weight compound having a molecular weight of 100 or more is preferable. Specifically, the molecular weight of the polyfunctional aliphatic thiol compound is more preferably 100 to 1,500, and still more preferably 150 to 1,000.

[0162] 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.

[0163] 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, 1,3,5-tris(2-(3-sulfanylbutanoyloxy)ethyl)-1,3,5-triazinane-2,4,6-trione, trimethylolethane tris(3-mercaptobutyrate), tris[(3-mercaptopropionyloxy)ethyl]isocyanurate, trimethylolpropane tris(3-mercaptopropionate), pentaerythritol tetrakis(3-mercaptopropionate), tetraethylene glycol bis(3-mercaptopropionate), dipentaerythritol hexakis(3-mercaptopropionate), ethylene glycol bisthiopropionate, 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 di(mercaptoethyl)ether. Among these, as the polyfunctional aliphatic thiol compound, at least one compound selected from the group consisting of 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 is preferable.

[0164] The aliphatic thiol compound may be used alone or in combination of two or more. The content of the aliphatic thiol compound is preferably 5% by mass or more, more preferably 5 to 50% by mass, still more preferably 5 to 30% by mass, and particularly preferably 8 to 20% by mass based on the total mass of the second photosensitive composition layer.

[0165] -Thermally crosslinkable compound- From the viewpoints of the strength of the resulting cured film and the adhesiveness of the resulting uncured film, the second photosensitive composition layer preferably contains a thermally crosslinkable compound. In the present specification, a thermally crosslinkable compound having an ethylenically unsaturated group, which will be described later, is not treated as an ethylenically unsaturated compound but is treated as a thermally crosslinkable compound. Examples of the thermally crosslinkable compound include an epoxy compound, an oxetane compound, a methylol compound, a melamine compound, and a blocked isocyanate compound. Among them, from the viewpoints of the strength of the resulting cured film and the adhesiveness of the resulting uncured film, a melamine compound or a blocked isocyanate compound is preferable. Further, when the second photosensitive composition layer contains a melamine compound, it is also preferable that the second photosensitive composition layer contains a bifunctional or higher-functional ethylenically unsaturated compound having no aromatic ring. Since the blocked isocyanate compound reacts with a hydroxy group and a carboxy group, for example, when at least one of a binder polymer and a radically polymerizable compound having an ethylenically unsaturated group has at least one of a hydroxy group and a carboxy group, the hydrophilicity of the formed film tends to decrease, and the function as a protective film tends to be enhanced. The blocked isocyanate compound means "a compound having a structure in which the isocyanate group of isocyanate is protected (so-called masked) with a blocking agent".

[0166] The dissociation temperature of the blocked isocyanate compound is not particularly limited, but is preferably 100 to 160°C, more preferably 130 to 150°C. The dissociation temperature of the blocked isocyanate means "the temperature of the endothermic peak accompanying the deprotection reaction of the blocked isocyanate when measured by DSC (Differential scanning calorimetry) analysis using a differential scanning calorimeter". As the 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 thereto.

[0167] As the blocking agent having a dissociation temperature of 100 to 160°C, active methylene compounds [malonic acid diesters (dimethyl malonate, diethyl malonate, di-n-butyl malonate, di-2-ethylhexyl malonate, etc.)], oxime compounds (formaldehyde oxime, acetaldehyde oxime, acetoxime, methyl ethyl ketoxime, and compounds having a structure represented by -C(=N-OH)- in the molecule such as cyclohexanone oxime) can be mentioned. Among them, as the blocking agent having a dissociation temperature of 100 to 160°C, for example, from the viewpoint of storage stability, an oxime compound is preferable.

[0168] The blocked isocyanate compound preferably has an isocyanurate structure, for example, from the viewpoints of improving the brittleness of the film and improving the adhesion to the transfer body. The blocked isocyanate compound having an isocyanurate structure can be obtained, for example, by isocyanurating and protecting hexamethylene diisocyanate. Among them, a compound having an oxime structure using an oxime compound as a blocking agent is preferable because it is easier to make the dissociation temperature fall within a preferable range and to reduce development residues compared to a compound not having an oxime structure.

[0169] The blocked isocyanate compound may have a polymerizable group. The polymerizable group is not particularly limited, and known polymerizable groups can be used, and a radical polymerizable group is preferable. Examples of the polymerizable group include ethylenically unsaturated groups such as (meth)acryloxy group, (meth)acrylamide group, and styryl group, and groups having an epoxy group such as glycidyl group. Among them, as the polymerizable group, an ethylenically unsaturated group is preferable, a (meth)acryloxy group is more preferable, and an acryloxy group is even more preferable.

[0170] Commercially available products can be used as the blocked isocyanate compound. Examples of commercially available blocked isocyanate compounds include Karenz (registered trademark) AOI-BM, Karenz (registered trademark) MOI-BM, Karenz (registered trademark) MOI-BP, etc. (manufactured by Showa Denko KK), and the blocked Duranate series (for example, Duranate (registered trademark) TPA-B80E, Duranate (registered trademark) WT32-B75P, etc., manufactured by Asahi Kasei Chemicals Corporation).

[0171] Examples of melamine compounds include alkylated melamine resins (for example, methylated melamine resins and butylated melamine resins, etc.), and mixed etherified melamine resins. Examples of commercially available melamine compounds include Nikalac MW-30M, MW-30, MW-22, MW-21, MX-43, MX-45, MX-500, and MX-520 (manufactured by Nippon Carbide Industries Co., Inc.), and Cymel 232, 235, 236, 238, 300, 301, 303, 350, and 506 (manufactured by Nippon Cytec Industries Inc.).

[0172] The thermally crosslinkable compound(s) may be used alone or in combination of two or more. The content of the thermally crosslinkable compound is preferably 1.0 to 50.0% by mass, more preferably 5.0 to 30.0% by mass, and still more preferably 5.0 to 25.0% by mass based on the total mass of the second photosensitive composition layer.

[0173] -Polymerization inhibitor- The second photosensitive composition layer may contain a polymerization inhibitor. The polymerization inhibitor means a compound having a function of delaying or inhibiting a polymerization reaction. As the polymerization inhibitor, for example, known compounds used as polymerization inhibitors can be used.

[0174] Examples of the polymerization inhibitor include phenothiazine compounds such as phenothiazine, bis-(1-dimethylbenzyl)phenothiazine, and 3,7-dioctylphenothiazine; hindered phenol compounds such as bis[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionic acid][ethylenebis(oxyethylene)]2,4-bis〔(laurylthio)methyl〕-o-cresol, 1,3,5-tris(3,5-di-t-butyl-4-hydroxybenzyl), 1,3,5-tris(4-t-butyl-3-hydroxy-2,6-dimethylbenzyl), 2,4-bis-(n-octylthio)-6-(4-hydroxy-3,5-di-t-butylanilino)-1,3,5-triazine, and pentaerythritol tetrakis 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate; nitroso compounds or salts thereof such as 4-nitrosophenol, N-nitrosodiphenylamine, N-nitrosocyclohexylhydroxylamine, and N-nitrosophenylhydroxylamine; quinone compounds such as methylhydroquinone, t-butylhydroquinone, 2,5-di-t-butylhydroquinone, and 4-benzoquinone; phenol compounds such as 4-methoxyphenol, 4-methoxy-1-naphthol, and t-butylcatechol; and metal salt compounds such as copper dibutyldithiocarbamate, copper diethyldithiocarbamate, manganese diethyldithiocarbamate, and manganese diphenyldithiocarbamate. Among them, at least one selected from the group consisting of phenothiazine compounds, nitroso compounds or salts thereof, and hindered phenol compounds is preferable as the polymerization inhibitor.

[0175] The polymerization inhibitor may be used alone or in combination of two or more. The content of the polymerization inhibitor is preferably 0.001 to 5.0% by mass, more preferably 0.01 to 3.0% by mass, and still more preferably 0.02 to 2.0% by mass with respect to the total mass of the second photosensitive composition layer. The content of the polymerization inhibitor is preferably 0.005 to 5.0% by mass, more preferably 0.01 to 3.0% by mass, and still more preferably 0.01 to 1.0% by mass with respect to the total mass of the polymerizable compound.

[0176] - Hydrogen donating compound - The second photosensitive composition layer may contain a hydrogen donating compound. The hydrogen donating compound has functions such as further improving the sensitivity of the photoinitiator to actinic rays and suppressing the polymerization inhibition of the polymerizable compound by oxygen.

[0177] Examples of the hydrogen donating compound include amines and amino acid compounds.

[0178] Examples of the amines include compounds described in "Journal of Polymer Society", Vol. 10, p. 3173 (1972) by M.R. Sander et al., Japanese Patent Publication No. 44-020189, Japanese Unexamined Patent Application Publication No. 51-082102, Japanese Unexamined Patent Application Publication No. 52-134692, Japanese Unexamined Patent Application Publication No. 59-138205, Japanese Unexamined Patent Application Publication No. 60-084305, Japanese Unexamined Patent Application Publication No. 62-018537, Japanese Unexamined Patent Application Publication No. 64-033104, and Research Disclosure No. 33825. More specifically, 4,4'-bis(diethylamino)benzophenone, tris(4-dimethylaminophenyl)methane (alias: leuco crystal violet), triethanolamine, ethyl p-dimethylaminobenzoate, p-formyldimethylaniline, and p-methylthiodimethylaniline are included. Among them, as the amines, at least one selected from the group consisting of 4,4'-bis(diethylamino)benzophenone and tris(4-dimethylaminophenyl)methane is preferable.

[0179] Examples of the amino acid compound include N-phenylglycine, N-methyl-N-phenylglycine, and N-ethyl-N-phenylglycine, and N-phenylglycine is preferable.

[0180] Examples of the hydrogen-donating compound include organometallic compounds (such as tributyltin acetate) described in Japanese Patent Publication No. 48-042965, hydrogen donors described in Japanese Patent Publication No. 55-034414, and sulfur compounds (such as trithiane) described in Japanese Patent Application Laid-Open No. 6-308727.

[0181] The hydrogen-donating compound may be used alone or in combination of two or more. From the viewpoint of improving the curing rate based on the balance between the polymerization growth rate and the chain transfer, the content of the hydrogen-donating compound is preferably 0.01 to 10.0% by mass, more preferably 0.01 to 8.0% by mass, and still more preferably 0.03 to 5.0% by mass with respect to the total mass of the second photosensitive composition layer.

[0182] -Impurities, etc.- The second photosensitive composition layer may contain a predetermined amount of impurities. Specific examples of the 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 likely to be mixed as impurities, so it is preferable to set the content as follows.

[0183] The content of the impurities in the second photosensitive composition layer is preferably 80 ppm or less, more preferably 10 ppm or less, and still more preferably 2 ppm or less on a mass basis. The content of the impurities in the second photosensitive composition layer can be 1 ppb or more or 0.1 ppm or more on a mass basis.

[0184] As a method for setting the impurities within the above range, selecting a raw material of the second photosensitive composition layer having a low content of impurities, preventing the mixing of impurities during the formation of the second photosensitive composition layer, and washing and removing them can be mentioned. By such a method, the amount of impurities can be made within the above range.

[0185] Impurities can be quantified by known methods such as, for example, inductively coupled plasma (ICP) optical emission spectrometry, atomic absorption spectrometry, and ion chromatography.

[0186] In the second photosensitive composition layer, the contents of compounds such as benzene, formaldehyde, trichloroethylene, 1,3-butadiene, carbon tetrachloride, chloroform, N,N-dimethylformamide, N,N-dimethylacetamide, and hexane are preferably low. As the content of these compounds in the second photosensitive composition layer, based on mass, 100 ppm or less is preferable, 20 ppm or less is more preferable, and 4 ppm or less is still more preferable. The lower limit can be 10 ppb or more and can be 100 ppb or more based on mass. The contents of these compounds can be suppressed by the same method as the above-mentioned metal impurities. Also, they can be quantified by known measurement methods.

[0187] From the viewpoint of improving reliability and laminatability, the water content in the second photosensitive composition layer is preferably 0.01 to 1.0% by mass, and more preferably 0.05 to 0.5% by mass.

[0188] - Residual monomer - The second photosensitive composition layer may contain residual monomers of each structural unit of the above-mentioned alkali-soluble resin. From the viewpoints of patterning property and reliability, the content of the residual monomer is preferably 5,000 ppm by mass or less, more preferably 2,000 ppm by mass or less, and still more preferably 500 ppm by mass or less with respect to the total mass of the alkali-soluble resin. The lower limit is preferably 1 ppm by mass or more, and more preferably 10 ppm by mass or more. From the viewpoints of patterning property and reliability, the residual monomer of each structural unit of the alkali-soluble resin is preferably 3,000 ppm by mass or less, more preferably 600 ppm by mass or less, and still more preferably 100 ppm by mass or less with respect to the total mass of the second photosensitive composition layer. The lower limit is not particularly limited, but is preferably 0.1 ppm by mass or more, and more preferably 1 ppm by mass or more.

[0189] When synthesizing an alkali-soluble resin by a polymer reaction, the amount of residual monomers of the monomers 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, it is preferable that the content of glycidyl acrylate is within the above range. The amount of residual monomers can be measured by known methods such as liquid chromatography and gas chromatography.

[0190] -Other Components- The second photosensitive composition layer may contain components other than the above-described components (hereinafter also referred to as "other components"). Examples of other components include surfactants, colorants, antioxidants, and particles (for example, metal oxide particles) that the first photosensitive composition layer may contain, and other additives described in paragraphs

[0058] to

[0071] of JP-A No. 2000-310706.

[0191] From the viewpoint of transparency, the second photosensitive composition layer preferably does not substantially contain a colorant. The content of the colorant is preferably less than 1% by mass, more preferably less than 0.1% by mass, based on the total mass of the second photosensitive composition layer.

[0192] Examples of antioxidants include 3-pyrazolidones such as 1-phenyl-3-pyrazolidone (alias: phenidone), 1-phenyl-4,4-dimethyl-3-pyrazolidone, and 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone; polyhydroxybenzenes such as hydroquinone, catechol, pyrogallol, methylhydroquinone, and chlorohydroquinone; paramethylaminophenol, para-aminophenol, parahydroxyphenylglycine, and paraphenylenediamine. Among them, 3-pyrazolidones are preferable, and 1-phenyl-3-pyrazolidone is more preferable.

[0193] As the particles, metal oxide particles are preferable. The metals in the metal oxide particles also include metalloids such as B, Si, Ge, As, Sb, and Te. The average primary particle diameter of the particles is preferably 1 to 200 nm, more preferably 3 to 80 nm, for example, from the viewpoint of the transparency of the cured film. The average primary particle diameter of the particles is calculated by measuring the particle diameters of any 200 particles using an electron microscope and calculating the arithmetic mean of the measurement results. When the shape of the particles is not spherical, the longest side is taken as the particle diameter.

[0194] <Protective film> The transfer film may have a protective film. As the protective film, a resin film having heat resistance and solvent resistance can be used. For example, polyolefin films such as polypropylene films and polyethylene films, polyester films such as polyethylene terephthalate films, polycarbonate films, and polystyrene films can be mentioned. Further, a resin film made of the same material as the above-mentioned temporary support may be used as the protective film. Among them, as the protective film, a polyolefin film is preferable, a polypropylene film or a polyethylene film is more preferable, and a polyethylene film is even more preferable.

[0195] The thickness of the protective film is preferably 1 to 100 μm, more preferably 5 to 50 μm, even more preferably 5 to 40 μm, and particularly preferably 15 to 30 μm. The thickness of the protective film is preferably 1 μm or more from the viewpoint of excellent mechanical strength, and preferably 100 μm or less from the viewpoint of relatively low cost.

[0196] In addition, in the protective film, the number of fish eyes having a diameter of 80 μm or more contained in the protective film is preferably 5 pieces / m 2 or less. Note that "fish eye" refers to a material obtained by melting, kneading, extruding a material, and manufacturing a film by methods such as a biaxial stretching method and a casting method, and foreign substances, undissolved substances, and oxidation degradation products of the material are incorporated into the film.

[0197] The number of particles with a diameter of 3 μm or more contained in the protective film is 30 particles / mm 2 or less is preferable, and 10 particles / mm 2 or less is more preferable, and 5 particles / mm 2 or less is even more preferable. Thereby, it is possible to suppress defects caused by the unevenness due to the particles contained in the protective film being transferred to the second photosensitive composition layer.

[0198] From the viewpoint of imparting winding property, the arithmetic mean roughness Ra of the surface of the protective film on the side opposite to the surface in contact with the second photosensitive composition layer is preferably 0.01 μm or more, more preferably 0.02 μm or more, and even more preferably 0.03 μm or more. On the other hand, it is preferably less than 0.50 μm, more preferably 0.40 μm or less, and even more preferably 0.30 μm or less. From the viewpoint of suppressing defects during transfer, the surface roughness Ra of the surface of the protective film in contact with the second photosensitive composition layer is preferably 0.01 μm or more, more preferably 0.02 μm or more, and even more preferably 0.03 μm or more. On the other hand, it is preferably less than 0.50 μm, more preferably 0.40 μm or less, and even more preferably 0.30 μm or less.

[0199] <Other members> The transfer film may contain members other than the above-described members (hereinafter also referred to as "other members"). Examples of other members include a thermoplastic resin layer and an intermediate layer.

[0200] 〔Method for manufacturing transfer film〕 The method for manufacturing the transfer film of the present invention is not particularly limited, and known methods can be used. As an example of a method for manufacturing the transfer film 10, for example, a coating liquid for the second photosensitive composition layer is applied onto the surface of the protective film 11 to form a coating film, and this coating film is further dried to form the second photosensitive composition layer 13; a coating liquid for the first photosensitive composition layer is applied onto the surface of the second photosensitive composition layer 13 to form a coating film, and this coating film is further dried to form the first photosensitive composition layer 15; and the transfer film 10 can be manufactured by a manufacturing method including a step of pressing a temporary support 17 onto the first photosensitive composition layer 15. Note that the transfer film 10 shown in FIG. 1 may be manufactured by forming the first photosensitive composition layer 15 on the temporary support 17, and further forming the second photosensitive composition layer 13 and the protective film 11 on the first photosensitive composition layer 15. Further, after manufacturing the transfer film, it may be wound up and stored as a roll-shaped transfer film. The roll-shaped transfer film can be provided in the form as it is in a bonding step with a member to be transferred by a roll-to-roll method described later.

[0201] <Method for forming photosensitive composition layer> The method for forming the photosensitive composition layer is not particularly limited, but a method of applying using a coating liquid is preferred. Examples of the coating method include a printing method, a spraying method, a roll coating method, a bar coating method, a curtain coating method, a spin coating method, and a die coating method (slot coating method). The coating liquid preferably contains various components that the above-described photosensitive composition layer may contain and a solvent described later. In the photosensitive composition layer, the preferred range of the content of various components with respect to the total solid content of the coating liquid is the same as the preferred range of the content of various components with respect to the total mass of the above-described photosensitive composition layer.

[0202] As the above solvent, there is no particular limitation as long as it can dissolve or disperse each component other than the solvent, and known solvents can be used. Specifically, for example, alkylene glycol ether solvents, alkylene glycol ether acetate solvents, alcohol solvents (such as methanol and ethanol), ketone solvents (such as acetone and methyl ethyl ketone), aromatic hydrocarbon solvents (such as toluene), aprotic polar solvents (such as N,N-dimethylformamide), cyclic ether solvents (such as tetrahydrofuran), ester solvents (such as n-propyl acetate), amide solvents, lactone solvents, and mixed solvents containing two or more of these can be mentioned.

[0203] As the solvent, it is preferably to contain at least one selected from the group consisting of alkylene glycol ether solvents and alkylene glycol ether acetate solvents, and a mixed solvent containing at least three kinds of at least one selected from the group consisting of alkylene glycol ether solvents and alkylene glycol ether acetate solvents, a ketone solvent, and a cyclic ether solvent is more preferable.

[0204] Examples of the alkylene glycol ether solvent include ethylene glycol monoalkyl ether, ethylene glycol dialkyl ether, propylene glycol monoalkyl ether (such as propylene glycol monomethyl ether acetate), propylene glycol dialkyl ether, diethylene glycol dialkyl ether, dipropylene glycol monoalkyl ether, and dipropylene glycol dialkyl ether. Examples of the alkylene glycol ether acetate solvent include ethylene glycol monoalkyl ether acetate, propylene glycol monoalkyl ether acetate, diethylene glycol monoalkyl ether acetate, and dipropylene glycol monoalkyl ether acetate. Examples of the solvent include the solvents described in paragraphs

[0092] to

[0094] of International Publication No. 2018 / 179640 and the solvents described in paragraph

[0014] of JP-A-2018-177889.

[0205] As a method for drying the coating film, heat drying or reduced-pressure drying is preferable. The method for attaching the protective film is not particularly limited, and known methods can be mentioned. Examples of the protective film laminating apparatus include known laminators such as a vacuum laminator and an auto-cut laminator. The laminator preferably includes any heatable roller such as a rubber roller and is capable of applying pressure and heat.

[0206] [Use of the Transfer Film] The transfer film of the present invention is preferably used for pattern formation and / or film formation. The above-mentioned film can be applied, for example, as an electrode protection film, an insulating film, a planarizing film, an overcoat film, a hard coat film, a passivation film, a partition wall, a spacer, a microlens, an optical filter, an antireflection film, an etching resist, and a plating member. More specifically, a protection film or an insulating film for a touch panel electrode, a protection film or an insulating film for a printed wiring board, a protection film or an insulating film for a TFT substrate, an interlayer insulating film in a build-up substrate of a semiconductor package, an organic interposer, a color filter, an overcoat film for a color filter, and an etching resist for wiring formation can be mentioned.

[0207] [Method for Manufacturing a Laminate] The method for manufacturing the laminate of the present invention is not particularly limited as long as it is a manufacturing method using the transfer film of the present invention. As a method for manufacturing the laminate of the present invention, a laminating step of laminating the second photosensitive composition layer in the transfer film and the surface on the conductive layer side of the member to be transferred having a base material and a conductive layer disposed on the base material, an exposure step of exposing the photosensitive composition layer, and a peeling step of peeling the temporary support body between the laminating step and the exposure step or after the exposure step are included, and a method for manufacturing a laminate is preferable.

[0208] <Member to be Transferred> The member to be transferred has a base material and a conductive layer disposed on the base material. The substrate is preferably transparent. Examples of the material of the substrate include resin materials and inorganic materials. Examples of the resin material include polyester (e.g., polyethylene terephthalate and polyethylene naphthalate, etc.), polyether ether ketone, acrylic resin, cycloolefin polymer, and polycarbonate. Examples of the inorganic material include glass and quartz, etc.

[0209] The substrate is preferably a resin film, more preferably a polyethylene terephthalate film, a polyethylene naphthalate film, or a cycloolefin polymer film.

[0210] From the viewpoints of transportability, electrical properties, and film-forming properties, the average thickness of the substrate is preferably 10 to 100 μm, more preferably 10 to 60 μm.

[0211] Examples of the conductive layer disposed on the substrate include known conductive layers. Further, the conductive layer may be a transparent electrode layer or a conductive pattern. Examples of the material of the transparent electrode layer include metal oxides and metal nanowires. Examples of the metal oxide include metal oxides containing at least one metal selected from the group consisting of In, Sn, Zn, Ga, Sb, Ti, Si, Zr, Mg, Al, Au, Ag, Cu, Pd, and W, indium-containing oxides such as indium-tin composite oxide (ITO: Indium Tin Oxide), or tin oxide containing antimony, etc. are preferable. Further, the conductive layer may be a conductive pattern composed of a metal oxide or a metal. Examples of the shape of the conductive pattern include stripe shape, square shape, and lattice shape.

[0212] Hereinafter, each step in the manufacturing method of the laminate will be described in detail.

[0213] 〔Lamination Process〕 The lamination process is a process of laminating the second photosensitive composition layer in the transfer film and the surface on the conductive layer side of the transfer member having a base material and a conductive layer disposed on the base material. In the case where the transfer film has a protective film, the lamination process is performed after peeling off the protective film.

[0214] In the above lamination, the surface on the conductive layer side of the transfer member and the surface of the second photosensitive composition layer are pressure-bonded so as to be in contact with each other. Examples of the method of the above pressure bonding include known transfer methods and lamination methods. For lamination, known laminators such as a vacuum laminator and an auto cut laminator can be used. The lamination temperature is preferably 70 to 130 °C.

[0215] 〔Exposure Process〕 The exposure process is a process of exposing the photosensitive composition layer. When the exposure process or pattern exposure is performed, the refractive index adjustment layer and the resin layer are formed on the transfer member by performing the development process described later. The resin layer can also function as a protective film for the transfer member. When pattern exposure is performed and the development process described later is performed, a resin pattern is formed. The photosensitive composition layer may be exposed from the side opposite to the transfer member, or may be exposed from the transfer member side of the photosensitive composition layer.

[0216] As the light source for exposure, if it can irradiate light in a wavelength range capable of curing at least the photosensitive composition layer (for example, 365 nm or 405 nm, etc.), it can be appropriately selected and used. Among them, the main wavelength of the exposure light for exposure is preferably 365 nm. The main wavelength is the wavelength with the highest intensity.

[0217] Examples of the light source include various lasers, light emitting diodes (LEDs), ultra-high pressure mercury lamps, high pressure mercury lamps, and metal halide lamps. The exposure amount is preferably 5 to 200 mJ / cm 2 and more preferably 10 to 200 mJ / cm2 is more preferable.

[0218] Preferable embodiments 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 the contents thereof are incorporated herein.

[0219] The exposure step is preferably pattern exposure. Here, "pattern exposure" refers to a form of exposure in a pattern shape, that is, exposure in a form in which an exposed portion and a non-exposed portion exist. The positional relationship between the exposed area and the non-exposed area in pattern exposure is not particularly limited and is adjusted as appropriate.

[0220] 〔Peeling step〕 The peeling step is a step of peeling the temporary support between the bonding step and the exposure step, or after the exposure step. When the development step is performed after the exposure step, the peeling step can be performed after the exposure step and before the development step. Examples of the peeling method include the cover film peeling described in paragraphs

[0161] to

[0162] of JP-A No. 2010-072589.

[0221] 〔Development step〕 The development step is a step of developing the exposed photosensitive composition layer to form a pattern. The development of the above composition layer can be performed using a developer. As the developer, an alkaline aqueous solution is preferable. Examples of the alkaline compound that can be contained in the alkaline aqueous solution include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, and choline (2-hydroxyethyltrimethylammonium hydroxide).

[0222] Examples of the development method include methods such as paddle development, shower development, spin development, and dip development.

[0223] Examples of the developer preferably used include, for example, the developer described in paragraph

[0194] of International Publication No. 2015 / 093271, and examples of the development method preferably used include, for example, the development method described in paragraph

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

[0224] [Post-exposure process and post-bake process] The method for manufacturing the laminate may include a step of exposing the pattern obtained by the above-described development step (post-exposure step) and / or a step of heating (post-bake step). When both the post-exposure step and the post-bake step are included, it is preferable to perform post-baking after post-exposure. The exposure amount of post-exposure is preferably 100 to 5000 mJ / cm 2 and more preferably 200 to 3000 mJ / cm 2 is even more preferable. The temperature of post-baking is preferably 80 to 250°C, and more preferably 90 to 160°C. The time of post-baking is preferably 1 to 180 minutes, and more preferably 10 to 60 minutes.

[0225] [Laminate] The laminate of the present invention is not particularly limited as long as it is a laminate manufactured by the above-described method for manufacturing a laminate. As the laminate, a laminate having a base material, a conductive layer disposed on the base material, a resin layer, and a refractive index adjustment layer in this order is preferable. In addition, in the laminate, it is preferable that the refractive index of the refractive index adjustment layer is 1.45 or less and is smaller than the refractive index of the resin layer, and the average film thickness of the resin layer is more than 30 μm. The resin layer is a cured film of the second photosensitive composition layer. The preferred embodiment of the resin layer is the same except for the components whose states change (react) by an exposure process or the like. Further, the refractive index adjustment layer is a cured film of the second photosensitive composition layer. The preferred embodiment of the refractive index adjustment layer is the same except for the components whose states change (react) by an exposure process or the like. Specifically, since the polymerizable compound and the polymerization initiator that the second photosensitive composition layer may contain react by the exposure process, it is preferable that the resin layer does not contain the polymerizable compound and the polymerization initiator.

Examples

[0226] The present invention will be described in more detail based on the following examples. The materials, amounts used, ratios, treatment details, treatment procedures, etc. shown in the following examples can be appropriately changed as long as they do not deviate from the spirit of the present invention. Therefore, the scope of the present invention should not be construed as being limited by the examples shown below.

[0227] The notations "parts" and "%" mean "parts by mass" and "mass %", respectively, unless otherwise specified. The acid value of the resin or binder polymer was measured according to the method described in JIS K0070:1992. The weight average molecular weight of the resin or binder polymer is intended to be the value measured by gel permeation chromatography (GPC) under the following conditions. The calibration curve was prepared from 8 samples of "Standard Sample TSK standard, polystyrene" manufactured by Tosoh Corporation: "F-40", "F-20", "F-4", "F-1", "A-5000", "A-2500", "A-1000", and "n-propylbenzene".

[0228] <Conditions> GPC: HLC (registered trademark)-8020GPC (manufactured by Tosoh Corporation) Column: TSKgel (registered trademark), Super Multipore HZ-H (manufactured by Tosoh Corporation, 4.6 mm ID × 15 cm), 3 columns Eluent: THF (tetrahydrofuran) Sample concentration: 0.45 mass % Flow rate: 0.35 mL / min Sample injection volume: 10 μL Measurement temperature: 40 °C Detector: Differential refractometer (RI)

[0229] [Preparation of the coating liquid for the first photosensitive composition layer] Based on the components and formulations shown in the following table, coating liquids A-1 to A-2 for the first photosensitive composition layer were prepared.

[0230] [Table 1]

[0231] "IPA": Isopropanol "Omnirad 2959": 2-Hydroxy-1-[4-(2-hydroxyethoxy)phenyl]-2-methylpropan-1-one (manufactured by IGM Resins B.V.) "BYK-345": Silicone surfactant (manufactured by BYK-Chemie Japan)

[0232] [Chemical formula]

[0233] [Preparation of the coating liquid for the second photosensitive composition layer] Based on the components and formulations shown in the following table, coating liquids B-1 to B-8 for the second photosensitive composition layer were prepared.

[0234] [Table 2]

[0235] "A-DPH": Dipentaerythritol hexaacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.) "A-NOD-N": 1,9-Nonanediol diacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.) "A-BPE-4": Ethoxylated bisphenol A diacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.) "MX-270": Methylated melamine resin (manufactured by Nippon Carbide Industries Co., Ltd.) "KAYARAD R-604": β,β-Dimethyl-1,3-dioxane-2-ethanol diacrylate (manufactured by Nippon Kayaku Co., Ltd.) "P-1": The binder polymer P-1 solution described below "Duranate TPA-B80E": Block isocyanate compound (manufactured by Asahi Kasei Corporation) "XIRAN EF-40": Copolymer of styrene / maleic anhydride = 4:1 (molar ratio) (acid anhydride value 1.94 mmol / g, Mw 10500, manufactured by BASF Japan Ltd.) "Megafac EFS-521": Silicone surfactant (manufactured by DIC Corporation)

[0236] <Binder polymer P-1 solution> A P-1 solution (a solution containing 36.3 mass% of the solid content of the binder polymer P-1) was obtained by the preparation method shown below.

[0237] A 1000 mL flask was charged with propylene glycol monomethyl ether (manufactured by FUJIFILM Wako Pure Chemical Corporation, 82.4 g) and heated to 90°C under a nitrogen stream. To the heated propylene glycol monomethyl ether, a solution prepared by dissolving styrene (manufactured by FUJIFILM Wako Pure Chemical Corporation, 38.4 g), dicyclopentanyl methacrylate (trade name: FUNCRYL (registered trademark) FA-513M, manufactured by Hitachi Chemical Company, Ltd., 30.1 g), and methacrylic acid (manufactured by FUJIFILM Wako Pure Chemical Corporation, 34.0 g) in propylene glycol monomethyl ether (20 g), and a solution prepared by dissolving the polymerization initiator dimethyl 2,2'-azobis(2-methylpropionate) (trade name: V-601, manufactured by FUJIFILM Wako Pure Chemical Corporation, 5.4 g) in propylene glycol monomethyl ether acetate (manufactured by FUJIFILM Wako Pure Chemical Corporation, 43.6 g) were simultaneously added dropwise over 3 hours. To the solution after completion of the dropwise addition, the polymerization initiator (V-601, 0.75 g) was added 3 times at 1-hour intervals. Subsequently, the solution after the addition was reacted for another 3 hours. Subsequently, the obtained solution was diluted using propylene glycol monomethyl ether acetate (58.4 g) and propylene glycol monomethyl ether (11.7 g). Furthermore, the diluted solution was heated to 100 °C under an air stream. To the heated solution, tetraethylammonium bromide (0.53 g, manufactured by FUJIFILM Wako Pure Chemical Corporation) and p-methoxyphenol (0.26 g, manufactured by FUJIFILM Wako Pure Chemical Corporation) were added. Subsequently, glycidyl methacrylate (trade name: Blemmer (registered trademark) GH, manufactured by NOF Corporation, 25.5 g) was added dropwise to the obtained solution over 20 minutes. The obtained solution was reacted at 100 °C for 7 hours to obtain 350.6 g of a 36.3 mass% solution of binder polymer P-1 in terms of solid content. The amount of residual monomer measured using gas chromatography (GC) was less than 0.1 mass% with respect to the solid content of binder polymer P-1 for any of the monomers used. Here, "solid content" means all components excluding the solvent in the solution of binder polymer P-1, and even if the physical properties of the above components are liquid, they are included in the solid content.

[0238] Binder polymer P-1 shows the constitutional units (mass ratio) and physical property values shown in the following table. Note that binder polymer P-1 corresponds to an alkali-soluble resin.

[0239]

Table 3

[0240] "St constitutional unit": A constitutional unit derived from styrene "MAA-GMA constitutional unit": A constitutional unit in which glycidyl methacrylate (GMA) is added to a constitutional unit derived from methacrylic acid (MAA) "DCPMA constitutional unit": A constitutional unit derived from dicyclopentanyl methacrylate

[0241] [Transfer film] On a peelable polyethylene terephthalate film (Celapil 25WZ, manufactured by Toray Industries, Inc.) serving as a protective film, using a slit nozzle, the coating liquid B-1 for the second photosensitive composition layer was applied with the coating amount adjusted so as to obtain the average film thickness shown in the following table after drying, and the solvent was volatilized in a drying zone at 80°C to form the second photosensitive composition layer. Next, on the second photosensitive composition layer, using a slit nozzle, the coating liquid A-1 for the first photosensitive composition layer was applied with the coating amount adjusted so as to obtain the average film thickness shown in the following table after drying, and then dried at a drying temperature of 70°C to form the first photosensitive composition layer. Furthermore, a polyethylene terephthalate having a thickness of 16 μm (Lumirror 16KS40, manufactured by Toray Industries, Inc.) serving as a temporary support was pressure-bonded to the surface of the first photosensitive composition layer to produce the transfer film of Example 1. The transfer film of Example 1 has a temporary support, a first photosensitive composition layer, a second photosensitive composition layer, and a protective film in this order. In addition, each transfer film was produced in the same procedure as the transfer film of Example 1 except that the changes were made as shown in the following table.

[0242] [Measurement of Refractive Index and Average Film Thickness of Each Layer of Transfer Film] The refractive index of each layer of the transfer film was measured based on the ellipsometry method using an M-2000 manufactured by J.A. Woollam Co., Ltd. as a measuring device. Specifically, it is as follows.

[0243] (1) Measurement of Refractive Index of Temporary Support One surface of the temporary support used in the production of each transfer film was roughened by sanding so as not to cause reflection. Next, using the above-mentioned measuring device based on the ellipsometry method, at 25°C, the reflection spectrum was measured at wavelengths of 400 to 1000 nm, and the refractive index of the temporary support at each wavelength was obtained by fitting using the Cauchy model.

[0244] (2) Measurement of Refractive Index and Average Film Thickness of Each Layer (First Layer) For each transfer film, a test sample A was prepared by forming only the layer (hereinafter also referred to as "layer A") that was disposed adjacent to the temporary support in the transfer film before the temporary support was peeled off on the temporary support. Specifically, in the transfer film of Example 1, since the first photosensitive composition layer corresponds to layer A, a test sample A having the first photosensitive composition layer formed on the temporary support was prepared. The preparation of test sample A was carried out in accordance with the above-described layer formation procedure (formation procedure by the coating method). Next, the same sanding treatment as in the above procedure (1) was performed on the surface of the temporary support in each of the obtained test samples A (the surface of the temporary support on the side where the layer of the temporary support was not formed). Then, using the above-described measuring apparatus based on the ellipsometry method, at 25 °C, the reflection spectrum (wavelength: 400 to 1000 nm) of the test sample A in which only the temporary support and layer A were laminated was measured, and the refractive index of layer A at each wavelength was obtained by fitting using the Cauchy model. Also, using the above test sample A, the average film thickness of layer A was also measured. The average film thickness of layer A was the average value of the film thicknesses measured at 10 points by observing the cross section cut by a microtome with SEM or TEM. However, those with a thickness of 1 μm or more were measured with SEM, and those with a thickness of less than 1 μm were measured with TEM.

[0245] (Second layer) Similarly, a test sample B having a layer B further formed on layer A formed on the temporary support in the above test sample A was prepared. Specifically, in the transfer film of Example 1 before the temporary support was peeled off, the second photosensitive composition layer disposed on the side opposite to the temporary support of the layer (layer A) disposed adjacent to the temporary support corresponds to layer B. Next, the reflection spectrum of test sample B was measured in the same manner as in the first layer described above, and the refractive index of layer B was obtained. Also, the average film thickness was obtained in the same manner as in the first layer described above.

[0246] Also, in the measurement, fitting was performed on each layer of test samples A and B, etc., assuming that the refractive index was uniform from one surface to the other surface of each layer. In the case where test samples A and B are samples having a layer with a gradient refractive index in which the refractive index changes from one surface to the other surface of the layer, a model in which the refractive index changes linearly from one surface to the other surface of the layer is established, and the above-described fitting is performed. The refractive indices shown in the following table are the refractive indices calculated at a wavelength of 550 nm.

[0247] [Measurement of Refractive Index and Average Film Thickness of Each Layer of the Laminate] Regarding each of the laminates described later, when the refractive index and film thickness were measured by the same method as the method described in [Measurement of Refractive Index and Average Film Thickness of Each Layer of the Transfer Film], both the refractive index and the average film thickness showed the same values as the refractive index and the average film thickness measured using the transfer film.

[0248] [Evaluation] [Reflectance] Using each transfer film, a laminate for reflectance evaluation was produced by the following procedure, and the reflectance was measured. A cycloolefin resin film with a film thickness of 38 μm and a refractive index of 1.53 was surface-modified by corona discharge treatment for 3 seconds under the conditions of an output voltage of 100%, an output of 250 W, a wire electrode with a diameter of 1.2 mm, an electrode length of 240 mm, and a distance between work electrodes of 1.5 mm using a high-frequency oscillator, and used as a transparent film substrate (corresponding to the base material). Next, the transparent film substrate was introduced into a vacuum chamber, and a DC magnetron sputtering (conditions: temperature of the transparent film substrate of 150°C, argon pressure of 0.13 Pa, oxygen pressure of 0.01 Pa) was performed using an ITO target with a SnO2 content of 10 mass% (indium:tin = 95:5 (molar ratio)) to form an ITO thin film with a thickness of 3 μm and a refractive index of 1.82 as a transparent electrode layer. The surface resistance of the ITO thin film was 85 Ω / □ (Ω per square). In this way, a transfer member having a base material and a transparent conductive layer disposed on the base material was produced. Next, the protective films of the produced transfer films were peeled off, and the peeled surfaces exposed by peeling off the protective films were brought into contact with the transparent conductive layer surfaces of the transfer members, and each transfer film was laminated on the transfer members under the following conditions to obtain a laminate.

[0249] <Condition> Temperature of the transparent film substrate: 40 °C Temperature of the rubber roller: 90 °C Line pressure: 3 N / cm Conveyor speed: 4 m / min

[0250] Next, using a proximity type exposure machine having an ultra-high pressure mercury lamp (manufactured by Hitachi High-Tech Electronics Engineering Co., Ltd.), the laminate was exposed to the entire surface at an exposure amount of 100 mJ / cm 2 (measured with i-line) through a temporary support. After that, the temporary support was peeled off from the laminate, and the laminate was exposed at an exposure amount of 400 mJ / cm 2 (measured with i-line) using a post-exposure machine having a high-pressure mercury lamp (manufactured by Ushio Electric Inc.) (post-exposure). Then, a post-bake treatment was performed at 145 °C for 30 minutes to form each laminate for reflectance evaluation. A black polyethylene terephthalate (PET) material was attached to the entire surface on the base material side of the obtained laminate to shield the surface on the base material side. The black PET material was attached using a transparent adhesive tape (product name: Transparent Double-Sided Tape 8146-2, manufactured by 3M Japan Ltd.). Then, with light incident from the side opposite to the side to which the black PET base material was attached, the reflectance of each laminate for reflectance evaluation with respect to the D65 light source was measured (incident angle 5°) using a spectrophotometer V-570 (manufactured by JASCO Corporation). Based on the obtained measurement results, evaluation was performed based on the following criteria. "A": Less than 2.3% "B": 2.3% or more and less than 2.8% "C": 2.8% or more and 3.8% or less "D": More than 3.8%

[0251] 〔Laminability〕 Using each transfer film, a laminate for laminate property evaluation was produced according to the following procedure, and the laminate property was measured.

[0252] <Fabrication of Photosensitive Film E1 for Etching> On a polyethylene terephthalate film (temporary support) with a thickness of 75 μm, the following coating solution H1 for a thermoplastic resin layer was applied using a slit nozzle and dried to form a thermoplastic resin layer. Next, the following coating solution P1 for an intermediate layer was applied on the thermoplastic resin layer and dried to form an intermediate layer. Furthermore, the coating solution E1 for a photosensitive resin layer for etching was applied and dried to form a photosensitive resin layer for etching. In this way, a thermoplastic resin layer with a dry film thickness of 15.1 μm, an intermediate layer with a dry film thickness of 1.6 μm, and a photosensitive resin layer for etching with a dry film thickness of 2.0 μm were formed on the temporary support. Finally, a protective film (a 12-μm-thick polypropylene film) was pressure-bonded onto the photosensitive resin layer for etching, and a photosensitive film E1 for etching having a temporary support, a thermoplastic resin layer, an intermediate layer (oxygen barrier film), and a photosensitive resin layer for etching was produced.

[0253] (Coating Solution H1 for Forming Thermoplastic Resin Layer) · Methanol: 11.1 parts by mass · Propylene glycol monomethyl ether acetate: 6.36 parts by mass · Methyl ethyl ketone: 52.4 parts by mass · Methyl methacrylate / 2-ethylhexyl acrylate / benzyl methacrylate / methacrylic acid copolymer (copolymer composition ratio (molar ratio) = 55 / 11.7 / 4.5 / 28.8, weight average molecular weight 100,000, Tg 70 °C): 5.83 parts by mass · Styrene / acrylic acid copolymer (copolymer composition ratio (molar ratio) = 63 / 37, weight average molecular weight 10,000, Tg 100 °C): 13.6 parts by mass · Monomer 1 (trade name: BPE-500, manufactured by Shin-Nakamura Chemical Co., Ltd.): 9.1 parts by mass · Fluorine-based polymer [the following components]: 0.54 parts by mass Fluorine-based polymer: C6F 13A copolymer of CH2CH2OCOCH=CH2 (40 parts by mass), (OCH(CH3)CH2)7OCOCH=CH2 (55 parts by mass), and H(OCHCH2)7OCOCH=CH2 (5 parts by mass) (weight average molecular weight 30,000, 30% by mass solution in methyl ethyl ketone, trade name: Megafac F780F, manufactured by DIC Corporation)

[0254] (Coating solution for forming intermediate layer: formulation P1) · Polyvinyl alcohol (trade name: PVA205, manufactured by Kuraray Co., Ltd., saponification degree = 88%, degree of polymerization 550): 32.2 parts by mass · Polyvinylpyrrolidone (trade name: K-30, manufactured by ISP Japan Co., Ltd.): 14.9 parts by mass · Distilled water: 524 parts by mass · Methanol: 429 parts by mass

[0255] (Coating solution E1 for photo-curable resin layer for etching) · Methyl methacrylate / styrene / methacrylic acid copolymer (copolymer composition (mass%): 31 / 40 / 29, weight average molecular weight 60,000, acid value 163 mgKOH / g): 16 parts by mass · Monomer 1 (trade name: BPE-500, manufactured by Shin-Nakamura Chemical Co., Ltd.): 5.6 parts by mass · Tetraethylene oxide monomethacrylate adduct of hexamethylene diisocyanate (0.5 mol addition): 7 parts by mass · Cyclohexane dimethanol monoacrylate as a compound having one polymerizable group in the molecule: 2.8 parts by mass · 2-Chloro-N-butyl acrydon: 0.42 parts by mass · 2,2-Bis(o-chlorophenyl)-4,4’,5,5’-tetraphenylbiimidazole: 2.17 parts by mass · Malachite green oxalate: 0.02 parts by mass · Leuco crystal violet: 0.26 parts by mass · Phenothiazine: 0.013 parts by mass · Surfactant (trade name: Megafac F-780F, manufactured by DIC Corporation): 0.03 parts by mass · Methyl ethyl ketone: 40 parts by mass · 1-Methoxy-2-propanol: 20 parts by mass Note that the viscosity of the coating liquid E1 for the photosensitive resin layer for etching at 100 °C after solvent removal was 2,500 Pa·sec.

[0256] <Formation of transparent electrode pattern> The peeled surface exposed by peeling the protective film from the photosensitive film E1 for etching was laminated on the transfer member in the above [Reflectance] to obtain a laminate (substrate temperature: 130 °C, rubber roller temperature 120 °C, linear pressure 100 N / cm, conveyance speed 2.2 m / min). After peeling the temporary support from the laminate, the distance between the surface of the exposure mask (quartz exposure mask having a line and space pattern (duty ratio 1:1) with a line width of 300 μm) and the photosensitive resin layer for etching was set to 200 μm, and the exposure amount was 50 mJ / cm 2 (i-line) for pattern exposure. Next, development treatment was performed at 25 °C for 100 seconds using a triethanolamine-based developer (a solution obtained by diluting a solution containing 30% by mass of triethanolamine, trade name: T-PD2 (manufactured by Fuji Film Co., Ltd.) 10 times with pure water), and cleaning treatment was performed at 33 °C for 20 seconds using a surfactant-containing cleaning liquid (a solution obtained by diluting a solution with trade name: T-SD3 (manufactured by Fuji Film Co., Ltd.) 10 times with pure water). The front panel after the cleaning treatment was rubbed with a rotating brush, and further, the residue was removed by spraying ultrapure water from an ultrahigh-pressure cleaning nozzle. Next, post-baking treatment was performed at 130 °C for 30 minutes to obtain a substrate on which a transparent electrode layer and a pattern of the photosensitive resin layer for etching were formed. The substrate on which the transparent electrode layer and the pattern of the photosensitive resin layer for etching were formed was immersed in an etching tank containing an ITO etchant (hydrochloric acid, potassium chloride aqueous solution, liquid temperature 30 °C), and treated (etched) for 100 seconds to dissolve and remove the transparent electrode layer in the exposed area not covered by the photosensitive resin layer for etching, and a substrate with a transparent electrode layer pattern with a pattern of the photosensitive resin layer for etching was obtained. Next, a substrate with a transparent electrode layer pattern having an etching photocurable resin layer pattern was immersed in a resist stripping tank filled with a resist stripper (N-methyl-2-pyrrolidone, monoethanolamine, surfactant (trade name: Surfynol 465, manufactured by Air Products), liquid temperature 45°C) and treated for 200 seconds (stripping treatment) to remove the etching photocurable resin layer, thereby obtaining a substrate (transfer member having a conductive pattern) with a transparent electrode pattern formed on a transparent substrate.

[0257] The protective film was peeled off from the prepared transfer film, and the exposed peeling surface was laminated on the transfer member having the obtained conductive pattern so as to be in contact with the conductive pattern to obtain a laminate (rubber roller temperature 100°C, line pressure 0.6 Pa, conveyance speed 4.0 m / min). The laminate was observed visually and with an optical microscope. "A": No bubbles were observed in the laminate, and the flatness of the laminate surface was also excellent without any problems. "B": No bubbles were observed between the conductive pattern and the photosensitive composition layer, but slightly bubbles were observed outside the area between the conductive pattern and the photosensitive composition layer. "C": Slightly bubbles were observed between the conductive pattern and the photosensitive composition layer. "D": Bubbles were observed between the conductive pattern and the photosensitive composition layer.

[0258] 〔Patternability〕 The protective film was peeled off from each of the prepared transfer films, and the exposed peeling surface was laminated on a 50-μm-thick PET film (Cosmo Shine A4360, manufactured by Toyobo Co., Ltd.) to obtain a laminate (rubber roller temperature 100°C, line pressure 0.6 Pa, conveyance speed 4.0 m / min). Next, a mask having a line-and-space pattern (duty ratio 1:1) with a line width of 50 to 500 μm was brought into contact with a temporary support while adjusting the exposure position (alignment), and exposed through the mask with an ultra-high pressure mercury lamp at an exposure amount of 200 mJ / cm 2After exposure (measured with i-line) and standing for 30 minutes, development was carried out to form a resin layer pattern. The development was performed for 60 seconds by shower development using an aqueous sodium carbonate solution of 1.0 mass% at 33 °C to obtain a substrate with a resin layer pattern. The above substrate was observed with an optical microscope, and further, the cross-section of the observed resin layer pattern was observed with a SEM to evaluate the patterning property based on the following criteria. "A": A pattern with a line width of 50 μm was resolved without problems, and there was no peeling on the refractive index adjustment layer on the pattern with a line width of 50 μm. "B": A pattern with a line width of 100 μm was resolved without problems, and there was no peeling on the refractive index adjustment layer on the pattern with a line width of 100 μm. "C": A pattern with a line width of 200 μm was resolved without problems, and there was no peeling on the refractive index adjustment layer on the pattern with a line width of 200 μm. "D": A pattern with a line width of 200 μm could not be resolved without problems, or there was peeling on the refractive index adjustment layer on the pattern with a line width of 200 μm.

[0259] 〔Reverse peelability〕 Each prepared transfer film was cut to a width of 40 mm, and a T-peel test for peeling the protective film from the cut piece was carried out at a speed of 100 mm / min using a surface property measuring instrument (TYPE: 14FW, manufactured by Shin-Tech Co., Ltd.). The peeled surface of the protective film was observed visually and with an optical microscope to evaluate the reverse peelability based on the following criteria. "A": No reversely transferred photosensitive composition layer was observed visually and with an optical microscope. "B": A reversely transferred photosensitive composition layer with a size of 5 μm or less in diameter was observed with an optical microscope. "C": A reversely transferred photosensitive composition layer with a size of more than 5 μm and 10 μm or less in diameter was observed with an optical microscope. "D": A reversely transferred photosensitive composition layer with a size of more than 10 μm in diameter was observed visually and with an optical microscope.

[0260]

Table 4

[0261] Protective film 1: Celapill 25WZ Temporary support 1: Lumirror 16KS40

[0262] From the above evaluation results, it was confirmed that the transfer film of the present invention has excellent laminating properties and a low reflectance of the laminate including the cured film obtained from the transferred photosensitive composition layer. From the comparison of Example 2 and Example 6 etc., it was confirmed that when the average film thickness of the first photosensitive composition layer is 200 nm or less, the reflectance is more excellent. From the comparison of Example 1 to 4 etc., it was confirmed that when the average film thickness of the second photosensitive composition layer is 40 to 300 μm, the laminating property is more excellent. From the comparison of Example 2 and 5 to 12 etc., the ratio of the complex viscosity B at 25 °C of the second photosensitive composition layer to the complex viscosity A at 90 °C of the second photosensitive composition layer (complex viscosity B / complex viscosity A) is 4.0×10 3 When it is the above, it was confirmed that the reverse peelability is more excellent. From the comparison of Example 2 and 9 to 12 etc., it was confirmed that when the second photosensitive composition layer contains Compound M, an ethylenically unsaturated compound having an acid group, and a thermally crosslinkable compound, the reverse peelability is more excellent. From the comparison of Example 2, 5, 7 and 8 etc., when the content of the ethylenically unsaturated compound having three or more functional groups is 22 to 40% by mass based on the total mass of the polymerizable compound, it is confirmed that it is more excellent than at least one of the laminating property, patterning property and reverse peelability.

Explanation of symbols

[0263] 10 Transfer film 11 Protective film 13 Second photosensitive composition layer 15 First photosensitive composition layer 17 Temporary support

Claims

1. A transfer film comprising a temporary support and a photosensitive composition layer, wherein the photosensitive composition layer has, in this order from the temporary support side, a first photosensitive composition layer and a second photosensitive composition layer, the first photosensitive composition layer contains a polymerization initiator, the refractive index of the first photosensitive composition layer is 1.45 or less and is smaller than the refractive index of the second photosensitive composition layer, the transfer film wherein the average film thickness of the second photosensitive composition layer exceeds 30 μm.

2. The ratio of the complex viscosity B of the second photosensitive composition layer at 25°C to the complex viscosity A of the second photosensitive composition layer at 90°C is 4.0×10 ３ or more. The transfer film according to claim 1.

3. The transfer film according to claim 1 or 2, wherein the first photosensitive composition layer contains refractive index adjusting particles.

4. The transfer film according to claim 1 or 2, wherein the average film thickness of the first photosensitive composition layer is 200 nm or less.

5. The transfer film according to claim 1 or 2, wherein the average film thickness of the second photosensitive composition layer is 40 to 300 μm.

6. A bonding step of bonding the second photosensitive composition layer in the transfer film according to claim 1 or 2 and the surface on the conductive layer side in a transfer member having a base material and a conductive layer disposed on the base material, an exposure step of exposing the photosensitive composition layer, and a method for producing a laminate, comprising a peeling step of peeling the temporary support during or after the bonding step and the exposure step or after the exposure step.

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