Transfer film, manufacturing method of laminate, and manufacturing method of laminate having conductive pattern

Abstract

To provide a transfer film which is excellent in adhesion to a transferred object of a cured film formed after a photosensitive layer has been transferred onto the transferred object, and is excellent in hardness of a surface on a side opposite to the transferred object of the cured film; and a method for manufacturing a laminate and a method for manufacturing a laminate having a conductor pattern.SOLUTION: A transfer film has a temporary support, and a photosensitive layer, wherein the photosensitive layer contains an alkali-soluble resin, a photopolymerizable compound and a photopolymerization initiator, and the photopolymerization initiator contains a compound represented by general formula (a-1).SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present invention relates to a transfer film, a method for manufacturing a laminate, and a method for manufacturing a laminate having a conductive pattern. [Background technology]

[0002] In display devices equipped with a touch panel such as a capacitance-type input device (specifically, examples of such display devices include organic electroluminescence (EL) display devices and liquid crystal display devices), conductor patterns such as an electrode pattern corresponding to the sensor of the visual recognition area, peripheral wiring portions, and wiring of the lead-out wiring portions are provided inside the touch panel. A resin pattern is usually disposed on the conductor pattern as a protective film to prevent problems such as metal corrosion, increased electrical resistance between the electrodes and the driving circuit, and disconnection. Furthermore, among the above display devices, particularly in liquid crystal display devices, a resin pattern is disposed as a photospacer on a lattice-shaped black matrix formed between pixels. These resin patterns are usually formed by photolithography using a photosensitive resin composition.

[0003] For example, Patent Document 1 discloses a photosensitive resin composition for forming a photospacer, which contains an alkali-soluble resin, a monomer having a predetermined structure, and a photopolymerization initiator, and in which the alkali-soluble resin and the monomer having a predetermined structure are blended in a predetermined ratio. Furthermore, Patent Document 1 discloses a compound having the following structure as the photopolymerization initiator.

[0004] [ka]

[0005] Incidentally, since the number of steps required to obtain a predetermined pattern is small, a method of forming a resin pattern using a transfer film in which a photosensitive layer is disposed on a temporary support is also widely used. A typical example of a method of forming a resin pattern using a transfer film is a formation method in which the photosensitive layer in the transfer film is transferred to an arbitrary substrate (transfer target), and this photosensitive layer is exposed to light through a mask and then developed. [Prior art documents] [Patent documents]

[0006] [Patent Document 1] International Publication No. 2019 / 065687 Summary of the Invention [Problem to be solved by the invention]

[0007] Recently, the present inventors have applied the photosensitive resin composition described in Patent Document 1 as a photosensitive layer of a transfer film and examined its performance, and have found that the cured film (a film formed by curing the photosensitive layer by exposure) formed after transferring the photosensitive layer to a transfer target may peel off from the transfer target. In other words, they have found that there is a problem with the adhesion of the cured film formed after transferring the photosensitive layer to a transfer target. Incidentally, the cured film obtained by curing the photosensitive layer is also required to have a high hardness on the surface of the cured film opposite to the transfer target, as a basic performance.

[0008] Therefore, based on the above findings, an object of the present invention is to provide a transfer film that has excellent adhesion of the cured film formed after transferring a photosensitive layer to a substrate, and that has excellent hardness on the surface of the cured film opposite to the substrate. Another object of the present invention is to provide a method for manufacturing a laminate and a method for manufacturing a laminate having a conductor pattern. [Means for solving the problem]

[0009] As a result of extensive investigation, the present inventors have found that the above-mentioned problems can be solved by the following configuration.

[0010] [1] A transfer film having a temporary support and a photosensitive layer, the photosensitive layer contains an alkali-soluble resin, a photopolymerizable compound, and a photopolymerization initiator; The photopolymerization initiator of the transfer film contains a compound represented by general formula (a-1) described below. [2] The oxime ester value of the compound represented by the general formula (a-1) is 2.0 × 10 -3 ~7.0×10 -3 The transfer film according to [1], wherein the molecular weight is mol / g. [3] The transfer film according to [1] or [2], wherein in the general formula (a-1), m+n represents 1 and l represents 0 or 1. [4] The transfer film according to any one of [1] to [3], wherein the compound represented by the general formula (a-1) includes at least one compound selected from the group consisting of a compound represented by the general formula (b-1) described later and a compound represented by the general formula (b-2) described later. [5] The photopolymerizable compound includes at least one of a bifunctional photopolymerizable compound and a trifunctional photopolymerizable compound, The transfer film according to any one of [1] to [4], wherein the total content of the bifunctional photopolymerizable compound and the trifunctional photopolymerizable compound is 40 mass% or more relative to the total mass of the photopolymerizable compounds. [6] The transfer film according to [5], wherein the total content of the bifunctional photopolymerizable compound and the trifunctional photopolymerizable compound is 45 mass% or more relative to the total mass of the photopolymerizable compounds. [7] a lamination step in which a surface of the transfer film according to any one of [1] to [6] opposite to the temporary support is brought into contact with a substrate having a conductive layer and laminated to obtain a substrate with a photosensitive layer having the substrate, the conductive layer, the photosensitive layer, and the temporary support in this order; an exposure step of pattern-exposing the photosensitive layer; a developing step of developing the exposed photosensitive layer to form a protective film pattern that protects the conductive layer; The method for producing a laminate further comprises a peeling step of peeling the temporary support from the photosensitive layer-formed substrate between the laminating step and the exposing step, or between the exposing step and the developing step. [8] a lamination step of bringing a surface of the transfer film according to any one of [1] to [6] opposite to the temporary support into contact with a substrate having a conductive layer to obtain a substrate with a photosensitive layer having the substrate, the conductive layer, the photosensitive layer, and the temporary support in this order; an exposure step of pattern-exposing the photosensitive layer; a developing step of developing the exposed photosensitive layer to form a resin pattern; an etching step of etching the conductive layer in an area where the resin pattern is not disposed; The method for producing a laminate having a conductive pattern further comprises a peeling step of peeling the temporary support from the substrate with the photosensitive layer between the laminating step and the exposure step, or between the exposure step and the development step. [Effects of the Invention]

[0011] According to the present invention, a transfer film can be provided in which the cured film formed after transferring a photosensitive layer to a transfer target has excellent adhesion, and the surface of the cured film opposite to the transfer target has excellent hardness. Furthermore, the present invention can provide a method for manufacturing a laminate and a method for manufacturing a laminate having a conductor pattern. [Brief explanation of the drawings]

[0012] [Figure 1] FIG. 2 is a schematic diagram showing an example of the configuration of the transfer film of the first embodiment. [Figure 2] FIG. 10 is a schematic diagram showing an example of the configuration of a transfer film according to a second embodiment. DETAILED DESCRIPTION OF THE INVENTION

[0013] The present invention will be described in detail below. In this specification, a numerical range expressed using "to" means a range that includes the numerical values ​​before and after "to" as the lower and upper limits. In the present specification, in the numerical ranges described in stages, the upper or lower limit value described in a certain numerical range may be replaced with the upper or lower limit value of another numerical range described in stages. Furthermore, in the numerical ranges described in the present specification, the upper or lower limit value described in a certain numerical range may be replaced with a value shown in the examples.

[0014] In this specification, the term "process" includes not only an independent process but also a process that cannot be clearly distinguished from other processes, as long as the intended purpose of the process is achieved.

[0015] In this specification, the term "transparent" means that the average transmittance of visible light with a wavelength of 400 to 700 nm is 80% or more, and preferably 90% or more. In this specification, the average transmittance of visible light is a value measured using a spectrophotometer, and can be measured using, for example, a spectrophotometer U-3310 manufactured by Hitachi, Ltd.

[0016] In this specification, unless otherwise specified, the weight-average molecular weight (Mw) and number-average molecular weight (Mn) are values ​​measured by a gel permeation chromatography (GPC) analyzer using a TSKgel GMHxL, TSKgel G4000HxL, or TSKgel G2000HxL (all trade names manufactured by Tosoh Corporation) column, THF (tetrahydrofuran) as an eluent, a differential refractometer as a detector, and polystyrene as a standard substance, and converted using polystyrene as the standard substance. In this specification, unless otherwise specified, the molecular weight of a compound having a molecular weight distribution is the weight average molecular weight (Mw). In this specification, unless otherwise specified, the content of metal elements is a value measured using an inductively coupled plasma (ICP) spectroscopic analyzer. In this specification, unless otherwise specified, the refractive index is a value measured using an ellipsometer at a wavelength of 550 nm. In this specification, unless otherwise specified, the hue is a value measured using a color difference meter (CR-221, manufactured by Minolta Co., Ltd.).

[0017] In this specification, "(meth)acrylic" is a concept that encompasses both acrylic and methacrylic, and "(meth)acryloxy group" is a concept that encompasses both acryloxy group and methacryloxy group.

[0018] In this specification, "alkali-soluble" means that the solubility in 100 g of a 1% by mass aqueous solution of sodium carbonate at 22°C is 0.1 g or more.

[0019] As used herein, "water-soluble" means that the solubility in 100 g of water having a pH of 7.0 and 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-mentioned solubility conditions.

[0020] In this specification, the "solid content" of a composition refers to the components that form a composition layer formed using the composition, and when the composition contains a solvent (organic solvent, water, etc.), it refers to all components excluding the solvent. Furthermore, liquid components that form a composition layer are also considered to be solid content. In other words, when the composition layer is a photosensitive layer formed using a photosensitive composition, all components of the photosensitive composition excluding the solvent fall under the category of "solid content."

[0021] In this specification, the acid value (mgKOH / g) is the mass [mg] of potassium hydroxide required to neutralize 1 g of sample. The acid value is measured in accordance with the method described in JIS K0070:1992.

[0022] [Transfer film] A characteristic feature of the transfer film of the present invention is that the photosensitive layer contains an alkali-soluble resin, a photopolymerizable compound, and a photopolymerization initiator, and the photopolymerization initiator contains a compound represented by general formula (a-1) described below (hereinafter also referred to as a "specific oxime ester compound"). By virtue of having the above-described characteristics, the transfer film of the present invention has excellent adhesion to the cured film formed after transferring the photosensitive layer to the substrate, and also has excellent hardness on the surface of the cured film opposite to the substrate.

[0023] Although the mechanism of action of the above-mentioned configuration and effect is not clear, the present inventors have speculated as follows: In the following, the speculated mechanism of action will be explained using a transfer film consisting of a temporary support / photosensitive layer / protective film as an example. When the transfer film from which the protective film has been peeled off is transferred to a transfer target (e.g., any substrate) and an exposure process is performed in which light is incident from the temporary support side, it has been revealed that due to the high light absorption of the specific oxime ester compound, the photopolymerizable compound exhibits high reactivity on the temporary support side of the photosensitive layer, while the reactivity of the photopolymerizable compound is low on the side of the photosensitive layer opposite the temporary support (in other words, the transfer target side). As a result, it is presumed that the cured film formed by exposing the photosensitive layer has high surface hardness on the temporary support side. On the other hand, on the transfer target side, the photopolymerizable compound reacts slowly during the exposure process, so the photosensitive layer is likely to harden in a state that follows the shape of the transfer target, which is presumed to result in high adhesion. The specific effects of the above-mentioned specific oxime ester compounds are apparent from a comparison between the examples and comparative examples in the Examples section. The present inventors have confirmed through their recent studies that although the reactivity of the photopolymerizable compound in the photosensitive layer differs between the temporary support side and the opposite side due to the specific oxime ester compound, the photosensitive layer as a whole has excellent reactivity. As a result, the inventors have confirmed that a photosensitive layer using the specific oxime ester compound as a photopolymerization initiator has excellent moisture permeability and is suitable as a protective film for a conductor pattern.

[0024] Hereinafter, better adhesion of the cured film formed after transferring the photosensitive layer to the transfer target and / or better hardness of the surface of the cured film opposite to the transfer target is also referred to as "better effects of the present invention."

[0025] The transfer film of the present invention will be described below. The transfer film of the present invention has a temporary support and a photosensitive layer. The photosensitive layer is preferably a negative photosensitive layer. Furthermore, the transfer film typically has a protective film on the surface opposite to the temporary support. It is also preferable that the transfer film of the present invention has a protective film on the surface opposite to the temporary support. The transfer film of the present invention may further include a layer other than the photosensitive layer between the temporary support and the protective film, such as a thermoplastic resin layer, an intermediate layer, and a refractive index adjusting layer.

[0026] Hereinafter, the layer disposed between the temporary support and the protective film may be referred to as a composition layer. The composition layer is not particularly limited as long as it contains a photosensitive layer, and may have a single-layer structure (in other words, a structure containing only a photosensitive layer) or a structure containing two or more layers. When the composition layer contains a composition layer other than the photosensitive layer, examples of the other composition layer include a thermoplastic resin layer, an intermediate layer, and a refractive index adjusting layer.

[0027] An example of the embodiment of the transfer film of the present invention is shown below, but the present invention is not limited to this. (1) "Temporary support / photosensitive layer / refractive index adjusting layer / protective film" (2) "Temporary support / photosensitive layer / protective film" (3) "Temporary support / intermediate layer / photosensitive layer / protective film" (4) "Temporary support / thermoplastic resin layer / intermediate layer / photosensitive layer / protective film" In each of the above-described configurations, the photosensitive layer is preferably a negative photosensitive layer, and is also preferably a colored resin layer. The transfer film of the present invention may be used as a transfer film for a wiring protective film, as will be described later, or as a transfer film for an etching resist. When the transfer film is used as a wiring protection film, the transfer film preferably has the structure (1) or (2) described above. When the transfer film is used as an etching resist, the transfer film preferably has the structure (2) to (4) described above.

[0028] When the composition layer of the transfer film further has another composition layer on the side opposite the temporary support side of the photosensitive layer, the total thickness of the other composition layer arranged on the side opposite the temporary support side of the photosensitive layer is preferably 0.1 to 30% of the thickness of the photosensitive layer, and more preferably 0.1 to 20%.

[0029] From the viewpoint of preventing the generation of bubbles in the lamination step described later, the maximum waviness width of the transfer film is preferably 300 μm or less, more preferably 200 μm or less, and even more preferably 60 μm or less. The lower limit of the maximum waviness width is 0 μm or more, preferably 0.1 μm or more, and more preferably 1 μm or more. The maximum width of the undulation of the transfer film is a value measured by the following procedure. First, the transfer film is cut perpendicular to the main surface to a size of 20 cm x 20 cm to prepare a test sample. If the transfer film has a protective film, the protective film is peeled off. Next, the test sample is placed on a flat, horizontal stage with the surface of the temporary support facing the stage. After the sample is placed, a 10 cm square area in the center of the test sample is scanned with a laser microscope (e.g., Keyence VK-9700SP) to obtain a three-dimensional surface image. The minimum concave height is subtracted from the maximum convex height observed in the obtained three-dimensional surface image. This procedure is performed on 10 test samples, and the arithmetic average value is taken as the "maximum waviness width of the transfer film."

[0030] The transfer film of the present invention will be described below by taking an example of a specific embodiment. The transfer film of the first embodiment below is suitable for use as a transfer film for a wiring protection film, and the transfer film of the second embodiment below is suitable for use as a transfer film for an etching resist.

[0031] [Transfer film of the first embodiment] An example of the transfer film of the first embodiment will be described below. The transfer film 10 shown in FIG. 1 has a temporary support 1, a composition layer 2 including a photosensitive layer 3 and a refractive index adjusting layer 5, and a protective film 7 in this order. Although the transfer film 10 shown in FIG. 1 has a protective film 7 disposed thereon, the protective film 7 does not necessarily have to be disposed. Furthermore, although the transfer film 10 shown in FIG. 1 has a refractive index matching layer 5 disposed thereon, the refractive index matching layer 5 does not necessarily have to be disposed. Each element constituting the transfer film will be described below.

[0032] <<Temporary support>> The transfer film has a temporary support. The temporary support is a member that supports the composition layer and is ultimately removed by a peeling treatment.

[0033] The temporary support may have a single-layer structure or a multi-layer structure. The temporary support is preferably a film, more preferably a resin film, which is flexible and does not significantly deform, shrink, or stretch under pressure or under pressure and heat. Examples of the film include polyethylene terephthalate film (for example, biaxially stretched polyethylene terephthalate film), polymethyl methacrylate film, cellulose triacetate film, polystyrene film, polyimide film, and polycarbonate film. Among these, a polyethylene terephthalate film is preferred as the temporary support. Furthermore, it is preferable that the film used as the temporary support is free from deformations such as wrinkles and scratches.

[0034] The temporary support preferably has high transparency so that pattern exposure can be performed through the temporary support, and the transmittance at 365 nm is preferably 60% or more, more preferably 70% or more. From the viewpoints of pattern formability during pattern exposure through the temporary support and transparency of the temporary support, it is preferable that the haze of the temporary support is small. Specifically, the haze value of the temporary support is preferably 2% or less, more preferably 0.5% or less, and even more preferably 0.1% or less. From the viewpoint of pattern formation during pattern exposure through the temporary support and the transparency of the temporary support, it is preferable that the number of fine particles, foreign matter, and defects contained in the temporary support is small. The number of fine particles, foreign matter, and defects with a diameter of 1 μm or more in the temporary support is 50 / 10 mm. 2 Preferably less than 10 pieces / 10mm 2 Less than 3 pieces / 10mm is more preferable. 2 Less than 0 pieces / 10mm is more preferable. 2 is particularly preferred.

[0035] The thickness of the temporary support is not particularly limited, but is preferably 5 to 200 μm, and from the viewpoint of ease of handling and versatility, more preferably 5 to 150 μm, even more preferably 5 to 50 μm, and most preferably 5 to 25 μm. The thickness of the temporary support is calculated as the average value of measurements taken at any five points by cross-sectional observation using an SEM (Scanning Electron Microscope).

[0036] In order to improve the adhesion between the temporary support and the composition layer, the side of the temporary support that comes into contact with the composition layer may be surface-modified by UV irradiation, corona discharge, plasma, or the like.

[0037] When surface modification is performed by UV irradiation, the exposure dose is 10 to 2000 mJ / cm 2is preferred, and 50 to 1000 mJ / cm 2 is more preferred.

[0038] Examples of light sources for UV irradiation include low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, carbon arc lamps, metal halide lamps, xenon lamps, chemical lamps, electrodeless discharge lamps, light-emitting diodes (LEDs), etc., which emit light in the 150 to 450 nm wavelength band. As long as the light irradiation amount is within this range, there are no particular limitations on the lamp output or illuminance.

[0039] Examples of the temporary support include a biaxially oriented polyethylene terephthalate film having a thickness of 16 μm, a biaxially oriented polyethylene terephthalate film having a thickness of 12 μm, and a biaxially oriented polyethylene terephthalate film having a thickness of 9 μm.

[0040] Preferred forms of the temporary support are described, for example, in paragraphs

[0017] to

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

[0019] to

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

[0019] to

[0026] of WO 2012 / 081680.

[0041]

[0057] and paragraphs

[0029] to

[0040] of International Publication No. 2018 / 179370, the contents of which are incorporated herein by reference.

[0041] To improve handling properties, 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. The thickness of the lubricant layer is preferably 0.05 to 1.0 μm. Commercially available temporary supports include Lumirror 16KS40 and Lumirror 16FB40 (both manufactured by Toray Industries, Inc.), and Cosmoshine A4100, Cosmoshine A4300, and Cosmoshine A8300 (all manufactured by Toyobo Co., Ltd.).

[0042] <<Photosensitive layer>> The transfer film has a photosensitive layer. After the photosensitive layer is transferred onto the transfer target, it is exposed to light and developed, thereby forming a pattern on the transfer target. The photosensitive layer is preferably a negative photosensitive layer. Note that a negative photosensitive layer is a photosensitive layer in which the solubility of the exposed portion in a developer decreases upon exposure. When the photosensitive layer is a negative photosensitive layer, the formed pattern corresponds to a hardened layer.

[0043] Components that can be contained in the photosensitive layer will be described in detail below.

[0044] <Binder polymer> The photosensitive layer contains an alkali-soluble resin as a binder polymer. The binder polymer of the photosensitive layer may be partially or entirely an alkali-soluble resin. The definition of alkali-solubility is as described above.

[0045] Examples of binder polymers that can be contained in the photosensitive layer include (meth)acrylic resins, styrene resins, epoxy resins, amide resins, amide epoxy resins, alkyd resins, phenolic resins, ester resins, urethane resins, epoxy acrylate resins obtained by reacting an epoxy resin with (meth)acrylic acid, and acid-modified epoxy acrylate resins obtained by reacting an epoxy acrylate resin with an acid anhydride.

[0046] One preferred embodiment of the binder polymer is a (meth)acrylic resin, which has excellent alkaline developability and film formability. In this specification, the term "(meth)acrylic resin" refers to a resin having structural units derived from (meth)acrylic compounds. The content of the structural units derived from (meth)acrylic compounds is preferably 50% by mass or more, more preferably 70% by mass or more, and even more preferably 90% by mass or more, based on the total structural units of the (meth)acrylic resin. The (meth)acrylic resin may be composed solely of structural units derived from (meth)acrylic compounds, or may contain structural units derived from polymerizable monomers other than (meth)acrylic compounds. That is, the upper limit of the content of structural units derived from (meth)acrylic compounds is 100% by mass or less of all structural units of the (meth)acrylic resin.

[0047] Examples of the (meth)acrylic compound include (meth)acrylic acid, (meth)acrylic acid esters, (meth)acrylamide, and (meth)acrylonitrile. Examples of (meth)acrylic acid esters include (meth)acrylic acid alkyl esters, (meth)acrylic acid tetrahydrofurfuryl esters, (meth)acrylic acid dimethylaminoethyl esters, (meth)acrylic acid diethylaminoethyl esters, (meth)acrylic acid glycidyl esters, (meth)acrylic acid benzyl esters, 2,2,2-trifluoroethyl (meth)acrylate, and 2,2,3,3-tetrafluoropropyl (meth)acrylate, and (meth)acrylic acid alkyl esters are preferred. Examples of (meth)acrylamides include acrylamides such as diacetone acrylamide.

[0048] The alkyl group of the (meth)acrylic acid alkyl ester may be linear or branched. Specific examples include (meth)acrylic acid alkyl esters having an alkyl group having 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, a (meth)acrylic acid alkyl ester having an alkyl group having 1 to 4 carbon atoms is preferred, and methyl (meth)acrylate or ethyl (meth)acrylate is more preferred.

[0049] The (meth)acrylic resin may have a structural unit other than the structural unit derived from the (meth)acrylic compound. The polymerizable monomer that forms the structural unit is not particularly limited as long as it is a compound other than a (meth)acrylic compound that is copolymerizable with a (meth)acrylic compound, and examples thereof include styrene compounds that may have a substituent at the α-position or on the aromatic ring, such as styrene, vinyltoluene, and α-methylstyrene; vinyl alcohol esters such as acrylonitrile and vinyl-n-butyl ether; maleic acid monoesters such as maleic acid, maleic anhydride, monomethyl maleate, monoethyl maleate, and monoisopropyl maleate; fumaric acid, cinnamic acid, α-cyanocinnamic acid, itaconic acid, and crotonic acid. These polymerizable monomers may be used alone or in combination of two or more.

[0050] In order to improve alkaline developability, the (meth)acrylic resin preferably contains a structural unit having an acid group, such as a carboxy group, a sulfo group, a phosphate group, or a phosphonate group. In particular, the (meth)acrylic resin more preferably has a structural unit having a carboxy group, and even more preferably has a structural unit derived from the above-mentioned (meth)acrylic acid.

[0051] The content of structural units having an acid group in the (meth)acrylic resin (preferably structural units derived from (meth)acrylic acid) is preferably 10% by mass or more relative to the total mass of the (meth)acrylic resin in terms of excellent developability. While there is no particular upper limit, it is preferably 50% by mass or less, more preferably 40% by mass or less, in terms of excellent alkali resistance.

[0052] Furthermore, the (meth)acrylic resin more preferably has a structural unit derived from the above-mentioned alkyl (meth)acrylate ester. The content of structural units derived from alkyl (meth)acrylate in the (meth)acrylic resin is preferably 50 to 90 mass %, more preferably 60 to 90 mass %, and even more preferably 65 to 90 mass %, based on all structural units of the (meth)acrylic resin.

[0053] As the (meth)acrylic resin, a resin having both a structural unit derived from (meth)acrylic acid and a structural unit derived from a (meth)acrylic acid alkyl ester is preferred, and a resin composed only of a structural unit derived from (meth)acrylic acid and a structural unit derived from a (meth)acrylic acid alkyl ester is more preferred. Furthermore, 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 preferred.

[0054] Furthermore, in order to achieve better effects of the present invention, the (meth)acrylic resin preferably has at least one selected from the group consisting of structural units derived from methacrylic acid and structural units derived from a methacrylic acid alkyl ester, and more preferably has both structural units derived from methacrylic acid and structural units derived from a methacrylic acid alkyl ester. The total content of the structural units derived from methacrylic acid and the structural units derived from alkyl methacrylate in the (meth)acrylic resin is preferably 40% by mass or more, more preferably 60% by mass or more, based on the total structural units of the (meth)acrylic resin, in order to obtain better effects of the present invention. The upper limit is not particularly limited, and may be 100% by mass or less, preferably 80% by mass or less.

[0055] In addition, in terms of achieving better effects of the present invention, it is also preferable that the (meth)acrylic resin has at least one selected from the group consisting of structural units derived from methacrylic acid and structural units derived from methacrylic acid alkyl esters, and at least one selected from the group consisting of structural units derived from acrylic acid and structural units derived from acrylic acid alkyl esters. In order to obtain a more excellent effect of the present invention, the total content of the structural units derived from methacrylic acid and the structural units derived from an alkyl methacrylate ester is preferably in a mass ratio of 60 / 40 to 80 / 20 relative to the total content of the structural units derived from acrylic acid and the structural units derived from an alkyl acrylate ester.

[0056] The (meth)acrylic resin preferably has an ester group at the end, in order to provide excellent developability of the photosensitive layer after transfer. The terminals of the (meth)acrylic resin are composed of moieties derived from the polymerization initiator used in the synthesis. A (meth)acrylic resin having an ester group at its terminal can be synthesized by using a polymerization initiator that generates a radical having an ester group.

[0057] One preferred embodiment of the binder polymer is, for example, a resin having an acid value of 60 mgKOH / g or more from the viewpoint of developability. Among these, the resin is more preferably a resin having a carboxy group with an acid value of 60 mgKOH / g or more (so-called carboxy group-containing resin) from the viewpoint of easily thermally crosslinking with the crosslinking component by heating to form a strong film, and even more preferably a (meth)acrylic resin having a carboxy group with an acid value of 60 mgKOH / g or more (so-called carboxy group-containing (meth)acrylic resin). When a resin having a carboxy group is used, the three-dimensional crosslinking density can be increased by, for example, adding a thermally crosslinkable compound such as a blocked isocyanate compound to cause thermal crosslinking. Furthermore, when the carboxy group of the resin having a carboxy group is dehydrated and made hydrophobic, the wet heat resistance can be improved.

[0058] 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-mentioned acid value condition, and can be appropriately selected from known (meth)acrylic resins. For example, among the polymers described in paragraph

[0025] of JP-A No. 2011-095716, carboxyl 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 No. 2010-237589, carboxyl group-containing acrylic resins having an acid value of 60 mgKOH / g or more can be preferably used.

[0059] A preferred embodiment of the binder polymer is a styrene-acrylic copolymer. In this specification, a styrene-acrylic copolymer refers to a resin having structural units derived from a styrene compound and structural units derived from a (meth)acrylic compound, and the total content of the structural units derived from the styrene compound and the structural units derived from the (meth)acrylic compound is preferably 30% by mass or more, and more preferably 50% by mass or more, of all structural units of the copolymer. The content of the structural units derived from the styrene compound is preferably 1% by mass or more, more preferably 5% by mass or more, and even more preferably 5 to 80% by mass, based on all structural units of the copolymer. The content of the structural units derived from the (meth)acrylic compound is preferably 5% by mass or more, more preferably 10% by mass or more, and even more preferably 20 to 95% by mass, based on all structural units of the copolymer.

[0060] The binder polymer preferably has an aromatic ring structure, and more preferably has a structural unit having an aromatic ring structure, in order to achieve better effects of the present invention. Examples of monomers that form structural units having an aromatic ring structure include monomers having an aralkyl group, styrene, and polymerizable styrene derivatives (e.g., methylstyrene, vinyltoluene, tert-butoxystyrene, acetoxystyrene, 4-vinylbenzoic acid, styrene dimer, and styrene trimer). Among these, monomers having an aralkyl group or styrene are preferred. Examples of aralkyl groups include substituted or unsubstituted phenylalkyl groups (excluding benzyl groups) and substituted or unsubstituted benzyl groups, with substituted or unsubstituted benzyl groups being preferred.

[0061] Examples of the monomer having a phenyl alkyl group include phenylethyl (meth)acrylate.

[0062] Examples of the monomer having a benzyl group include (meth)acrylates having a benzyl group, such as benzyl (meth)acrylate and chlorobenzyl (meth)acrylate, and vinyl monomers having a benzyl group, such as vinylbenzyl chloride and vinylbenzyl alcohol. Of these, benzyl (meth)acrylate is preferred.

[0063] Furthermore, the binder polymer more preferably has a structural unit represented by the following formula (S) (a structural unit derived from styrene), in terms of achieving better effects of the present invention.

[0064] [ka]

[0065] 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 mass %, more preferably 10 to 70 mass %, and even more preferably 20 to 60 mass %, based on the total structural units of the binder polymer, in terms of better effects of the present invention. Furthermore, the content of the structural units having an aromatic ring structure in the binder polymer is preferably 5 to 70 mol %, more preferably 10 to 60 mol %, and even more preferably 20 to 60 mol %, based on the total structural units of the binder polymer, in order to achieve better effects of the present invention. Furthermore, the content of the structural unit represented by the above formula (S) in the binder polymer is preferably 5 to 70 mol %, more preferably 10 to 60 mol %, even more preferably 20 to 60 mol %, and particularly preferably 20 to 50 mol %, based on the total structural units of the binder polymer, in order to achieve better effects of the present invention. In this specification, when the content of a "structural unit" is specified by a molar ratio, the "structural unit" is considered to have the same meaning as a "monomer unit." In addition, in this specification, the "monomer unit" may be modified after polymerization by a polymer reaction or the like. The same applies hereinafter.

[0066] The binder polymer preferably has an aliphatic hydrocarbon ring structure in order to obtain better effects of the present invention. That is, the binder polymer preferably has a structural unit having an aliphatic hydrocarbon ring structure. The aliphatic hydrocarbon ring structure may be monocyclic or polycyclic. In particular, the binder polymer more preferably has a ring structure in which two or more aliphatic hydrocarbon rings are condensed.

[0067] Examples of the ring that constitutes 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 isoborone ring. Among these, in view of the superior effect of the present invention, a ring in which two or more aliphatic hydrocarbon rings are condensed is preferred, and a tetrahydrodicyclopentadiene ring (tricyclo[5.2.1.0] 2,6 ]decane ring) is more preferred. Examples of monomers that form a structural unit having an aliphatic hydrocarbon ring structure include dicyclopentanyl (meth)acrylate, cyclohexyl (meth)acrylate, and isobornyl (meth)acrylate. Furthermore, in terms of achieving better effects of the present invention, the binder polymer more preferably has a structural unit represented by the following formula (Cy), and more preferably has a structural unit represented by the above formula (S) and a structural unit represented by the following formula (Cy).

[0068] [ka]

[0069] In the formula (Cy), R M represents a hydrogen atom or a methyl group, and R Cy represents a monovalent group having an aliphatic hydrocarbon ring structure.

[0070] R in formula (Cy) M is preferably a methyl group. R in formula (Cy) Cy is preferably a monovalent group having an aliphatic hydrocarbon ring structure of 5 to 20 carbon atoms, more preferably a monovalent group having an aliphatic hydrocarbon ring structure of 6 to 16 carbon atoms, and even more preferably a monovalent group having an aliphatic hydrocarbon ring structure of 8 to 14 carbon atoms, in terms of better effects of the present invention. Also, R in formula (Cy) Cy In terms of achieving better effects of the present invention, the aliphatic hydrocarbon ring structure in is preferably a cyclopentane ring structure, a cyclohexane ring structure, a tetrahydrodicyclopentadiene ring structure, a norbornane ring structure, or an isoborone ring structure, more preferably a cyclohexane ring structure or a tetrahydrodicyclopentadiene ring structure, and even more preferably a tetrahydrodicyclopentadiene ring structure. Furthermore, R in formula (Cy) Cy In terms of achieving better effects of the present invention, the aliphatic hydrocarbon ring structure in is preferably a ring structure in which two or more aliphatic hydrocarbon rings are condensed, and more preferably a ring in which two to four aliphatic hydrocarbon rings are condensed. Furthermore, R in formula (Cy) Cyis preferably a group in which the oxygen atom of —C(═O)O— in formula (Cy) is directly bonded to an aliphatic hydrocarbon ring structure, i.e., an aliphatic hydrocarbon ring group, and more preferably a cyclohexyl group or a dicyclopentanyl group, in terms of achieving better effects of the present invention.

[0071] The binder polymer may have one type of structural unit having an aliphatic hydrocarbon ring structure, or may have two or more types of structural units. 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 mass %, more preferably 10 to 80 mass %, and even more preferably 20 to 70 mass %, based on the total structural units of the binder polymer, in terms of better effects of the present invention. Furthermore, the content of the structural units having an aliphatic hydrocarbon ring structure in the binder polymer is preferably 5 to 70 mol %, more preferably 10 to 60 mol %, and even more preferably 20 to 50 mol %, based on the total structural units of the binder polymer, in order to achieve better effects of the present invention. Furthermore, the content of the structural unit represented by the above formula (Cy) in the binder polymer is preferably 5 to 70 mol %, more preferably 10 to 60 mol %, and even more preferably 20 to 50 mol %, based on the total structural units of the binder polymer, in order to achieve better effects of the present invention.

[0072] 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 units having an aromatic ring structure and the structural units having an aliphatic hydrocarbon ring structure is preferably 10 to 90 mass%, more preferably 20 to 80 mass%, and even more preferably 40 to 75 mass%, based on the total structural units of the binder polymer, in terms of better effects of the present invention. Furthermore, the total content of the structural units having an aromatic ring structure and the structural units having an aliphatic hydrocarbon ring structure in the binder polymer is preferably 10 to 80 mol %, more preferably 20 to 70 mol %, and even more preferably 40 to 60 mol %, based on the total structural units of the binder polymer, in order to achieve better effects of the present invention. Furthermore, the total content of the structural units represented by the above formula (S) and the structural units represented by the above formula (Cy) in the binder polymer is preferably 10 to 80 mol %, more preferably 20 to 70 mol %, and even more preferably 40 to 60 mol %, based on the total structural units of the binder polymer, in order to achieve better effects of the present invention. Furthermore, in order to obtain better effects of the present invention, the molar amount nS of the structural unit represented by the above formula (S) and the molar amount nCy of the structural unit represented by the above formula (Cy) in the binder polymer preferably satisfy the relationship shown in the following formula (SCy), more preferably satisfy the following formula (SCy-1), and even more preferably satisfy the following formula (SCy-2). 0.2≦nS / (nS+nCy)≦0.8 Formula (SCy) 0.30≦nS / (nS+nCy)≦0.75 Formula (SCy-1) 0.40≦nS / (nS+nCy)≦0.70 Formula (SCy-2)

[0073] The binder polymer preferably has a structural unit having an acid group, in order to obtain better effects of the present invention. Examples of the acid group include a carboxy group, a sulfo group, a phosphonic acid group, and a phosphoric acid group, with a carboxy group being preferred. As the structural unit having an acid group, a structural unit derived from (meth)acrylic acid shown below is preferred, and a structural unit derived from methacrylic acid is more preferred.

[0074] [ka]

[0075] The binder polymer may have one type of structural unit having an acid group, or two or more types 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 mass %, more preferably 5 to 40 mass %, and even more preferably 10 to 30 mass %, based on the total structural units of the binder polymer, in terms of better effects of the present invention. Furthermore, the content of the structural units having an acid group in the binder polymer is preferably 5 to 70 mol %, more preferably 10 to 50 mol %, and even more preferably 20 to 40 mol %, based on the total structural units of the binder polymer, in order to achieve better effects of the present invention. Furthermore, the content of the (meth)acrylic acid-derived structural units in the binder polymer is preferably 5 to 70 mol %, more preferably 10 to 50 mol %, and even more preferably 20 to 40 mol %, based on the total structural units of the binder polymer, in order to achieve better effects of the present invention.

[0076] The binder polymer preferably has a reactive group, and more preferably has a structural unit having a reactive group, in order to achieve better effects of the present invention. The reactive group is preferably a radically polymerizable group, more preferably an ethylenically unsaturated group. When the binder polymer has an ethylenically unsaturated group, the binder polymer preferably has a structural unit having an ethylenically unsaturated group in a side chain. In this specification, the term "main chain" refers to the relatively longest bond chain in the molecule of the polymer compound that constitutes the resin, and the term "side chain" refers to an atomic group branching off from the main chain. The ethylenically unsaturated group is more preferably an allyl group or a (meth)acryloxy group. Examples of structural units having a reactive group include, but are not limited to, those shown below.

[0077] [ka]

[0078] The binder polymer may have one type of structural unit having a reactive group, or two or more types of structural units. 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 mass %, more preferably 10 to 50 mass %, and even more preferably 20 to 40 mass %, based on the total structural units of the binder polymer, in terms of better effects of the present invention. Furthermore, the content of the structural unit having a reactive group in the binder polymer is preferably 5 to 70 mol %, more preferably 10 to 60 mol %, and even more preferably 20 to 50 mol %, based on the total structural units of the binder polymer, in order to achieve better effects of the present invention.

[0079] Examples of a method for introducing a reactive group into a binder polymer include a method of reacting a functional group such as a hydroxy group, a carboxy group, a primary amino group, a secondary amino group, an acetoacetyl group, or 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, or a carboxylic acid anhydride. A preferred example of a method for introducing a reactive group into a binder polymer is to synthesize a polymer having a carboxy group by polymerization, and then react some of the carboxy groups of the resulting polymer with glycidyl (meth)acrylate by a polymer reaction to introduce a (meth)acryloxy group into the polymer. By this method, a binder polymer having a (meth)acryloxy group in the side chain can be obtained. The polymerization reaction is preferably carried out at a temperature of 70 to 100°C, more preferably at a temperature of 80 to 90°C. The polymerization initiator used in the polymerization reaction is preferably an azo-based initiator, more preferably V-601 (trade name) or V-65 (trade name) manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. The polymerization reaction is preferably carried out at a temperature of 80 to 110°C. In the polymerization reaction, it is preferable to use a catalyst such as an ammonium salt.

[0080] As the binder polymer, the following polymers X1 to X4 are preferred in terms of achieving better effects of the present invention. Note that the content ratios (a to d) of the respective structural units shown below and the weight average molecular weight Mw can be appropriately changed depending on the purpose, but the following structures are particularly preferred in terms of achieving better effects of the present invention. (Polymer X1) a: 20-60% by mass, b: 10-50% by mass, c: 5.0-25% by mass, d: 10-50% by mass. (Polymer X2) a: 20-60% by mass, b: 10-50% by mass, c: 5.0-25% by mass, d: 10-50% by mass. (Polymer X3) a: 30-65% by mass, b: 1.0-20% by mass, c: 5.0-25% by mass, d: 10-50% by mass. (Polymer X4) a: 1.0-20% by mass, b: 20-60% by mass, c: 5.0-25% by mass, d: 10-50% by mass.

[0081] [ka] JPEG0007742236000007.jpg4398

[0082] [ka] JPEG0007742236000009.jpg4394

[0083] The binder polymer may also contain a polymer having a structural unit with a carboxylic acid anhydride structure (hereinafter also referred to as "polymer X"). The carboxylic acid anhydride structure may be either a chain carboxylic acid anhydride structure or a cyclic carboxylic acid anhydride structure, but is preferably a cyclic carboxylic acid anhydride structure. The ring of the cyclic carboxylic acid anhydride structure is preferably a 5- to 7-membered ring, more preferably a 5- or 6-membered ring, and even more preferably a 5-membered ring.

[0084] The structural unit having a carboxylic acid anhydride structure is preferably a structural unit containing, in its main chain, a divalent group obtained by removing two hydrogen atoms from a compound represented by the following formula P-1, or a structural unit in which a monovalent group obtained by removing one hydrogen atom from a compound represented by the following formula P-1 is bonded to the main chain directly or via a divalent linking group.

[0085] [ka]

[0086] In formula P-1, R A1a represents a substituent, n 1a R A1a may be the same or different, and Z 1a represents a divalent group forming a ring containing -C(=O)-OC(=O)-, and n 1a represents an integer greater than or equal to 0.

[0087] R A1a Examples of the substituent represented by the formula include an alkyl group. Z 1a As the alkylene group, an alkylene group having 2 to 4 carbon atoms is preferable, an alkylene group having 2 or 3 carbon atoms is more preferable, and an alkylene group having 2 carbon atoms is even more preferable. n 1a represents an integer greater than or equal to 0. 1a When represents an alkylene group having 2 to 4 carbon atoms, n 1a is preferably an integer of 0 to 4, more preferably an integer of 0 to 2, and even more preferably 0. n 1a If represents an integer of 2 or more, there are multiple R A1a may be the same or different. A1a may be bonded to each other to form a ring, but preferably do not bond to each other to form a ring.

[0088] As a structural unit having a carboxylic acid anhydride structure, a structural unit derived from an unsaturated carboxylic acid anhydride is preferred, a structural unit derived from an unsaturated cyclic carboxylic acid anhydride is more preferred, a structural unit derived from an unsaturated aliphatic cyclic carboxylic acid 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.

[0089] Specific examples of structural units having a carboxylic acid anhydride structure are listed below, but the structural units having a carboxylic acid anhydride structure are 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.

[0090] [ka]

[0091] [ka]

[0092] The polymer X may contain one type of structural unit having a carboxylic acid anhydride structure, or two or more types of structural units.

[0093] The total content of structural units having a carboxylic acid anhydride structure relative to all structural units of polymer X is preferably from 0 to 60 mol %, more preferably from 5 to 40 mol %, and even more preferably from 10 to 35 mol %.

[0094] The photosensitive layer may contain only one type of polymer X, or may contain two or more types. When the photosensitive layer contains polymer X, the content of polymer X is preferably 0.1 to 30 mass %, more preferably 0.2 to 20 mass %, even more preferably 0.5 to 20 mass %, still more preferably 0.8 to 20 mass %, and particularly preferably 0.8 to 10 mass %, relative to the total mass of the photosensitive layer, in order to obtain better effects of the present invention. As a commercially available product of polymer X, for example, XIRAN EF-40 (manufactured by Polyscope Polymers BV) can be used.

[0095] The weight average molecular weight (Mw) of the binder polymer is preferably 5,000 or more, more preferably 10,000 or more, further preferably from 10,000 to 50,000, and particularly preferably from 20,000 to 30,000, in terms of achieving better effects of the present invention.

[0096] The acid value of the binder polymer is preferably 10 to 200 mgKOH / g, more preferably 60 to 200 mgKOH / g, still more preferably 60 to 150 mgKOH / g, and particularly preferably 70 to 125 mgKOH / g, as measured according to the method described in JIS K0070:1992. From the viewpoint of developability, the dispersity of the binder polymer is preferably from 1.0 to 6.0, more preferably from 1.0 to 5.0, still more preferably from 1.0 to 4.0, and particularly preferably from 1.0 to 3.0.

[0097] The photosensitive layer may contain only one type of binder polymer, or may contain two or more types. However, some or all of the binder polymers in the photosensitive layer are alkali-soluble resins. In particular, it is preferable that all of the binder polymers in the photosensitive layer are alkali-soluble resins. The content of the binder polymer is preferably from 10 to 90% by mass, more preferably from 20 to 80% by mass, and even more preferably from 30 to 70% by mass, based on the total mass of the photosensitive layer, in terms of achieving better effects of the present invention.

[0098] <Photopolymerizable compound> The photosensitive layer contains a photopolymerizable compound. The photopolymerizable compound is a compound having a photopolymerizable group. The term "photopolymerizable compound" refers to a compound that is polymerized by the action of a photopolymerization initiator, which will be described later, and is different from the binder polymer described above. It preferably has a molecular weight of 5,000 or less.

[0099] The molecular weight of the photopolymerizable compound is preferably from 200 to 3,000, more preferably from 250 to 2,600, even more preferably from 280 to 2,200, and particularly preferably from 300 to 2,200.

[0100] Examples of the polymerizable group possessed by the photopolymerizable compound include groups having an ethylenically unsaturated group such as a vinyl group, an acryloyl group, a methacryloyl group, a styryl group, and a maleimide group; and groups having a cationic polymerizable group such as an epoxy group and an oxetane group.

[0101] The number of polymerizable groups possessed by the photopolymerizable compound is not particularly limited as long as it is 1 or more, but is more preferably 2 or more. In other words, the photopolymerizable compound is preferably a compound having 2 or more polymerizable groups (hereinafter also referred to as a "polyfunctional photopolymerizable compound"). In addition, the number of polymerizable groups that the photopolymerizable compound has in the molecule is preferably 1 to 6, more preferably 1 to 3, and even more preferably 2 or 3, in terms of better effects of the present invention.

[0102] In terms of obtaining better effects of the present invention, the photosensitive layer preferably contains at least one of a bifunctional photopolymerizable compound and a trifunctional photopolymerizable compound. The total content of the bifunctional photopolymerizable compound and the trifunctional photopolymerizable compound is preferably 30% by mass or more, more preferably 40% by mass or more, and even more preferably 45% by mass or more, based on the total mass of the photopolymerizable compounds, and is not particularly limited to the upper limit, but is, for example, 100% by mass or less.

[0103] Among them, the photopolymerizable compound preferably contains a polymerizable compound having an ethylenically unsaturated group (hereinafter also referred to as "ethylenically unsaturated compound"). Of these, the ethylenically unsaturated group is more preferably an acryloyl group or a methacryloyl group. That is, the photopolymerizable compound is preferably a (meth)acrylate compound having a (meth)acryloyl group as the polymerizable group.

[0104] The number of ethylenically unsaturated groups in the ethylenically unsaturated compound is not particularly limited as long as it is 1 or more, but is more preferably 2 or more. In other words, the ethylenically unsaturated compound is preferably a compound having 2 or more ethylenically unsaturated groups (hereinafter also referred to as a "polyfunctional ethylenically unsaturated compound"). In addition, the number of ethylenically unsaturated groups that the ethylenically unsaturated compound has in the molecule is preferably 1 to 6, more preferably 1 to 3, and even more preferably 2 or 3, in terms of better effects of the present invention.

[0105] In terms of achieving better effects of the present invention, the photosensitive layer preferably contains at least one of a difunctional ethylenically unsaturated compound and a trifunctional ethylenically unsaturated compound. The total content of the bifunctional ethylenically unsaturated compound and the trifunctional ethylenically unsaturated compound is preferably 30% by mass or more, more preferably 40% by mass or more, and even more preferably 45% by mass or more, based on the total mass of the photopolymerizable compound, and the upper limit is not particularly limited, but is, for example, 100% by mass or less.

[0106] One preferred embodiment of the photopolymerizable compound is a polyfunctional ethylenically unsaturated compound, which means a compound having two or more ethylenically unsaturated groups in one molecule. The ethylenically unsaturated group in the ethylenically unsaturated compound is preferably a (meth)acryloyl group, and the ethylenically unsaturated compound is preferably a (meth)acrylate compound.

[0107] An example of a suitable embodiment of the bifunctional ethylenically unsaturated compound is a compound represented by the following formula (M) (also simply referred to as "compound M"). Q 2 -R 1 -Q 1 Formula (M) In formula (M), Q 1 and Q 2 each independently represents a (meth)acryloyloxy group, R 1 represents a divalent linking group having a chain structure.

[0108] Q in formula (M) 1 and Q 2 In terms of ease of synthesis, Q 1 and Q 2 are preferably the same group. Also, Q in formula (M) 1 and Q 2 is preferably an acryloyloxy group from the viewpoint of reactivity. R in formula (M) 1 As the alkylene group, an alkyleneoxyalkylene group (-L 1 -OL 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 further preferred, and a linear alkylene group having 6 to 18 carbon atoms is particularly preferred. The hydrocarbon group may have a chain structure at least in part, and the portion other than the chain structure is not particularly limited and may be, for example, a branched, cyclic, or linear alkylene group having 1 to 5 carbon atoms, an arylene group, an ether bond, or a combination thereof. An alkylene group or a group combining 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 even more preferred. In addition, the above L 1 each independently represents an alkylene group, preferably an ethylene group, a propylene group, or a butylene group, and more preferably an ethylene group or a 1,2-propylene group. p represents an integer of 2 or more, preferably an integer of 2 to 10.

[0109] Also, Q in compound M 1 and Q 2The number of atoms in the shortest linking chain between is preferably 3 to 50, more preferably 4 to 40, even more preferably 6 to 20, and particularly preferably 8 to 12, in terms of achieving better effects of the present invention. As used herein, "Q 1 and Q 2 The number of atoms in the shortest chain connecting the 1 Connect to R 1 Q from atoms in 2 Connect to R 1 is the shortest number of atoms that connects to the atom in

[0110] Specific 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 the above compounds, in terms of achieving better effects of the present invention, 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 is preferred, at least one compound selected from the group consisting of 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, and 1,10-decanediol di(meth)acrylate is more preferred, and at least one compound selected from the group consisting of 1,9-nonanediol di(meth)acrylate and 1,10-decanediol di(meth)acrylate is even more preferred.

[0111] Further, other examples of suitable embodiments of the bifunctional ethylenically unsaturated compound (bifunctional ethylenically unsaturated compound other than the compound M) include tricyclodecane dimethanol di(meth)acrylate, 1,4-cyclohexanediol di(meth)acrylate, and (2,2-dimethylethylene)(5-ethyl-1,3-dioxane-2,5-diyl)methylene bisacrylate.

[0112] Commercially available bifunctional ethylenically unsaturated compounds include tricyclodecane dimethanol diacrylate (trade name: NK Ester A-DCP, manufactured by Shin-Nakamura Chemical Co., Ltd.), tricyclodecane dimenanol dimethacrylate (trade name: NK Ester DCP, manufactured by Shin-Nakamura Chemical Co., Ltd.), 1,9-nonanediol diacrylate (trade name: NK Ester A-NOD-N, manufactured by Shin-Nakamura Chemical Co., Ltd.), 1,6-hexanediol diacrylate (trade name: NK Ester A-HD-N, manufactured by Shin-Nakamura Chemical Co., Ltd.), and (2,2-dimethylethylene)(5-ethyl-1,3-dioxane-2,5-diyl)methylene bisacrylate (trade name: KAYARAD R-604, manufactured by Nippon Kayaku Co., Ltd.).

[0113] The tri- or higher functional ethylenically unsaturated compound is not particularly limited and can be appropriately selected from known compounds. Examples of tri- or higher functional ethylenically unsaturated compounds include dipentaerythritol (tri / tetra / penta / hexa)(meth)acrylate, pentaerythritol (tri / tetra)(meth)acrylate, trimethylolpropane tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, isocyanuric acid (meth)acrylate, and (meth)acrylate compounds having a glycerin tri(meth)acrylate skeleton.

[0114] Here, "(tri / tetra / penta / hexa)(meth)acrylate" is a concept that encompasses tri(meth)acrylate, tetra(meth)acrylate, penta(meth)acrylate, and hexa(meth)acrylate, and "(tri / tetra)(meth)acrylate" is a concept that encompasses tri(meth)acrylate and tetra(meth)acrylate.

[0115] Further, examples of the ethylenically unsaturated compound include caprolactone-modified (meth)acrylate compounds (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 (meth)acrylate compounds (KAYARAD (registered trademark) RP-1040 manufactured by Nippon Kayaku Co., Ltd., ATM-35E and A-9300 manufactured by Shin-Nakamura Chemical Co., Ltd., EBECRYL (registered trademark) 135 manufactured by Daicel-Allnex Corporation, etc.), and ethoxylated glycerin triacrylate (NK Ester A-GLY-9E manufactured by Shin-Nakamura Chemical Co., Ltd., etc.).

[0116] Further, the ethylenically unsaturated compound also includes a urethane (meth)acrylate compound. Examples of urethane (meth)acrylates include urethane di(meth)acrylates, such as propylene oxide-modified urethane di(meth)acrylates and ethylene oxide and propylene oxide-modified urethane di(meth)acrylates. Further, the urethane (meth)acrylate may be a trifunctional or higher functional urethane (meth)acrylate. The lower limit of the number of functional groups is preferably 6 or more, and more preferably 8 or more. The upper limit of the number of functional groups is preferably 20 or less. Examples of trifunctional or higher functional urethane (meth)acrylates include 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.).

[0117] One preferred embodiment of the ethylenically unsaturated compound is an ethylenically unsaturated compound having an acid group. Examples of the acid group include a phosphate group, a sulfo group, and a carboxy group, with the carboxy group being preferred. Examples of the ethylenically unsaturated compound having an acid group include a tri- or tetrafunctional ethylenically unsaturated compound having an acid group [a compound having a carboxy group introduced into a pentaerythritol tri- or tetraacrylate (PETA) skeleton (acid value: 80 to 120 mg KOH / g)], a penta- or hexafunctional ethylenically unsaturated compound having an acid group [a compound having a carboxy group introduced into a dipentaerythritol penta- or hexaacrylate (DPHA) skeleton (acid value: 25 to 70 mg KOH / g)], and the like. These tri- or higher functional ethylenically unsaturated compounds having an acid group may be used in combination with a difunctional ethylenically unsaturated compound having an acid group, if necessary.

[0118] The ethylenically unsaturated compound having an acid group is preferably at least one selected from the group consisting of di- or higher functional ethylenically unsaturated compounds having a carboxy group and carboxylic acid anhydrides thereof. When the ethylenically unsaturated compound having an acid group is at least one selected from the group consisting of di- or higher functional ethylenically unsaturated compounds having a carboxy group and carboxylic acid anhydrides thereof, the developability and film strength are further improved. The di- or higher functional ethylenically unsaturated compound having a carboxy group is not particularly limited and can be appropriately selected from known compounds. Examples of difunctional or higher ethylenically unsaturated compounds 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.).

[0119] As the ethylenically unsaturated compound having an acid group, the photopolymerizable compound having an acid group described in paragraphs

[0025] to

[0030] of JP-A-2004-239942 is preferred, and the contents of this publication are incorporated herein by reference.

[0120] Examples of the ethylenically unsaturated 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, phthalic acid compounds such as γ-chloro-β-hydroxypropyl-β'-(meth)acryloyloxyethyl-o-phthalate, β-hydroxyethyl-β'-(meth)acryloyloxyethyl-o-phthalate, and β-hydroxypropyl-β'-(meth)acryloyloxyethyl-o-phthalate, and alkyl (meth)acrylates. These may be used alone or in combination of two or more.

[0121] Examples of compounds 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; Examples of the acrylate include trimethylolpropane di(meth)acrylate, trimethylolpropane tri(meth)acrylate, trimethylolpropane ethoxy tri(meth)acrylate, trimethylolpropane diethoxy tri(meth)acrylate, trimethylolpropane triethoxy tri(meth)acrylate, trimethylolpropane tetraethoxy tri(meth)acrylate, trimethylolpropane pentaethoxy tri(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 these, ethylenically unsaturated compounds having a tetramethylolmethane structure or a trimethylolpropane structure are preferred, and tetramethylolmethane tri(meth)acrylate, tetramethylolmethane tetra(meth)acrylate, trimethylolpropane tri(meth)acrylate, or di(trimethylolpropane)tetraacrylate is more preferred.

[0122] Among these, ethylenically unsaturated compounds, those containing an ester bond are also preferred, as they provide excellent developability of the photosensitive 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. However, in terms of excellent effects of the present invention, an ethylenically unsaturated compound having a tetramethylolmethane structure or a trimethylolpropane structure is preferred, and tetramethylolmethane tri(meth)acrylate, tetramethylolmethane tetra(meth)acrylate, trimethylolpropane tri(meth)acrylate, or di(trimethylolpropane)tetraacrylate is more preferred. From the viewpoint of providing reliability, the ethylenically unsaturated compound preferably contains an ethylenically unsaturated compound having an aliphatic group having 6 to 20 carbon atoms and the above-mentioned ethylenically unsaturated compound having a tetramethylolmethane structure or a trimethylolpropane structure. Examples of ethylenically unsaturated compounds 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.

[0123] One preferred embodiment of the photopolymerizable compound is an ethylenically unsaturated compound having an aliphatic hydrocarbon ring structure (preferably a bifunctional ethylenically unsaturated compound). The above-mentioned ethylenically unsaturated compound is preferably an ethylenically unsaturated 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), more preferably a bifunctional ethylenically unsaturated compound having a ring structure in which two or more aliphatic hydrocarbon rings are fused, and even more preferably tricyclodecane dimethanol di(meth)acrylate. The aliphatic hydrocarbon ring structure is preferably a cyclopentane structure, a cyclohexane structure, a tricyclodecane structure, a tricyclodecene structure, a norbornane structure, or an isoborone structure, in terms of achieving better effects of the present invention.

[0124] One preferred embodiment of the photosensitive layer includes a difunctional ethylenically unsaturated compound, a penta- or hexafunctional dipentaerythritol polyacrylate, and an ethylenically unsaturated compound having an acid group.

[0125] In addition, one of the preferred embodiments of the photosensitive layer is an embodiment in which the photosensitive layer contains a bifunctional ethylenically unsaturated compound (preferably a bifunctional (meth)acrylate compound) and a trifunctional or higher ethylenically unsaturated compound (preferably a trifunctional or higher (meth)acrylate compound) from the viewpoints of suppressing development residues and rust prevention. Furthermore, one preferred embodiment of the photosensitive layer is one that contains tricyclodecane dimethanol diacrylate, a urethane acrylate compound, and a polyfunctional ethylenically unsaturated compound having a carboxylic acid group, in that the photosensitive layer is superior in at least one of adhesion, suppression of development residues, and rust prevention properties. Furthermore, one preferred embodiment of the photosensitive layer is one that contains 1,9-nonanediol diacrylate, tricyclodecane dimethanol diacrylate, a penta- or hexa-functional dipentaerythritol polyacrylate, and a polyfunctional ethylenically unsaturated compound having a carboxylic acid group, in that the photosensitive layer is superior in at least one of adhesion, suppression of development residues, and rust prevention properties.

[0126] The photopolymerizable compound (particularly, the ethylenically unsaturated compound) may be used alone or in combination of two or more kinds. The content of the photopolymerizable compound (particularly, the ethylenically unsaturated compound) in the photosensitive layer is preferably 1 to 70 mass %, more preferably 5 to 70 mass %, even more preferably 5 to 60 mass %, particularly preferably 5 to 50 mass %, and most preferably 15 to 50 mass %, relative to the total mass of the photosensitive layer.

[0127] <Photopolymerization initiator> The photosensitive layer contains a photopolymerization initiator. In the photosensitive layer, the photopolymerization initiator may be used alone or in combination of two or more kinds. The content of the photopolymerization initiator in the photosensitive layer is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, based on the total mass of the photosensitive layer, and the upper limit is preferably 10% by mass or less, more preferably 5% by mass or less, based on the total mass of the photosensitive layer.

[0128] (Compound represented by general formula (a-1) (specific oxime ester compound)) The photopolymerization initiator includes a compound (specific oxime ester compound) represented by the following general formula (a-1).

[0129] [ka]

[0130] In the formula, R a1 , R a2 , R b1 , and R b2 each independently represents a hydrocarbon group having 1 to 6 carbon atoms. R a1 , R a2 , R b1 , and R b2 The hydrocarbon group having 1 to 6 carbon atoms represented by the formula (I) may be linear, branched, or cyclic, and is preferably linear or branched, more preferably linear. R a1 , R a2 , R b1 , and R b2 The hydrocarbon group having 1 to 6 carbon atoms represented by the formula (I) is preferably an aliphatic hydrocarbon group such as an alkyl group, an alkenyl group, or an alkynyl group, and more preferably an alkyl group. R a1 , R a2 , R b1 , and R b2 The number of carbon atoms in the hydrocarbon group having 1 to 6 carbon atoms represented by the formula (I) is preferably 1 to 3, more preferably 1 or 2, and even more preferably 1, in terms of achieving better effects of the present invention. R a1 , R a2 , Rb1 , and R b2 The hydrocarbon group having 1 to 6 carbon atoms represented by the formula may further have a substituent.

[0131] R c and R d each independently represents a linear or branched hydrocarbon group having 1 to 6 carbon atoms, or a cyclic hydrocarbon group. R c and R d The linear or branched hydrocarbon group having 1 to 6 carbon atoms represented by the formula (I) is preferably an aliphatic hydrocarbon group such as an alkyl group, an alkenyl group, or an alkynyl group, and more preferably an alkyl group. R c and R d The number of carbon atoms in the linear or branched hydrocarbon group having 1 to 6 carbon atoms represented by the formula (I) is preferably 1 to 4, and more preferably 1 to 3, in terms of achieving better effects of the present invention. R c and R d The cyclic hydrocarbon group represented by the formula (I) may be an alicyclic hydrocarbon ring group or an aromatic hydrocarbon ring group, but is preferably an alicyclic hydrocarbon ring group. The alicyclic hydrocarbon ring group and the aromatic hydrocarbon ring group may be monocyclic or polycyclic. The alicyclic hydrocarbon ring group and aromatic hydrocarbon ring group have 5 to 18 ring members, for example, and 5 to 10 ring members are preferable. Examples of the alicyclic hydrocarbon ring group include monocyclic cycloalkyl groups such as a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group, and polycyclic cycloalkyl groups such as a norbornyl group, a tricyclodecanyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, and an adamantyl group. Examples of the aromatic hydrocarbon ring group include a benzene ring group and a naphthalene ring group.

[0132] l and m each independently represent an integer of 0 to 4. n represents 0 or 1, provided that m+n represents an integer of 1 or greater. Among these, l and m are preferably 0 or 1. m+n is preferably 1 to 5, more preferably 1 or 2, and even more preferably 1. It is preferable that m+n represents 1 and l represents 0 or 1, in that the effects of the present invention are more excellent.

[0133] In the formula, R a1 and R c may be bonded to form a ring structure. a2 and R d may be bonded to form a ring structure. a1 and R c and R form a ring structure. a2 and R d When R and R are bonded to form a ring structure, a1 and R c and a group formed by bonding with R a2 and R d The group formed by bonding with R is -CH-, and is preferably -CH- or -CH-CH-, more preferably -CH-. a1 and R c and R are bonded to form a ring structure, and a1 and R c The group formed by bonding with is -CH2-.

[0134] When l is an integer of 1 to 4, -C(=O)-C(R a1 )=NOC(=O)-R b1 and an oxime ester-containing group represented by R c In the benzene ring substituted with the oxime ester-containing group and the R c and each are substituted on adjacent carbon atoms on a benzene ring, and R in the oxime ester-containing group a1 and the above R c and are bonded to form a ring.

[0135] Also, -C(=O)-C(R a1 )=NOC(=O)-R b1 is preferably substituted at the para position relative to the sulfur atom shown in general formula (a-1) in the benzene ring on which the oxime ester-containing group is substituted (the benzene ring on the right side shown in general formula (a-1)).

[0136] Also, when n is 1, -C(=O)-C(R a2 )=NOC(=O)-R b2 is preferably substituted at the para position relative to the sulfur atom shown in general formula (a-1) in the benzene ring on which the oxime ester-containing group is substituted (the benzene ring on the left side shown in general formula (a-1)). Furthermore, when n represents 0 and m represents any one of 1 to 4, R d At least one of the above R d In the benzene ring substituted by (the benzene ring on the left side shown in general formula (a-1)), it is preferably substituted at the para position relative to the sulfur atom shown in general formula (a-1).

[0137] The compound represented by general formula (a-1) is preferably at least one of the compounds represented by the following general formula (a-1X) and the compounds represented by the following general formula (a-1Y), and more preferably at least one of the compounds represented by the following general formula (b-1) and the compounds represented by the following general formula (b-2), in terms of more excellent effects of the present invention.

[0138] [ka]

[0139] In general formula (a-1X), R b1 and R d are R in general formula (a-1), b1 and R d The same definition and preferred embodiments are also the same. In general formula (a-1Y), R a1 , Ra2 , R b1 , and R d are R in general formula (a-1), a1 , R a2 , R b1 , and R d The same definition and preferred embodiments are also the same.

[0140] [ka] JPEG0007742236000016.jpg2199

[0141] The oxime ester value (mol / g) of the compound represented by general formula (a-1) is 2.0 × 10 -3 ~7.0×10 -3 mol / g, preferably 4.0×10 -3 ~7.0×10 -3 For example, the oxime ester value of the compound represented by the general formula (b-1) is preferably 2.8×10 -3 mol / g, and the oxime ester value of the compound represented by the general formula (b-2) is 4.5 × 10 -3 mol / g. The oxime ester value (mol / g) is the ratio of the oxime ester structural moiety (oxime ester structural moiety: -C(R a1 )=NOC(=O)- and -C(R a2 )=NOC(=O)-) is the molar amount.

[0142] Commercially available products of the compound represented by the general formula (a-1) include, for example, Omnirad1312 and Omnirad1316 manufactured by IGM Resins BV.

[0143] The content of the compound represented by the general formula (a-1) in the photopolymerization initiator is preferably 10% by mass or more, more preferably 20% by mass or more, based on the total mass of the photopolymerization initiator, and the upper limit is preferably 100% by mass or less, more preferably 70% by mass or less.

[0144] (Photopolymerization initiators other than specific oxime ester compounds) The photosensitive layer may contain a photopolymerization initiator other than the specific oxime ester compound (hereinafter referred to as "another photopolymerization initiator"). The other photopolymerization initiator is not particularly limited, and known photopolymerization initiators can be used. Examples of other photopolymerization initiators include photopolymerization initiators having an oxime ester structure other than the specific oxime ester compound, photopolymerization initiators having an α-aminoalkylphenone structure, photopolymerization initiators having an α-hydroxyalkylphenone structure, photopolymerization initiators having an acylphosphine oxide structure, photopolymerization initiators having a morpholine structure, and photopolymerization initiators having an N-phenylglycine structure. As the other photopolymerization initiator, photopolymerization initiators having an α-aminoalkylphenone structure or photopolymerization initiators having a morpholine structure are preferred.

[0145] Furthermore, as other photopolymerization initiators, for example, polymerization initiators described in paragraphs

[0031] to

[0042] of JP2011-095716A and paragraphs

[0064] to

[0081] of JP2015-014783A may be used.

[0146] Other commercially available photopolymerization initiators include 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-acetyloxime) [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], and the like. BV], 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one [trade name: Omnirad® 907, IGM Resins BV], 2-hydroxy-1-{4-[4-(2-hydroxy-2-methylpropionyl)benzyl]phenyl}-2-methylpropan-1-one [trade name: Omnirad® 127, IGM Resins BV], 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butanone-1 [trade name: Omnirad® 369, IGM Resins BV], 2-hydroxy-2-methyl-1-phenylpropan-1-one [trade name: Omnirad® 1173, IGM Resins BV], 1-hydroxycyclohexyl phenyl ketone [trade name: Omnirad® 184, IGM Resins BV] BV)], 2,2-dimethoxy-1,2-diphenylethan-1-one (trade name: Omnirad (registered trademark) 651, IGM Resins B.oxime esters [trade name: Lunar (registered trademark) 6, manufactured by DKSH Japan Co., Ltd.], 1-[4-(phenylthio)phenyl]-3-cyclopentylpropane-1,2-dione-2-(O-benzoyloxime) (trade name: TR-PBG-305, manufactured by Changzhou Strong Electronic New Materials Co., Ltd.), 1,2-propanedione, 3-cyclohexyl-1-[9-ethyl-6-(2-furanylcarbonyl)-9H-carbazol-3-yl]-2-(O-acetyloxime) (trade name: TR-PBG -326, manufactured by Changzhou Powerful Electronic New Materials Co., Ltd.), 3-cyclohexyl-1-(6-(2-(benzoyloxyimino)hexanoyl)-9-ethyl-9H-carbazol-3-yl)-propane-1,2-dione-2-(O-benzoyloxime) (trade name: TR-PBG-391, manufactured by Changzhou Powerful Electronic New Materials Co., Ltd.), and APi-307 (1-(biphenyl-4-yl)-2-methyl-2-morpholinopropan-1-one, manufactured by Shenzhen UV-ChemTech Ltd.).

[0147] <Heterocyclic compounds> The photosensitive layer may contain a heterocyclic compound. The heterocyclic ring contained in the heterocyclic compound may be either a monocyclic or polycyclic heterocyclic ring. Examples of heteroatoms contained in the heterocyclic compound include a nitrogen atom, an oxygen atom, and a sulfur atom. The heterocyclic compound preferably contains at least one atom selected from the group consisting of a nitrogen atom, an oxygen atom, and a sulfur atom, and more preferably contains a nitrogen atom.

[0148] Examples of heterocyclic compounds include triazole compounds, benzotriazole compounds, tetrazole compounds, thiadiazole compounds, triazine compounds, rhodanine compounds, thiazole compounds, benzothiazole compounds, benzimidazole compounds, benzoxazole compounds, and pyrimidine compounds. Among the above, the heterocyclic compound is preferably at least one compound selected from the group consisting of triazole compounds, benzotriazole compounds, tetrazole compounds, thiadiazole compounds, triazine compounds, rhodanine compounds, thiazole compounds, benzimidazole compounds, and benzoxazole compounds, and more preferably at least one compound selected from the group consisting of triazole compounds, benzotriazole compounds, tetrazole compounds, thiadiazole compounds, thiazole compounds, benzothiazole compounds, benzimidazole compounds, and benzoxazole compounds.

[0149] Preferred specific examples of the heterocyclic compound are shown below. Examples of the triazole compound and benzotriazole compound include the following compounds.

[0150] [ka]

[0151] [ka]

[0152] Examples of the tetrazole compound include the following compounds.

[0153] [ka]

[0154] [ka]

[0155] Examples of the thiadiazole compound include the following compounds:

[0156] [ka]

[0157] Examples of the triazine compound include the following compounds:

[0158] [ka]

[0159] Examples of rhodanine compounds include the following compounds:

[0160] [ka]

[0161] Examples of the thiazole compound include the following compounds:

[0162] [ka]

[0163] Examples of the benzothiazole compound include the following compounds:

[0164] [ka]

[0165] Examples of the benzimidazole compound include the following compounds:

[0166] [ka]

[0167] [ka]

[0168] Examples of the benzoxazole compound include the following compounds:

[0169] [ka]

[0170] The heterocyclic compounds may be used alone or in combination of two or more. When the photosensitive layer contains a heterocyclic compound, the content of the heterocyclic compound is preferably from 0.01 to 20.0% by mass, more preferably from 0.10 to 10.0% by mass, based on the total mass of the photosensitive layer.

[0171] <Aliphatic thiol compounds> The photosensitive layer may contain an aliphatic thiol compound. When the photosensitive layer contains an aliphatic thiol compound, the aliphatic thiol compound undergoes an ene-thiol reaction with the radical polymerizable compound having an ethylenically unsaturated group, thereby suppressing the cure shrinkage of the film formed and alleviating stress.

[0172] The aliphatic thiol compound is preferably a monofunctional aliphatic thiol compound or a polyfunctional aliphatic thiol compound (that is, a di- or higher functional aliphatic thiol compound).

[0173] Among the above, polyfunctional aliphatic thiol compounds are preferred as the aliphatic thiol compounds, since they provide better adhesion to the cured film of the photosensitive layer after exposure.

[0174] In this specification, the term "polyfunctional aliphatic thiol compound" refers to an aliphatic compound having two or more thiol groups (also called "mercapto groups") in the molecule.

[0175] The polyfunctional aliphatic thiol compound is preferably a low molecular weight compound having a molecular weight of at least 100. Specifically, the molecular weight of the polyfunctional aliphatic thiol compound is more preferably 100 to 1,500, and even more preferably 150 to 1,000.

[0176] The number of functional groups in the polyfunctional aliphatic thiol compound is preferably 2 to 10, more preferably 2 to 8, and even more preferably 2 to 6, in order to provide a cured film of the photosensitive layer with better adhesion after exposure.

[0177] Examples of polyfunctional aliphatic thiol compounds include trimethylolpropane tris(3-mercaptobutyrate), 1,4-bis(3-mercaptobutyryloxy)butane, pentaerythritol tetrakis(3-mercaptobutyrate), 1,3,5-tris(3-mercaptobutyryloxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, trimethylolethane tris(3-mercaptobutyrate), and tris[(3-mercaptopropionyloxy)ethyl] Examples of suitable mercaptoesters include 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.

[0178] Among the above, the polyfunctional aliphatic thiol compound is preferably 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.

[0179] Examples of monofunctional aliphatic thiol compounds 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.

[0180] The photosensitive layer may contain one kind of aliphatic thiol compound alone, or may contain two or more kinds of aliphatic thiol compounds.

[0181] When the photosensitive layer contains an aliphatic thiol compound, the content of the aliphatic thiol compound is preferably 5% by mass or more, more preferably 5 to 50% by mass, even more preferably 5 to 30% by mass, and particularly preferably 8 to 20% by mass, relative to the total mass of the photosensitive layer.

[0182] <Thermal crosslinkable compound> The photosensitive layer preferably contains a thermally crosslinkable compound from the viewpoints of the strength of the cured film obtained and the adhesiveness of the uncured film obtained. In this specification, a thermally crosslinkable compound having an ethylenically unsaturated group, which will be described later, is not considered to be an ethylenically unsaturated compound but is considered to be a thermally crosslinkable compound. Examples of the thermally crosslinkable compound include epoxy compounds, oxetane compounds, methylol compounds, and blocked isocyanate compounds. Among these, blocked isocyanate compounds are preferred in terms of the strength of the resulting cured film and the adhesiveness of the resulting uncured film. The blocked isocyanate compound reacts with a hydroxy group and a carboxy group. Therefore, for example, when at least one of the binder polymer and the radically polymerizable compound having an ethylenically unsaturated group has at least one of 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 refers to a compound having a structure in which the isocyanate group of an isocyanate is protected (so-called masked) with a blocking agent.

[0183] 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 a 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 suitably used. However, the differential scanning calorimeter is not limited to this.

[0184] Examples of blocking agents having a dissociation temperature of 100 to 160°C include active methylene compounds [malonic acid diesters (dimethyl malonate, diethyl malonate, di-n-butyl malonate, di-2-ethylhexyl malonate, etc.)], and oxime compounds (compounds having a structure represented by -C(=N-OH)- in the molecule, such as formaldoxime, acetaldoxime, acetoxime, methyl ethyl ketoxime, and cyclohexanone oxime). Among these, as the blocking agent having a dissociation temperature of 100 to 160° C., at least one selected from oxime compounds is preferred from the viewpoint of storage stability, for example.

[0185] The blocked isocyanate compound preferably has an isocyanurate structure, for example, from the viewpoint of improving the brittleness of the film and improving the adhesive strength to the transfer target. A blocked isocyanate compound having an isocyanurate structure can be obtained, for example, by protecting hexamethylene diisocyanate by isocyanuration. Among blocked isocyanate compounds having an isocyanurate structure, compounds having an oxime structure in which an oxime compound is used as a blocking agent are preferred because the dissociation temperature can be more easily adjusted to a preferred range and development residues can be reduced compared to compounds not having an oxime structure.

[0186] The blocked isocyanate compound may have a polymerizable group. The polymerizable group is not particularly limited, and any known polymerizable group can be used, with a radical polymerizable group being preferred. Examples of the polymerizable group include ethylenically unsaturated groups such as a (meth)acryloxy group, a (meth)acrylamide group, and a styryl group, as well as groups having an epoxy group such as a glycidyl group. Of these, the polymerizable group is preferably an ethylenically unsaturated group, more preferably a (meth)acryloxy group, and even more preferably an acryloxy group.

[0187] Furthermore, compounds having the following structure can also be used as the blocked isocyanate compound.

[0188] [ka]

[0189] As the blocked isocyanate compound, commercially available products can also be used. Examples of commercially available blocked isocyanate compounds include Karenz (registered trademark) AOI-BM, Karenz (registered trademark) MOI-BM, Karenz (registered trademark) MOI-BP, and the like (all manufactured by Showa Denko K.K.), and the blocked Duranate series (e.g., Duranate (registered trademark) MF-K60B, Duranate (registered trademark) SBN-70D, Duranate (registered trademark) TPA-B80E, Duranate (registered trademark) WT32-B75P, and the like, manufactured by Asahi Kasei Chemicals Corporation).

[0190] The thermally crosslinkable compound may be used alone or in combination of two or more kinds. When the photosensitive layer contains a thermally crosslinkable compound, the content of the thermally crosslinkable compound is preferably 1 to 50 mass %, more preferably 2 to 30 mass %, and even more preferably 2 to 20 mass %, relative to the total mass of the photosensitive layer.

[0191] <Surfactant> The photosensitive layer may contain a surfactant. Examples of surfactants include those described in paragraph

[0017] of Japanese Patent No. 4502784 and paragraphs

[0060] to

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

[0192] The surfactant is preferably a nonionic surfactant, a fluorine-based surfactant, or a silicone-based surfactant. Commercially available fluorine-based surfactants include, for example, 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-566, F-567, F-568, F-569, F-570, F-571, F-572, F-573, F-574, F-575, F-576, F-577, F-579, F-582, F-583, F-584, F-585, F-586, F-587, F-588, F-589, F-589, F-580, F-581 ...90, F-591, F-592, F-593, F-594, F-595, F-596, F-597, F-598, F-599, F-599, F-590, F -563, F-568, F-575, F-780, EXP, MFS-330, MFS-578, MFS-579, MFS-586, MFS-587, R-41, R-41-LM, R-01, R-40, R-40-LM, RS-43, TF-1956, RS-90, R-94, RS-72-K, DS-21 (all manufactured by DIC Corporation), Fluorard FC430, FC431, FC171 (all manufactured by Sumitomo 3M Limited), Surflon S-382, SC-101, SC-103, SC-104, SC-105, SC-1068, SC-381, SC-383, S-393, KH-40 (all manufactured by AGC Inc.), PolyFox PF636, PF656, PF6320, PF6520, PF7002 (all manufactured by OMNOVA), Futergent Examples include 710FL, 710FM, 610FM, 601AD, 601ADH2, 602A, 215M, 245F, 251, 212M, 250, 209F, 222F, 208G, 710LA, 710FS, 730LM, 650AC, 681, and 683 (all manufactured by NEOS Corporation). Also suitable for use as fluorosurfactants are acrylic compounds that have a molecular structure with a functional group containing a fluorine atom, and when heated, the functional group containing the fluorine atom is cleaved, causing the fluorine atom to volatilize. Examples of such fluorosurfactants include the Megafac DS series manufactured by DIC Corporation (The Chemical Daily, February 22, 2016; The Nikkei Business Daily, February 23, 2016), such as Megafac DS-21. As the fluorine-based surfactant, it is also preferable to use a polymer of a fluorine atom-containing vinyl ether compound having a fluorinated alkyl group or a fluorinated alkylene ether group and a hydrophilic vinyl ether compound. Furthermore, a block polymer can also be used as the fluorine-based surfactant. Furthermore, as the fluorine-based surfactant, 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 ethyleneoxy groups, propyleneoxy groups) can also be preferably used. As the fluorine-based surfactant, a fluorine-containing polymer having an ethylenically unsaturated bond-containing group in the side chain can also be used, such as Megafac RS-101, RS-102, RS-718K, and RS-72-K (all manufactured by DIC Corporation).

[0193] From the viewpoint of improving environmental friendliness, it is preferable that the fluorine-based surfactant be a surfactant derived from an alternative material to compounds having a linear perfluoroalkyl group having seven or more carbon atoms, such as perfluorooctanoic acid (PFOA) and perfluorooctanesulfonic acid (PFOS). Examples of nonionic surfactants include glycerol, trimethylolpropane, trimethylolethane, and their ethoxylates and propoxylates (for example, glycerol propoxylate, glycerol ethoxylate, etc.), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid esters, Pluronic (registered trademark) L10, L31, L61, L62, 10R5, 17R2, 25R2 (all manufactured by BASF), Tetronic 304, 701, 704, 901, 904, 150R1 (all manufactured by BASF), and Solsperse 20000 (all manufactured by Lubrizol Nippon Co., Ltd.), NCW-101, NCW-1001, NCW-1002 (all manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), Paionin D-6112, D-6112-W, D-6315 (all manufactured by Takemoto Oil & Fat Co., Ltd.), Olfine E1010, Surfynol 104, 400, 440 (all manufactured by Nissin Chemical Industry Co., Ltd.), and the like.

[0194] Examples of silicone surfactants include linear polymers consisting of siloxane bonds and modified siloxane polymers in which organic groups have been introduced into the side chains or terminals.

[0195] Specific examples of silicone surfactants include DOWSIL 8032 ADDITIVE, Toray Silicone DC3PA, Toray Silicone SH7PA, Toray Silicone DC11PA, Toray Silicone SH21PA, Toray Silicone SH28PA, Toray Silicone SH29PA, Toray Silicone SH30PA, and Toray Silicone SH8400 (all manufactured by Toray Dow Corning Co., Ltd.), as well as X-22-4952, X-22-4272, X-22-6266, KF-351A, K354L, KF-355A, and 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 Silicones Co., Ltd.), F-4440, TSF-4300, TSF-4445, TSF-4460, TSF-4452 (all manufactured by Momentive Performance Materials), BYK307, BYK323, BYK330 (all manufactured by BYK-Chemie), and the like.

[0196] The surfactants may be used alone or in combination of two or more. When the photosensitive layer contains a surfactant, the content of the surfactant is preferably 0.01 to 3.0% by mass, more preferably 0.01 to 1.0% by mass, and even more preferably 0.05 to 0.80% by mass, based on the total mass of the photosensitive layer.

[0197] <Polymerization inhibitor> The photosensitive layer may contain a polymerization inhibitor. The polymerization inhibitor means a compound having the function of delaying or inhibiting a polymerization reaction. As the polymerization inhibitor, for example, a known compound used as a polymerization inhibitor can be used.

[0198] Examples of the polymerization inhibitor include phenothiazine compounds such as phenothiazine, bis-(1-dimethylbenzyl)phenothiazine, and 3,7-dioctylphenothiazine; bis[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionic acid][ethylenebis(oxyethylene)]2,4-bis[(laurylthio)methyl]-o-cresol, 1,3,5-tris(3,5-di-t-butyl-4-hydroxybenzyl), 1,3,5-tris(4-t-butyl-3-hydroxy-2,6-dimethylbenzyl), 2,4-bis-(n-octylthio)-6-(4-hydroxy-3,5-di-t-butylanilino)-1,3,5-triazine, and pentaerythritol tetrakis 3-(3,5-di-te 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 these, in terms of achieving better effects of the present invention, the polymerization inhibitor is preferably at least one selected from the group consisting of phenothiazine compounds, nitroso compounds or salts thereof, and hindered phenol compounds, and more preferably phenothiazine, 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), p-methoxyphenol, and N-nitrosophenylhydroxylamine aluminum salt.

[0199] The polymerization inhibitor may be used alone or in combination of two or more kinds. When the photosensitive layer contains a polymerization inhibitor, the content of the polymerization inhibitor is preferably 0.001 to 5.0 mass%, more preferably 0.01 to 3.0 mass%, and even more preferably 0.02 to 2.0 mass%, relative to the total mass of the photosensitive layer. The content of the polymerization inhibitor is preferably 0.005 to 5.0 mass%, more preferably 0.01 to 3.0 mass%, and even more preferably 0.01 to 1.0 mass%, relative to the total mass of the photopolymerizable compound.

[0200] <Hydrogen donor compounds> The photosensitive layer may contain a hydrogen donating compound. The hydrogen donor compound has the effect of further improving the sensitivity of the photopolymerization initiator to actinic rays and suppressing the inhibition of polymerization of the photopolymerizable compound by oxygen.

[0201] Examples of hydrogen donor compounds include amines and amino acid compounds.

[0202] Examples of amines include compounds described in MRSander et al., Journal of Polymer Society, Vol. 10, p. 3173 (1972), JP-B-44-020189, JP-A-51-082102, JP-A-52-134692, JP-A-59-138205, JP-A-60-084305, JP-A-62-018537, JP-A-64-033104, and Research Disclosure No. 33825. More specific examples include 4,4'-bis(diethylamino)benzophenone, tris(4-dimethylaminophenyl)methane (also known as leuco crystal violet), triethanolamine, p-dimethylaminobenzoic acid ethyl ester, p-formyldimethylaniline, and p-methylthiodimethylaniline. Among these, at least one amine selected from the group consisting of 4,4'-bis(diethylamino)benzophenone and tris(4-dimethylaminophenyl)methane is preferred as the amine, as it provides better effects of the present invention.

[0203] Examples of the amino acid compound include N-phenylglycine, N-methyl-N-phenylglycine, and N-ethyl-N-phenylglycine. Among these, N-phenylglycine is preferred as the amino acid compound in that it provides a more excellent effect of the present invention.

[0204] Further, examples of the hydrogen donor compound include organometallic compounds (such as tributyltin acetate) described in JP-B-48-042965, hydrogen donors described in JP-B-55-034414, and sulfur compounds (such as trithiane) described in JP-A-6-308727.

[0205] The hydrogen donor compounds may be used alone or in combination of two or more. When the photosensitive layer contains a hydrogen donor compound, the content of the hydrogen donor compound is preferably 0.01 to 10.0 mass %, more preferably 0.01 to 8.0 mass %, and even more preferably 0.03 to 5.0 mass %, relative to the total mass of the photosensitive layer, from the viewpoint of improving the curing rate through a balance between the polymerization growth rate and chain transfer.

[0206] <Impurities, etc.> The photosensitive layer may contain a certain amount of impurities. Specific examples of impurities include sodium, potassium, magnesium, calcium, iron, manganese, copper, aluminum, titanium, chromium, cobalt, nickel, zinc, tin, halogens, and ions thereof. Among these, halide ions, sodium ions, and potassium ions are likely to be mixed in as impurities, so it is preferable to set the contents to the following values.

[0207] The content of impurities in the photosensitive layer is preferably 80 ppm or less, more preferably 10 ppm or less, and even more preferably 2 ppm or less, by mass. The content of impurities in the photosensitive layer can be 1 ppb or more, or 0.1 ppm or more, by mass.

[0208] Methods for keeping the impurity content within the above range include selecting raw materials for the photosensitive layer that contain a small amount of impurities, preventing impurities from being mixed in during the formation of the photosensitive layer, and removing them by washing. By using these methods, the amount of impurities can be kept within the above range.

[0209] The amount of impurities can be determined by known methods such as ICP (Inductively Coupled Plasma) emission spectroscopy, atomic absorption spectroscopy, and ion chromatography.

[0210] The content of compounds such as benzene, formaldehyde, trichloroethylene, 1,3-butadiene, carbon tetrachloride, chloroform, N,N-dimethylformamide, N,N-dimethylacetamide, and hexane in the photosensitive layer is preferably low. The content of these compounds in the photosensitive layer is preferably 100 ppm or less by mass, more preferably 20 ppm or less, and even more preferably 4 ppm or less. The lower limit can be 10 ppb or more, and even more preferably 100 ppb or more, by mass. The content of these compounds can be reduced in the same manner as for the metal impurities described above. Furthermore, they can be quantified by known measurement methods.

[0211] The content of water in the photosensitive layer is preferably from 0.01 to 1.0% by mass, more preferably from 0.05 to 0.5% by mass, from the viewpoint of improving reliability and lamination properties.

[0212] <Residual monomer> The photosensitive layer may contain residual monomers of the constituent units of the alkali-soluble resin described above. 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 even more preferably 500 ppm by mass or less, relative to the total mass of the alkali-soluble resin. Although there is no particular lower limit, it is preferably 1 ppm by mass or more, and more preferably 10 ppm by mass or more. From the viewpoints of patterning ability and reliability, the residual monomer content 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 even more preferably 100 ppm by mass or less, relative to the total mass of the photosensitive layer. Although there is no particular lower limit, it is preferably 0.1 ppm by mass or more, and more preferably 1 ppm by mass or more.

[0213] The amount of residual monomers in the synthesis of an alkali-soluble resin by a polymer reaction is also preferably within the above range. For example, when the alkali-soluble resin is synthesized by reacting glycidyl acrylate with a carboxylic acid side chain, the content of glycidyl acrylate is preferably within the above range. The amount of residual monomer can be measured by known methods such as liquid chromatography and gas chromatography.

[0214] <Other ingredients> The photosensitive layer may contain components other than those already described (hereinafter also referred to as "other components"). Examples of other components include colorants, antioxidants, and particles (e.g., metal oxide particles). Other components also include other additives described in paragraphs

[0058] to

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

[0215] -particle- The particles are preferably metal oxide particles. The metals in the metal oxide particles also include metalloids such as B, Si, Ge, As, Sb, and Te. The average primary particle size of the particles is preferably from 1 to 200 nm, more preferably from 3 to 80 nm, from the viewpoint of the transparency of the cured film, for example. The average primary particle size of particles is calculated by measuring the particle sizes of 200 random particles using an electron microscope and calculating the arithmetic mean of the measurement results. If the particle shape is not spherical, the particle size is taken to be the longest side.

[0216] When the photosensitive layer contains particles, it may contain only one type of particles or two or more types of particles differing in metal type, size, etc. The photosensitive layer does not contain particles, or if it does contain particles, the particle content is preferably more than 0% by mass and not more than 35% by mass, relative to the total mass of the photosensitive layer; more preferably, the photosensitive layer does not contain particles, or the particle content is more than 0% by mass and not more than 10% by mass, relative to the total mass of the photosensitive layer; even more preferably, the photosensitive layer does not contain particles, or the particle content is more than 0% by mass and not more than 5% by mass, relative to the total mass of the photosensitive layer; even more preferably, the photosensitive layer does not contain particles, or the particle content is more than 0% by mass and not more than 1% by mass, relative to the total mass of the photosensitive layer; and particularly preferably, the photosensitive layer does not contain particles.

[0217] -Coloring agent- The photosensitive layer may contain a small amount of colorant (pigment, dye, etc.), but preferably does not substantially contain a colorant, for example, from the viewpoint of transparency. When the photosensitive layer contains 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 photosensitive layer.

[0218] -Antioxidants- Examples of antioxidants include 3-pyrazolidones such as 1-phenyl-3-pyrazolidone (also known as 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, paraaminophenol, parahydroxyphenylglycine, and paraphenylenediamine. Among these, 3-pyrazolidones are preferred as the antioxidant, and 1-phenyl-3-pyrazolidone is more preferred, as they provide better effects of the present invention.

[0219] When the photosensitive layer contains an antioxidant, the content of the antioxidant is preferably 0.001% by mass or more, more preferably 0.005% by mass or more, and even more preferably 0.01% by mass or more, relative to the total mass of the photosensitive layer. There is no upper limit, but it is preferably 1% by mass or less.

[0220] <Thickness of photosensitive layer> The thickness of the photosensitive layer is not particularly limited, but is often 30 μm or less, and is preferably 20 μm or less, more preferably 15 μm or less, and even more preferably 10 μm or less, from the viewpoint of obtaining a superior effect of the present invention. The lower limit of the thickness is preferably 0.60 μm or more, and more preferably 1.5 μm or more, from the viewpoint of obtaining a film having excellent strength by curing the photosensitive layer. The thickness of the photosensitive layer can be calculated, for example, as the average value of measurements taken at any five points by cross-sectional observation using a scanning electron microscope (SEM).

[0221] <Refractive index of photosensitive layer> The refractive index of the photosensitive layer is preferably from 1.41 to 1.59, more preferably from 1.47 to 1.56.

[0222] <Color of photosensitive layer> The photosensitive layer is preferably achromatic. Specifically, the total reflection (incident angle 8°, light source: D-65 (2° visual field)) is preferably achromatic in the CIE 1976 (L*, a*, b*) color space. * The value is preferably 10 to 90, and a * The value is preferably -1.0 to 1.0, and b * The value is preferably between -1.0 and 1.0.

[0223] The pattern obtained by curing the photosensitive layer (cured film of the photosensitive layer) is preferably achromatic. Specifically, total reflection (incident angle 8°, light source: D-65 (2° field of view)) is * The value is preferably 10 to 90, and the pattern a * The value is preferably -1.0 to 1.0, and the b * The value is preferably between -1.0 and 1.0.

[0224] <Transmittance of photosensitive layer> The visible light transmittance per 1.0 μm of film thickness of the photosensitive layer is preferably 80% or more, more preferably 90% or more, and most preferably 95% or more. It is preferable that the average transmittance at wavelengths of 400 nm to 800 nm, the minimum transmittance at wavelengths of 400 nm to 800 nm, and the transmittance at a wavelength of 400 nm all satisfy the above. Preferred transmittance values ​​include, for example, 87%, 92%, and 98%. The same applies to the transmittance per 1.0 μm of film thickness of the cured film of the photosensitive layer.

[0225] <Moisture permeability of photosensitive layer> The moisture permeability of the pattern (cured film of the photosensitive layer) obtained by curing the photosensitive layer at a film thickness of 40 μm is 500 g / m from the viewpoint of rust prevention of the electrodes or wiring and reliability of the device. 2 / 24hr or less is preferable, and 300g / m 2 / 24hr or less is more preferable, and 100g / m 2 It is more preferable that the time is 24 hours or less. The moisture permeability was measured by exposing the photosensitive layer to i-rays at an exposure dose of 300 mJ / cm 2 After exposure at 145°C for 30 minutes, the photosensitive layer is cured and the cured film is measured. The moisture permeability is measured in accordance with the cup method of JIS Z0208. It is preferable that the moisture permeability is within the above range under any of the test conditions of 40°C temperature / 90% humidity, 65°C temperature / 90% humidity, and 80°C temperature / 95% humidity. Specific preferred values ​​are, for example, 80 g / m 2 / 24hr, 150g / m 2 / 24hr, 220g / m 2 / 24hr, etc.

[0226] <Dissolution rate of photosensitive layer> The dissolution rate of the photosensitive layer in a 1.0% aqueous solution of sodium carbonate is preferably 0.01 μm / sec or more, more preferably 0.10 μm / sec or more, and even more preferably 0.20 μm / sec or more, from the viewpoint of suppressing residues during development. From the viewpoint of the edge shape of the pattern, it is preferably 5.0 μm / sec or less, more preferably 4.0 μm / sec or less, and even more preferably 3.0 μm / sec or less. Specific preferred values ​​include, for example, 1.8 μm / sec, 1.0 μm / sec, and 0.7 μm / sec. The dissolution rate per unit time of the photosensitive layer in a 1.0% by mass aqueous solution of sodium carbonate is measured as follows. The photosensitive layer (thickness: 1.0 to 10 μm) formed on the glass substrate and from which the solvent has been thoroughly removed is subjected to shower development at 25°C using a 1.0 mass % aqueous solution of sodium carbonate until the photosensitive layer is completely dissolved (however, this should be limited to a maximum of 2 minutes). The thickness of the photosensitive layer is calculated by dividing the thickness of the photosensitive layer by the time it takes for the photosensitive layer to completely dissolve. If the photosensitive layer does not completely dissolve within 2 minutes, the thickness is calculated in the same way from the amount of change in film thickness up to that point. The dissolution rate of the cured film of the photosensitive layer (within the range of film thickness 1.0 to 10 μm) in a 1.0% aqueous solution of sodium carbonate is preferably 3.0 μm / sec or less, more preferably 2.0 μm / sec or less, even more preferably 1.0 μm / sec or less, and most preferably 0.2 μm / sec or less. The cured film of the photosensitive layer is obtained by exposing the photosensitive layer to i-rays at an exposure dose of 300 mJ / cm. 2 This film is obtained by exposure at 1000 rpm. Specific preferred values ​​include, for example, 0.8 μm / sec, 0.2 μm / sec, and 0.001 μm / sec. Development is performed using a 1 / 4 MIN JJX030PP shower nozzle manufactured by Ikeuchi Co., Ltd., with a shower spray pressure of 0.08 MPa. Under the above conditions, the shower flow rate per unit time is 1,800 mL / min.

[0227] <Swelling ratio of photosensitive layer> From the viewpoint of improving pattern formability, the swelling ratio of the photosensitive layer after exposure to a 1.0 mass % aqueous sodium carbonate solution is preferably 100% or less, more preferably 50% or less, and even more preferably 30% or less. Swelling ratio of the photosensitive layer after exposure to a 1.0 mass % aqueous sodium carbonate solution is measured as follows. The photosensitive layer (thickness 1.0-10μm) formed on the glass substrate and from which the solvent had been thoroughly removed was exposed to 500mJ / cm2 of ultra-high pressure mercury lamp. 2 The film is exposed to light (i-line measurement). The glass substrate is immersed in a 1.0 mass % sodium carbonate aqueous solution at 25°C, and the film thickness is measured after 30 seconds. The percentage increase in film thickness after immersion relative to the film thickness before immersion is calculated. Specific preferred values ​​include, for example, 4%, 13%, and 25%.

[0228] <Foreign matter in the photosensitive layer> From the viewpoint of pattern formation, the number of foreign particles with a diameter of 1.0 μm or more in the photosensitive layer should be 10 / mm 2 It is preferable that the number of particles is less than 5 / mm 2 The number of foreign particles is measured as follows: Five randomly selected regions (1 mm x 1 mm) on the surface of the photosensitive layer are visually observed using an optical microscope from the normal direction of the surface of the photosensitive layer, and the number of foreign particles with a diameter of 1.0 μm or more in each region is counted, and the arithmetic average of these is calculated as the number of foreign particles. A specific preferred numerical value is, for example, 0 particles / mm 2 , 1 piece / mm 2 , 4 pieces / mm 2 , 8 pieces / mm 2 etc.

[0229] <Haze of the dissolved material in the photosensitive layer> To prevent the formation of aggregates during development, the haze of the solution obtained by dissolving 1.0 cm3 of the photosensitive resin layer in 1.0 L of a 30°C aqueous solution of 1.0% by mass sodium carbonate is preferably 60% or less, more preferably 30% or less, even more preferably 10% or less, and most preferably 1% or less. Haze is measured as follows: First, a 1.0% by mass aqueous solution of sodium carbonate is prepared and the liquid temperature is adjusted to 30°C. 1.0 cm3 of the photosensitive resin layer is placed in 1.0 L of the aqueous sodium carbonate solution. The solution is stirred at 30°C for 4 hours, taking care to avoid introducing air bubbles. After stirring, the haze of the solution containing the dissolved photosensitive layer is measured. Haze is measured using a haze meter (product name "NDH4000" manufactured by Nippon Denshoku Industries Co., Ltd.) with a liquid measurement unit and a dedicated liquid measurement cell with an optical path length of 20 mm. Specific preferred values ​​include 0.4%, 1.0%, 9%, and 24%, for example.

[0230] <<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, and examples thereof include polyolefin films such as polypropylene film and polyethylene film, polyester films such as polyethylene terephthalate film, polycarbonate film, and polystyrene film. Furthermore, a resin film made of the same material as the temporary support may be used as the protective film. Among these, the protective film is preferably a polyolefin film, more preferably a polypropylene film or a polyethylene film, and even more preferably a polyethylene film.

[0231] The thickness of the protective film is preferably from 1 to 100 μm, more preferably from 5 to 50 μm, even more preferably from 5 to 40 μm, and particularly preferably from 15 to 30 μm. The thickness of the protective film is preferably 1 μm or more in terms of excellent mechanical strength, and is preferably 100 μm or less in terms of being relatively inexpensive.

[0232] In addition, the number of fisheyes with a diameter of 80 μm or more contained in the protective film is 5 / m 2 It is preferable that: "Fisheyes" are foreign matter, unmelted material, and oxidized degradation products of the material that are trapped in the film when the material is thermally melted and then kneaded, extruded, biaxially stretched, or cast to produce the film.

[0233] The number of particles with a diameter of 3 μm or more contained in the protective film is 30 / mm 2 Preferably less than 10 pieces / mm 2 Less than 5 pieces / mm is more preferable. 2 The following is even more preferred: This makes it possible to suppress defects caused by the transfer of irregularities due to particles contained in the protective film to the photosensitive layer or the conductive layer.

[0234] In order to provide good winding properties, the arithmetic mean roughness Ra of the surface of the protective film opposite to the surface in contact with the 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, and is preferably less than 0.50 μm, more preferably 0.40 μm or less, and even more preferably 0.30 μm or less. In order to prevent defects during transfer, the surface roughness Ra of the protective film on the surface in contact with the 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, and is preferably less than 0.50 μm, more preferably 0.40 μm or less, and even more preferably 0.30 μm or less.

[0235] <<Suitable relationship between the physical properties of the temporary support, photosensitive layer, and protective film>> In the following description, it is preferable that the physical properties of the temporary support, the photosensitive layer, and the protective film of the transfer film exhibit the following characteristics. The transfer film preferably satisfies one or more of Preferred Mode 1, Preferred Mode 2, Preferred Mode 3, Preferred Mode 4, and Preferred Mode 5, and more preferably satisfies all of them.

[0236] Hereinafter, the "breaking elongation of the cured film obtained by curing the photosensitive layer" refers to the breaking elongation of a 20 μm thick photosensitive layer exposed to 120 mJ / cm 2 of an ultra-high pressure mercury lamp. 2 After curing by exposure, it is irradiated with a high-pressure mercury lamp at 400mJ / cm 2 The cured film is then subjected to additional exposure at 145°C for 30 minutes, and then subjected to a tensile test.

[0237] <Preferred embodiment 1> In the transfer film, the physical properties of the temporary support, the photosensitive layer, and the protective film preferably satisfy all of the following conditions (P1) to (P3). (P1) The cured film obtained by curing the photosensitive layer has a breaking elongation of 15% or more at 120°C. (P2) The arithmetic mean roughness Ra of the surface of the temporary support on the intermediate layer side is 50 nm or less. (P3) The arithmetic mean roughness Ra of the surface of the protective film on the photosensitive layer side is 150 nm or less.

[0238] <Preferred embodiment 2> The physical properties of the temporary support and the photosensitive layer of the transfer film preferably satisfy the following formula (1). X×Y<1500 Formula (1) In formula (1), X represents the breaking elongation (%) of the cured film obtained by curing the photosensitive layer at 120°C, and Y represents the arithmetic mean roughness Ra (nm) of the surface of the temporary support on the intermediate layer side. In the above formula (1), the value represented by X×Y is preferably 750 or less. Specific values ​​of X include 18%, 25%, 30%, 35%, etc. Specific values ​​of Y include 4 nm, 8 nm, 15 nm, 30 nm, etc. Specific values ​​of X×Y include 150, 200, 300, 360, 900, etc.

[0239] <Preferred Embodiment 3> The photosensitive physical properties of the transfer film preferably satisfy the following condition (P4). (P4) The breaking elongation at 120°C is more than twice as large as the breaking elongation at 23°C of the cured film obtained by curing the photosensitive layer.

[0240] <Preferred Embodiment 4> The physical properties of the temporary support and the photosensitive layer of the transfer film preferably satisfy the following formula (2). Y ≦ Z Equation (2) Here, in formula (2), Y represents the arithmetic mean roughness Ra (nm) of the surface of the temporary support on the intermediate layer side, and Z represents the arithmetic mean roughness Ra (nm) of the surface of the protective film on the photosensitive layer side.

[0241] <<Refractive index adjustment layer>> The transfer film preferably has a refractive index adjusting layer. The refractive index adjusting layer may be a known refractive index adjusting layer. Examples of materials contained in the refractive index adjusting layer include binder polymers, polymerizable compounds, metal salts, and particles. The method for controlling the refractive index of the refractive index adjusting layer is not particularly limited, and examples thereof include a method of using a resin having a predetermined refractive index alone, a method of using a resin and particles, and a method of using a complex of a metal salt and a resin.

[0242] Examples of the binder polymer and polymerizable compound include the binder polymer and polymerizable compound described above in the section "Photosensitive Layer."

[0243] Examples of particles include metal oxide particles and metal particles. The type of metal oxide particles is not particularly limited, and known metal oxide particles can be used. The metals in the metal oxide particles include semimetals such as B, Si, Ge, As, Sb, and Te.

[0244] The average primary particle size of the particles is preferably from 1 to 200 nm, more preferably from 3 to 80 nm, from the viewpoint of the transparency of the cured film, for example. The average primary particle size of particles is calculated by measuring the particle sizes of 200 random particles using an electron microscope and calculating the arithmetic mean of the measurement results. If the particle shape is not spherical, the particle size is taken to be the longest side.

[0245] Specifically, the metal oxide particles are preferably at least one selected from the group consisting of zirconium oxide particles (ZrO2 particles), Nb2O5 particles, titanium oxide particles (TiO2 particles), silicon dioxide particles (SiO2 particles), and composite particles thereof. Among these, at least one type of metal oxide particles selected from the group consisting of zirconium oxide particles and titanium oxide particles is more preferred, for example, because the refractive index can be easily adjusted.

[0246] Commercially available metal oxide particles include calcined zirconium oxide particles (manufactured by CIK Nanotech Co., Ltd., product name: ZRPGM15WT%-F04), calcined zirconium oxide particles (manufactured by CIK Nanotech Co., Ltd., product name: ZRPGM15WT%-F74), calcined zirconium oxide particles (manufactured by CIK Nanotech Co., Ltd., product name: ZRPGM15WT%-F75), calcined zirconium oxide particles (manufactured by CIK Nanotech Co., Ltd., product name: ZRPGM15WT%-F76), zirconium oxide particles (Nanouse OZ-S30M, manufactured by Nissan Chemical Industries, Ltd.), and zirconium oxide particles (Nanouse OZ-S30K, manufactured by Nissan Chemical Industries, Ltd.).

[0247] The particles may be used alone or in combination of two or more types. The content of particles in the refractive index-matching layer is preferably 1 to 95 mass %, more preferably 20 to 90 mass %, and even more preferably 30 to 85 mass %, based on the total mass of the refractive index-matching layer. When titanium oxide is used as the metal oxide particles, the content of the titanium oxide particles is preferably 1 to 95 mass %, more preferably 20 to 90 mass %, and even more preferably 30 to 85 mass %, based on the total mass of the refractive index adjusting layer.

[0248] The refractive index of the refractive index-adjusting layer is preferably higher than the refractive index of the photosensitive layer. The refractive index of the refractive index-matching layer is preferably 1.50 or more, more preferably 1.55 or more, even more preferably 1.60 or more, and particularly preferably 1.65 or more. The upper limit of the refractive index of the refractive index-matching layer is preferably 2.10 or less, more preferably 1.85 or less, and even more preferably 1.78 or less.

[0249] The thickness of the refractive index adjusting layer is preferably from 50 to 500 nm, more preferably from 55 to 110 nm, and even more preferably from 60 to 100 nm. The thickness of the refractive index adjusting layer is calculated as the average value of measurements at any five points measured by cross-sectional observation using a scanning electron microscope (SEM).

[0250] <<Method for manufacturing transfer film according to the first embodiment>> The method for producing the transfer film of the first embodiment is not particularly limited, and any known method can be used. Examples of a method for manufacturing the transfer film 10 include a method including the steps of applying a photosensitive composition to the surface of the temporary support 1 to form a coating film, and then drying this coating film to form the photosensitive layer 3, and applying a composition for forming a refractive index adjusting layer to the surface of the photosensitive layer 3 to form a coating film, and then drying this coating film to form the refractive index adjusting layer 5.

[0251] The transfer film 10 is produced by pressing the protective film 7 onto the refractive index adjusting layer 5 of the laminate produced by the above-mentioned production method. As a manufacturing method for the transfer film of the first embodiment, it is preferable to include a step of providing a protective film 7 so that it is in contact with the side of the refractive index adjusting layer 5 opposite the side having the temporary support 1, thereby manufacturing a transfer film 10 comprising the temporary support 1, the photosensitive layer 3, the refractive index adjusting layer 5, and the protective film 7. After the transfer film 10 is manufactured by the above manufacturing method, the transfer film 10 may be wound up to produce and store a transfer film in roll form. The transfer film in roll form can be provided in its original form for the lamination step with a substrate in a roll-to-roll system described below.

[0252] The transfer film 10 may be produced by forming the refractive index adjusting layer 5 on the protective film 7 and then forming the photosensitive layer 13 on the surface of the refractive index adjusting layer 5 . In addition, the manufacturing method of the above-mentioned transfer film 10 may be a method in which a photosensitive layer 3 is formed on a temporary support 1, a refractive index adjusting layer 5 is separately formed on a protective film 7, and the refractive index adjusting layer 5 is bonded to the photosensitive layer 3.

[0253] <Photosensitive composition and method for forming photosensitive layer> In terms of excellent productivity, the photosensitive layer in the transfer film is desirably formed by a coating method using a photosensitive composition containing the components constituting the photosensitive layer described above (e.g., an alkali-soluble resin, a photopolymerizable compound, and a photopolymerization initiator, etc.) and a solvent. Specifically, a preferred method for producing the transfer film of the first embodiment is a method in which the photosensitive composition is applied to a temporary support to form a coating film, and this coating film is dried at a predetermined temperature to form the photosensitive layer.

[0254] The solvent that can be contained in the photosensitive composition is preferably an organic solvent, such as methyl ethyl ketone, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate (also known as 1-methoxy-2-propyl acetate), diethylene glycol ethyl methyl ether, cyclohexanone, methyl isobutyl ketone, ethyl lactate, methyl lactate, caprolactam, n-propanol, and 2-propanol.

[0255] Furthermore, as the solvent, an organic solvent having a boiling point of 180 to 250° C. (high boiling point solvent) can also be used, if necessary.

[0256] The solvents may be used alone or in combination of two or more. The total solid content of the photosensitive composition is preferably from 5 to 80 mass %, more preferably from 5 to 40 mass %, and even more preferably from 5 to 30 mass %, based on the total mass of the photosensitive composition. That is, the content of the solvent in the photosensitive composition is preferably 20 to 95 mass %, more preferably 60 to 95 mass %, and even more preferably 70 to 95 mass %, based on the total mass of the photosensitive composition.

[0257] The viscosity of the photosensitive composition at 25°C is, for example, preferably 1 to 50 mPa·s, more preferably 2 to 40 mPa·s, and even more preferably 3 to 30 mPa·s, from the viewpoint of coatability. The viscosity is measured using a viscometer. For example, a viscometer manufactured by Toki Sangyo Co., Ltd. (product name: VISCOMETER TV-22) can be suitably used. However, the viscometer is not limited to the above-mentioned viscometers.

[0258] The surface tension of the photosensitive composition at 25°C is preferably 5 to 100 mN / m, more preferably 10 to 80 mN / m, and even more preferably 15 to 40 mN / m, from the viewpoint of coatability. The surface tension is measured using a surface tensiometer. For example, a surface tensiometer manufactured by Kyowa Interface Science Co., Ltd. (trade name: Automatic Surface Tensiometer CBVP-Z) can be suitably used. However, the surface tensiometer is not limited to the above-mentioned surface tensiometer.

[0259] Examples of methods for applying the photosensitive composition include printing, spraying, roll coating, bar coating, curtain coating, spin coating, and die coating (that is, slit coating).

[0260] Heat drying and vacuum drying are preferred methods for drying the coating film of the photosensitive composition. In this specification, "drying" means removing at least a portion of the solvent contained in the composition. Examples of drying methods include natural drying, heat drying, and vacuum drying. The above methods can be applied alone or in combination. The drying temperature is preferably 80° C. or higher, more preferably 90° C. or higher, and the upper limit is preferably 130° C. or lower, more preferably 120° C. or lower. Drying can also be performed by continuously changing the temperature. The drying time is preferably 20 seconds or more, more preferably 40 seconds or more, and even more preferably 60 seconds or more. There is no upper limit, but the drying time is preferably 600 seconds or less, and more preferably 300 seconds or less.

[0261] <Composition for forming refractive index adjusting layer and method for forming refractive index adjusting layer> The composition for forming the refractive index adjusting layer preferably contains the various components for forming the refractive index adjusting layer described above and a solvent. Note that in the composition for forming the refractive index adjusting layer, the preferred range of the content of each component relative to the total solid content of the composition is the same as the preferred range of the content of each component relative to the total mass of the refractive index adjusting layer described above. The solvent is not particularly limited as long as it can dissolve or disperse the components contained in the refractive index adjusting layer, and at least one selected from the group consisting of water and water-miscible organic solvents is preferred, and water or a mixed solvent of water and a water-miscible organic solvent is more preferred. Examples of water-miscible organic solvents include alcohols having 1 to 3 carbon atoms, acetone, ethylene glycol, and glycerin, with alcohols having 1 to 3 carbon atoms being preferred, and methanol or ethanol being more preferred. The solvents may be used alone or in combination of two or more. The content of the solvent is preferably 50 to 2,500 parts by mass, more preferably 50 to 1,900 parts by mass, and even more preferably 100 to 900 parts by mass, relative to 100 parts by mass of the total solid content of the composition.

[0262] The method for forming the refractive index adjusting layer is not particularly limited as long as it is a method capable of forming a layer containing the above components, and examples thereof include known coating methods (slit coating, spin coating, curtain coating, inkjet coating, etc.).

[0263] Moreover, by laminating the protective film to the refractive index adjusting layer, the transfer film of the first embodiment can be produced. The method for attaching the protective film to the refractive index adjusting layer is not particularly limited, and known methods can be used. Examples of a device for laminating the protective film to the refractive index adjusting layer include known laminators such as a vacuum laminator and an auto-cut laminator. The laminator is preferably equipped with any heatable roller such as a rubber roller and is capable of applying pressure and heat.

[0264] [Transfer film of second embodiment] An example of the transfer film of the second embodiment will be described below. The transfer film 20 shown in FIG. 2 has a temporary support 11, a composition layer 12 including a thermoplastic resin layer 13, an intermediate layer 15, and a photosensitive layer 17, and a protective film 19, in this order. Although the transfer film 20 shown in FIG. 2 has the protective film 19 disposed thereon, the protective film 19 does not necessarily have to be disposed. Furthermore, the transfer film 20 shown in FIG. 2 has the thermoplastic resin layer 13 and the intermediate layer 15 arranged therein, but the thermoplastic resin layer 13 and the intermediate layer 15 do not necessarily have to be arranged. Each element constituting the transfer film will be described below. In the transfer film of the second embodiment, the temporary support 11 and the protective film 19 may be the same as the temporary support 1 and the protective film 7 of the first embodiment described above, and the preferred embodiments are also the same.

[0265] <<Photosensitive layer>> The transfer film has a photosensitive layer. After the photosensitive layer is transferred onto the transfer target, it is exposed to light and developed, thereby forming a pattern on the transfer target. The photosensitive layer is preferably a negative photosensitive layer. Note that a negative photosensitive layer is a photosensitive layer in which the solubility of the exposed portion in a developer decreases upon exposure. When the photosensitive layer is a negative photosensitive layer, the formed pattern corresponds to a hardened layer.

[0266] Components that can be contained in the photosensitive layer will be described in detail below.

[0267] <Binder polymer> The photosensitive layer contains an alkali-soluble resin as a binder polymer. The binder polymer of the photosensitive layer may be partially or entirely an alkali-soluble resin. The definition of alkali-solubility is as described above.

[0268] The acid value of the binder polymer is preferably 220 mgKOH / g or less, more preferably less than 200 mgKOH / g, and even more preferably less than 190 mgKOH / g, from the viewpoint of suppressing swelling of the photosensitive layer by the developer and thereby achieving better resolution. The lower limit of the acid value of the binder polymer is not particularly limited, but from the viewpoint of better developability, it is preferably 60 mgKOH / g or more, more preferably 120 mgKOH / g or more, even more preferably 150 mgKOH / g or more, and particularly preferably 170 mgKOH / g or more. The acid value of the binder polymer may be adjusted by changing the type of structural unit that constitutes the binder polymer and the content of the structural unit containing an acid group.

[0269] The weight-average molecular weight of the binder polymer is preferably 5,000 to 500,000. A weight-average molecular weight of 500,000 or less is preferred from the viewpoint of improving resolution and developability. A weight-average molecular weight of 100,000 or less is more preferred, and 60,000 or less is even more preferred. On the other hand, a weight-average molecular weight of 5,000 or more is preferred from the viewpoint of controlling the properties of development aggregates and the properties of the unexposed film, such as the edge fusing property and cut-chip property of the transfer film. A weight-average molecular weight of 10,000 or more is more preferred, more preferably 20,000 or more, and particularly preferably 30,000 or more. Edge fusing property refers to the degree to which the photosensitive layer protrudes from the edge of a roll when wound into a roll as a transfer film. Cut-chip property refers to the degree to which chips fly off when the unexposed film is cut with a cutter. If these chips adhere to the upper surface of the transfer film, they will be transferred to the mask in a subsequent exposure process, causing defective products. The dispersity of the binder polymer is preferably 1.0 to 6.0, more preferably 1.0 to 5.0, even more preferably 1.0 to 4.0, and particularly preferably 1.0 to 3.0. The dispersity is the ratio of the weight average molecular weight to the number average molecular weight (weight average molecular weight / number average molecular weight). The weight average molecular weight and number average molecular weight are values ​​measured using gel permeation chromatography.

[0270] From the viewpoint of suppressing line width thickening and deterioration of resolution when the focal position is shifted during exposure, the binder polymer preferably contains a structural unit based on a monomer having an aromatic hydrocarbon group. Examples of such aromatic hydrocarbon groups include substituted or unsubstituted phenyl groups and substituted or unsubstituted aralkyl groups. The content of the structural unit based on the monomer having an aromatic hydrocarbon group in the binder polymer is preferably 20% by mass or more, more preferably 30% by mass or more, based on the total mass of the binder polymer. While there is no particular upper limit, it is preferably 95% by mass or less, more preferably 85% by mass or less. When multiple types of binder polymers are included, it is preferable that the average content of the structural unit based on the monomer having an aromatic hydrocarbon group falls within the above range.

[0271] Examples of the monomer having an aromatic hydrocarbon group include a monomer having an aralkyl group, styrene, and polymerizable styrene derivatives (e.g., methylstyrene, vinyltoluene, tert-butoxystyrene, acetoxystyrene, 4-vinylbenzoic acid, styrene dimer, and styrene trimer). Of these, a monomer having an aralkyl group or styrene is preferred. In one embodiment, when the monomer component having an aromatic hydrocarbon group in the binder polymer is styrene, the content of structural units based on styrene is preferably 20 to 70 mass %, more preferably 25 to 65 mass %, still more preferably 30 to 60 mass %, and particularly preferably 30 to 55 mass %, relative to the total mass of the binder polymer. Note that when the photosensitive layer contains multiple types of binder polymers, the content of structural units having an aromatic hydrocarbon group is determined as a weight average value.

[0272] Examples of the aralkyl group include a substituted or unsubstituted phenylalkyl group (excluding a benzyl group) and a substituted or unsubstituted benzyl group, with a substituted or unsubstituted benzyl group being preferred.

[0273] Examples of the monomer having a phenyl alkyl group include phenylethyl (meth)acrylate.

[0274] Examples of the monomer having a benzyl group include (meth)acrylates having a benzyl group, such as benzyl (meth)acrylate and chlorobenzyl (meth)acrylate; and vinyl monomers having a benzyl group, such as vinylbenzyl chloride and vinylbenzyl alcohol. Of these, benzyl (meth)acrylate is preferred. In one embodiment, when the monomer component having an aromatic hydrocarbon group in the binder polymer is benzyl (meth)acrylate, the content of the structural unit based on benzyl (meth)acrylate is preferably 50 to 95% by mass, more preferably 60 to 90% by mass, even more preferably 70 to 90% by mass, and particularly preferably 75 to 90% by mass, relative to the total mass of the binder polymer.

[0275] The binder polymer containing a constituent unit based on a monomer having an aromatic hydrocarbon group is preferably obtained by polymerizing the monomer having an aromatic hydrocarbon group with at least one type of first monomer described below and / or at least one type of second monomer described below.

[0276] The binder polymer that does not contain a constituent unit based on a monomer having an aromatic hydrocarbon group is preferably obtained by polymerizing at least one type of first monomer described below, and more preferably obtained by copolymerizing at least one type of first monomer with at least one type of second monomer described below.

[0277] The first monomer is a monomer having a carboxyl group in the molecule. Examples of the first monomer include (meth)acrylic acid, fumaric acid, cinnamic acid, crotonic acid, itaconic acid, 4-vinylbenzoic acid, maleic anhydride, and maleic acid half ester. Among these, (meth)acrylic acid is preferred. The content of the structural units based on the first monomer in the binder polymer is preferably from 5 to 50 mass %, more preferably from 10 to 40 mass %, and even more preferably from 15 to 30 mass %, based on the total mass of the binder polymer. A content of 5% by mass or more is preferred from the viewpoints of achieving good developability and controlling edge fusing, etc. A content of 50% by mass or less is preferred from the viewpoints of high resolution and bottom shape of the resist pattern, as well as chemical resistance of the resist pattern.

[0278] The second monomer is non-acidic and has at least one polymerizable unsaturated group in the molecule. Examples of the second monomer include (meth)acrylates such as methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, cyclohexyl (meth)acrylate, and 2-ethylhexyl (meth)acrylate; vinyl alcohol esters such as vinyl acetate; and (meth)acrylonitrile. Among these, methyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, or n-butyl (meth)acrylate is preferred, and methyl (meth)acrylate is more preferred. The content of the structural units based on the second monomer in the binder polymer is preferably from 5 to 60 mass %, more preferably from 15 to 50 mass %, and even more preferably from 17 to 45 mass %, based on the total mass of the binder polymer.

[0279] When the binder polymer contains a structural unit based on a monomer having an aralkyl group and / or a structural unit based on a monomer of styrene, it is preferable from the viewpoint of suppressing line width thickening and deterioration of resolution when the focal position is shifted during exposure. For example, a copolymer containing a structural unit based on methacrylic acid, a structural unit based on benzyl methacrylate, and a structural unit based on styrene, or a copolymer containing a structural unit based on methacrylic acid, a structural unit based on methyl methacrylate, a structural unit based on benzyl methacrylate, and a structural unit based on styrene, is preferred. In one embodiment, the binder polymer is preferably a polymer containing 25 to 55 mass% of structural units based on a monomer having an aromatic hydrocarbon group, 20 to 35 mass% of structural units based on a first monomer, and 15 to 45 mass% of structural units based on a second monomer. In another embodiment, the binder polymer is preferably a polymer containing 70 to 90 mass% of structural units based on a monomer having an aromatic hydrocarbon group, and 10 to 25 mass% of structural units based on the first monomer.

[0280] The binder polymer may have a linear structure, a branched structure, or an alicyclic structure in the side chain. By using a monomer containing a group having a branched structure in the side chain or a monomer containing a group having an alicyclic structure in the side chain, it is possible to introduce a branched structure or an alicyclic structure into the side chain of the binder polymer. The group having an alicyclic structure may be monocyclic or polycyclic. Specific examples of monomers containing a group having a branched structure in the side chain include isopropyl (meth)acrylate, isobutyl (meth)acrylate, sec-butyl (meth)acrylate, tert-butyl (meth)acrylate, isoamyl (meth)acrylate, tert-amyl (meth)acrylate, sec-amyl (meth)acrylate, 2-octyl (meth)acrylate, 3-octyl (meth)acrylate, and tert-octyl (meth)acrylate, etc. Among these, isopropyl (meth)acrylate, isobutyl (meth)acrylate, and tert-butyl methacrylate are preferred, and isopropyl methacrylate or tert-butyl methacrylate is more preferred. Specific examples of monomers containing a group having an alicyclic structure in the side chain include monomers having a monocyclic aliphatic hydrocarbon group and monomers having a polycyclic aliphatic hydrocarbon group, as well as (meth)acrylates having an alicyclic hydrocarbon group with 5 to 20 carbon atoms. More specific examples include (bicyclo[2.2.1]heptyl-2)(meth)acrylate, 1-adamantyl (meth)acrylate, 2-adamantyl (meth)acrylate, 3-methyl-1-adamantyl (meth)acrylate, 3,5-dimethyl-1-adamantyl (meth)acrylate, 3-ethyladamantyl (meth)acrylate, 3-methyl-5-ethyl-1-adamantyl (meth)acrylate, 3,5,8-triethyl-1-adamantyl (meth)acrylate, 3,5-dimethyl-8-ethyl-1-adamantyl (meth)acrylate, 2-methyl-2-adamantyl (meth)acrylate, 2-ethyl-2-adamantyl (meth)acrylate, 3-hydroxybenzoic acid (meth)acrylate, and 2-hydroxybenzoic acid (meth)acrylate. Examples include 1-adamantyl (meth)acrylate, octahydro-4,7-menthanoinden-5-yl (meth)acrylate, octahydro-4,7-menthanoinden-1-ylmethyl (meth)acrylate, 1-menthyl (meth)acrylate, tricyclodecane (meth)acrylate, 3-hydroxy-2,6,6-trimethyl-bicyclo[3.1.1]heptyl (meth)acrylate, 3,7,7-trimethyl-4-hydroxy-bicyclo[4.1.0]heptyl (meth)acrylate, (nor)bornyl (meth)acrylate, isobornyl (meth)acrylate, fenchyl (meth)acrylate, 2,2,5-trimethylcyclohexyl (meth)acrylate, and cyclohexyl (meth)acrylate.Among these (meth)acrylic acid esters, cyclohexyl (meth)acrylate, (nor)bornyl (meth)acrylate, isobornyl (meth)acrylate, 1-adamantyl (meth)acrylate, 2-adamantyl (meth)acrylate, fenchyl (meth)acrylate, 1-menthyl (meth)acrylate, and tricyclodecane (meth)acrylate are preferred, and cyclohexyl (meth)acrylate, (nor)bornyl (meth)acrylate, isobornyl (meth)acrylate, 2-adamantyl (meth)acrylate, and tricyclodecane (meth)acrylate are more preferred.

[0281] The binder polymer may be used alone or in combination of two or more. When two or more types are used, it is preferable to mix two types of binder polymers containing structural units based on a monomer having an aromatic hydrocarbon group, or to mix a binder polymer containing structural units based on a monomer having an aromatic hydrocarbon group with a binder polymer that does not contain structural units based on a monomer having an aromatic hydrocarbon group. In the latter case, the proportion of the binder polymer containing structural units based on a monomer having an aromatic hydrocarbon group is preferably 50% by mass or more, more preferably 70% by mass or more, preferably 80% by mass or more, and more preferably 90% by mass or more, based on the total mass of the binder polymer.

[0282] The binder polymer is preferably synthesized by adding an appropriate amount of a radical polymerization initiator such as benzoyl peroxide and azoisobutyronitrile to a solution obtained by diluting one or more of the above-mentioned monomers with a solvent such as acetone, methyl ethyl ketone, or isopropanol, and then heating and stirring the mixture. The synthesis may be carried out while adding a portion of the mixture dropwise to the reaction solution. After the reaction is complete, further solvent may be added to adjust the concentration to the desired level. As a synthesis method, bulk polymerization, suspension polymerization, or emulsion polymerization may be used in addition to solution polymerization.

[0283] The glass transition temperature Tg of the binder polymer is preferably 30 to 135°C. By using a binder polymer having a Tg of 135°C or less, it is possible to suppress line width thickening and deterioration of resolution when the focal position is shifted during exposure. From this viewpoint, the Tg of the binder polymer is more preferably 130°C or less, more preferably 120°C or less, and particularly preferably 110°C or less. Furthermore, using a binder polymer having a Tg of 30°C or more is preferred from the viewpoint of improving edge fuse resistance. From this viewpoint, the Tg of the binder polymer is more preferably 40°C or more, even more preferably 50°C or more, particularly preferably 60°C or more, and most preferably 70°C or more.

[0284] The photosensitive layer may contain a resin other than those mentioned above as a binder polymer. Other resins include acrylic resins, styrene-acrylic copolymers, polyurethane resins, polyvinyl alcohol, polyvinyl formal, polyamide resins, polyester resins, polyamide resins, epoxy resins, polyacetal resins, polyhydroxystyrene resins, polyimide resins, polybenzoxazole resins, polysiloxane resins, polyethyleneimine, polyallylamine, and polyalkylene glycols.

[0285] As the binder polymer, an alkali-soluble resin, which will be described later in the description of the thermoplastic resin layer, may be used.

[0286] The content of the binder polymer is preferably 10 to 90% by mass, more preferably 20 to 80% by mass, even more preferably 30 to 70% by mass, and particularly preferably 40 to 60% by mass, based on the total mass of the photosensitive layer. A binder polymer content of 90% by mass or less is preferred from the viewpoint of controlling the development time. On the other hand, a binder polymer content of 10% by mass or more is preferred from the viewpoint of improving edge fuse resistance.

[0287] <Photopolymerizable compound> The photosensitive layer contains a photopolymerizable compound. The term "photopolymerizable compound" refers to a compound that is polymerized by the action of a photopolymerization initiator, which will be described later, and is different from the binder polymer described above. It preferably has a molecular weight of 5,000 or less.

[0288] Examples of the polymerizable group possessed by the photopolymerizable compound include groups having an ethylenically unsaturated group such as a vinyl group, an acryloyl group, a methacryloyl group, a styryl group, and a maleimide group; and groups having a cationic polymerizable group such as an epoxy group and an oxetane group.

[0289] The number of polymerizable groups possessed by the photopolymerizable compound is not particularly limited as long as it is 1 or more, but is more preferably 2 or more. In other words, the photopolymerizable compound is preferably a compound having 2 or more polymerizable groups (a polyfunctional photopolymerizable compound). In addition, the number of polymerizable groups that the photopolymerizable compound has in the molecule is preferably 1 to 6, more preferably 1 to 3, and even more preferably 2 or 3, in terms of better effects of the present invention.

[0290] In terms of obtaining better effects of the present invention, the photosensitive layer preferably contains at least one of a bifunctional photopolymerizable compound and a trifunctional photopolymerizable compound. The total content of the bifunctional photopolymerizable compound and the trifunctional photopolymerizable compound is preferably 30% by mass or more, more preferably 40% by mass or more, and even more preferably 45% by mass or more, based on the total mass of the photopolymerizable compounds, and is not particularly limited to the upper limit, but is, for example, 100% by mass or less.

[0291] Among them, the photopolymerizable compound preferably contains a polymerizable compound having an ethylenically unsaturated group (hereinafter also referred to as "ethylenically unsaturated compound"). Of these, the ethylenically unsaturated group is more preferably an acryloyl group or a methacryloyl group. That is, the photopolymerizable compound is preferably a (meth)acrylate compound having a (meth)acryloyl group as the polymerizable group.

[0292] The number of ethylenically unsaturated groups in the ethylenically unsaturated compound is not particularly limited as long as it is 1 or more, but is more preferably 2 or more. In other words, the ethylenically unsaturated compound is preferably a compound having 2 or more ethylenically unsaturated groups (hereinafter also referred to as a "polyfunctional ethylenically unsaturated compound"). In addition, the number of ethylenically unsaturated groups that the ethylenically unsaturated compound has in the molecule is preferably 1 to 6, more preferably 1 to 3, and even more preferably 2 or 3, in terms of better effects of the present invention.

[0293] In terms of achieving better effects of the present invention, the photosensitive layer preferably contains at least one of a difunctional ethylenically unsaturated compound and a trifunctional ethylenically unsaturated compound. The total content of the bifunctional ethylenically unsaturated compound and the trifunctional ethylenically unsaturated compound is preferably 30% by mass or more, more preferably 40% by mass or more, and even more preferably 45% by mass or more, based on the total mass of the photopolymerizable compound, and the upper limit is not particularly limited, but is, for example, 100% by mass or less.

[0294] The ethylenically unsaturated compound may have an alkyleneoxy group. The alkylene group is preferably an ethyleneoxy group or a propyleneoxy group, more preferably an ethyleneoxy group. The number of alkyleneoxy groups added to the ethylenically unsaturated compound per molecule is preferably 2 to 60, more preferably 2 to 30, and even more preferably 2 to 20. The content of the ethylenically unsaturated compound having an alkyleneoxy group (preferably an ethyleneoxy group) is preferably 10 to 100% by mass, more preferably 60 to 100% by mass, and even more preferably 90 to 100% by mass, relative to the photopolymerizable compound in the photosensitive layer.

[0295] (Photopolymerizable compound B1) The photosensitive layer preferably contains a photopolymerizable compound B1 having an aromatic ring and two ethylenically unsaturated groups. The photopolymerizable compound B1 is a bifunctional ethylenically unsaturated compound having one or more aromatic rings in one molecule, among the above-mentioned photopolymerizable compounds B1.

[0296] In the photosensitive layer, the mass ratio of the content of the photopolymerizable compound B1 to the total mass of the photopolymerizable compounds is preferably 40% by mass or more, more preferably 50% by mass or more, even more preferably 55% by mass or more, and particularly preferably 60% by mass or more, from the viewpoint of better resolution. The upper limit is not particularly limited, but from the viewpoint of peelability, it is, for example, 100% by mass or less, preferably 99% by mass or less, more preferably 95% by mass or less, even more preferably 90% by mass or less, and particularly preferably 85% by mass or less.

[0297] The aromatic ring of the photopolymerizable compound B1 may be, for example, an aromatic hydrocarbon ring such as a benzene ring, a naphthalene ring, or an anthracene ring, or an aromatic heterocycle such as a thiophene ring, a furan ring, a pyrrole ring, an imidazole ring, a triazole ring, or a pyridine ring, or a condensed ring thereof, and the aromatic hydrocarbon ring is preferred, and the benzene ring is more preferred. Note that the aromatic ring may have a substituent. The photopolymerizable compound B1 may have only one aromatic ring, or may have two or more aromatic rings.

[0298] The photopolymerizable compound B1 preferably has a bisphenol structure, from the viewpoint of improving resolution by suppressing swelling of the photosensitive layer due to a developer. Examples of the bisphenol structure include a bisphenol A structure derived from bisphenol A (2,2-bis(4-hydroxyphenyl)propane), a bisphenol F structure derived from bisphenol F (2,2-bis(4-hydroxyphenyl)methane), and a bisphenol B structure derived from bisphenol B (2,2-bis(4-hydroxyphenyl)butane), with the bisphenol A structure being preferred.

[0299] Examples of the photopolymerizable compound B1 having a bisphenol structure include a compound having a bisphenol structure and two polymerizable groups (preferably (meth)acryloyl groups) bonded to both ends of the bisphenol structure. The two polymerizable groups may be bonded to both ends of the bisphenol structure directly or via one or more alkyleneoxy groups. The alkyleneoxy groups added to both ends of the bisphenol structure are preferably ethyleneoxy groups or propyleneoxy groups, more preferably ethyleneoxy groups. The number of alkyleneoxy groups added to the bisphenol structure is not particularly limited, but is preferably 4 to 16, more preferably 6 to 14 per molecule. The photopolymerizable compound B1 having a bisphenol structure is described in paragraphs 0072 to 0080 of JP-A-2016-224162, the contents of which are incorporated herein by reference.

[0300] As the photopolymerizable compound B1, a bifunctional ethylenically unsaturated compound having a bisphenol A structure is preferred, and 2,2-bis(4-((meth)acryloxypolyalkoxy)phenyl)propane is more preferred. Examples of 2,2-bis(4-((meth)acryloxypolyalkoxy)phenyl)propane include 2,2-bis(4-(methacryloxydiethoxy)phenyl)propane (FA-324M, manufactured by Hitachi Chemical Co., Ltd.), 2,2-bis(4-(methacryloxyethoxypropoxy)phenyl)propane, 2,2-bis(4-(methacryloxypentaethoxy)phenyl)propane (BPE-500, manufactured by Shin-Nakamura Chemical Co., Ltd.), and 2,2-bis(4-(methacryloxydodecaethoxy)phenyl)propane. Examples of suitable ethoxylated bisphenol A diacrylates include 2,2-bis(4-(methacryloxytetrapropoxy)phenyl)propane (FA-3200MY, manufactured by Hitachi Chemical Co., Ltd.), 2,2-bis(4-(methacryloxypentadecaethoxy)phenyl)propane (BPE-1300, manufactured by Shin-Nakamura Chemical Co., Ltd.), 2,2-bis(4-(methacryloxydiethoxy)phenyl)propane (BPE-200, manufactured by Shin-Nakamura Chemical Co., Ltd.), and ethoxylated (10) bisphenol A diacrylate (NK Ester A-BPE-10, manufactured by Shin-Nakamura Chemical Co., Ltd.).

[0301] The photopolymerizable compound B1 is also preferably a compound represented by the following general formula (B1).

[0302] [ka]

[0303] In general formula B1, R1 and R2 each independently represent a hydrogen atom or a methyl group. A represents C2H4. B represents C3H6. n1 and n3 each independently represent an integer of 1 to 39, and n1 + n3 is an integer of 2 to 40. n2 and n4 each independently represent an integer of 0 to 29, and n2 + n4 is an integer of 0 to 30. The arrangement of the -(AO)- and -(BO)- structural units may be random or in a block. In the case of a block, either -(AO)- or -(BO)- may be on the bisphenyl group side. In one embodiment, n1+n2+n3+n4 is preferably 2 to 20, more preferably 2 to 16, and even more preferably 4 to 12. Furthermore, n2+n4 is preferably 0 to 10, more preferably 0 to 4, even more preferably 0 to 2, and particularly preferably 0.

[0304] The photopolymerizable compound B1 may be used alone or in combination of two or more. The content of the photopolymerizable compound B1 is preferably 10% by mass or more, more preferably 20% by mass or more, based on the total mass of the photosensitive layer from the viewpoint of better resolution. The upper limit is not particularly limited, but from the viewpoints of transferability and edge fusion (a phenomenon in which the photosensitive resin oozes out from the edge of the transfer member), it is preferably 70% by mass or less, more preferably 60% by mass or less.

[0305] The photosensitive layer may contain a photopolymerizable compound other than the above-mentioned photopolymerizable compound B1. The photopolymerizable compound other than the photopolymerizable compound B1 is not particularly limited and can be appropriately selected from known compounds, such as a compound having one ethylenically unsaturated group in one molecule (monofunctional ethylenically unsaturated compound), a bifunctional ethylenically unsaturated compound having no aromatic ring, and a trifunctional or higher ethylenically unsaturated compound.

[0306] Examples of monofunctional ethylenically unsaturated compounds include ethyl (meth)acrylate, ethylhexyl (meth)acrylate, 2-(meth)acryloyloxyethyl succinate, polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, and phenoxyethyl (meth)acrylate.

[0307] Examples of the difunctional ethylenically unsaturated compound having no aromatic ring include alkylene glycol di(meth)acrylate, polyalkylene glycol di(meth)acrylate, urethane di(meth)acrylate, and trimethylolpropane diacrylate. Examples of alkylene glycol di(meth)acrylates include tricyclodecane dimethanol diacrylate (A-DCP, manufactured by Shin-Nakamura Chemical Co., Ltd.), tricyclodecane dimethanol dimethacrylate (DCP, manufactured by Shin-Nakamura Chemical Co., Ltd.), 1,9-nonanediol diacrylate (A-NOD-N, manufactured by Shin-Nakamura Chemical Co., Ltd.), 1,6-hexanediol diacrylate (A-HD-N, manufactured by Shin-Nakamura Chemical Co., Ltd.), ethylene glycol dimethacrylate, 1,10-decanediol diacrylate, and neopentyl glycol di(meth)acrylate. Examples of polyalkylene glycol di(meth)acrylates include polyethylene glycol di(meth)acrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, and polypropylene glycol di(meth)acrylate. Examples of urethane di(meth)acrylates include propylene oxide-modified urethane di(meth)acrylates and ethylene oxide and propylene oxide-modified urethane di(meth)acrylates. Commercially available products include 8UX-015A (manufactured by Taisei Fine Chemical Co., Ltd.), UA-32P (manufactured by Shin-Nakamura Chemical Co., Ltd.), and UA-1100H (manufactured by Shin-Nakamura Chemical Co., Ltd.).

[0308] Examples of tri- or higher functional ethylenically unsaturated compounds include dipentaerythritol (tri / tetra / penta / hexa)(meth)acrylate, pentaerythritol (tri / tetra)(meth)acrylate, trimethylolpropane tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, trimethylolethane tri(meth)acrylate, isocyanuric acid tri(meth)acrylate, glycerin tri(meth)acrylate, and alkylene oxide-modified products thereof. Here, "(tri / tetra / penta / hexa)(meth)acrylate" is a concept that encompasses tri(meth)acrylate, tetra(meth)acrylate, penta(meth)acrylate, and hexa(meth)acrylate, and "(tri / tetra)(meth)acrylate" is a concept that encompasses tri(meth)acrylate and tetra(meth)acrylate. In one embodiment, the photosensitive layer preferably contains the above-described photopolymerizable compound B1 and a trifunctional or higher ethylenically unsaturated compound, and more preferably contains the above-described photopolymerizable compound B1 and two or more trifunctional or higher ethylenically unsaturated compounds. In this case, the mass ratio of the photopolymerizable compound B1 to the trifunctional or higher ethylenically unsaturated compounds (total mass of the photopolymerizable compound B1):(total mass of the trifunctional or higher ethylenically unsaturated compounds) is preferably 1:1 to 5:1, more preferably 1.2:1 to 4:1, and even more preferably 1.5:1 to 3:1. In one embodiment, the photosensitive layer preferably contains the above-mentioned photopolymerizable compound B1 and two or more trifunctional ethylenically unsaturated compounds.

[0309] Examples of alkylene oxide-modified tri- or higher functional ethylenically unsaturated compounds include caprolactone-modified (meth)acrylate compounds (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 (meth)acrylate compounds (KAYARAD RP-1040 manufactured by Nippon Kayaku Co., Ltd., ATM-35E and A-9300 manufactured by Shin-Nakamura Chemical Co., Ltd., EBECRYL (registered trademark) 135 manufactured by Daicel-Allnex Corporation, etc.), ethoxylated glycerin triacrylate (A-GLY-9E manufactured by Shin-Nakamura Chemical Co., Ltd., etc.), ARONIX (registered trademark) TO-2349 (manufactured by Toagosei Co., Ltd.), ARONIX M-520 (manufactured by Toagosei Co., Ltd.), and ARONIX M-510 (manufactured by Toagosei Co., Ltd.).

[0310] Furthermore, a photopolymerizable compound having an acid group (such as a carboxy group) may be used as the photopolymerizable compound. The acid group may form an acid anhydride group. Examples of photopolymerizable compounds having an acid 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.). As the photopolymerizable compound having an acid group, for example, the photopolymerizable compounds having an acid group described in paragraphs 0025 to 0030 of JP-A No. 2004-239942 may be used.

[0311] The photopolymerizable compounds may be used alone or in combination of two or more. The content of the photopolymerizable compound is preferably from 10 to 70% by mass, more preferably from 15 to 70% by mass, still more preferably from 20 to 70% by mass, and particularly preferably from 30 to 60% by mass, based on the total mass of the photosensitive layer.

[0312] The molecular weight (weight average molecular weight when the photopolymerizable compound (including photopolymerizable compound B1) has a molecular weight distribution) is preferably from 200 to 3,000, more preferably from 280 to 2,200, and even more preferably from 300 to 2,200.

[0313] <Photopolymerization initiator> The photosensitive layer contains a photopolymerization initiator. In the photosensitive layer, the photopolymerization initiator may be used alone or in combination of two or more kinds. The content of the photopolymerization initiator in the photosensitive layer is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and even more preferably 1.0% by mass or more, based on the total mass of the photosensitive layer, and the upper limit thereof is preferably 10% by mass or less, based on the total mass of the photosensitive layer.

[0314] (Compound represented by general formula (a-1) (specific oxime ester compound)) The photopolymerization initiator includes the compound (specific oxime ester compound) represented by the general formula (a-1) described above. The compound represented by the general formula (a-1) and preferred embodiments thereof are as described above.

[0315] The content of the compound represented by the general formula (a-1) in the photopolymerization initiator is preferably 10% by mass or more, more preferably 20% by mass or more, even more preferably 50% by mass or more, and particularly preferably 60% by mass or more, based on the total mass of the photopolymerization initiator, and the upper limit is preferably 100% by mass or less.

[0316] (Photopolymerization initiators other than specific oxime ester compounds) The photosensitive layer may contain a photopolymerization initiator other than the specific oxime ester compound (hereinafter referred to as "another photopolymerization initiator"). The other photopolymerization initiator is not particularly limited, and known photopolymerization initiators can be used.

[0317] Examples of other photopolymerization initiators include photopolymerization initiators having an oxime ester structure other than the specific oxime ester compound, photopolymerization initiators having an α-aminoalkylphenone structure, photopolymerization initiators having an α-hydroxyalkylphenone structure, photopolymerization initiators having an acylphosphine oxide structure, and photopolymerization initiators having an N-phenylglycine structure.

[0318] In addition, from the viewpoints of photosensitivity, visibility of exposed and unexposed areas, and resolution, at least one other photopolymerization initiator selected from the group consisting of 2,4,5-triarylimidazole dimers and derivatives thereof is also preferred. Note that the two 2,4,5-triarylimidazole structures in the 2,4,5-triarylimidazole dimers and derivatives thereof may be the same or different. Examples of derivatives of 2,4,5-triarylimidazole dimers include 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer, 2-(o-chlorophenyl)-4,5-di(methoxyphenyl)imidazole dimer, 2-(o-fluorophenyl)-4,5-diphenylimidazole dimer, 2-(o-methoxyphenyl)-4,5-diphenylimidazole dimer, and 2-(p-methoxyphenyl)-4,5-diphenylimidazole dimer.

[0319] Other preferred photopolymerization initiators include those described in, for example, paragraphs 0031 to 0042 of JP-A No. 2011-95716 and paragraphs 0064 to 0081 of JP-A No. 2015-14783.

[0320] Other examples of the photopolymerization initiator include ethyl dimethylaminobenzoate (DBE, CAS No. 10287-53-3), benzoin methyl ether, anisyl (p,p'-dimethoxybenzyl), TAZ-110 (trade name: manufactured by Midori Chemical Industry Co., Ltd.), benzophenone, 4,4'-bis(diethylamino)benzophenone, TAZ-111 (trade name: manufactured by Midori Chemical Industry Co., Ltd.), IrgacureOXE01, OXE02, OXE03, OXE04 (manufactured by BASF), Omnirad 651 and 369 (trade names: manufactured by IGM Resins BV), and 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole (manufactured by Tokyo Chemical Industry Co., Ltd.).

[0321] Other commercially available photopolymerization initiators include, for example, 1-[4-(phenylthio)]-1,2-octanedione-2-(O-benzoyloxime) (trade name: IRGACURE (registered trademark) OXE-01, manufactured by BASF), 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone-1-(O-acetyloxime) (trade name: IRGACURE OXE-02, manufactured by BASF), IRGACURE OXE-03 (manufactured by BASF), IRGACURE OXE-04 (manufactured by BASF), 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone (trade name: Omnirad 379EG, manufactured by IGM Resins), and the like. BV), 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one (trade name: Omnirad 907, IGM Resins BV), 2-hydroxy-1-{4-[4-(2-hydroxy-2-methylpropionyl)benzyl]phenyl}-2-methylpropan-1-one (trade name: Omnirad 127, IGM Resins BV), 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butanone-1 (trade name: Omnirad 369, IGM Resins BV), 2-hydroxy-2-methyl-1-phenylpropan-1-one (trade name: Omnirad 1173, IGM Resins BV), 1-hydroxycyclohexyl phenyl ketone (trade name: Omnirad 184, IGM Resins BV), BV), 2,2-dimethoxy-1,2-diphenylethan-1-one (trade name: Omnirad 651, IGM Resins BV), 2,4,6-trimethylbenzoyl-diphenylphosphine oxide (trade name: Omnirad TPO H, IGM Resins BV), bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide (trade name: Omnirad 819, IGM Resins BV)(trade name: Lunar 6, manufactured by DKSH Japan Co., Ltd.), oxime ester photoinitiator (trade name: Lunar 6, manufactured by DKSH Japan Co., Ltd.), 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbisimidazole (2-(2-chlorophenyl)-4,5-diphenylimidazole dimer) (trade name: B-CIM, manufactured by Hampford Chemical Industry Co., Ltd.), and 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer (trade name: BCTB, manufactured by Tokyo Chemical Industry Co., Ltd.), 1-[4-(phenylthio)phenyl]-3-cyclopentylpropane-1,2-dione-2-(o-benzoyloxime) (trade name: TR-PBG-305, manufactured by Changzhou Chemical Industry Co., Ltd.), Examples of suitable oxime include 1,2-propanedione, 3-cyclohexyl-1-[9-ethyl-6-(2-furanylcarbonyl)-9H-carbazol-3-yl]-, 2-(O-acetyloxime) (trade name: TR-PBG-326, Changzhou Strong Electronic New Materials Co., Ltd.), and 3-cyclohexyl-1-(6-(2-(benzoyloxyimino)hexanoyl)-9-ethyl-9H-carbazol-3-yl)-propane-1,2-dione-2-(O-benzoyloxime) (trade name: TR-PBG-391, Changzhou Strong Electronic New Materials Co., Ltd.).

[0322] When the photopolymerizable compound contains a cationically polymerizable compound, the photosensitive layer may contain a photocationic polymerization initiator (photoacid generator) as the photopolymerization initiator. The cationic photopolymerization initiator is preferably a compound that responds to actinic rays with a wavelength of 300 nm or more, preferably 300 to 450 nm, and generates an acid, but the chemical structure is not limited thereto. Furthermore, even if the cationic photopolymerization initiator is not directly sensitive to actinic rays with a wavelength of 300 nm or more, it can be preferably used in combination with a sensitizer, as long as it responds to actinic rays with a wavelength of 300 nm or more and generates an acid when used in combination with a sensitizer. The cationic photopolymerization initiator is preferably a cationic photopolymerization initiator that generates an acid with a pKa of 4 or less, more preferably a cationic photopolymerization initiator that generates an acid with a pKa of 3 or less, and particularly preferably a cationic photopolymerization initiator that generates an acid with a pKa of 2 or less. There is no particular restriction on the lower limit of the pKa, but it is preferably, for example, −10.0 or more.

[0323] Examples of the photocationic polymerization initiator include an ionic photocationic polymerization initiator and a nonionic photocationic polymerization initiator. Examples of the ionic photocationic polymerization initiator include onium salt compounds such as diaryliodonium salts and triarylsulfonium salts, and quaternary ammonium salts. As the ionic photocationic polymerization initiator, the ionic photocationic polymerization initiators described in paragraphs 0114 to 0133 of JP-A No. 2014-085643 may be used.

[0324] Examples of nonionic photocationic polymerization initiators include trichloromethyl-s-triazines, diazomethane compounds, imide sulfonate compounds, and oxime sulfonate compounds. Examples of trichloromethyl-s-triazines, diazomethane compounds, and imide sulfonate compounds include those described in paragraphs 0083 to 0088 of JP 2011-221494 A. Examples of oxime sulfonate compounds include those described in paragraphs 0084 to 0088 of WO 2018 / 179640 A.

[0325] <Dye> From the viewpoints of the visibility of exposed and unexposed areas, the pattern visibility after development, and resolution, the photosensitive layer preferably contains a dye (also referred to as "dye N") whose maximum absorption wavelength in the wavelength range of 400 to 780 nm during color development is 450 nm or more and whose maximum absorption wavelength changes in response to an acid, a base, or a radical. When dye N is contained, adhesion to adjacent layers (for example, a water-soluble resin layer) is improved, resulting in better resolution, although the detailed mechanism is unknown.

[0326] In this specification, the expression "the maximum absorption wavelength of a dye changes in response to an acid, a base, or a radical" may mean any of an embodiment in which a dye in a colored state is decolorized by an acid, a base, or a radical, an embodiment in which a dye in a decolorized state develops color in response to an acid, a base, or a radical, and an embodiment in which a dye in a colored state changes to a colored state of another hue. Specifically, dye N may be a compound that changes from a decolorized state to a colored state upon exposure, or a compound that changes from a colored state to a decolored state upon exposure. In this case, the dye may be one whose colored or decolored state changes when an acid, base, or radical is generated and acts within the photosensitive layer upon exposure, or one whose colored or decolored state changes when an acid, base, or radical changes the state (e.g., pH) within the photosensitive layer. Alternatively, the dye may be one whose colored or decolored state changes upon direct stimulation by an acid, base, or radical without exposure.

[0327] In particular, from the viewpoint of the visibility and resolution of exposed and unexposed areas, dye N is preferably a dye whose maximum absorption wavelength changes in response to an acid or a radical, and more preferably a dye whose maximum absorption wavelength changes in response to a radical. From the viewpoint of the visibility of exposed and unexposed areas and resolution, the photosensitive layer preferably contains both a dye N whose maximum absorption wavelength changes in response to radicals, and a photoradical polymerization initiator. In addition, from the viewpoint of visibility of exposed and unexposed areas, it is preferable that the dye N is a dye that develops color in response to an acid, a base, or a radical.

[0328] An example of the color-developing mechanism of dye N is an embodiment in which a photoradical polymerization initiator, a cationic photopolymerization initiator (photoacid generator), or a photobase generator is added to the photosensitive layer, and after exposure, a radical-reactive dye, an acid-reactive dye, or a base-reactive dye (e.g., a leuco dye) develops color due to a radical, acid, or base generated from the photoradical polymerization initiator, the cationic photopolymerization initiator, or the photobase generator.

[0329] From the viewpoint of visibility of exposed and unexposed areas, dye N preferably has a maximum absorption wavelength of 550 nm or more in the wavelength range of 400 to 780 nm upon color development, more preferably 550 to 700 nm, and even more preferably 550 to 650 nm. Furthermore, dye N may have only one or two or more maximum absorption wavelengths in the wavelength range of 400 to 780 nm when it develops color. When dye N has two or more maximum absorption wavelengths in the wavelength range of 400 to 780 nm when it develops color, it is sufficient that the maximum absorption wavelength with the highest absorbance among the two or more maximum absorption wavelengths is 450 nm or longer.

[0330] The maximum absorption wavelength of dye N can be obtained by measuring the transmission spectrum of a solution containing dye N (liquid temperature 25°C) in the range of 400 to 780 nm using a spectrophotometer UV3100 (Shimadzu Corporation) in an atmospheric environment and detecting the wavelength at which the light intensity is minimum (maximum absorption wavelength).

[0331] Examples of dyes that develop or lose color upon exposure include leuco compounds. Examples of dyes that are decolorized by exposure include leuco compounds, diarylmethane dyes, oxazine dyes, xanthene dyes, iminonaphthoquinone dyes, azomethine dyes, and anthraquinone dyes. As the dye N, a leuco compound is preferred from the viewpoint of visibility of exposed and unexposed areas.

[0332] Examples of leuco compounds include leuco compounds having a triarylmethane skeleton (triarylmethane-based dyes), leuco compounds having a spiropyran skeleton (spiropyran-based dyes), leuco compounds having a fluoran skeleton (fluoran-based dyes), leuco compounds having a diarylmethane skeleton (diarylmethane-based dyes), leuco compounds having a rhodamine lactam skeleton (rhodamine lactam-based dyes), leuco compounds having an indolylphthalide skeleton (indolylphthalide-based dyes), and leuco compounds having a leucoauramine skeleton (leucoauramine-based dyes). Among these, triarylmethane dyes or fluoran dyes are preferred, and leuco compounds having a triphenylmethane skeleton (triphenylmethane dyes) or fluoran dyes are more preferred.

[0333] From the viewpoint of visibility of exposed and unexposed areas, the leuco compound preferably has a lactone ring, a sultine ring, or a sultone ring. This allows the lactone ring, sultine ring, or sultone ring of the leuco compound to react with a radical generated from a photoradical polymerization initiator or an acid generated from a photocationic polymerization initiator, thereby converting the leuco compound into a ring-closed state and thereby discoloring, or converting the leuco compound into a ring-open state and thereby developing a color. The leuco compound is preferably a compound having a lactone ring, a sultine ring, or a sultone ring, which develops a color upon ring-opening of the lactone ring, the sultine ring, or the sultone ring by a radical or an acid, and more preferably a compound having a lactone ring, which develops a color upon ring-opening of the lactone ring by a radical or an acid.

[0334] Examples of the dye N include the following dyes and leuco compounds. Specific examples of dyes among the dyes N include brilliant green, ethyl violet, methyl green, crystal violet, basic fuchsin, methyl violet 2B, quinaldine red, rose bengal, metanil yellow, thymolsulfophthalein, xylenol blue, methyl orange, paramethyl red, Congo red, benzopurpurin 4B, α-naphthyl red, Nile blue 2B, Nile blue A, methyl violet, malachite green, parafuchsin, Victoria Pure Blue naphthalene sulfonate, Victoria Pure Blue BOH (manufactured by Hodogaya Chemical Co., Ltd.), Oil Blue #603 (manufactured by Orient Chemical Co., Ltd.), Oil Pink #312 (manufactured by Orient Chemical Co., Ltd.), Oil Red 5B (manufactured by Orient Chemical Co., Ltd.), and Oil Scarlet #308 (manufactured by Orient Chemical Co., Ltd.). Examples of suitable anti-inflammatory agents include Orient Chemical Industry Co., Ltd.), Oil Red OG (Orient Chemical Industry Co., Ltd.), Oil Red RR (Orient Chemical Industry Co., Ltd.), Oil Green #502 (Orient Chemical Industry Co., Ltd.), Spiron Red BEH Special (Hodogaya Chemical Co., Ltd.), m-cresol purple, cresol red, rhodamine B, rhodamine 6G, sulforhodamine B, auramine, 4-p-diethylaminophenyliminonaphthoquinone, 2-carboxyanilino-4-p-diethylaminophenyliminonaphthoquinone, 2-carboxystearylamino-4-pN,N-bis(hydroxyethyl)amino-phenyliminonaphthoquinone, 1-phenyl-3-methyl-4-p-diethylaminophenylimino-5-pyrazolone, and 1-β-naphthyl-4-p-diethylaminophenylimino-5-pyrazolone.

[0335] Specific examples of the leuco compounds among the dyes N include p,p',p"-hexamethyltriaminotriphenylmethane (leuco crystal violet), Pergascript Blue SRB (manufactured by Ciba-Geigy), crystal violet lactone, malachite green lactone, benzoyl leucomethylene blue, 2-(N-phenyl-N-methylamino)-6-(Np-tolyl-N-ethyl)aminofluoran, 2-anilino-3-methyl-6-(N-ethyl-p-toluidino)fluoran, 3,6-dimethoxyfluoran, 3-(N,N-diethylamino)-5-methyl-7-(N,N-dibenzylamino)fluoran, 3-(N-cyclohexyl-N-methylamino)- 6-methyl-7-anilinofluoran, 3-(N,N-diethylamino)-6-methyl-7-anilinofluoran, 3-(N,N-diethylamino)-6-methyl-7-xylidinofluoran, 3-(N,N-diethylamino)-6-methyl-7-chlorofluoran, 3-(N,N-diethylamino)-6-methoxy-7-aminofluoran, 3-(N,N-diethylamino)-7-(4-chloroanilino)fluoran, 3-(N,N-diethylamino)-7-chlorofluoran, 3-(N,N-di 3-(N,N-Diethylamino)-7-benzylaminofluoran, 3-(N,N-Diethylamino)-7,8-benzofluoran, 3-(N,N-Dibutylamino)-6-methyl-7-anilinofluoran, 3-(N,N-Dibutylamino)-6-methyl-7-xylidinofluoran, 3-Piperidino-6-methyl-7-anilinofluoran, 3-Pyrrolidino-6-methyl-7-anilinofluoran, 3,3-Bis(1-ethyl-2-methylindol-3-yl)phthalide, 3,3-Bis(1-n-butyl-2- 3-(4-diethylamino-2-ethoxyphenyl)-3-(1-ethyl-2-methylindol-3-yl)phthalide, 3,3-bis(p-dimethylaminophenyl)-6-dimethylaminophthalide, 3-(4-diethylamino-2-ethoxyphenyl)-3-(1-ethyl-2-methylindol-3-yl)phthalide, 3-(4-diethylaminophenyl)-3-(1-ethyl-2-methylindol-3-yl)phthalide, and 3',6'-bis(diphenylamino)spiroisobenzofuran-1(3H),9'-[9H]xanthen-3-one.

[0336] From the viewpoints of visibility of exposed and unexposed areas, pattern visibility after development, and resolution, dye N is preferably a dye whose maximum absorption wavelength changes in response to radicals, and more preferably a dye that develops color in response to radicals. As dye N, leuco crystal violet, crystal violet lactone, brilliant green, or Victoria Pure Blue-naphthalene sulfonate is preferred.

[0337] The dye N may be used alone or in combination of two or more. From the viewpoints of visibility of exposed and unexposed areas, pattern visibility after development, and resolution, the content of dye N is preferably 0.1 mass % or more, more preferably 0.1 to 10 mass %, even more preferably 0.1 to 5 mass %, and particularly preferably 0.1 to 1 mass %, relative to the total mass of the photosensitive layer.

[0338] The content of dye N means the content of dye when all of dye N contained in the total mass of the photosensitive layer is in a color-developing state. A method for quantifying the content of dye N will be explained below using a dye that develops color by radicals as an example. Solutions were prepared by dissolving 0.001 g and 0.01 g of dye in 100 mL of methyl ethyl ketone. The photoradical polymerization initiator Irgacure OXE01 (BASF Japan Ltd.) was added to each solution, and radicals were generated by irradiating with 365 nm light, causing all dyes to develop color. The absorbance of each solution was then measured at 25°C using a spectrophotometer (UV3100, Shimadzu Corporation) under atmospheric conditions, and a calibration curve was created. Next, the absorbance of the solution in which all the dye has developed is measured in the same manner as above, except that 3 g of the photosensitive layer is dissolved in methyl ethyl ketone instead of the dye.The content of the dye contained in the photosensitive layer is calculated based on the absorbance of the resulting solution containing the photosensitive layer and a calibration curve. The photosensitive layer 3g is the same as the total solid content 3g in the photosensitive composition.

[0339] <Thermal crosslinkable compound> From the viewpoints of the strength of the cured film obtained and the adhesiveness of the uncured film obtained, the photosensitive layer preferably contains a thermally crosslinkable compound. In this specification, a thermally crosslinkable compound having an ethylenically unsaturated group, which will be described later, is not considered a photopolymerizable compound but is considered a thermally crosslinkable compound. Examples of the thermally crosslinkable compound include methylol compounds and blocked isocyanate compounds. Among these, blocked isocyanate compounds are preferred from the viewpoints of the strength of the resulting cured film and the adhesiveness of the resulting uncured film. Since the blocked isocyanate compound reacts with a hydroxy group and a carboxy group, for example, when a resin and / or a photopolymerizable compound has at least one of a hydroxy group and a carboxy group, the hydrophilicity of the formed film tends to decrease, and the functionality of the film obtained by curing the photosensitive layer when used as a protective film tends to be enhanced. The blocked isocyanate compound refers to a compound having a structure in which the isocyanate group of an isocyanate is protected (so-called masked) with a blocking agent.

[0340] 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 a 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 suitably used, but the differential scanning calorimeter is not limited to this.

[0341] Examples of blocking agents having a dissociation temperature of 100 to 160°C include active methylene compounds [malonic acid diesters (dimethyl malonate, diethyl malonate, di-n-butyl malonate, di-2-ethylhexyl malonate, etc.)] and oxime compounds (compounds having a structure represented by -C(=N-OH)- in the molecule, such as formaldoxime, acetaldoxime, acetoxime, methyl ethyl ketoxime, and cyclohexanone oxime). Among these, as the blocking agent having a dissociation temperature of 100 to 160° C., at least one selected from oxime compounds is preferred from the viewpoint of storage stability, for example.

[0342] The blocked isocyanate compound preferably has an isocyanurate structure, for example, from the viewpoint of improving the brittleness of the film and improving the adhesive strength to the transfer target. A blocked isocyanate compound having an isocyanurate structure can be obtained, for example, by protecting hexamethylene diisocyanate by isocyanuration. Among blocked isocyanate compounds having an isocyanurate structure, compounds having an oxime structure in which an oxime compound is used as a blocking agent are preferred from the viewpoints that the dissociation temperature can be more easily adjusted to a preferred range and development residues can be reduced compared to compounds not having an oxime structure.

[0343] The blocked isocyanate compound may have a polymerizable group. The polymerizable group is not particularly limited, and any known polymerizable group can be used, with a radical polymerizable group being preferred. Examples of the polymerizable group include ethylenically unsaturated groups such as a (meth)acryloxy group, a (meth)acrylamide group, and a styryl group, as well as groups having an epoxy group such as a glycidyl group. Of these, the polymerizable group is preferably an ethylenically unsaturated group, more preferably a (meth)acryloxy group, and even more preferably an acryloxy group.

[0344] As the blocked isocyanate compound, commercially available products can be used. Examples of commercially available blocked isocyanate compounds include Karenz (registered trademark) AOI-BM, Karenz (registered trademark) MOI-BM, Karenz (registered trademark) MOI-BP, and the like (all manufactured by Showa Denko K.K.), and the blocked Duranate series (e.g., Duranate (registered trademark) TPA-B80E, Duranate (registered trademark) WT32-B75P, and the like, manufactured by Asahi Kasei Chemicals Corporation). Furthermore, as the blocked isocyanate compound, a compound having the following structure can also be used.

[0345] [ka]

[0346] The thermally crosslinkable compounds may be used alone or in combination of two or more. When the photosensitive layer contains a thermally crosslinkable compound, the content of the thermally crosslinkable compound is preferably from 1 to 50% by mass, more preferably from 5 to 30% by mass, based on the total mass of the photosensitive layer.

[0347] <Other additives> In addition to the above components, the photosensitive layer may contain known additives as needed. Examples of additives include radical polymerization inhibitors, sensitizers, plasticizers, heterocyclic compounds (such as triazoles), benzotriazoles, carboxybenzotriazoles, pyridines (such as isonicotinamide), purine bases (such as adenine), and surfactants. Each additive may be used alone or in combination of two or more.

[0348] The photosensitive layer may contain a radical polymerization inhibitor. Examples of radical polymerization inhibitors include the thermal polymerization inhibitors described in paragraph 0018 of Japanese Patent No. 4502784. Among these, phenothiazine, phenoxazine, or 4-methoxyphenol is preferred. Other radical polymerization inhibitors include naphthylamine, cuprous chloride, nitrosophenylhydroxyamine aluminum salt, and diphenylnitrosamine. In order to avoid impairing the sensitivity of the photosensitive layer, it is preferable to use nitrosophenylhydroxyamine aluminum salt as the radical polymerization inhibitor. The preferred content of the radical polymerization inhibitor is the same as in the first embodiment.

[0349] Examples of benzotriazoles include 1,2,3-benzotriazole, 1-chloro-1,2,3-benzotriazole, bis(N-2-ethylhexyl)aminomethylene-1,2,3-benzotriazole, bis(N-2-ethylhexyl)aminomethylene-1,2,3-tolyltriazole, and bis(N-2-hydroxyethyl)aminomethylene-1,2,3-benzotriazole.

[0350] Examples of carboxybenzotriazoles include 4-carboxy-1,2,3-benzotriazole, 5-carboxy-1,2,3-benzotriazole, N-(N,N-di-2-ethylhexyl)aminomethylenecarboxybenzotriazole, N-(N,N-di-2-hydroxyethyl)aminomethylenecarboxybenzotriazole, and N-(N,N-di-2-ethylhexyl)aminoethylenecarboxybenzotriazole. Examples of carboxybenzotriazoles that can be used include commercially available products such as CBT-1 (Johoku Chemical Industry Co., Ltd.).

[0351] The total content of benzotriazoles and carboxybenzotriazoles is preferably 0.01 to 3% by mass, more preferably 0.05 to 1% by mass, based on the total mass of the photosensitive layer. When the content is 0.01% by mass or more, the storage stability of the photosensitive layer is improved. On the other hand, when the content is 3% by mass or less, the sensitivity is maintained and the decolorization of the dye is suppressed better.

[0352] The photosensitive layer may contain a sensitizer. The sensitizer is not particularly limited, and known sensitizers, dyes, and pigments can be used. Examples of the sensitizer include dialkylaminobenzophenone compounds, pyrazoline compounds, anthracene compounds, coumarin compounds, xanthone compounds, thioxanthone compounds, acridone compounds, oxazole compounds, benzoxazole compounds, thiazole compounds, benzothiazole compounds, triazole compounds (e.g., 1,2,4-triazole), stilbene compounds, triazine compounds, thiophene compounds, naphthalimide compounds, triarylamine compounds, and aminoacridine compounds.

[0353] The sensitizers may be used alone or in combination of two or more. When the photosensitive layer contains a sensitizer, the content of the sensitizer can be appropriately selected depending on the purpose. From the viewpoints of improving sensitivity to the light source and improving the curing rate by balancing the polymerization rate and chain transfer, the content is preferably 0.01 to 5 mass %, and more preferably 0.05 to 1 mass %, relative to the total mass of the photosensitive layer.

[0354] The photosensitive layer may contain at least one selected from the group consisting of plasticizers and heterocyclic compounds. Examples of the plasticizer and heterocyclic compound include the compounds described in paragraphs 0097 to 0103 and 0111 to 0118 of WO 2018 / 179640. The photosensitive layer preferably contains a surfactant. Examples of the surfactant include the same surfactants as those in the first embodiment, and preferred embodiments are also the same.

[0355] The photosensitive layer may further contain known additives such as metal oxide particles, antioxidants, dispersants, acid multipliers, development accelerators, conductive fibers, ultraviolet absorbers, thickeners, crosslinkers, and organic or inorganic suspending agents. Additives contained in the photosensitive layer are described in paragraphs 0165 to 0184 of JP-A No. 2014-085643, the contents of which are incorporated herein by reference.

[0356] The content of water in the photosensitive layer is preferably from 0.01 to 1.0% by mass, more preferably from 0.05 to 0.5% by mass, from the viewpoint of improving reliability and lamination properties.

[0357] The thickness (film thickness) of the photosensitive layer is generally 0.1 to 300 μm, preferably 0.2 to 100 μm, more preferably 0.5 to 50 μm, still more preferably 0.5 to 15 μm, particularly preferably 0.5 to 10 μm, and most preferably 0.5 to 8 μm, which can improve the developability of the photosensitive layer and the resolution. In one embodiment, the thickness is preferably 0.5 to 5 μm, more preferably 0.5 to 4 μm, and even more preferably 0.5 to 3 μm.

[0358] In order to obtain a cured film of the photosensitive layer with better adhesion after exposure, the transmittance of the photosensitive layer at a wavelength of 365 nm is preferably 10% or more, more preferably 30% or more, and even more preferably 50% or more. There is no particular upper limit, but it is preferably 99.9% or less.

[0359] <Impurities, etc.> The photosensitive layer may contain a certain amount of impurities. Specific examples of impurities include sodium, potassium, magnesium, calcium, iron, manganese, copper, aluminum, titanium, chromium, cobalt, nickel, zinc, tin, halogens, and ions thereof. Among these, halide ions, sodium ions, and potassium ions are likely to be mixed in as impurities, so it is preferable to set the contents to the following ranges.

[0360] The content of impurities in the photosensitive layer is preferably 80 ppm or less, more preferably 10 ppm or less, and even more preferably 2 ppm or less, by mass. The content of impurities can be 1 ppb or more, or may be 0.1 ppm or more, by mass.

[0361] Methods for controlling the impurity content within the above range include selecting raw materials for the composition that contain a small amount of impurities, preventing impurities from being mixed in during the preparation of the photosensitive layer, and removing impurities by washing.

[0362] The amount of impurities can be determined by known methods such as ICP (Inductively Coupled Plasma) emission spectroscopy, atomic absorption spectroscopy, and ion chromatography.

[0363] The content of compounds such as benzene, formaldehyde, trichloroethylene, 1,3-butadiene, carbon tetrachloride, chloroform, N,N-dimethylformamide, N,N-dimethylacetamide, and hexane in the photosensitive layer is preferably small, and the content of these compounds relative to the total mass of the photosensitive layer is preferably 100 ppm or less, more preferably 20 ppm or less, and even more preferably 4 ppm or less, by mass. The lower limit, based on mass, can be 10 ppb or more, or 100 ppb or more, based on the total mass of the photosensitive layer. The content of these compounds can be reduced in the same manner as for the metal impurities described above. Furthermore, they can be quantified by known measurement methods.

[0364] The content of water in the photosensitive layer is preferably from 0.01 to 1.0% by mass, more preferably from 0.05 to 0.5% by mass, from the viewpoint of improving reliability and lamination properties.

[0365] <Pigments> The photosensitive layer may be a colored resin layer containing a pigment. In order to protect the liquid crystal display window of recent electronic devices, a cover glass having a black frame-shaped light-shielding layer formed on the periphery of the back surface of a transparent glass substrate or the like is sometimes attached. A colored resin layer can be used to form such a light-shielding layer. The pigment may be appropriately selected according to the desired hue, and may be selected from black pigments, white pigments, and pigments of chromatic colors other than black and white. In particular, when a black pattern is to be formed, a black pigment is preferably selected as the pigment.

[0366] As the black pigment, any known black pigment (organic pigment, inorganic pigment, etc.) can be appropriately selected as long as the effects of the present invention are not impaired. Among them, from the viewpoint of optical density, suitable black pigments include, for example, carbon black, titanium oxide, titanium carbide, iron oxide, titanium oxide, and graphite, with carbon black being particularly preferred. As the carbon black, from the viewpoint of surface resistance, carbon black at least a portion of the surface of which is coated with a resin is preferred.

[0367] From the viewpoint of dispersion stability, the particle size of the black pigment is preferably 0.001 to 0.1 μm, more preferably 0.01 to 0.08 μm, in terms of number average particle size. Here, the particle size refers to the diameter of a circle whose area is equal to the area of ​​a pigment particle, calculated from a photograph of the pigment particle taken with an electron microscope, and the number average particle size is the average value obtained by calculating the particle size for 100 random particles and averaging the particle sizes of the 100 particles.

[0368] As a pigment other than black pigments, the white pigments described in paragraphs 0015 and 0114 of JP-A No. 2005-007765 can be used. Specifically, among the white pigments, inorganic pigments such as titanium oxide, zinc oxide, lithopone, precipitated calcium carbonate, white carbon, aluminum oxide, aluminum hydroxide, and barium sulfate are preferred, titanium oxide or zinc oxide is more preferred, and titanium oxide is even more preferred. As the inorganic pigment, rutile or anatase titanium oxide is more preferred, and rutile titanium oxide is particularly preferred. The surface of titanium oxide may be subjected to a silica treatment, alumina treatment, titania treatment, zirconia treatment, or organic treatment, or may be subjected to two or more of these treatments, which suppresses the catalytic activity of titanium oxide and improves heat resistance, fading resistance, etc. From the viewpoint of reducing the thickness of the photosensitive layer after heating, the surface treatment of the titanium oxide is preferably at least one of alumina treatment and zirconia treatment, and particularly preferably both alumina treatment and zirconia treatment.

[0369] Furthermore, when the photosensitive layer is a colored resin layer, it is also preferable that the photosensitive layer further contains a chromatic pigment other than a black pigment and a white pigment, from the viewpoint of transferability. When a chromatic pigment is contained, the particle size of the chromatic pigment is preferably 0.1 μm or less, and more preferably 0.08 μm or less, in terms of better dispersibility. Examples of chromatic pigments include Victoria Pure Blue BO (Color Index (CI) 42595), Auramine (CI 41000), Fat Black HB (CI 26150), Monolight Yellow GT (CI Pigment Yellow 12), Permanent Yellow GR (CI Pigment Yellow 17), Permanent Yellow HR (CI Pigment Yellow 83), Permanent Carmine FBB (CI Pigment Red 146), Hoster Balm Red ESB (CI Pigment Violet 19), Permanent Ruby FBH (CI Pigment Red 11), Fastel Pink B Supra (CI Pigment Red 81), Monastral Fast Blue (CI Pigment Red 146), and Permanent Yellow GR (CI Pigment Yellow 17). Examples of pigments that can be used include CI Pigment Blue 15), Monolight Fast Black B (CI Pigment Black 1) and carbon, CI Pigment Red 97, CI Pigment Red 122, CI Pigment Red 149, CI Pigment Red 168, CI Pigment Red 177, CI Pigment Red 180, CI Pigment Red 192, CI Pigment Red 215, CI Pigment Green 7, CI Pigment Blue 15:1, CI Pigment Blue 15:4, CI Pigment Blue 22, CI Pigment Blue 60, CI Pigment Blue 64, and CI Pigment Violet 23. Of these, CI Pigment Red 177 is preferred.

[0370] When the photosensitive layer contains a pigment, the content of the pigment is preferably more than 3% by mass and not more than 40% by mass, more preferably more than 3% by mass and not more than 35% by mass, even more preferably more than 5% by mass and not more than 35% by mass, and particularly preferably 10% by mass or more and not more than 35% by mass, relative to the total mass of the photosensitive layer.

[0371] When the photosensitive layer contains pigments other than black pigments (white pigments and chromatic pigments), the content of the pigments other than black pigments is preferably 30% by mass or less, more preferably 1 to 20% by mass, and even more preferably 3 to 15% by mass, relative to the black pigment.

[0372] When the photosensitive layer contains a black pigment and is formed from a photosensitive composition, the black pigment (preferably carbon black) is preferably introduced into the photosensitive composition in the form of a pigment dispersion. The dispersion may be prepared by premixing a black pigment and a pigment dispersant, adding the resulting mixture to an organic solvent (or vehicle), and dispersing the mixture using a disperser. The pigment dispersant may be selected depending on the pigment and solvent, and commercially available dispersants may be used, for example. The vehicle refers to the medium in which the pigment is dispersed when a pigment dispersion is prepared. The vehicle is liquid and includes a binder component that maintains the black pigment in a dispersed state and a solvent component (organic solvent) that dissolves and dilutes the binder component.

[0373] The dispersing machine is not particularly limited, and examples thereof include known dispersing machines such as a kneader, a roll mill, an attritor, a super mill, a dissolver, a homomixer, and a sand mill. Furthermore, fine pulverization may be performed by utilizing frictional force through mechanical grinding. For details about dispersing machines and fine pulverization, please refer to the descriptions in "Pigment Dictionary" (Kunizo Asakura, 1st Edition, Asakura Shoten, 2000, pp. 438 and 310).

[0374] <<Relationship between temporary support, photosensitive layer, and protective film>> In the second embodiment, it is also preferable that the relationships among the temporary support, the photosensitive layer, and the protective film described in the first embodiment are satisfied.

[0375] <<Thermoplastic resin layer>> The thermoplastic resin layer is usually disposed between the temporary support and the photosensitive layer. By providing the transfer film with the thermoplastic resin layer, the conformability to the substrate during the lamination process between the transfer film and the substrate is improved, and the inclusion of air bubbles between the substrate and the transfer film can be suppressed. As a result, the adhesion between the thermoplastic resin layer and an adjacent layer (e.g., temporary support) is further improved.

[0376] The thermoplastic resin layer contains a resin. The resin contains a thermoplastic resin as a part or the whole. That is, in one embodiment, the thermoplastic resin layer preferably contains a thermoplastic resin.

[0377] <Alkali-soluble resin (thermoplastic resin)> The thermoplastic resin is preferably an alkali-soluble resin. Examples of alkali-soluble resins include acrylic resins, polystyrene resins, styrene-acrylic copolymers, polyurethane resins, polyvinyl alcohol, polyvinyl formal, polyamide resins, polyester resins, polyamide resins, epoxy resins, polyacetal resins, polyhydroxystyrene resins, polyimide resins, polybenzoxazole resins, polysiloxane resins, polyethyleneimine, polyallylamine, and polyalkylene glycols.

[0378] As the alkali-soluble resin, an acrylic resin is preferred from the viewpoint of developability and adhesion to adjacent layers. Here, the acrylic resin means a resin having at least one type of structural unit selected from the group consisting of structural units derived from (meth)acrylic acid, structural units derived from (meth)acrylic acid esters, and structural units derived from (meth)acrylic acid amides. The acrylic resin preferably contains structural units derived from (meth)acrylic acid, structural units derived from (meth)acrylic acid esters, and structural units derived from (meth)acrylic acid amides in a total content of 50% by mass or more relative to the total mass of the acrylic resin. In particular, the total content of the structural units derived from (meth)acrylic acid and the structural units derived from (meth)acrylic acid ester is preferably 30 to 100 mass %, more preferably 50 to 100 mass %, relative to the total mass of the acrylic resin.

[0379] The alkali-soluble resin is preferably a polymer 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, with a carboxy group being preferred. From the viewpoint of developability, the alkali-soluble resin is preferably an alkali-soluble resin having an acid value of 60 mgKOH / g or more, and more preferably a carboxyl group-containing acrylic resin having an acid value of 60 mgKOH / g or more. The upper limit of the acid value of the alkali-soluble resin is not particularly limited, but is preferably 300 mgKOH / g or less, more preferably 250 mgKOH / g or less, even more preferably 200 mgKOH / g or less, and particularly preferably 150 mgKOH / g or less.

[0380] The carboxyl group-containing acrylic resin having an acid value of 60 mgKOH / g or more is not particularly limited, and can be appropriately selected from known resins. Examples include alkali-soluble resins that are carboxyl group-containing acrylic resins having an acid value of 60 mgKOH / g or more among the polymers described in paragraph 0025 of JP-A 2011-095716, carboxyl group-containing acrylic resins having an acid value of 60 mgKOH / g or more among the polymers described in paragraphs 0033 to 0052 of JP-A 2010-237589, and carboxyl group-containing acrylic resins having an acid value of 60 mgKOH / g or more among the binder polymers described in paragraphs 0053 to 0068 of JP-A 2016-224162. The copolymerization ratio of the structural unit having a carboxy group in the carboxy group-containing acrylic resin is preferably 5 to 50 mass %, more preferably 10 to 40 mass %, and even more preferably 12 to 30 mass %, relative to the total mass of the acrylic resin. As the alkali-soluble resin, from the viewpoint of developability and adhesion to adjacent layers, an acrylic resin having a structural unit derived from (meth)acrylic acid is particularly preferred.

[0381] The alkali-soluble resin may have a reactive group, which may be an addition-polymerizable group, such as an ethylenically unsaturated group, a polycondensable group such as a hydroxy group or a carboxy group, or a polyaddition-reactive group such as an epoxy group or a (blocked) isocyanate group.

[0382] The weight average molecular weight (Mw) of the alkali-soluble resin is preferably 1,000 or more, more preferably from 10,000 to 100,000, and even more preferably from 20,000 to 50,000.

[0383] The alkali-soluble resins may be used alone or in combination of two or more. From the viewpoints of developability and adhesion to adjacent layers, the content of the alkali-soluble resin is preferably 10 to 99% by mass, more preferably 20 to 90% by mass, even more preferably 40 to 80% by mass, and particularly preferably 50 to 75% by mass, relative to the total mass of the thermoplastic resin layer.

[0384] <Dye> The thermoplastic resin layer preferably contains a dye (also simply referred to as "dye B") whose maximum absorption wavelength in the wavelength range of 400 to 780 nm during color development is 450 nm or more and whose maximum absorption wavelength changes with an acid, a base, or a radical. Preferred embodiments of dye B are the same as the preferred embodiments of dye N described above, except for the points described below.

[0385] From the viewpoints of visibility of exposed and unexposed areas and resolution, dye B is preferably a dye whose maximum absorption wavelength changes in response to an acid or radical, and more preferably a dye whose maximum absorption wavelength changes in response to an acid. From the viewpoints of visibility and resolution of exposed and unexposed areas, the thermoplastic resin layer preferably contains both a dye whose maximum absorption wavelength changes in response to acid as dye B, and a compound that generates acid when exposed to light, as described below.

[0386] The dye B may be used alone or in combination of two or more. From the viewpoint of visibility of exposed and unexposed areas, the content of dye B is preferably 0.2 mass% or more, more preferably 0.2 to 6 mass%, even more preferably 0.2 to 5 mass%, and particularly preferably 0.25 to 3.0 mass%, relative to the total mass of the thermoplastic resin layer.

[0387] Here, the content of dye B means the content of dye when all of the dye B contained in the thermoplastic resin layer is in a color-developing state. A method for quantifying the content of dye B will be described below using a dye that develops color by radicals as an example. Solutions were prepared by dissolving 0.001 g and 0.01 g of dye in 100 mL of methyl ethyl ketone. The photoradical polymerization initiator Irgacure OXE01 (BASF Japan Ltd.) was added to each solution, and radicals were generated by irradiating with 365 nm light, causing all dyes to develop color. The absorbance of each solution was then measured at 25°C using a spectrophotometer (UV3100, Shimadzu Corporation) under atmospheric conditions, and a calibration curve was created. Next, the absorbance of the solution in which all the dye has developed is measured in the same manner as above, except that 0.1 g of the thermoplastic resin layer is dissolved in methyl ethyl ketone instead of the dye. The amount of the dye contained in the thermoplastic resin layer is calculated based on the absorbance of the obtained solution containing the thermoplastic resin layer and a calibration curve. The thermoplastic resin layer 3g is the same as the 3g of solid content of the composition.

[0388] <Compounds that generate acids, bases, or radicals when exposed to light> The thermoplastic resin layer may contain a compound that generates an acid, a base, or a radical when exposed to light (also simply referred to as "compound C"). Compound C is preferably a compound that generates an acid, a base, or a radical when exposed to actinic rays such as ultraviolet light and visible light. As the compound C, known photoacid generators, photobase generators, and photoradical polymerization initiators (photoradical generators) can be used.

[0389] (Photoacid generator) The thermoplastic resin layer may contain a photoacid generator from the viewpoint of resolution. Examples of the photoacid generator include the cationic photopolymerization initiators that may be contained in the photosensitive layer described above, and preferred embodiments are the same except for the points described below.

[0390] From the viewpoints of sensitivity and resolution, the photoacid generator preferably contains at least one compound selected from the group consisting of an onium salt compound and an oxime sulfonate compound, and from the viewpoints of sensitivity, resolution, and adhesion, it is more preferable that the photoacid generator contains an oxime sulfonate compound. Furthermore, as the photoacid generator, a photoacid generator having the following structure is also preferred.

[0391] [ka]

[0392] (Photoradical polymerization initiator) The thermoplastic resin layer may contain a photoradical polymerization initiator. Examples of the photoradical polymerization initiator include the photoradical polymerization initiators that may be contained in the photosensitive layer described above, and preferred embodiments are also the same.

[0393] (Photobase Generator) The thermoplastic resin composition may contain a photobase generator. The photobase generator is not particularly limited as long as it is a known photobase generator, and examples thereof include 2-nitrobenzylcyclohexylcarbamate, triphenylmethanol, O-carbamoylhydroxylamide, O-carbamoyloxime, [[(2,6-dinitrobenzyl)oxy]carbonyl]cyclohexylamine, bis[[(2-nitrobenzyl)oxy]carbonyl]hexane 1,6-diamine, 4-(methylthiobenzoyl)-1-methyl-1-morpholinoethane, (4-morpholinobenzoyl)- Examples include 1-benzyl-1-dimethylaminopropane, N-(2-nitrobenzyloxycarbonyl)pyrrolidine, hexaamminecobalt(III) tris(triphenylmethylborate), 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone, 2,6-dimethyl-3,5-diacetyl-4-(2-nitrophenyl)-1,4-dihydropyridine, and 2,6-dimethyl-3,5-diacetyl-4-(2,4-dinitrophenyl)-1,4-dihydropyridine.

[0394] The compound C may be used alone or in combination of two or more. The content of compound C is preferably 0.1 to 10% by mass, more preferably 0.5 to 5% by mass, based on the total mass of the thermoplastic resin layer, from the viewpoints of visibility and resolution of exposed and unexposed areas.

[0395] <Plasticizer> The thermoplastic resin layer preferably contains a plasticizer from the viewpoints of resolution, adhesion to adjacent layers, and developability. The plasticizer preferably has a smaller molecular weight (weight average molecular weight when it is an oligomer or polymer and has a molecular weight distribution) than the alkali-soluble resin. The molecular weight (weight average molecular weight) of the plasticizer is preferably 200 to 2,000. The plasticizer is not particularly limited as long as it is a compound that is compatible with the alkali-soluble resin and exhibits plasticity, but from the viewpoint of imparting plasticity, the plasticizer preferably has an alkyleneoxy group in the molecule, more preferably a polyalkylene glycol compound, and the alkyleneoxy group contained in the plasticizer more preferably has a polyethyleneoxy structure or a polypropyleneoxy structure.

[0396] From the viewpoints of resolution and storage stability, the plasticizer preferably contains a (meth)acrylate compound. From the viewpoints of compatibility, resolution, and adhesion to adjacent layers, it is more preferable that the alkali-soluble resin is an acrylic resin and the plasticizer contains a (meth)acrylate compound. Examples of the (meth)acrylate compound used as the plasticizer include the (meth)acrylate compounds described above as the photopolymerizable compound contained in the photosensitive layer. In the transfer film, when the thermoplastic resin layer and the photosensitive layer are laminated in direct contact with each other, it is preferable that both the thermoplastic resin layer and the photosensitive layer contain the same (meth)acrylate compound, because the thermoplastic resin layer and the photosensitive layer each contain the same (meth)acrylate compound, which suppresses component diffusion between the layers and improves storage stability.

[0397] When the thermoplastic resin layer contains a (meth)acrylate compound as a plasticizer, it is preferable that the (meth)acrylate compound does not polymerize even in the exposed area after exposure, from the viewpoint of adhesion between the thermoplastic resin layer and the adjacent layer. Furthermore, as the (meth)acrylate compound used as a plasticizer, from the viewpoints of the resolution of the thermoplastic resin layer, adhesion to adjacent layers, and developability, a polyfunctional (meth)acrylate compound having two or more (meth)acryloyl groups in one molecule is preferred. Furthermore, as the (meth)acrylate compound used as a plasticizer, a (meth)acrylate compound having an acid group or a urethane (meth)acrylate compound is also preferred.

[0398] The plasticizers may be used alone or in combination of two or more. From the viewpoints of the resolution of the thermoplastic resin layer, adhesion to adjacent layers, and developability, the content of the plasticizer is preferably 1 to 70 mass %, more preferably 10 to 60 mass %, and even more preferably 20 to 50 mass %, relative to the total mass of the thermoplastic resin layer.

[0399] <Sensitizer> The thermoplastic resin layer may contain a sensitizer. The sensitizer is not particularly limited, and examples thereof include the sensitizers that may be contained in the photosensitive layer described above.

[0400] The sensitizers may be used alone or in combination of two or more. The content of the sensitizer can be appropriately selected depending on the purpose, but from the viewpoint of improving sensitivity to the light source and visibility of exposed and unexposed areas, it is preferably 0.01 to 5 mass %, and more preferably 0.05 to 1 mass %, relative to the total mass of the thermoplastic resin layer.

[0401] <Additives, etc.> In addition to the above components, the thermoplastic resin layer may contain known additives such as surfactants, if necessary. The thermoplastic resin layer is described in paragraphs 0189 to 0193 of JP-A No. 2014-085643, the contents of which are incorporated herein by reference.

[0402] The thickness of the thermoplastic resin layer is not particularly limited, but is preferably 1 μm or more, more preferably 2 μm or more, from the viewpoint of adhesion to adjacent layers. The upper limit is not particularly limited, but is preferably 20 μm or less, more preferably 10 μm or less, and even more preferably 8 μm or less, from the viewpoint of developability and resolution.

[0403] <<Middle Class>> In the transfer film 20, the intermediate layer 15 is present between the thermoplastic resin layer 13 and the photosensitive layer 17, thereby suppressing mixing of components that may occur during the coating and formation of the thermoplastic resin layer 13 and the photosensitive layer 17 and during storage after coating and formation. As the intermediate layer, a water-soluble resin layer containing a water-soluble resin can be used. The intermediate layer may also be an oxygen-blocking layer having an oxygen-blocking function, as described as a "separation layer" in JP-A-5-072724. When the intermediate layer is an oxygen-blocking layer, the sensitivity during exposure is improved, the time load on the exposure machine is reduced, and productivity is improved, which is preferable. The oxygen-blocking layer used as the intermediate layer may be appropriately selected from known layers described in the above publications, etc. Among them, an oxygen-blocking layer that exhibits low oxygen permeability and disperses or dissolves in water or an alkaline aqueous solution (a 1% by mass aqueous solution of sodium carbonate at 22°C) is preferred.

[0404] Hereinafter, each component that may be contained in the water-soluble resin layer (intermediate layer) will be described.

[0405] The water-soluble resin layer (intermediate layer) contains a resin. The resin includes a water-soluble resin as a part or the whole thereof. Examples of resins that can be used as the water-soluble resin include polyvinyl alcohol-based resins, polyvinylpyrrolidone-based resins, cellulose-based resins, acrylamide-based resins, polyethylene oxide-based resins, gelatin, vinyl ether-based resins, polyamide resins, and copolymers thereof. Furthermore, as the water-soluble resin, a copolymer of (meth)acrylic acid / vinyl compound can also be used. As the copolymer of (meth)acrylic acid / vinyl compound, a copolymer of (meth)acrylic acid / allyl (meth)acrylate is preferred, and a copolymer of methacrylic acid / allyl methacrylate is more preferred. When the water-soluble resin is a copolymer of (meth)acrylic acid and a vinyl compound, the composition ratio (mol %) is, for example, preferably from 90 / 10 to 20 / 80, and more preferably from 80 / 20 to 30 / 70.

[0406] The lower limit of the weight-average molecular weight of the water-soluble resin is preferably 5,000 or more, more preferably 7,000 or more, and even more preferably 10,000 or more, and the upper limit is preferably 200,000 or less, more preferably 100,000 or less, and even more preferably 50,000 or less. The dispersity (Mw / Mn) of the water-soluble resin is preferably 1-10, and more preferably 1-5.

[0407] In order to further improve the ability of the water-soluble resin layer (intermediate layer) to suppress interlayer mixing, it is preferable that the resin in the water-soluble resin layer (intermediate layer) be different from the resin contained in the layer disposed on one side of the water-soluble resin layer (intermediate layer) and the resin contained in the layer disposed on the other side. For example, when the photosensitive layer 17 contains a binder polymer and the thermoplastic resin layer 13 contains a thermoplastic resin (alkali-soluble resin), it is preferable that the resin in the water-soluble resin layer (intermediate layer) 15 be different from the binder polymer and the thermoplastic resin (alkali-soluble resin).

[0408] The water-soluble resin preferably contains polyvinyl alcohol, more preferably both polyvinyl alcohol and polyvinylpyrrolidone, in order to further improve the oxygen barrier property and the ability to inhibit interlayer mixing.

[0409] The water-soluble resins may be used alone or in combination of two or more. The content of the water-soluble resin is not particularly limited, but from the viewpoint of further improving the oxygen barrier property and the interlayer mixing suppression ability, it is preferably 50% by mass or more, more preferably 70% by mass or more, even more preferably 80% by mass or more, and particularly preferably 90% by mass or more, based on the total mass of the water-soluble resin layer (intermediate layer). The upper limit is not particularly limited, but for example, it is preferably 99.9% by mass or less, and more preferably 99.8% by mass or less. The intermediate layer may contain known additives such as surfactants, if necessary.

[0410] The thickness of the water-soluble resin layer (intermediate layer) is not particularly limited, but is preferably 0.1 to 5 μm, more preferably 0.5 to 3 μm. When the thickness of the water-soluble resin layer (intermediate layer) is within the above range, the oxygen barrier property is not reduced and the ability to suppress interlayer mixing is excellent. Furthermore, the increase in the time required to remove the water-soluble resin layer (intermediate layer) during development can be suppressed.

[0411] <<Method for manufacturing transfer film according to the second embodiment>> The method for producing the transfer film of the second embodiment is not particularly limited, and any known method can be used. Examples of methods for manufacturing the transfer film 20 include the steps of applying a thermoplastic resin composition to the surface of the temporary support 11 to form a coating film, and then drying the coating film to form the thermoplastic resin layer 13; applying a water-soluble resin composition to the surface of the thermoplastic resin layer 13 to form a coating film, and then drying the coating film to form the intermediate layer 15; and applying a photosensitive composition to the surface of the intermediate layer 15 to form a coating film, and then drying the coating film to form the photosensitive layer 17.

[0412] A protective film 19 is pressed onto the photosensitive layer 17 of the laminate produced by the above-described production method, thereby producing a transfer film 20. As a manufacturing method for the transfer film of the second embodiment, it is preferable to include a step of providing a protective film 19 so that it is in contact with the side of the photosensitive layer 17 opposite the side having the temporary support 11, thereby manufacturing a transfer film 20 having the temporary support 11, a thermoplastic resin layer 13, an intermediate layer 15, the photosensitive layer 17, and the protective film 19. After the transfer film 20 is manufactured by the above manufacturing method, the transfer film 20 may be wound up to produce and store a transfer film in a roll form. The transfer film in a roll form can be provided in that form as it is to the lamination step with a substrate in a roll-to-roll system described below.

[0413] Alternatively, the method for manufacturing the transfer film 20 may involve forming the photosensitive layer 17 and intermediate layer 15 on the protective film 19, and then forming the thermoplastic resin layer 13 on the surface of the intermediate layer 15.

[0414] <Composition for forming thermoplastic resin layer and method for forming thermoplastic resin layer> The method for forming the thermoplastic resin layer on the temporary support is not particularly limited, and any known method can be used. For example, the thermoplastic resin layer can be formed by applying a composition for forming a thermoplastic resin layer on the temporary support and drying it as necessary. The thermoplastic resin layer-forming composition preferably contains the various components for forming the thermoplastic resin layer described above and a solvent. Note that, in the thermoplastic resin layer-forming composition, the preferred range of the content of each component relative to the total solid content of the composition is the same as the preferred range of the content of each component relative to the total mass of the thermoplastic resin layer described above. The solvent is not particularly limited as long as it can dissolve or disperse the components other than the solvent, and any known solvent can be used. Examples of the solvent include the same solvents as those contained in the photosensitive composition described below, and preferred embodiments are also the same. The content of the solvent is preferably 50 to 1,900 parts by mass, more preferably 100 to 900 parts by mass, per 100 parts by mass of the total solid content of the composition.

[0415] The method for forming the thermoplastic resin layer is not particularly limited as long as it is a method capable of forming a layer containing the above components, and examples thereof include known coating methods (slit coating, spin coating, curtain coating, inkjet coating, etc.).

[0416] <Water-soluble resin composition and method for forming intermediate layer (water-soluble resin layer)> The water-soluble resin composition preferably contains the various components forming the intermediate layer (water-soluble resin layer) described above and a solvent. Note that in the water-soluble resin composition, the preferred range of the content of each component relative to the total solid content of the composition is the same as the preferred range of the content of each component relative to the total mass of the water-soluble resin layer described above. The solvent is not particularly limited as long as it can dissolve or disperse the water-soluble resin, and is preferably at least one selected from the group consisting of water and water-miscible organic solvents, and more preferably water or a mixed solvent of water and a water-miscible organic solvent. Examples of water-miscible organic solvents include alcohols having 1 to 3 carbon atoms, acetone, ethylene glycol, and glycerin, with alcohols having 1 to 3 carbon atoms being preferred, and methanol or ethanol being more preferred. The solvents may be used alone or in combination of two or more. The content of the solvent is preferably 50 to 2,500 parts by mass, more preferably 50 to 1,900 parts by mass, and even more preferably 100 to 900 parts by mass, relative to 100 parts by mass of the total solid content of the composition.

[0417] The method for forming the water-soluble resin layer is not particularly limited as long as it is a method capable of forming a layer containing the above components, and examples thereof include known coating methods (slit coating, spin coating, curtain coating, inkjet coating, etc.).

[0418] <Photosensitive composition and method for forming photosensitive layer> In terms of superior productivity, it is desirable to form the photosensitive layer by a coating method using a photosensitive composition containing the components constituting the photosensitive layer described above (e.g., an alkali-soluble resin layer, a photopolymerizable compound, a photopolymerization initiator, etc.) and a solvent. Specifically, a preferred method for manufacturing the transfer film of the second embodiment is to apply a photosensitive composition onto an intermediate layer to form a coating film, and then dry the coating film at a predetermined temperature to form a photosensitive layer.

[0419] The photosensitive composition preferably contains the various components forming the photosensitive layer described above and a solvent. Note that the preferred range of the content of each component in the photosensitive composition relative to the total solid content of the composition is the same as the preferred range of the content of each component relative to the total mass of the photosensitive layer described above. The solvent is not particularly limited as long as it can dissolve or disperse each component other than the solvent, and any known solvent can be used. Specific examples include alkylene glycol ether solvents, alkylene glycol ether acetate solvents, alcohol solvents (methanol, ethanol, etc.), ketone solvents (acetone, methyl ethyl ketone, etc.), aromatic hydrocarbon solvents (toluene, etc.), aprotic polar solvents (N,N-dimethylformamide, etc.), cyclic ether solvents (tetrahydrofuran, etc.), ester solvents (n-propyl acetate, etc.), amide solvents, lactone solvents, and mixed solvents containing two or more of these.

[0420] The solvent preferably contains at least one selected from the group consisting of alkylene glycol ether solvents and alkylene glycol ether acetate solvents. Among these, a mixed solvent containing at least one selected from the group consisting of alkylene glycol ether solvents and alkylene glycol ether acetate solvents and at least one selected from the group consisting of ketone solvents and cyclic ether solvents is more preferred, and a mixed solvent containing at least three 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 even more preferred.

[0421] Examples of alkylene glycol ether solvents include ethylene glycol monoalkyl ethers, ethylene glycol dialkyl ethers, propylene glycol monoalkyl ethers (such as propylene glycol monomethyl ether acetate), propylene glycol dialkyl ethers, diethylene glycol dialkyl ethers, dipropylene glycol monoalkyl ethers, and dipropylene glycol dialkyl ethers. Alkylene glycol ether acetate solvents include, for example, ethylene glycol monoalkyl ether acetate, propylene glycol monoalkyl ether acetate, diethylene glycol monoalkyl ether acetate, and dipropylene glycol monoalkyl ether acetate. As the solvent, the solvents described in paragraphs 0092 to 0094 of WO 2018 / 179640 and the solvents described in paragraph 0014 of JP 2018-177889 A may be used, the contents of which are incorporated herein by reference. The solvents may be used alone or in combination of two or more. The content of the solvent is preferably 50 to 1,900 parts by mass, more preferably 100 to 1,200 parts by mass, and even more preferably 100 to 900 parts by mass, relative to 100 parts by mass of the total solid content of the composition.

[0422] Examples of methods for applying the photosensitive composition include printing, spraying, roll coating, bar coating, curtain coating, spin coating, and die coating (that is, slit coating).

[0423] As a method for drying the coating film of the photosensitive composition, heat drying and reduced pressure drying are preferred. The drying temperature is preferably 80° C. or higher, more preferably 90° C. or higher, and the upper limit is preferably 130° C. or lower, more preferably 120° C. or lower. Drying can also be performed by continuously changing the temperature. The drying time is preferably 20 seconds or more, more preferably 40 seconds or more, and even more preferably 60 seconds or more. There is no upper limit, but the drying time is preferably 600 seconds or less, and more preferably 300 seconds or less.

[0424] Furthermore, by laminating a protective film to the photosensitive layer, the transfer film of the second embodiment can be produced. The method for laminating the protective film to the photosensitive layer is not particularly limited, and known methods can be used. Examples of a device for laminating the protective film to the photosensitive layer include known laminators such as a vacuum laminator and an auto-cut laminator. The laminator is preferably equipped with any heatable roller such as a rubber roller and is capable of applying pressure and heat.

[0425] [Method of manufacturing laminate] By using the transfer film described above, the composition layer can be transferred to an object to be transferred. In particular, the transfer film of the present invention is preferably used in the production of a touch panel. Among these, the method for producing a laminate of the present invention includes a lamination step of contacting a surface of a transfer film opposite to the temporary support with a substrate having a conductive layer and laminating the two together to obtain a substrate with a photosensitive layer having a substrate, a conductive layer, a photosensitive layer, and a temporary support in this order; an exposure step of pattern-exposing the photosensitive layer; a development step of developing the exposed photosensitive layer to form a protective film pattern that protects the conductive layer; Furthermore, the method for producing a laminate preferably includes a peeling step of peeling the temporary support from the substrate with the photosensitive layer between the laminating step and the exposure step, or between the exposure step and the development step. The procedure of the above steps will be described in detail below. If the transfer film has a protective film, the protective film is peeled off before the lamination step. If the transfer film has a layer other than the photosensitive layer on the temporary support (in other words, if the composition layer on the temporary support has a layer other than the photosensitive layer), the substrate with the photosensitive layer obtained in the lamination step will have further layers between the conductive layer and the photosensitive layer and / or between the photosensitive layer and the temporary support.

[0426] [Lamination process] The lamination process is a process in which the surface of the transfer film opposite the temporary support is brought into contact with a substrate having a conductive layer and laminated to obtain a substrate with a photosensitive layer having a substrate, a conductive layer, a photosensitive layer, and a temporary support in that order.

[0427] In the lamination, the conductive layer and the composition layer are pressed together so that the surface of the conductive layer and the surface of the composition layer opposite to the temporary support are in contact with each other. The method of pressure bonding is not particularly limited, and known transfer methods and lamination methods can be used. Among them, it is preferable to place the surface of the composition layer opposite to the temporary support on a substrate having a conductive layer, and then apply pressure and heat with a roll or the like. For lamination, a known laminator such as a vacuum laminator or an auto-cut laminator can be used. The lamination temperature is not particularly limited, but is preferably 70 to 130°C, for example.

[0428] A substrate having a conductive layer has a conductive layer on a substrate, and may have any layer formed thereon as necessary. That is, a substrate having a conductive layer is a conductive substrate having at least a substrate and a conductive layer disposed on the substrate.

[0429] Examples of the substrate include a resin substrate, a glass substrate, and a semiconductor substrate. A preferred embodiment of the substrate is described, for example, in paragraph

[0140] of International Publication No. 2018 / 155193, the contents of which are incorporated herein by reference. Preferred materials for the resin substrate are cycloolefin polymers and polyimides. The thickness of the resin substrate is preferably 5 to 200 μm, more preferably 10 to 100 μm.

[0430] From the viewpoints of conductivity and fine line formability, the conductive layer is preferably at least one layer selected from the group consisting of a metal layer, a conductive metal oxide layer, a graphene layer, a carbon nanotube layer, and a conductive polymer layer. Furthermore, only one conductive layer may be disposed on the substrate, or two or more conductive layers may be disposed on the substrate. When two or more conductive layers are disposed, it is preferable that the conductive layers are made of different materials. A preferred embodiment of the conductive layer is described, for example, in paragraph

[0141] of WO 2018 / 155193, the contents of which are incorporated herein by reference.

[0431] The substrate having a conductive layer is preferably a substrate having at least one of a transparent electrode and a routed wiring. Such a substrate can be suitably used as a touch panel substrate. The transparent electrode can function favorably as an electrode for a touch panel, and is preferably made of a metal oxide film such as ITO (indium tin oxide) or IZO (indium zinc oxide), or a metal mesh or a metal thin wire such as a metal nanowire. Examples of the thin metal wires include thin wires of silver, copper, etc. Among these, conductive silver materials such as silver mesh and silver nanowires are preferred.

[0432] The material of the lead wiring is preferably metal. Examples of metals that can be used for the wiring include gold, silver, copper, molybdenum, aluminum, titanium, chromium, zinc, and manganese, as well as alloys of two or more of these metal elements. The wiring is preferably made of copper, molybdenum, aluminum, or titanium, with copper being particularly preferred.

[0433] The electrode protective film for a touch panel formed using the photosensitive layer in the transfer film of the present invention is preferably provided so as to cover the electrodes, etc. (i.e., at least one of the electrodes for a touch panel and the wiring for a touch panel) directly or via another layer, for the purpose of protecting the electrodes, etc.

[0434] [Exposure process] The exposure step is a step of pattern-exposing the photosensitive layer. Here, the term "pattern exposure" refers to a form of patterned exposure, that is, exposure in a form in which exposed areas and non-exposed areas exist. The positional relationship between the exposed and unexposed regions in the pattern exposure is not particularly limited and may be adjusted as appropriate. Preferably, the photosensitive layer is exposed from the side opposite the substrate.

[0435] The light source for pattern exposure can be appropriately selected and used as long as it can irradiate light in a wavelength range (e.g., 365 nm or 405 nm) that can at least cure the photosensitive layer. In particular, the dominant wavelength of the exposure light for pattern exposure is preferably 365 nm. The dominant wavelength is the wavelength with the highest intensity.

[0436] Examples of light sources include various lasers, light-emitting diodes (LEDs), ultra-high pressure mercury lamps, high pressure mercury lamps, and metal halide lamps. The exposure dose is 5 to 200 mJ / cm 2 is preferred, and 10 to 200 mJ / cm 2 is more preferred.

[0437] Preferred embodiments of the light source, exposure dose, and exposure method used for exposure are described, for example, in paragraphs

[0146] to

[0147] of WO 2018 / 155193, the contents of which are incorporated herein by reference.

[0438] By carrying out the exposure step and the development step described below, a protective film pattern that protects at least a part of the conductive layer is formed on the conductive layer on the substrate.

[0439] [Peeling process] The peeling step is a step of peeling the temporary support from the substrate with the photosensitive layer between the laminating step and the exposure step, or between the exposure step and the development step described below. The peeling method is not particularly limited, and a mechanism similar to the cover film peeling mechanism described in paragraphs

[0161] to

[0162] of JP-A-2010-072589 can be used.

[0440] [Development process] The development step is a step in which the exposed photosensitive layer is developed to form a pattern. The photosensitive layer can be developed using a developer. The developer is preferably an alkaline aqueous solution. Examples of alkaline compounds 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).

[0441] Examples of the development method include puddle development, shower development, spin development, and dip development.

[0442] In the present specification, examples of the developer that can be suitably used include the developer described in paragraph

[0194] of WO 2015 / 093271, and examples of the development method that can be suitably used include the development method described in paragraph

[0195] of WO 2015 / 093271.

[0443] [Post-exposure process and post-bake process] The method for producing the laminate may include a step of exposing the pattern obtained by the development step to light (post-exposure step) and / or a step of heating (post-baking step). When both the post-exposure step and the post-bake step are included, it is preferable to carry out post-bake after the post-exposure. The exposure dose of the post-exposure is 100 to 5000 mJ / cm. 2 is preferred, and 200 to 3000 mJ / cm 2 The post-baking temperature is preferably 80° C. to 250° C., more preferably 90° C. to 160° C. The post-baking time is preferably 1 minute to 180 minutes, more preferably 10 minutes to 60 minutes.

[0444] [Uses of laminate] The laminate produced by the laminate producing method of the present invention can be applied to various devices. Examples of devices equipped with the laminate include input devices, preferably touch panels, and more preferably capacitance touch panels. Furthermore, the input devices can be applied to display devices such as organic electroluminescence display devices and liquid crystal display devices. When the laminate is applied to a touch panel, the pattern formed from the photosensitive layer is preferably used as a protective film for electrodes or wiring for a touch panel. That is, the photosensitive layer included in the transfer film is preferably used to form an electrode protective film for a touch panel or wiring for a touch panel.

[0445] [Method of manufacturing a laminate having a conductive pattern] By using the transfer film described above, a laminate having a conductor pattern can also be produced. Among these, the method for producing a laminate having a conductive pattern of the present invention includes a lamination step of bringing the surface of the transfer film opposite to the temporary support into contact with a substrate having a conductive layer to obtain a substrate with a photosensitive layer having a substrate, a conductive layer, a photosensitive layer, and a temporary support in this order. an exposure step of pattern-exposing the photosensitive layer; a developing step of developing the exposed photosensitive layer to form a resin pattern; an etching step of etching the conductive layer in an area where the resin pattern is not disposed; Furthermore, the production method preferably includes a peeling step of peeling the temporary support from the substrate with the photosensitive layer between the laminating step and the exposure step, or between the exposure step and the development step. By the above-described manufacturing method, a laminate having a conductive pattern formed by etching the conductive layer can be manufactured.

[0446] The specific steps of the method for manufacturing a laminate having a conductive pattern will be described below. The laminating step, exposing step, developing step, and peeling step in the manufacturing method of a laminate having a conductive pattern are the same as the laminating step, exposing step, developing step, and peeling step in the manufacturing method of the laminate described above, and the preferred embodiments are also the same.

[0447] [Etching process] The method for manufacturing a laminate having a conductive pattern includes a step of etching the conductive layer in an area where the resin pattern is not arranged in a laminate in which a substrate, a conductive layer (a conductive layer of the substrate), and a resin pattern (more preferably, a resin pattern manufactured by a manufacturing method including the laminating step, the exposing step, and the developing step) are laminated in this order (etching step). In the etching step, the resin pattern obtained from the photosensitive layer in the developing step is used as an etching resist to etch the conductive layer. As the etching method, known methods can be applied, and examples thereof include the method described in paragraphs

[0209] to

[0210] of JP 2017-120435 A, the method described in paragraphs

[0048] to

[0054] of JP 2010-152155 A, a wet etching method in which the substrate is immersed in an etching solution, and a dry etching method such as plasma etching.

[0448] The etching solution used in the wet etching may be an acidic or alkaline etching solution that is appropriately selected depending on the target to be etched. Examples of acidic etching solutions include aqueous solutions of an acidic component selected from hydrochloric acid, sulfuric acid, nitric acid, acetic acid, hydrofluoric acid, oxalic acid, and phosphoric acid, and aqueous solutions of a mixture of an acidic component and a salt selected from ferric chloride, ammonium fluoride, and potassium permanganate. The acidic component may be a combination of multiple acidic components. Examples of alkaline etching solutions include aqueous solutions of alkaline components selected from sodium hydroxide, potassium hydroxide, ammonia, organic amines, and salts of organic amines (e.g., tetramethylammonium hydroxide), as well as aqueous solutions of mixtures of alkaline components and salts (e.g., potassium permanganate). The alkaline component may be a combination of multiple alkaline components.

[0449] [Removal process] In the method for producing a laminate having a conductive pattern, it is preferable to carry out a step of removing the remaining resin pattern (removal step). The removal step is not particularly limited and can be carried out as needed, but is preferably carried out after the etching step. The method for removing the remaining resin pattern is not particularly limited, but includes a method of removing it by chemical treatment, and a method of removing it using a remover is preferred. The photosensitive layer can be removed by immersing the substrate having the remaining resin pattern in a stirring removal solution having a liquid temperature of preferably 30 to 80°C, more preferably 50 to 80°C, for 1 to 30 minutes.

[0450] Examples of the removal solution include a removal solution obtained by dissolving an inorganic or organic alkaline component in water, dimethyl sulfoxide, N-methylpyrrolidone, or a mixture thereof. Examples of the inorganic alkaline component include sodium hydroxide and potassium hydroxide. Examples of the organic alkaline component include primary amine compounds, secondary amine compounds, tertiary amine compounds, and quaternary ammonium salt compounds. Alternatively, the removal may be carried out by a known method such as a spray method, a shower method, or a puddle method using a removal solution.

[0451] [Other steps] The method for manufacturing a laminate having a conductive pattern may include any steps (other steps) other than the steps described above. For example, examples include a process for reducing visible light reflectance described in paragraph

[0172] of WO 2019 / 022089, and a process for forming a new conductive layer on an insulating film described in paragraph

[0172] of WO 2019 / 022089, but are not limited to these processes.

[0452] <Step of reducing visible light reflectance> The method for producing a laminate having a conductive pattern may include a step of performing a treatment to reduce the visible light reflectance of some or all of the plurality of conductive layers of the substrate. An example of a treatment for reducing the visible light reflectance is oxidation treatment. When the substrate has a conductive layer containing copper, the visible light reflectance of the conductive layer can be reduced by oxidizing the copper to copper oxide and blackening the conductive layer. Treatments for reducing visible light reflectance are described in paragraphs 0017 to 0025 of JP 2014-150118 A and paragraphs 0041, 0042, 0048, and 0058 of JP 2013-206315 A, and the contents of these publications are incorporated herein by reference.

[0453] <Step of forming an insulating film, step of forming a new conductive layer on the surface of the insulating film> The method for producing a laminate having a conductive pattern preferably includes the steps of forming an insulating film on the surface of the conductive pattern, and forming a new conductive layer on the surface of the insulating film. By the above steps, a second electrode pattern insulated from the first electrode pattern can be formed. The step of forming the insulating film is not particularly limited, and may include a known method for forming a permanent film. Alternatively, an insulating film having a desired pattern may be formed by photolithography using a photosensitive material having insulating properties. The step of forming a new conductive layer on the insulating film is not particularly limited, and for example, a new conductive layer having a desired pattern may be formed by photolithography using a photosensitive material having conductivity.

[0454] A preferred method for producing a laminate having a conductive pattern is to use a substrate having a plurality of conductive layers on both surfaces of a base material, and to sequentially or simultaneously form circuits on the conductive layers formed on both surfaces of the base material. This configuration allows for the formation of a laminate having a first conductive pattern on one surface of the base material and a second conductive pattern on the other surface. It is also preferred to form such a laminate from both surfaces of the base material using a roll-to-roll process.

[0455] [Uses of laminates having conductive patterns] The laminate having a conductive pattern manufactured by the manufacturing method of the laminate having a conductive pattern can be applied to various devices. An example of a device including such a laminate having a conductive pattern is an input device, preferably a touch panel, more preferably a capacitive touch panel. Furthermore, the input device can be applied to display devices such as organic electroluminescence (EL) display devices and liquid crystal display devices. [Example]

[0456] The present invention will be described in more detail below with reference to examples. The materials, amounts used, ratios, treatment details, treatment procedures, etc. shown in the following examples can be changed as appropriate without departing 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. Unless otherwise specified, "parts" and "%" are by mass. In the following examples, the weight average molecular weight of the resin is determined by gel permeation chromatography (GPC) in terms of polystyrene.

[0457] [Various synthesis examples] [Components of the photosensitive layer] <<Alkali-soluble resin>> <Synthesis of binder polymer P-1> Propylene glycol monomethyl ether (82.4 g, Fujifilm Wako Pure Chemical Corporation) was charged into a flask to prepare a solution. The resulting solution was heated to 90 °C under a nitrogen stream. A solution of styrene (38.4 g, Fujifilm Wako Pure Chemical Corporation), dicyclopentanyl methacrylate (30.1 g, Fancryl FA-513M, Hitachi Chemical Co., Ltd.), and methacrylic acid (34.0 g, Fujifilm Wako Pure Chemical Corporation) dissolved in propylene glycol monomethyl ether (20 g), and a solution of polymerization initiator V-601 (5.4 g, Fujifilm Wako Pure Chemical Corporation) dissolved in propylene glycol monomethyl ether acetate (43.6 g, Fujifilm Wako Pure Chemical Corporation) were simultaneously added dropwise to the heated solution over a 3-hour period. After the dropwise addition was completed, V-601 (0.75 g) was added to the solution three times at hourly intervals. The solution was then allowed to react for an additional 3 hours. The resulting solution was then diluted with propylene glycol monomethyl ether acetate (58.4 g) and propylene glycol monomethyl ether (11.7 g). The diluted solution was heated to 100°C under an air stream, and tetraethylammonium bromide (0.53 g, Fujifilm Wako Pure Chemical Industries, Ltd.) and p-methoxyphenol (0.26 g, Fujifilm Wako Pure Chemical Industries, Ltd.) were added to the solution. Glycidyl methacrylate (25.5 g, NOF Corporation, Blenmer GH) was added dropwise to the resulting solution over 20 minutes. The resulting solution was allowed to react at 100°C for 7 hours to obtain a solution of binder polymer P-1. The solids concentration of the resulting solution was 36.3% by mass. The obtained binder polymer had the structural units shown in Table 1, and had a weight average molecular weight (Mw) of 17,000 in terms of standard polystyrene measured by GPC, a polydispersity of 2.4, and an acid value of 94.5 mg KOH / g. The amount of residual monomer measured by gas chromatography was less than 0.1 mass% of the solid content of the binder polymer for each monomer. The solid content refers to the components excluding the solvent. Even if the above components are in a liquid state, they are included in the solid content.

[0458] <Synthesis of binder polymer P-2> Into a 2000 mL flask, 60 g of propylene glycol monomethyl ether acetate (manufactured by Sanwa Chemical Industry Co., Ltd., product name "PGM-AC"; hereinafter referred to as "PGM-AC") and 240 g of propylene glycol monomethyl ether (manufactured by Sanwa Chemical Industry Co., Ltd., product name PGM) were introduced. The resulting liquid was heated to 90°C while being stirred at a stirring speed of 250 rpm. To prepare the dropping liquid (1), 107.1 g of methacrylic acid (manufactured by Mitsubishi Rayon, trade name: Acryester M), 5.46 g of methyl methacrylate (manufactured by Mitsubishi Gas Chemical, trade name: MMA), and 231.42 g of cyclohexyl methacrylate (manufactured by Mitsubishi Gas Chemical, trade name: CHMA) were mixed and diluted with 60 g of PGM-AC, thereby obtaining the dropping liquid (1). The dropping liquid (2) was prepared by dissolving 9.637 g of dimethyl 2,2'-azobis(2-methylpropionate) (manufactured by Wako Pure Chemical Industries, Ltd., trade name V-601) in 136.56 g of PGM-AC. Dropping liquid (1) and dropping liquid (2) were simultaneously added dropwise over 3 hours to the above-mentioned 2000 mL flask (specifically, a 2000 mL flask containing a liquid heated to 90°C). Next, the container for dropping liquid (1) was washed with 12 g of PGM-AC, and the washing liquid was added dropwise to the above-mentioned 2000 mL flask. Next, the container for dropping liquid (2) was washed with 6 g of PGM-AC, and the washing liquid was added dropwise to the above-mentioned 2000 mL flask. During these additions, the reaction liquid in the above-mentioned 2000 mL flask was kept at 90°C and stirred at a stirring speed of 250 rpm. Furthermore, as a post-reaction, stirring was carried out at 90°C for 1 hour. To the reaction solution after the post-reaction, 2.401 g of V-601 was added as the first additional initiator addition. Furthermore, the V-601 container was washed with 6 g of PGM-AC, and the washings were introduced into the reaction solution. Then, the mixture was stirred at 90 °C for 1 hour. Next, 2.401 g of V-601 was added to the reaction solution as the second additional initiator addition. The V-601 container was then washed with 6 g of PGM-AC, and the washings were added to the reaction solution. The mixture was then stirred at 90°C for 1 hour. Next, 2.401 g of V-601 was added to the reaction solution as the third additional initiator addition. Furthermore, the V-601 container was washed with 6 g of PGM-AC, and the washings were introduced into the reaction solution. Thereafter, the mixture was stirred at 90 °C for 3 hours.

[0459] After stirring at 90°C for 3 hours, 178.66 g of PGM-AC was added to the reaction solution. Next, 1.8 g of tetraethylammonium bromide (Wako Pure Chemical Industries, Ltd.) and 0.8 g of hydroquinone monomethyl ether (Wako Pure Chemical Industries, Ltd.) were added to the reaction solution. Furthermore, each vessel was washed with 6 g of PGM-AC, and the washings were introduced into the reaction solution. The temperature of the reaction solution was then raised to 100°C. Next, 76.03 g of glycidyl methacrylate (NOF Corporation, trade name: Blenmer G) was added dropwise to the reaction solution over 1 hour. The Blenmer G vessel was washed with 6 g of PGM-AC, and the washings were introduced into the reaction solution. After this, the mixture was stirred at 100°C for 6 hours as an addition reaction. The reaction mixture was then cooled and filtered through a 100 mesh filter to obtain 1,158 g of a binder polymer P-2 solution (solid content: 36.3% by mass). The binder polymer P-2 thus obtained had the structural units shown in Table 1, a weight-average molecular weight of 27,000, a number-average molecular weight of 15,000, and an acid value of 95 mgKOH / g.

[0460] Table 1 below shows the compositions of binder polymers P-1 and P-2. In Table 1, the structural units other than the structural unit having a (meth)acryloyl group are shown by the abbreviation of the monomer that forms each structural unit. Structural units having a (meth)acryloyl group are shown in the form of an addition structure between monomers. For example, MAA-GMA means a structural unit in which glycidyl methacrylate is added to a structural unit derived from methacrylic acid. St: styrene CHMA: Cyclohexyl methacrylate MAA-GMA: A structural unit in which glycidyl methacrylate is added to a structural unit derived from methacrylic acid MAA: methacrylic acid MMA: methyl methacrylate DCPMA: dicyclopentanyl methacrylate

[0461] [Table 1]

[0462] <Synthesis of Binder Polymer A-1> Propylene glycol monomethyl ether acetate (PGMEA, 116.5 parts) was placed in a three-neck flask and heated to 90°C under a nitrogen atmosphere. Next, a solution containing styrene ("St", 52.0 parts), methyl methacrylate ("MMA", 19.0 parts), methacrylic acid ("MAA", 29.0 parts), dimethyl 2,2'-azobis(2-methylpropionate) (manufactured by Wako Pure Chemical Industries, Ltd., trade name "V-601", 4.0 parts), and PGMEA (116.5 parts) was added dropwise over 2 hours to a three-necked flask solution maintained at 90 ° C. ± 2 ° C. After the addition was completed, the mixture was stirred at 90 ° C. ± 2 ° C. for 2 hours to obtain a solution containing binder polymer A-1 (solids concentration 30.0%).

[0463] <Synthesis of Binder Polymer A-2> The types of monomers and the like were changed as shown in Table 2 below, and other conditions were the same as for binder polymer A-1, to obtain a solution containing binder polymer A-2 (solid concentration 30.0%).

[0464] Table 2 below shows the compositions of binder polymers A-1 and A-2. In Table 2, the abbreviations of the monomers that form each structural unit of the binder polymer are shown. St: styrene BzMA: benzyl methacrylate MAA: methacrylic acid AA: acrylic acid MMA: methyl methacrylate

[0465] [Table 2]

[0466] <<Crosslinkable compound>> <Blocked isocyanate compound Q-1 (compound Q-1)> Butanone oxime (453 g, manufactured by Idemitsu Kosan Co., Ltd.) was dissolved in methyl ethyl ketone (700 g) under a nitrogen stream to obtain a solution. 1,3-bis(isocyanatomethyl)cyclohexane (500 g, cis-trans isomer mixture, manufactured by Mitsui Chemicals, Takenate 600) was added dropwise to the obtained solution over 1 hour under ice cooling, and the solution was further reacted for 1 hour after the dropwise addition. The obtained solution was then heated to 40°C and further reacted for 1 hour. 1 Completion of the reaction was confirmed by H-NMR and HPLC, yielding a methyl ethyl ketone solution of blocked isocyanate compound Q-1 represented by the following structural formula.

[0467] [ka]

[0468] <<Photoacid generator>> <Synthesis of Photoacid Generator C-1> The compound having the structure shown below was synthesized according to the method described in paragraph 0227 of JP-A-2013-047765.

[0469] [ka]

[0470] [Components of refractive index adjusting layer] <<Synthesis of binder polymer P'-1>> Propylene glycol monomethyl ether (270.0 g) was added to a three-neck flask and heated to 70 °C under a nitrogen stream while stirring. Allyl methacrylate (45.6 g, Fujifilm Wako Pure Chemical Industries, Ltd.) and methacrylic acid (14.4 g) were dissolved in propylene glycol monomethyl ether (270.0 g), and V-65 (3.94 g, Fujifilm Wako Pure Chemical Industries, Ltd.) was then dissolved to prepare a dropwise solution. The resulting dropwise solution was added dropwise to the three-neck flask over 2.5 hours. The resulting solution was allowed to react for 2 hours while stirring. After allowing the resulting solution to cool to room temperature, the resulting solution was added dropwise to ion-exchanged water (2.7 L) while stirring, resulting in reprecipitation and obtaining a suspension. The suspension was filtered using a funnel lined with filter paper, and the filtrate was further washed with ion-exchanged water to obtain a wet binder polymer P'-1 powder. Next, the mixture was subjected to air drying at 45° C., and it was confirmed that the weight had reached a constant value, whereby binder polymer P′-1 was obtained as a powder in a yield of 70%. The structural formula of binder polymer P'-1 is shown below: In the structural formula below, the proportion of each structural unit is expressed in mass %.

[0471] [ka]

[0472] [Preparation of various compositions] Preparation of Photosensitive Composition and Thermoplastic Composition Photosensitive compositions (compositions X-1 to X-10) and a thermoplastic composition (composition X-11) were prepared according to the formulations shown in Table 3. In Table 3, the numerical values ​​for each component other than the alkali-soluble resin represent the blend amount (parts by mass) of each component itself, and the numerical value for the alkali-soluble resin represents the blend amount (parts by mass) of the binder polymer solution containing the alkali-soluble resin. In addition, in Table 3 (and Table 6 described below), "content of bifunctional and trifunctional photopolymerizable compounds (mass %)" represents the total content (mass %) of bifunctional photopolymerizable compounds and trifunctional photopolymerizable compounds relative to the total mass of the photopolymerizable compounds.

[0473] [Table 3]

[0474] Specific structures of the photopolymerizable compounds shown in Table 3 are shown below. Monomer having a carboxy group (Aronix TO-2349 (manufactured by Toagosei Co., Ltd.): a mixture of dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, and a succinic acid derivative of dipentaerythritol pentaacrylate) 8UX-015A (manufactured by Taisei Fine Chemical Co., Ltd.): 15-functional urethane acrylate A-DPH (Shin-Nakamura Chemical Co., Ltd.): Penta- to hexa-functional dipentaerythritol polyacrylate

[0475] A-NOD-N (Shin-Nakamura Chemical Co., Ltd.): 1,9-nonanediol diacrylate NK Ester BPE-500 (Shin-Nakamura Chemical Co., Ltd.): 2,2-bis(4-(methacryloxypentaethoxy)phenyl)propane Aronix M-270 (manufactured by Toagosei Co., Ltd.): Polypropylene glycol diacrylate (n≒12) KAYARAD R-604 (Nippon Kayaku Co., Ltd.): bis(2,2-dimethylethylene)(5-ethyl-1,3-dioxane-2,5-diyl)methylene bisacrylate

[0476] In addition, the specific structures of the photopolymerization initiators shown in Table 3 are shown below.

[0477] [ka] JPEG0007742236000040.jpg5383

[0478] In Table 3, the binder polymers P-1, P-2, A-1, A-2, compound Q-1, and photoacid generator C-1 are those synthesized in the above synthesis examples. The binder polymers P-1, P-2, A-1, and A-2 correspond to alkali-soluble resins. The definition of alkali-solubility is as described above. In addition, CBT-1 in Table 3 corresponds to carboxybenzotriazoles. In addition, XIRAN EF-40 in Table 3 corresponds to a styrene-maleic anhydride copolymer.

[0479] [Preparation of Refractive Index Adjusting Layer Forming Composition] A composition for forming a refractive index-adjusting layer (composition Y-1) was prepared having the composition shown in Table 4. The amount of each component is expressed in parts by mass. In Table 4, the binder polymer P'-1 used was the one synthesized in the above synthesis example.

[0480] [Table 4]

[0481] [Preparation of Water-Soluble Resin Composition] A water-soluble resin composition (composition Z-1) was prepared having the composition shown in Table 5. The amount of each component is expressed in parts by mass.

[0482] [Table 5]

[0483] Example 1 A 16 μm thick PET film (Toray Industries, Inc., Lumirror 16KS40) was used as a temporary support, and a slit nozzle was used to apply a coating amount of photosensitive composition X-1 that would result in a dried thickness of 8.5 μm. The solvent was then evaporated in a drying zone at 100 ° C. to form a photosensitive layer. Furthermore, a slit nozzle was used to apply a coating amount of refractive index adjusting layer-forming composition Y-1 that would result in a dried thickness of 70 nm on the photosensitive layer, and the coating was dried at a drying temperature of 80 ° C. to form a refractive index adjusting layer. A 16 μm thick PET film (Toray Industries, Inc., Lumirror 16KS40) was then pressure-bonded onto the refractive index adjusting layer as a protective film, and the film was then wound into a roll to produce transfer film 1 of Example 1.

[0484] [Examples 2 to 7 and Comparative Examples 1 and 2] Transfer films 2 to 7 and 9 to 10 of Examples 2 to 7 and Comparative Examples 1 to 2 were produced in the same manner as in Example 1, except that the components, compositions, thicknesses, etc. were changed according to Table 6.

[0485] Example 8 Thermoplastic composition X-11 was applied to a 16 μm thick PET film (Lumirror 16KS40, manufactured by Toray Industries, Inc.) as a temporary support using a slit nozzle so that the thickness after drying would be 4 μm, and the film was passed through a drying zone at 80°C for 40 seconds to form a thermoplastic resin layer. Thereafter, the water-soluble resin composition Z-1 was applied onto the thermoplastic resin layer using a slit nozzle so that the thickness after drying would be 1.1 μm, and the applied layer was passed through a drying zone at 80°C for 40 seconds to form a water-soluble resin layer (intermediate layer). Furthermore, photosensitive composition X-8 was applied onto the water-soluble resin layer (intermediate layer) using a slit nozzle so that the thickness after drying would be 3.0 μm, and the coating was passed through a drying zone at 80°C for 40 seconds to form a photosensitive layer. Next, a PET film (Lumirror 16KS40, manufactured by Toray Industries, Inc.) was pressure-bonded onto the photosensitive layer as a protective film, and then the resulting film was taken up in a roll to prepare Transfer Film 8 of Example 8.

[0486] [evaluation] The prepared transfer films 1 to 10 were evaluated as follows.

[0487] [Evaluation of pencil hardness] After unwinding each of the prepared transfer films 1 to 10, the protective film was peeled off and laminated onto a 0.7 mm thick glass plate under lamination conditions of a roll temperature of 100°C, a linear pressure of 1.0 MPa, and a linear speed of 4.0 m / min. The glass plate laminated with the resulting transfer film was exposed to UV light using an ultra-high pressure mercury lamp at the dose listed in Table 6. The temporary support was then peeled off and the glass plate was sprayed with a 1.0% aqueous sodium carbonate solution at 25°C using a shower for 30 seconds. The glass plate was then washed with pure water.

[0488] The cured photosensitive layer (cured film) of the sample obtained by the above procedure was subjected to a pencil scratch test in accordance with JIS K5600, and evaluated according to the following evaluation criteria: The pencil hardness was 3H, 2H, H, F, HB, and B, in descending order of hardness. "A": Pencil hardness of the cured film is 2H or more (hardness of the cured film is very high) "B": Pencil hardness of the cured film is H to HB (hardness of the cured film is slightly high) "C": Pencil hardness of the cured film is B or less (hardness of the cured film is low) The evaluation results are shown in Table 6.

[0489] [Evaluation of Adhesion] After unwinding each of the prepared transfer films 1 to 10, the protective film was peeled off and laminated onto the ITO surface of a commercially available ITO substrate (Merck, 749737-5EA) under lamination conditions of a roll temperature of 100°C, a linear pressure of 1.0 MPa, and a linear speed of 4.0 m / min. The ITO film laminated with the resulting transfer film was exposed to UV light using an ultra-high pressure mercury lamp at the dose listed in Table 6. The temporary support was then peeled off and the film was sprayed with a 1.0% aqueous sodium carbonate solution at 25°C using a shower for 30 seconds. The film was then washed with pure water.

[0490] The cured photosensitive layer (cured film) of the sample obtained by the above procedure was subjected to a cross-cut peeling tape test in accordance with ASTM D 3359. Evaluation was based on the percentage of squares that did not peel from the ITO film, and was evaluated based on the following criteria. The adhesion performance in the peeling tape test was ranked in descending order of adhesion performance as 5B, 4B, 3B, 2B, 1B, and 0B. "A": The adhesive strength of the cured film is 4B or higher (the adhesiveness of the cured film is very high) "B": The pencil hardness of the cured film is 3B (the adhesion of the cured film is somewhat high) "C": The adhesive strength of the cured film is 2B or less (poor adhesiveness of the cured film) The evaluation results are shown in Table 6.

[0491] [Table 6]

[0492] The results in Table 6 clearly show that the transfer films of the examples have excellent adhesion of the cured film formed after transferring the photosensitive layer to the substrate, and also have excellent hardness on the surface of the cured film opposite to the substrate. Comparing Examples 1 to 8, it was confirmed that when the photopolymerizable compound contained in the photosensitive layer includes at least one of a bifunctional photopolymerizable compound and a trifunctional photopolymerizable compound, and the total content of the bifunctional photopolymerizable compound and the trifunctional photopolymerizable compound is 45 mass% or more relative to the total mass of the photopolymerizable compound, the adhesion of the cured film formed after transferring the photosensitive layer to the substrate is superior, and the hardness of the surface of the cured film opposite to the substrate is superior.

[0493] On the other hand, the transfer film of the comparative example could not achieve both of the desired performances.

[0494] Example 9 A transfer film (transfer film 11) was produced in the same manner as in Example 1, except that the refractive index adjusting layer was not formed, and the same evaluation was carried out. The transfer film of Example 9 showed the same results as the transfer film of Example 1.

[0495] Examples 10 to 15 In Examples 2 to 7, transfer films (transfer films 12 to 17) were prepared and evaluated in the same manner as in Examples 2 to 7, except that no refractive index adjusting layer was formed. The transfer films of Examples 10 to 15 gave the same results as the transfer films of Examples 2 to 7, respectively.

[0496] Examples 16 to 22 Using each of the transfer films of Examples 1 to 7, liquid crystal display devices equipped with touch panels of Examples 16 to 22 were fabricated as follows, and the display characteristics and operation were confirmed.

[0497] <Preparation of laminate> A substrate was prepared having an ITO transparent electrode pattern and copper wiring in this order on a cycloolefin transparent film. The transfer films of Examples 1 to 7 from which the protective films had been peeled were laminated to the substrate so that the photosensitive layer covered the ITO transparent electrode pattern and the copper wiring on the substrate. The lamination was performed using a vacuum laminator manufactured by MCK Corporation under the following conditions: cycloolefin transparent film temperature: 40°C, rubber roller temperature: 100°C, linear pressure: 3 N / cm, and conveying speed: 2 m / min. Thereafter, a proximity exposure machine (manufactured by Hitachi High-Tech Electronics Engineering Co., Ltd.) equipped with an ultra-high pressure mercury lamp was used to bring the exposure mask (a quartz exposure mask having a pattern for forming an overcoat) into close contact with the temporary support, and an exposure dose of 100 mJ / cm 2 was applied through the temporary support. 2 The pattern was exposed to light (measured with i-line). After peeling off the temporary support, development was carried out using a 1.0% by mass aqueous solution of sodium carbonate at 25° C. for 45 seconds. After that, the developed transparent film substrate was sprayed with ultrapure water from an ultrahigh-pressure cleaning nozzle to remove residues, and then air was blown to remove moisture, followed by post-baking at 145°C for 30 minutes to form a transparent laminate having an ITO transparent electrode pattern, copper wiring, a refractive index adjustment layer, and a cured film pattern on the cycloolefin transparent film in this order. A touch panel was manufactured by a known method using the produced transparent laminate, and the manufactured touch panel was attached to a liquid crystal display element manufactured by the method described in paragraphs 0097 to 0119 of JP 2009-047936 A, to manufacture a liquid crystal display device equipped with a touch panel.

[0498] It was confirmed that the LCD device equipped with a touch panel had no problems with display characteristics or operation.

[0499] Examples 23 to 29 Liquid crystal display devices equipped with touch panels of Examples 23 to 29 were produced in the same manner as in Examples 16 to 22, except that the transfer films of Examples 9 to 15 were used. It was confirmed that the LCD device equipped with a touch panel had no problems with display characteristics or operation.

[0500] Example 30 <Preparation of laminate> A copper layer with a thickness of 200 nm was formed on a polyethylene terephthalate (PET) film with a thickness of 100 μm by sputtering to prepare a PET substrate with a copper layer.

[0501] The transfer film of Example 8 from which the protective film had been peeled off was laminated onto the above-mentioned copper layered PET substrate under lamination conditions of a linear pressure of 0.6 MPa and a linear speed (laminating speed) of 3.6 m / min. Thereafter, a mask having a line-and-space pattern (duty ratio 1:1) with a line width of 3 to 20 μm is brought into contact with the temporary support while adjusting the exposure position (alignment), and an exposure dose of 100 mJ / cm 2 is applied to the temporary support with an ultra-high pressure mercury lamp through the mask. 2The resist was exposed to light with an i-ray (measured with i-rays). After leaving the resist to stand for 30 minutes after exposure, it was developed to form a resin pattern. Development was carried out using a 1.0% by mass aqueous solution of sodium carbonate at 28°C by shower development for 40 seconds.

[0502] The patterned sample was etched with a copper etching solution (Cu-02, manufactured by Kanto Chemical Co., Inc.) at 23° C. for 30 seconds, and the resist was removed using a 4 mass % sodium hydroxide solution to produce a copper pattern. When observed under a microscope, there was no peeling or chipping, and the pattern was clean. [Explanation of symbols]

[0503] 1, 11 Temporary support 2, 12 composition layer 3, 17 Photosensitive layer 5 Refractive index adjustment layer 13 Thermoplastic resin layer 15 Middle Class 7, 19 Protective film 10, 20 Transfer film

Claims

1. A transfer film having a temporary support and a photosensitive layer, the photosensitive layer contains an alkali-soluble resin, a photopolymerizable compound, and a photopolymerization initiator; The photopolymerization initiator contains a compound represented by the following general formula (a-1): the photopolymerizable compound includes at least one of a bifunctional photopolymerizable compound and a trifunctional photopolymerizable compound, the total content of the bifunctional photopolymerizable compound and the trifunctional photopolymerizable compound is 45% by mass or more based on the total mass of the photopolymerizable compounds; the content of the alkali-soluble resin is 20 to 80% by mass based on the total mass of the photosensitive layer; The compound represented by the general formula (a-1) comprises at least one compound selected from the group consisting of a compound represented by the following general formula (b-1) and a compound represented by the following general formula (b-2): 【Chemical 1】 In the formula, R ａ１ , R ａ２ , R ｂ１ , and R ｂ２ R each independently represents a hydrocarbon group having 1 to 6 carbon atoms. ｃ and R ｄ Each of R independently represents a linear or branched hydrocarbon group having 1 to 6 carbon atoms, or a cyclic hydrocarbon group. Each of l and m independently represents an integer of 0 to 4. n represents 0 or 1, provided that m+n represents an integer of 1 or more. ａ１ and R ｃ may be bonded to form a ring structure. ａ２ and R ｄ may be bonded to form a ring structure. 【Chemistry 2】 【change】

2. A lamination process in which the surface of the transfer film described in claim 1 opposite to the temporary support is brought into contact with a substrate having a conductive layer and laminated to obtain a substrate with a photosensitive layer having the substrate, the conductive layer, the photosensitive layer, and the temporary support in this order; an exposure step of pattern-exposing the photosensitive layer; a developing step of developing the exposed photosensitive layer to form a protective film pattern that protects the conductive layer; The method for producing a laminate further comprises a peeling step of peeling the temporary support from the substrate with the photosensitive layer between the laminating step and the exposing step, or between the exposing step and the developing step.

3. A lamination process in which the surface of the transfer film described in claim 1 opposite to the temporary support is brought into contact with a substrate having a conductive layer to obtain a substrate with a photosensitive layer having the substrate, the conductive layer, the photosensitive layer, and the temporary support in this order; an exposure step of pattern-exposing the photosensitive layer; a developing step of developing the exposed photosensitive layer to form a resin pattern; an etching step of etching the conductive layer in an area where the resin pattern is not disposed; The method for producing a laminate having a conductive pattern further comprises a peeling step of peeling the temporary support from the substrate with the photosensitive layer between the laminating step and the exposure step, or between the exposure step and the development step.

4. A method for manufacturing a laminate using a transfer film, The transfer film is A transfer film having a temporary support and a photosensitive layer, the photosensitive layer contains an alkali-soluble resin, a photopolymerizable compound, and a photopolymerization initiator; The photopolymerization initiator contains a compound represented by the following general formula (a-1): the photopolymerizable compound includes at least one of a bifunctional photopolymerizable compound and a trifunctional photopolymerizable compound, the total content of the bifunctional photopolymerizable compound and the trifunctional photopolymerizable compound is 45% by mass or more based on the total mass of the photopolymerizable compounds; the content of the alkali-soluble resin is 20 to 80% by mass based on the total mass of the photosensitive layer; a lamination step of contacting and laminating a surface of the transfer film opposite to the temporary support to a substrate having a conductive layer, thereby obtaining a substrate with a photosensitive layer having the substrate, the conductive layer, the photosensitive layer, and the temporary support in this order; an exposure step of pattern-exposing the photosensitive layer; a developing step of developing the exposed photosensitive layer to form a protective film pattern that protects the conductive layer; The method for producing a laminate further comprises a peeling step of peeling the temporary support from the photosensitive layer-formed substrate between the laminating step and the exposing step, or between the exposing step and the developing step. 【Chemistry 3】 In the formula, R a1 , R a2 , R b1 , and R b2 each independently represent a hydrocarbon group having 1 to 6 carbon atoms. R c and R d each independently represent a linear or branched hydrocarbon group or a cyclic hydrocarbon group having 1 to 6 carbon atoms. 1 and m each independently represent an integer of 0 to 4. n represents 0 or 1. However, m+n represents an integer of 1 or more. R a1 and R c may be bonded to form a ring structure. Furthermore, R a2 and R d may be bonded to form a ring structure.

5. The method for producing a laminate according to claim 4, wherein the compound represented by general formula (a-1) has an oxime ester value of 2.0×10 −3 to 7.0×10 −3 mol / g.

6. A method for producing a laminate described in claim 4 or 5, wherein in the general formula (a-1), m+n represents 1 and l represents 0 or 1.

7. A method for manufacturing a laminate having a conductor pattern using a transfer film, The transfer film is A transfer film having a temporary support and a photosensitive layer, the photosensitive layer contains an alkali-soluble resin, a photopolymerizable compound, and a photopolymerization initiator; The photopolymerization initiator contains a compound represented by the following general formula (a-1): the photopolymerizable compound includes at least one of a bifunctional photopolymerizable compound and a trifunctional photopolymerizable compound, the total content of the bifunctional photopolymerizable compound and the trifunctional photopolymerizable compound is 45% by mass or more based on the total mass of the photopolymerizable compounds; the content of the alkali-soluble resin is 20 to 80% by mass based on the total mass of the photosensitive layer; a lamination step of bringing a surface of the transfer film opposite to the temporary support into contact with a substrate having a conductive layer to obtain a substrate with a photosensitive layer having the substrate, the conductive layer, the photosensitive layer, and the temporary support in this order; an exposure step of pattern-exposing the photosensitive layer; a developing step of developing the exposed photosensitive layer to form a resin pattern; an etching step of etching the conductive layer in an area where the resin pattern is not disposed; The method for producing a laminate having a conductive pattern further comprises a peeling step of peeling the temporary support from the substrate with the photosensitive layer between the laminating step and the exposure step, or between the exposure step and the development step. 【Chemistry 4】 In the formula, R a1 , R a2 , R b1 , and R b2 each independently represent a hydrocarbon group having 1 to 6 carbon atoms. R c and R d each independently represent a linear or branched hydrocarbon group or a cyclic hydrocarbon group having 1 to 6 carbon atoms. 1 and m each independently represent an integer of 0 to 4. n represents 0 or 1. However, m+n represents an integer of 1 or more. R a1 and R c may be bonded to form a ring structure. Furthermore, R a2 and R d may be bonded to form a ring structure.

8. The method for producing a laminate having a conductive pattern according to claim 7, wherein the compound represented by general formula (a-1) has an oxime ester value of 2.0×10 −3 to 7.0×10 −3 mol / g.

9. A method for manufacturing a laminate having a conductive pattern described in claim 7 or 8, wherein in the general formula (a-1), m+n represents 1 and l represents 0 or 1.

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