Transfer film and method for manufacturing laminate having conductor pattern

Abstract

The first problem addressed by the present invention is to provide a transfer film that has excellent long-term stability. The second problem addressed by the present invention is to provide a method for manufacturing a laminate having a conductor pattern related to the transfer film. A transfer film according to the present invention has a provisional support, a thermoplastic resin layer, and a photosensitive composition layer. The thermoplastic resin layer contains an alkali-soluble thermoplastic resin, a plasticizer, and a nitrone compound, the unsaturated double bond value of the thermoplastic resin layer is 2.50 mmol / g or less, and the acid value of the thermoplastic resin layer is 20.0-100.0 mgKOH / g.

Description

Transfer film, method for manufacturing a laminate having a conductive pattern

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

[0002] In display devices equipped with touch panels, such as capacitive input devices (organic electroluminescent (EL) display devices and liquid crystal display devices, etc.), conductive patterns such as electrode patterns corresponding to the sensor in the viewing area, peripheral wiring sections, and output wiring sections are provided inside the touch panel. In printed circuit board wiring, wiring patterns are also formed by etching and plating processes. To form the above conductive patterns, a method is used in which a patterned layer is formed on a conductive layer, and then the conductive layer is subjected to etching and plating. For the formation of such patterned layers, a method is widely used in which a photosensitive composition layer is placed on an arbitrary substrate using a transfer film, and then the photosensitive composition layer is pattern-exposed and developed, because it requires fewer steps to obtain the required pattern shape.

[0003] For example, Patent Document 1 discloses a photosensitive transfer material (transfer film) comprising a temporary support, a thermoplastic resin layer, a water-soluble resin layer (intermediate layer), and a photosensitive resin layer in that order. Furthermore, Patent Document 1 discloses a method for manufacturing a resin pattern, comprising the steps of laminating the transfer film and a substrate to be transferred to such that the photosensitive composition layer side is in contact with the substrate, pattern exposing the photosensitive composition layer from the side opposite to the substrate, and developing the photosensitive composition layer after exposure to form a resin pattern.

[0004] WO2022 / 163301 publication

[0005] Recently, there has been a constant demand for further improvement in the resolution of patterns formed from transfer films. The present inventors, aiming to further improve the resolution of patterns formed from transfer films by having the thermoplastic resin layer of the transfer film described in Patent Document 1 function as a contrast enhancement layer (CEL), prepared a transfer film in which a nitrone compound was introduced as a photodecolorizing compound into the thermoplastic resin layer and investigated its performance. They found that the resolution of patterns formed from the transfer film after long-term storage was sometimes inferior to the resolution of patterns formed from the transfer film immediately after preparation. In other words, they found that it is necessary to improve the time-dependent stability of the transfer film.

[0006] Therefore, the object of the present invention is to provide a transfer film with excellent stability over time. Another object of the present invention is to provide a method for manufacturing a laminate having a conductive pattern related to the above-mentioned transfer film.

[0007] As a result of diligent research to solve the above problems, the inventors have found that the problems can be solved by the following configuration.

[0008] [1] A transfer film having a temporary support, a thermoplastic resin layer, and a photosensitive composition layer, wherein the thermoplastic resin layer contains an alkali-soluble thermoplastic resin, a plasticizer, and a nitrone compound, the unsaturated double bond value of the thermoplastic resin layer is 2.50 mmol / g or less, and the acid value of the thermoplastic resin layer is 20.0 to 100.0 mg KOH / g. [2] The transfer film according to [1], wherein the content of the plasticizer is 10.0 to 60.0% by mass relative to the total mass of the thermoplastic resin layer. [3] The transfer film according to [1] or [2], wherein the thickness of the thermoplastic resin layer is 3 to 15 μm. [4] The transfer film according to any one of [1] to [3], further comprising an intermediate layer between the photosensitive composition layer and the thermoplastic resin layer. [5] The transfer film according to [4], wherein the intermediate layer contains a photodecolorizing compound. [6] A transfer film according to any one of [1] to [5] that satisfies at least one of the following requirements A and requirement B. Requirement A: The unsaturated double bond value of the thermoplastic resin layer is 2.30 mmol / g or less. Requirement B: The acid value of the thermoplastic resin layer is 20.0 to 95.0 mg KOH / g. [7] A transfer film according to any one of [1] to [6], wherein the unsaturated double bond value of the thermoplastic resin layer is 1.00 mmol / g or less. [8] A method for manufacturing a laminate having a conductive pattern, comprising: a bonding step of bonding a transfer film according to any one of [1] to [7] such that the photosensitive composition layer side is in contact with the metal layer of a substrate having a metal layer on its surface; an exposure step of pattern-exposing the photosensitive composition layer from the side opposite to the substrate side; a developing step of developing the exposed photosensitive composition layer using an alkaline developer to form a resist pattern; an etching step of etching the metal layer in an area where the resist pattern is not arranged to form a conductive pattern, and a plating step of plating the metal layer; a resist peeling step of peeling off the resist pattern; and, if the plating step is included, a removal step of removing the metal layer exposed by the resist peeling step to form a conductive pattern on the substrate.[9] A method for manufacturing a laminate having a conductive pattern as described in [8], comprising the step of peeling off the temporary support before the exposure step.

[0009] According to the present invention, a transfer film with excellent stability over time can be provided. Furthermore, according to the present invention, a method for manufacturing a laminate having a conductive pattern related to the above-mentioned transfer film can be provided.

[0010] This is a schematic diagram showing an example of the configuration of the transfer film of the present invention.

[0011] The present invention will be described in detail below. The following descriptions of constituent elements may be based on typical embodiments of the present invention, but the present invention is not limited to such embodiments.

[0012] In this specification, a numerical range expressed using "~" means a range that includes the numbers written before and after "~" as the lower and upper limits. Also in this specification, if there are two or more types of a component, the "content" of that component means the total content of those two or more types of components. In this specification, in numerical ranges described in steps, the upper or lower limit stated in one numerical range may be replaced with the upper or lower limit of another numerical range described in steps. Also, in numerical ranges described in this specification, the upper or lower limit stated in one numerical range may be replaced with the value shown in the example. In this specification, a combination of two or more preferred embodiments is a more preferred embodiment.

[0013] In this specification, the term "process" includes not only independent processes but also processes that cannot be clearly distinguished from other processes, as long as their intended purpose is achieved.

[0014] In this specification, "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. The average transmittance of visible light is a value measured using a spectrophotometer, and can be measured using, for example, a Hitachi U-3310 spectrophotometer manufactured by Hitachi, Ltd.

[0015] In this specification, unless otherwise specified, the weight-average molecular weight (Mw) and number-average molecular weight (Mn) are values ​​converted using polystyrene as the standard substance, measured by a gel permeation chromatography (GPC) analyzer using TSKgel GMHxL, TSKgel G4000HxL, or TSKgel G2000HxL (all product names of Tosoh Corporation) as the column, THF (tetrahydrofuran) as the eluent, a differential refractometer as the detector, and polystyrene as the standard substance. In this specification, unless otherwise specified, the ratio of constituent units of a polymer is the mass ratio. In this specification, unless otherwise specified, the molecular weight of a compound with a molecular weight distribution is the weight-average molecular weight (Mw). In this specification, unless otherwise specified, the refractive index is the value measured using an ellipsometer at a wavelength of 550 nm. In this specification, unless otherwise specified, hue values ​​are those measured using a colorimeter (CR-221, manufactured by Minolta, Inc.).

[0016] In this specification, "(meth)acrylic" is a concept that encompasses both acrylic and methacrylic, "(meth)acryloyl" is a concept that encompasses both acryloyl and methacryloyl, and "(meth)acrylate" is a concept that encompasses both acrylate and methacrylate.

[0017] 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. In this specification, "water-soluble" means that the solubility in 100 g of water with a pH of 7.0 at a liquid temperature of 22°C is 0.1 g or more. For example, a water-soluble resin refers to a resin that satisfies the above solubility conditions.

[0018] In this specification, "solids" of a composition means the components that form the composition layer formed using the composition, and if the composition contains a solvent (organic solvent, water, etc.), it means all components excluding the solvent. Furthermore, any liquid components that form the composition layer are also considered to be solids.

[0019] In this specification, unless otherwise specified, when a group (atomic group) is not denoted as substituted or unsubstituted, it includes both substituted and unsubstituted groups. For example, "alkyl group" includes not only unsubstituted alkyl groups but also substituted alkyl groups. In this specification, when there are multiple substituents and linking groups, etc. (hereinafter referred to as substituents, etc.) indicated by a specific symbol, or when multiple substituents, etc. are specified simultaneously, it means that each substituent, etc. may be identical or different from the others. The same applies to the specification of the number of substituents, etc.

[0020] In this specification, with respect to compounds that may have stereoisomers, the general formula or structural formula representing the compound may, for convenience, be described in only one form. Even in such cases, unless otherwise specified, the form of the compound is not limited to either stereoisomer, and either stereoisomer may be used alone, or multiple stereoisomers may be used in combination.

[0021] The film thickness of each layer in the transfer film can be measured using a Zygo white light interferometer (NewView 7200).

[0022] [Transfer Film] The transfer film of the present invention is a transfer film having a temporary support, a thermoplastic resin layer, and a photosensitive composition layer, wherein the thermoplastic resin layer contains an alkali-soluble thermoplastic resin, a plasticizer, and a nitrone compound, the unsaturated double bond value of the thermoplastic resin layer is 2.50 mmol / g or less, and the acid value of the thermoplastic resin layer is 20.0 to 100.0 mgKOH / g.

[0023] The reason why a transfer film having the above configuration can solve the problems of the present invention is not necessarily clear, but the inventors speculate as follows. Note that the following speculation does not limit the mechanism by which the effect is obtained. In other words, even if the effect is obtained by a mechanism other than those described below, it is still within the scope of the present invention. The inventors have now investigated a transfer film comprising a thermoplastic resin layer containing a nitrone compound and have found that under long-term storage conditions, a 1,3-dipole cycloaddition reaction occurs between the nitrone compound and unsaturated double bond group-containing components that may be contained in the thermoplastic resin layer (for example, plasticizers having unsaturated double bond groups), and as a result, the photodecolorization function of the nitrone compound may be impaired. Furthermore, the inventors have clarified that if the thermoplastic resin layer contains a large amount of acid group-containing components (for example, alkali-soluble thermoplastic resins such as carboxyl group-containing polymers, and plasticizers having carboxyl groups), and the thermoplastic resin layer becomes too acidic, under long-term storage conditions, the nitrone compound may undergo a structural change due to hydrolysis, impairing its photodecolorization function. The transfer film of the present invention is based on the above findings and comprises a thermoplastic resin layer containing a nitrone compound, with the amount of unsaturated double bonds and the acid value of the thermoplastic resin layer being within a predetermined numerical range. Due to the above configuration, the degradation of the photodecolorization function of the nitrone compound over time is suppressed in the transfer film of the present invention, so that even when used after long-term storage, it can form a pattern with resolution comparable to that of a transfer film made immediately after production. In other words, the transfer film of the present invention has excellent stability over time.

[0024] Hereinafter, the ability to form a pattern with excellent resolution using the transfer film will simply be referred to as "excellent resolution." Furthermore, the superior temporal stability of the transfer film will be referred to as "the superior effects of the present invention."

[0025] Figure 1 is a schematic cross-sectional view showing an example of an embodiment of the transfer film of the present invention. The transfer film 10 shown in Figure 1 has a structure in which a temporary support 12, a thermoplastic resin layer 14, an intermediate layer 16, a photosensitive composition layer 18, and a protective film 20 are laminated in this order. Although the transfer film 10 shown in Figure 1 has a protective film 20, the protective film 20 may be omitted. Also, although the transfer film 10 shown in Figure 1 has an intermediate layer 16, the intermediate layer 16 may be omitted.

[0026] The following details each component that makes up the transfer film.

[0027] [Temporary Support] The temporary support is a component that supports the thermoplastic resin layer, the intermediate layer, and the photosensitive composition layer, and is ultimately removed by a peeling process. The temporary support may have either a single-layer structure or a multi-layer structure. A film that is flexible and does not undergo significant deformation, shrinkage, or elongation under pressure, or under pressure and heat, is also preferred as the temporary support. Examples of such films include polyethylene terephthalate (PET) film (e.g., biaxially oriented polyethylene terephthalate film), polymethyl methacrylate film, cellulose triacetate film, polystyrene film, polyimide film, and polycarbonate film, with polyethylene terephthalate film being preferred. Furthermore, it is preferable that the temporary support does not have deformations such as wrinkles or scratches.

[0028] Furthermore, examples of provisional supports include paragraphs

[0017] to

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

[0019] to

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

[0041] to

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

[0029] to

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

[0029] Examples of commercially available temporary supports include Lumirror 16FB40, Lumirror 16KS40, Lumirror #38-U48, Lumirror #75-U34, and Lumirror #25T60 (all manufactured by Toray Industries, Inc.); and Cosmoshine A4100, Cosmoshine A4160, Cosmoshine A4300, Cosmoshine A4360, and Cosmoshine A8300 (all manufactured by Toyobo Co., Ltd.).

[0030] [Thermoplastic Resin Layer] The transfer film has a thermoplastic resin layer. The thermoplastic resin layer contains an alkali-soluble thermoplastic resin, a plasticizer, and a nitrone compound. The components that the thermoplastic resin layer may contain are described in detail below.

[0031] <Alkali-soluble thermoplastic resins> Examples of alkali-soluble thermoplastic resins include (meth)acrylic resins, polystyrene resins, styrene-(meth)acrylic copolymers, polyurethane resins, polyvinyl alcohol, polyvinyl formal, polyamide resins, polyester resins, epoxy resins, polyacetal resins, polyhydroxystyrene resins, polyimide resins, polybenzoxazole resins, polysiloxane resins, polyethyleneimine, polyallylamine, and polyalkylene glycols.

[0032] The alkali-soluble thermoplastic resin is preferably a polymer containing constituent units derived from vinyl monomers, in terms of developability and adhesion to adjacent layers. Here, vinyl monomers typically refer to compounds having vinyl groups that can constitute polymer chains. Examples of vinyl monomers include (meth)acrylic monomers and styrene monomers. (Meth)acrylic monomers include (meth)acrylic acid, (meth)acrylic acid esters, and (meth)acrylamide. The content of constituent units derived from vinyl monomers in the alkali-soluble thermoplastic resin is preferably 30% by mass or more, more preferably 40% by mass or more, and even more preferably 50% by mass or more, based on the total mass of the thermoplastic resin. The upper limit is 100% by mass or less.

[0033] Among alkali-soluble thermoplastic resins, (meth)acrylic resin is preferred in terms of developability and adhesion to adjacent layers. Here, (meth)acrylic resin means a resin having at least one constituent unit selected from the group consisting of constituent units derived from (meth)acrylic acid, constituent units derived from (meth)acrylic acid ester, and constituent units derived from (meth)acrylamide. Preferably, the total content of constituent units derived from (meth)acrylic acid, (meth)acrylic acid ester, and (meth)acrylamide is 50% by mass or more of the total mass of the (meth)acrylic resin. In particular, the total content of constituent units derived from (meth)acrylic acid and (meth)acrylic acid ester is preferably 30 to 100% by mass, and more preferably 50 to 100% by mass, of the total mass of the (meth)acrylic resin.

[0034] As for (meth)acrylic acid esters, it is preferable that they have aromatic hydrocarbon groups because they tend to have excellent resolution. Examples of (meth)acrylic acid esters having aromatic hydrocarbon groups include (meth)acrylates having aralkyl groups. Examples of aralkyl groups include optionally substituted phenylalkyl groups, and optionally substituted benzyl groups. Specific examples of (meth)acrylates having aralkyl groups include benzyl (meth)acrylate, chlorobenzyl (meth)acrylate, and phenylethyl (meth)acrylate. The content of constituent units derived from the (meth)acrylic acid ester having aromatic hydrocarbon groups is preferably 25 to 85% by mass, more preferably 30 to 80% by mass, and even more preferably 50 to 80% by mass, relative to the total constituent units of the alkali-soluble thermoplastic resin. Another example of the content of constituent units derived from the (meth)acrylic acid ester having aromatic hydrocarbon groups is also preferably 25 to 70% by mass, more preferably 30 to 65% by mass, and even more preferably 40 to 60% by mass, relative to the total constituent units of the alkali-soluble thermoplastic resin.

[0035] Furthermore, alkali-soluble thermoplastic resins preferably have acidic groups. Examples of acidic groups include carboxyl groups, sulfol groups, phosphate groups, and phosphonic acid groups, with carboxyl groups being preferred. In particular, alkali-soluble thermoplastic resins preferably have acidic groups as repeating units having acidic groups.

[0036] From the viewpoint of developability, alkali-soluble thermoplastic resins are more preferably alkali-soluble thermoplastic resins with an acid value of 60 mg KOH / g or higher, and even more preferably carboxyl group-containing (meth)acrylic resins with an acid value of 60 mg KOH / g or higher. The lower limit of the above acid value is not particularly limited, but from the viewpoint of superior developability, 120 mg KOH / g or higher is more preferably, 150 mg KOH / g or higher is even more preferably, and 170 mg KOH / g or higher is particularly preferred. The upper limit of the acid value of the alkali-soluble thermoplastic resin is not particularly limited, but 320 mg KOH / g or less is preferred, 300 mg KOH / g or less is more preferably, 250 mg KOH / g or less is even more preferably, and 200 mg KOH / g or less is particularly preferred. The acid value (mg KOH / g) is the mass [mg] of potassium hydroxide required to neutralize 1 g of the sample. The acid value can be calculated, for example, from the average content of acid groups in the compound. The acid value of an alkali-soluble thermoplastic resin can be adjusted by the type of constituent units that make up the resin (for example, the content of constituent units containing acid groups).

[0037] The carboxyl group-containing (meth)acrylic resin with an acid value of 60 mg KOH / g or more is not particularly limited and can be appropriately selected from known resins. For example, examples include an alkali-soluble thermoplastic resin which is a carboxyl group-containing (meth)acrylic resin with an acid value of 60 mg KOH / g or more from the polymers described in paragraph 0025 of Japanese Patent Application Publication No. 2011-095716, a carboxyl group-containing (meth)acrylic resin with an acid value of 60 mg KOH / g or more from the polymers described in paragraphs 0033 to 0052 of Japanese Patent Application Publication No. 2010-237589, and a carboxyl group-containing (meth)acrylic resin with an acid value of 60 mg KOH / g or more from the binder polymers described in paragraphs 0053 to 0068 of Japanese Patent Application Publication No. 2016-224162. The copolymerization ratio of the carboxyl group-containing (meth)acrylic resin is preferably 5 to 70% by mass, more preferably 15 to 60% by mass, and even more preferably 20 to 55% by mass, based on the total mass of the (meth)acrylic resin. Another example of the copolymerization ratio of the carboxyl group-containing (meth)acrylic resin is also preferably 20 to 60% by mass, and more preferably 30 to 55% by mass, based on the total mass of the (meth)acrylic resin. As for the alkali-soluble thermoplastic resin, a (meth)acrylic resin having constituent units derived from (meth)acrylic acid is particularly preferred from the viewpoint of developability and adhesion to adjacent layers.

[0038] Alkali-soluble thermoplastic resins may have reactive groups. Reactive groups can be any groups capable of addition polymerization, including polycondensable groups such as unsaturated double bond groups (ethylenically unsaturated groups), hydroxyl groups, and carboxyl groups; and polyaddition reactive groups such as epoxy groups and (blocked) isocyanate groups.

[0039] The weight-average molecular weight (Mw) of the alkali-soluble thermoplastic resin is preferably 1,000 or more, more preferably over 2,000, even more preferably 10,000 to 100,000, and particularly preferably 20,000 to 50,000. The polydispersity of the alkali-soluble thermoplastic resin 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.

[0040] The alkali-soluble thermoplastic resin may be used alone or in combination of two or more types. The content of the alkali-soluble thermoplastic resin is preferably 20.0 to 80.0% by mass, more preferably 20.0 to 60.0% by mass, even more preferably 25.0 to 60.0% by mass, and particularly preferably 30.0 to 55.0% by mass, relative to the total mass of the thermoplastic resin layer, in terms of superior resolution. Another example of the alkali-soluble thermoplastic resin content is also preferably 35.0 to 60.0% by mass, and more preferably 35.0 to 55.0% by mass, relative to the total mass of the thermoplastic resin layer.

[0041] <Plasticizer> The thermoplastic resin layer of the present invention contains a plasticizer. The plasticizer preferably has a molecular weight (or weight-average molecular weight if it is an oligomer or polymer and has a molecular weight distribution) smaller than that of the alkali-soluble thermoplastic resin. The molecular weight (weight-average molecular weight) of the plasticizer is preferably 200 to 2,000. The plasticizer is preferably liquid at 25°C (1 atm). The plasticizer is preferably 10,000 mPa·s or less in viscosity at 25°C.

[0042] An example of a plasticizer is a plasticizer having polymerizable groups, which offers excellent compatibility with the photosensitive composition layer. The polymerizable groups of the plasticizer are preferably radical polymerizable groups, more preferably unsaturated double bond groups (ethylenically unsaturated groups), and even more preferably (meth)acryloyl groups. In particular, from the viewpoint of compatibility, adhesion to adjacent layers, and resolution, it is more preferable that the alkali-soluble thermoplastic resin is a (meth)acrylic resin and the plasticizer having polymerizable groups is a compound having (meth)acryloyl groups. The number of polymerizable groups in the plasticizer is one or more, may be two or more, and is preferably two or more. There is no particular upper limit, but it is often six or less, and is preferably four or less. From the viewpoint of plasticity, the plasticizer having polymerizable groups preferably has an alkylene oxide chain. The alkylene group in the alkylene oxide chain may be linear, branched, or cyclic, with linear or branched being preferred, and linear being more preferred. The number of carbon atoms in the alkylene group is preferably 1 to 6, and more preferably 2 or 3. The alkylene oxide chain may also be a polyalkylene oxide chain in which two or more alkylene oxides are linked together. In particular, the plasticizer having polymerizable groups is preferably having at least one structure selected from the group consisting of ethylene oxide chains and propylene oxide chains. Examples of plasticizers having two polymerizable groups include tricyclodecanedimethanol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, and 2,2-bis(4-methacryloxypolyethoxyphenyl)propane.More specifically, for example, tricyclodecanedimethanol diacrylate (A-DCP, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), tricyclodecanedimethanol dimethacrylate (DCP, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), 1,9-nonanediol diacrylate (A-NOD-N, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), 1,6-hexanediol diacrylate (A-HD-N Examples include 2,2-bis(4-(methacryloxypentaethoxy)phenyl)propane (BPE-500, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), 2,2-bis(4-(methacryloxypentadecaethoxy)phenyl)propane (BPE-1300, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), 2,2-bis(4-(methacryloxydiethoxy)phenyl)propane (BPE-200, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), ethoxylated (10)bisphenol A diacrylate (NK ester A-BPE-10, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), and ethoxylated bisphenol A dimethacrylate (BPE-100, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.).

[0043] Examples of plasticizers having three or more polymerizable groups 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 with a glycerin tri(meth)acrylate skeleton. 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.

[0044] Examples of plasticizers having polymerizable groups include caprolactone-modified (meth)acrylate compounds (such as KAYARAD® DPCA-20 from Nippon Kayaku Co., Ltd., and A-9300-1CL from Shin Nakamura Chemical Industry Co., Ltd.), alkylene oxide-modified (meth)acrylate compounds (such as KAYARAD RP-1040 from Nippon Kayaku Co., Ltd., ATM-35E and A-9300 from Shin Nakamura Chemical Industry Co., Ltd., and EBECRYL® 135 from Daicel Ornex Co., Ltd.), and ethoxylated glycerin triacrylate (such as A-GLY-9E from Shin Nakamura Chemical Industry Co., Ltd.).

[0045] Examples of plasticizers having polymerizable groups include urethane (meth)acrylates (preferably trifunctional or more functional urethane (meth)acrylates). Examples of urethane (meth)acrylate compounds include propylene oxide-modified urethane di(meth)acrylates and ethylene oxide and propylene oxide-modified urethane di(meth)acrylates. Examples of urethane (meth)acrylates include 8UX-015A (manufactured by Taisei Fine Chemical Co., Ltd.); UA-32P, U-15HA and UA-1100H (all manufactured by Shin Nakamura Chemical Industry Co., Ltd.); AH-600 (manufactured by Kyoeisha Chemical Co., Ltd.); UA-306H, UA-306T, UA-306I, UA-510H and UX-5000 (all manufactured by Nippon Kayaku Co., Ltd.).

[0046] Furthermore, it is preferable that the plasticizer having a polymerizable group also has an acidic group. Examples of acidic groups include carboxylic acid groups, which may be groups derived from acid anhydrides. Examples of plasticizers having an acidic group and a polymerizable group include Arronix® TO-2349 (manufactured by Toagosei Co., Ltd.), Arronix® M-520 (manufactured by Toagosei Co., Ltd.), and Arronix® M-510 (manufactured by Toagosei Co., Ltd.). As a plasticizer having an acidic group and a polymerizable group, for example, (meth)acrylate compounds having an acidic group described in paragraphs

[0025] to

[0030] of Japanese Patent Application Publication No. 2004-239942 can also be used.

[0047] Furthermore, plasticizers that do not have polymerizable groups can also be used. Specific examples of the above plasticizers include carboxylic acid group-containing acrylic polymers (oligomers), which tend to have excellent developability. Examples of carboxylic acid group-containing acrylic polymers include copolymers of poly(meth)acrylic acid esters such as n-butyl polyacrylate and 2-ethylhexyl polyacrylate with poly(meth)acrylic acid. An example of a carboxylic acid group-containing acrylic polymer (oligomer) is ARFON UC3510 (manufactured by Toagosei Co., Ltd.).

[0048] The plasticizer may be used alone or in combination of two or more types. The content of the polymerizable plasticizer is preferably 10.0 to 60.0% by mass, more preferably 15.0 to 45.0% by mass, and even more preferably 25.0 to 40.0% by mass, relative to the total mass of the thermoplastic resin layer, in terms of adhesion to adjacent layers, developability, and resolution. The content of the plasticizer is preferably 10.0 to 60.0% by mass, more preferably 15.0 to 45.0% by mass, and even more preferably 25.0 to 40.0% by mass, relative to the total mass of the thermoplastic resin layer, in terms of adhesion to adjacent layers, developability, and resolution. Furthermore, as another example of the content of the plasticizer having polymerizable groups, it is preferably 10.0 to 50.0% by mass, more preferably 15.0 to 36.0% by mass, and even more preferably 25.0 to 36.0% by mass, based on the total mass of the thermoplastic resin layer.

[0049] <Nitron Compounds> The thermoplastic resin layer contains nitron compounds. Nitron compounds contain nitron groups (>C=N ＋ (-O －)-R (wherein R represents a substituent)), which is a compound that exhibits reduced absorption at the exposure wavelength and increased transmittance after exposure (in other words, is decolorized by exposure) (a so-called photobleachable compound). In the nitrone compound, it is preferable that the substituent of the nitrogen atom constituting the nitrone group (the substituent represented by R above) is an aromatic ring group. The nitrone compound is preferably decolorized by exposure light used when exposing (pattern exposure) the photosensitive composition layer after transfer to a transfer target, specifically, it is preferably decolorized by light with a wavelength of 190 to 500 nm, more preferably decolorized by light with a wavelength of 365 nm or 405 nm, and still more preferably decolorized by light with a wavelength of 365 nm.

[0050] The molar extinction coefficient of the nitrone compound at a wavelength of 365 nm is 10,000 L·mol －１ ·cm －１ or more is preferable, and 13,000 L·mol －１ ·cm －１ or more is more preferable, and 15,000 L·mol －１ ·cm －１ or more is still more preferable. The upper limit of the above molar extinction coefficient is not particularly limited, but it is 20,000 L·mol －１ ·cm －１ or less in most cases. The molar extinction coefficient at the wavelength of 365 nm is a value before exposure (that is, before decolorization). The molar extinction coefficient at the wavelength of 365 nm can be measured using a spectrophotometer (for example, UV-3100 manufactured by Shimadzu Corporation). The difference in molar extinction coefficient at a wavelength of 365 nm before and after decolorization of the nitrone compound (value of (molar extinction coefficient at 365 nm before decolorization) - (molar extinction coefficient at 365 nm after decolorization)) is 8,000 L·mol －１ ·cm －１ or more is preferable, 10,000 L·mol －１ ·cm －１ or more is more preferable, 12,000 L·mol －１ ·cm －１ or more is still more preferable, and 15,000 L·mol －１ ·cm －１ or more is even more preferable. The upper limit is not particularly limited, and is 23,000 L·mol －１・cm －１ The following is a common case, specifically 20,000 L·mol －１ ・cm －１ The following is often the case.

[0051] The nitrone compound is preferably a compound represented by formula (1) (hereinafter also referred to as "compound (1)").

[0052]

[0053] In formula (1), Ar １ and Ar ２ Each of these independently represents an aromatic ring group which may have substituents.

[0054] The aromatic ring in the above aromatic ring group may be either a monoring structure or a fused ring structure (i.e., either a monoring aromatic ring group or a fused aromatic ring group). When the above aromatic ring group is a fused aromatic ring group, it is preferable that it is a fused aromatic ring group formed by the fusion of two or three monorings. A preferred embodiment of the above aromatic ring group is a five- or six-membered monoring aromatic ring group, or a fused aromatic ring group formed by the fusion of two or three five- or six-membered rings.

[0055] The above aromatic ring group may be either an aromatic hydrocarbon group or an aromatic heterocyclic group. Examples of the above aromatic hydrocarbon group include a benzene ring group and a naphthalene ring group. The above aromatic heterocyclic group preferably contains at least one heteroatom selected from nitrogen, oxygen, and sulfur atoms as a ring member atom. Examples of the above aromatic heterocyclic group include aromatic heterocycles with 4 to 20 ring member atoms, such as a thiophene ring group, pyrrole ring group, furan ring group, benzothiophene ring group, benzopyrrole ring group, benzofuran ring group, imidazole ring group, benzimidazole ring group, triazole ring group, thiadiazole ring group, thiazole ring group, pyridine ring group, and triazine ring group.

[0056] The above aromatic ring group may have substituents. The substituents that the above aromatic ring group may have are not particularly limited, but the substituents exemplified by the group of substituents W below are preferred.

[0057] (Substituent group W) Alkyl groups, alkoxy groups, aralkyl groups, acyl groups, acyloxy groups, alkoxycarbonyl groups, carbamoyl groups, carbamoyloxy groups, acylamino groups, alkoxycarbonylamino groups, alkylthio groups, acylthio groups, alkylsulfonyl groups, alkylsulfinyl groups, sulfamoyl groups, alkylsulfonylamino groups, (hetero)aryl groups, (hetero)aryloxy groups, (hetero)arylcarbonyl groups, (hetero)arylcarbonylamino groups, (hetero)aryloxycarbonyl groups, (hetero)aryloxycarbonylamino groups, (hetero)arylsulfonylamino groups, (hetero)arylsulfinyl groups, (hetero)arylsulfonyl groups, (hetero)arylamide groups, (hetero)arylthio groups, halogen atoms, hydroxyl groups, nitro groups, cyano groups, carboxylic acid groups, sulfonic acid groups, mercapto groups, and primary to tertiary amino groups, etc.

[0058] Furthermore, each of the above-mentioned groups may have further substituents (for example, one or more of the above-mentioned groups) if possible. For example, an alkyl group which may have substituents is also included as one form of substituent group W. Also, if a group exemplified as substituent group W has carbon atoms, the number of carbon atoms in the group is, for example, 1 to 20. Also, the number of atoms other than hydrogen atoms in a group exemplified as substituent group W is, for example, 1 to 30.

[0059] In the substituent group W, the number of carbon atoms in the alkyl group is preferably 1 to 20, more preferably 1 to 10, and even more preferably 1 to 6. The alkyl group may be linear, branched, or cyclic. When the alkyl group is a cyclic alkyl group (cycloalkyl group), the cycloalkyl group may be monocyclic or fused. An example of a fused cycloalkyl group is a bicycloalkyl group.

[0060] In the substituent group W, the alkyl portion of each group, such as the alkoxy group, acyl group, acyloxy group, alkoxycarbonyl group, acylamino group, alkoxycarbonylamino group, alkylthio group, acylthio group, alkylsulfonyl group, alkylsulfinyl group, and alkylsulfonylamino group, can be in the same form as the alkyl group (linear or branched) described above.

[0061] The above-mentioned aralkyl group refers to a group in which at least one hydrogen atom of an alkyl group is substituted with an aryl group. The number of carbon atoms in the alkyl group is preferably 1 to 20, more preferably 1 to 10, and even more preferably 1 to 6. The aryl group is preferably an aryl group having 6 to 10 carbon atoms, and more preferably a phenyl group. Specific examples of aralkyl groups include the benzyl group.

[0062] In substituent group W, (hetero)aryl refers to both aryl and heteroaryl groups. In substituent group W, the aromatic hydrocarbon ring constituting the aryl group may be either a monocycle or a fused ring (e.g., 2 to 6 rings). The number of ring member atoms of the aryl group is preferably 5 to 15, more preferably 6 to 10, and even more preferably 6. In substituent group W, the aryl group portion of each group, such as aryloxy group, arylcarbonyl group, arylcarbonylamino group, aryloxycarbonyl group, arylcarbonyloxy group, aryloxycarbonylamino group, arylsulfonylamino group, arylsulfinyl group, arylsulfonyl group, arylamide group, and arylthio group, can be the same as that of the aryl group described above.

[0063] In substituent group W, the aromatic heterocycle constituting the heteroaryl group may be either a monocycle or a fused ring (for example, 2 to 6 rings). The number of ring member atoms of the heteroaryl group is preferably 5 to 15, more preferably 5 or 6. In the heteroaryl group, the number of heteroatoms as ring member atoms is, for example, 1 to 10, preferably 1 to 3, more preferably 1 or 2. Examples of the heteroatoms include nitrogen atoms, sulfur atoms, and oxygen atoms. In substituent group W, the heteroaryl group portion of each group, such as heteroaryloxy group, heteroarylcarbonyl group, heteroarylcarbonylamino group, heteroaryloxycarbonyl group, heteroarylcarbonyloxy group, heteroaryloxycarbonylamino group, heteroarylsulfonylamino group, heteroarylsulfinyl group, heteroarylsulfonyl group, heteroarylamide group, and heteroarylthio group, can be the same as that of the heteroaryl group described above.

[0064] Examples of halogen atoms in the substituent group W include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms.

[0065] In the substituent group W, the amino group portion in the amino group and the carbamoyl group is an unsubstituted amino group (-NH ２ ) and substituted amino groups (-NHR Ｘ１ , or -NR Ｘ２ R Ｘ３ ) may be any of the following. R in the substituted amino group Ｘ１ ~R Ｘ３ represents a monovalent organic group. Among monovalent organic groups, alkyl groups are preferred. Linear or branched alkyl groups are preferred. The number of carbon atoms is preferably 1 to 10, and more preferably 1 to 6. Also, -NR Ｘ２ R Ｘ３ In R Ｘ２ and R Ｘ３ These may bond to each other to form a ring (for example, a five-membered or six-membered ring) which may have substituents (for example, alkyl groups). Ｘ２ and R Ｘ３It may contain one or more heteroatoms other than the nitrogen atom to which it is bonded (for example, a nitrogen atom and an oxygen atom).

[0066] In the substituent group W, the imino group portion of each group—acylamino group, alkoxycarbonylamino group, (hetero)arylcarbonylamino group, (hetero)aryloxycarbonylamino group, (hetero)arylsulfonylamino group, and (hetero)arylamide group—is either an unsubstituted imino group (-NH-) or a substituted imino group (-NR Ｘ４ -) Either of the following may be used. R in the substituted imino group Ｘ４ This represents a monovalent organic group. Among monovalent organic groups, alkyl groups are preferred. Linear or branched alkyl groups are preferred. The number of carbon atoms is preferably 1 to 10, and more preferably 1 to 6.

[0067] In formula (1), Ar １ and Ar ２ Preferably, at least one of these represents an aromatic heterocyclic group which may have substituents. The aromatic heterocyclic group which may have substituents is preferably a group represented by either formula (1-1) or formula (1-2), and is preferably a group represented by formula (1-1), in terms of superior effects of the present invention.

[0068]

[0069] In formula (1-1), X １ is an oxygen atom, a sulfur atom, or -NR Ａ１ Represents -. R Ａ１ R represents a hydrogen atom or substituent. Ａ１ The substituents represented by are not particularly limited, for example, the above Ar １ and Ar ２ Examples of substituents that the aromatic ring group represented by may have include the groups shown. Ａ１The substituent represented by is preferably an alkyl group, an alkoxy group, an aralkyl group, an alkoxycarbonyl group, or an acyloxy group, as these are more likely to exhibit the effects of the present invention. The number of carbon atoms in the alkyl group is preferably 1 to 10, and more preferably 1 to 6. The number of carbon atoms in the alkoxy group is preferably 1 to 10, and more preferably 1 to 6. The aralkyl group is intended to be a group in which at least one hydrogen atom of the alkyl group is substituted with an aryl group. The number of carbon atoms in the alkyl group is preferably 1 to 10, and more preferably 1 to 6. The aryl group is preferably an aryl group with 6 to 10 carbon atoms, and more preferably a phenyl group. Specific examples of aralkyl groups include benzyl groups. The number of carbon atoms in the alkoxycarbonyl group is preferably 2 to 10, and more preferably 2 to 6. The number of carbon atoms in the acyloxy group is preferably 2 to 10, and more preferably 2 to 6.

[0070] X １ The present invention offers superior effects, particularly with sulfur atoms or -NR Ａ１ - is preferred, and includes a sulfur atom, -NH-, -NMe-, -N(CH ２ Ph)-, -N(COMe)-, or -N(COOtBu)- are more preferred, and a sulfur atom, -NH-, or -NMe- are even more preferred. Hereinafter, Me represents a methyl group, Ph represents a phenyl group, and tBu represents a branched (tert) butyl group.

[0071] In formula (1-1), R １１ ~R １３ Each of these independently represents a hydrogen atom or a substituent. １１ ~R １３ The substituents represented by are not particularly limited, but examples include the substituents exemplified by the substituent group W described above. Hereinafter, R １１ ~R １３ The following are specific examples of substituents represented by . In the examples below, * indicates the bond position.

[0072]

[0073]

[0074]

[0075]

[0076]

[0077] In formula (1-1), R １１ ~R １３ Among them, adjacent elements (specifically, R １１ and R １２ , R １２ and R １３ These elements may bond to each other to form a ring which may have substituents. The ring may be either an aromatic ring or an alicyclic ring. The number of members in the ring is not particularly limited, but for example, it is 5 to 10, and 6 is preferred. The ring may also have substituents. The substituents are not particularly limited, but for example, the substituents exemplified as the substituent group W above can be cited.

[0078] In equation (1-1), * indicates the bonding position.

[0079] In formula (1-2), X ２ is an oxygen atom, a sulfur atom, or -NR Ａ２ Represents -. R Ａ２ R represents a hydrogen atom or substituent. Ａ２ The substituent represented by is R in formula (1-1). Ａ１ This is synonymous with the substituent represented by , and the preferred embodiment is the same. ２ The present invention offers superior effects, particularly with oxygen atoms, sulfur atoms, -NH-, -NMe-, and -N(CH). ２ Ph)-, -N(COMe)-, or -N(COOtBu)- are preferred, and a sulfur atom, -NH-, or -NMe- are more preferred.

[0080] In formula (1-2), R １４ ~R １６ Each of these independently represents a hydrogen atom or a substituent. １４ ~R １６ Specific examples of substituents represented by R １１ ~R １３ The substituent represented by is the same, and the preferred embodiment is also the same. １５ and R １６These elements may bond to each other to form a ring which may have substituents. The ring may be either an aromatic ring or an alicyclic ring. The number of members in the ring is not particularly limited, but for example, it is 5 to 10, and 6 is preferred. The ring may also have substituents. The substituents are not particularly limited, but examples include the substituents exemplified by the substituent group W described above.

[0081] In equation (1-2), * indicates the bonding position.

[0082] In terms of superior sensitivity characteristics, in equation (1), Ar １ and Ar ２ It is also preferable that each of these independently represents an aromatic ring group having one or more electron-withdrawing groups as substituents. In this specification, an electron-withdrawing group means a substituent whose substituent constant σp value in Hammett's rule is 0.1 or greater. In other words, in formula (1), Ar １ and Ar ２ It is also preferable that each of these independently represents an aromatic ring group having one or more substituents with a Hammett substitution constant σp value of 0.1 or higher. Examples of electron-withdrawing groups include halogen groups, nitro groups, cyano groups, formyl groups, carbonyl groups, carboxyl groups, alkoxycarbonyl groups, amide groups, sulfo groups, trifluoromethyl groups, and imino groups. For example, the σp value of a cyano group is 0.66, and the σp value of a COOMe group is 0.45. In this specification, the substituent constant σp value in Hammett's rule is based on literature values. References include Chem. Rev., 1991, 91, 165-195. In terms of superior sensitivity characteristics, the σp value of the above-mentioned electron-withdrawing groups is preferably 0.2 or higher, and more preferably 0.4 or higher.

[0083] Furthermore, in terms of superior sensitivity characteristics, Ar in equation (1) １ and Ar ２ It is also preferable that at least one of these represents an aromatic heterocyclic group having one or more electron-withdrawing groups as substituents. In other words, in formula (1), Ar １ and Ar ２It is also preferable that at least one of them represents an aromatic heterocyclic group having one or more substituents whose substituent constant σp value according to Hammett's rule is 0.1 or more. From the viewpoint of more excellent sensitivity characteristics, the σp value of the electron-withdrawing group described above is preferably 0.2 or more, and more preferably 0.4 or more. Note that the definition of the electron-withdrawing group is as described above.

[0084] Further, from the viewpoint of more excellent sensitivity characteristics, in formula (1-1), R １１ to R １３ , it is also preferable that at least one of them represents an electron-withdrawing group. In other words, in formula (1-1), R １１ to R １３ , it is also preferable that at least one of them represents a substituent whose substituent constant σp value according to Hammett's rule is 0.1 or more. R １１ to R １３ , when a plurality of them each represent a substituent whose substituent constant σp value according to Hammett's rule is 0.1 or more, they may be the same as or different from each other. Note that the definition of the electron-withdrawing group is as described above. From the viewpoint of more excellent sensitivity characteristics, the σp value of the electron-withdrawing group described above is preferably 0.2 or more, and more preferably 0.4 or more.

[0085] From the viewpoint of more excellent sensitivity characteristics, in formula (1-2), R １４ to R １６ , it is also preferable that at least one of them represents an electron-withdrawing group. In other words, in formula (1-2), R １４ to R １６ , it is also preferable that at least one of them represents a substituent whose substituent constant σp value according to Hammett's rule is 0.1 or more. R １４ to R １６ , when a plurality of them each represent a substituent whose substituent constant σp value according to Hammett's rule is 0.1 or more, they may be the same as or different from each other. Note that the definition of the electron-withdrawing group is as described above. From the viewpoint of more excellent sensitivity characteristics, the σp value of the electron-withdrawing group described above is preferably 0.2 or more, and more preferably 0.4 or more.

[0086] In formula (1), R １ to R ３Each of these independently comprises a hydrogen atom, an optionally substituted alkyl group, an optionally substituted aromatic ring group, or -CO-R ４ The group represented is Ar. The number of carbon atoms in the alkyl group is preferably 1 to 10, and more preferably 1 to 6. The aromatic ring group is Ar １ and Ar ２ Examples of groups similar to the aromatic ring group represented by can be cited, and the preferred embodiments are the same. Furthermore, examples of substituents that the alkyl group and the aromatic ring group may have include the substituents exemplified as the substituent group W described above.

[0087] R ４ This represents a hydroxyl group, an optionally substituted alkoxy group, an optionally substituted alkyl group, or an optionally substituted aromatic ring group. The number of carbon atoms in the alkoxy group is preferably 1 to 10, and more preferably 1 to 6. The number of carbon atoms in the alkyl group is preferably 1 to 10, and more preferably 1 to 6. The aromatic ring group is Ar １ and Ar ２ Examples of groups similar to the aromatic ring group represented by can be cited, and the preferred embodiments are the same. Furthermore, examples of substituents that the alkoxy group, alkyl group, and aromatic ring group may have include the substituents exemplified as the substituent group W described above.

[0088] In formula (1), R １ ~R ３ It is preferable that this represents a hydrogen atom.

[0089] In formula (1), n ​​is an integer greater than or equal to 0. There is no particular upper limit to n, but it is preferably 6 or less. In terms of achieving superior effects of the present invention, n is preferably an integer from 0 to 3, more preferably an integer from 0 to 2, and even more preferably 0 or 1. Note that when n represents 0, R in formula (1) ３ The carbon atom that is substituted and Ar １ and are directly joined together.

[0090] In terms of the superior effect of the present invention, compound (1) is Ar １ and Ar ２Preferably, one of the compounds represents an aromatic heterocyclic group which may have substituents, and the other represents an aromatic hydrocarbon ring group which may have substituents, and Ar １ and Ar ２ It is more preferable that one of the compounds represents a group represented by either formula (1-1) or formula (1-2), and the other represents an aromatic hydrocarbon ring group which may have substituents; it is even more preferable that the compound is represented by formula (2); it is particularly preferable that the compound is represented by formula (3); and it is most preferable that the compound is represented by formula (4).

[0091]

[0092] In formula (2), X １ and R １１ ~R １３ This is X in equation (1-1). １ and R １１ ~R １３ This is synonymous with the same thing, and the preferred embodiment is also the same.

[0093] In formula (2), R １７ ~R ２１ Each of these independently represents a hydrogen atom or a substituent. １７ ~R ２１ Examples of substituents represented by include those exemplified as the substituent group W mentioned above. １７ ~R ２１ Among them, adjacent groups (for example, R １７ and R １８ , R １８ and R １９ , R １９ and R ２０ , R ２０ and R ２１ These elements may bond to each other to form a ring which may have substituents. The ring may be either an aromatic ring or an alicyclic ring. The number of members in the ring is not particularly limited, but for example, it is 5 to 10, and 6 is preferred. The ring may also have substituents. The substituents are not particularly limited, but for example, the substituents exemplified as the substituent group W above can be cited.

[0094] R １７ ~R ２１ Of these, at least R１７ and R ２１ It is preferable that this represents a hydrogen atom.

[0095] Furthermore, in terms of superior sensitivity characteristics, in equation (2), R １１ ~R １３ At least one of the following, and R １７ ~R ２１ Preferably, at least one of them independently represents an electron-withdrawing group. In other words, in formula (2), R １１ ~R １３ At least one of the following, and R １７ ~R ２１ It is preferable that at least one of them independently represents a substituent with a substituent constant σp value of 0.1 or greater in Hammett's rule. １１ ~R １３ If several of these represent substituents with a substituent constant σp value of 0.1 or greater in Hammett's rule, they may be identical or different. Also, R １７ ~R ２１ If several of these represent substituents with a substituent constant σp value of 0.1 or higher in the Hammett rule, they may be the same or different from each other. The definition of an electron-withdrawing group is as previously described. In terms of superior sensitivity characteristics, the σp value of the electron-withdrawing group described above is preferably 0.2 or higher, and more preferably 0.4 or higher.

[0096]

[0097] In formula (3), X １ and R １１ ~R １３ This is X in equation (1-1). １ and R １１ ~R １３ This is synonymous with the same as the preferred embodiment. In formula (3), R １８ ~R ２０ R in equation (2) １８ ~R ２０ This is synonymous with the same thing, and the preferred embodiment is also the same.

[0098] Furthermore, in terms of superior sensitivity characteristics, R in equation (3) １１ ~R １３ At least one of the following, and R１８ ~R ２０ Preferably, at least one of them independently represents an electron-withdrawing group. In other words, in formula (3), R １１ ~R １３ At least one of the following, and R １８ ~R ２０ It is preferable that at least one of them independently represents a substituent with a substituent constant σp value of 0.1 or greater in Hammett's rule. １１ ~R １３ If several of these represent substituents with a substituent constant σp value of 0.1 or greater in Hammett's rule, they may be identical or different. Also, R １８ ~R ２０ If several of these represent substituents with a substituent constant σp value of 0.1 or higher in the Hammett rule, they may be the same or different from each other. The definition of an electron-withdrawing group is as previously described. In terms of superior sensitivity characteristics, the σp value of the electron-withdrawing group described above is preferably 0.2 or higher, and more preferably 0.4 or higher.

[0099]

[0100] In formula (4), R １１ ~R １３ R in equation (1-1) １１ ~R １３ This is synonymous with the same as the preferred embodiment. In formula (4), R １８ ~R ２０ R in equation (2) １８ ~R ２０ This is synonymous with the same as the preferred embodiment. In formula (4), X １１ represents a sulfur atom, -NH-, or -NMe-.

[0101] Furthermore, in terms of superior sensitivity characteristics, R in equation (4) １１ ~R １３ At least one of the following, and R １８ ~R ２０ Preferably, at least one of them independently represents an electron-withdrawing group. In other words, in formula (4), R １１ ~R １３ At least one of the following, and R １８ ~R２０ It is preferable that at least one of them represents a substituent with a substituent constant σp value of 0.1 or greater in Hammett's rule. １１ ~R １３ If several of these represent substituents with a substituent constant σp value of 0.1 or greater in Hammett's rule, they may be identical or different. Also, R １８ ~R ２０ If several of these represent substituents with a substituent constant σp value of 0.1 or higher in the Hammett rule, they may be the same or different from each other. The definition of an electron-withdrawing group is as previously described. In terms of superior sensitivity characteristics, the σp value of the electron-withdrawing group described above is preferably 0.2 or higher, and more preferably 0.4 or higher.

[0102] Nitron compounds can be synthesized by known methods. Specifically, they can be synthesized from aldehyde compounds and nitro compounds by a reduction reaction using zinc and acetic acid followed by a condensation reaction (for example, refer to the synthesis method described in Synlett 2001, 1281-1283).

[0103] The nitrone compound may be used alone or in combination of two or more types. The content of the nitrone compound is preferably 1.00 to 50.0% by mass, more preferably 5.00 to 40.0% by mass, even more preferably 8.00 to 40.0% by mass, particularly preferably 8.00 to 30.0% by mass, and most preferably 8.00 to 25.0% by mass, based on the total mass of the thermoplastic resin layer.

[0104] <Other Components> The thermoplastic resin layer may contain other components not listed above. Examples of other components include polymerization inhibitors, surfactants, and rust inhibitors.

[0105] (Polymerization Inhibitors) Known polymerization inhibitors can be used. Specific examples of polymerization inhibitors 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 tetrakis3-(3,5-di-tert-butyl-4-hydroxyphenyl Examples include hindered phenol compounds such as nyl)propionate; phenoxazine compounds such as phenoxazine; 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, with phenothiazine compounds being preferred.

[0106] The polymerization inhibitor may be used alone or in combination of two or more types. The content of the polymerization inhibitor is preferably 0.01 to 5.00% by mass, more preferably 0.03 to 0.50% by mass, and even more preferably 0.04 to 0.35% by mass, based on the total mass of the thermoplastic resin layer.

[0107] (Surfactants) The thermoplastic resin layer may contain surfactants. Examples of surfactants include anionic surfactants, cationic surfactants, nonionic surfactants, and amphoteric surfactants, with nonionic surfactants being preferred. Examples of surfactants include those described in paragraph 0017 of Japanese Patent No. 4502784 and paragraphs 0060 to 0071 of Japanese Patent Application Publication No. 2009-237362.

[0108] Among the surfactants, fluorinated surfactants or silicone surfactants are preferred. Examples of fluorinated surfactants include (meth)acrylic compounds that have a molecular structure containing a functional group having a fluorine atom, and when heated, the functional group having a fluorine atom is cleaved and the fluorine atom volatilizes. Examples of such fluorinated surfactants include the Megafac DS series (manufactured by DIC Corporation, Chemical Daily (February 22, 2016), Nikkei Sangyo Shimbun (February 23, 2016), and Megafac DS-21, etc.). Alternatively, the fluorinated surfactant may be 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. The fluorinated surfactant may also be a block polymer.

[0109] Fluorine-based surfactants may include fluorine-containing polymer compounds comprising repeating units derived from a (meth)acrylate compound having a fluorine atom and repeating units derived from a (meth)acrylate compound having two or more (preferably five or more) alkylene oxy groups (preferably ethylene oxy groups or propylene oxy groups). Furthermore, fluorine-based surfactants may also include, for example, fluorine-containing polymers having ethylenically unsaturated groups in their side chains. Specifically, examples include Megafac RS-101, RS-102, RS-718K, and RS-72-K (all manufactured by DIC Corporation). As fluorine-based surfactants, those derived from alternative materials of compounds having linear perfluoroalkyl groups with seven or more carbon atoms, such as perfluorooctanoic acid (PFOA) and perfluorooctanesulfonic acid (PFOS), are preferred in terms of improved environmental suitability.

[0110] Examples of commercially available fluorine-based surfactants include Megafac F-171, F-172, F-173, F-176, F-177, F-141, F-142, F-143, F-144, F-437, F-475, F-477, F-479, F-482, F-551-A, F-552, F-554, F-555-A, F-556, F-557, F-558, F-559, F-560, F-561, F-565, F-563, F-568, F-575, and F-780 (all manufactured by DIC Corporation); EXP. MFS-324, EXP. MFS-330, EXP. MFS-578, EXP. MFS-578-2, EXP. MFS-579, EXP. MFS-586, EXP. MFS-587, EXP. MFS-628, EXP. MFS-631, EXP. MFS-603, R-41, R-41-LM, R-01, R-40, R-40-LM, RS-43, TF-1956, RS-90, R-94, RS-72-K, and DS-21 (all manufactured by DIC Corporation); Florard FC430, FC431, and FC171 (all manufactured by Sumitomo 3M Corporation); Surflon S-382, SC-101, SC-103, SC-104, SC-105, SC-1068, SC-381, SC-383, S-393, and KH-40 (all manufactured by AGC Corporation); PolyFox Examples include PF636, PF656, PF6320, PF6520, and PF7002 (all manufactured by OMNOVA); Futtergent 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); and U-120E (manufactured by Unichem).

[0111] Examples of silicone-based surfactants include linear polymers consisting of siloxane bonds, modified siloxane polymers in which organic groups are introduced into the side chains and / or terminals, repeating units having hydrophilic groups in the side chains, and polymers having repeating units having groups with siloxane bonds in the side chains. Among silicone-based surfactants, polymers having repeating units with hydrophilic groups in the side chains and repeating units having groups with siloxane bonds in the side chains are preferred.

[0112] Examples of commercially available silicone-based surfactants include EXP. S-309-2, EXP. S-315, EXP. S-503-2, EXP. S-505-2, and S-506 (all manufactured by DIC Corporation); 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 Corporation); X-22-4952, X-22-4272, X-22-6 266, KF-351A, K354L, KF-355A, KF-945, KF-640, KF-642, KF-643, X-22-6191, X-22-4515, KF-6004, KF-6 001, KF-6002, KP-101, KP-103, KP-104, KP-105, KP-106, KP-109, KP-112, KP-120, KP-121, KP-124, KP-12 5. KP-301, KP-306, KP-310, KP-322, KP-323, KP-327, KP-341, KP-368, KP-369, KP-611, KP-620, KP-621, KP-626, and KP-652 (all manufactured by Shin-Etsu Silicone Co., Ltd.); F-4440, TSF-4300, TSF-4445, TSF-4460, and TSF-4452 (all manufactured by Momentive P Examples include BYK300, BYK306, BYK307, BYK310, BYK320, BYK323, BYK325, BYK330, BYK313, BYK315N, BYK331, BYK333, BYK345, BYK347, BYK348, BYK349, BYK370, BYK377, and BYK378 (all manufactured by Bic Chemie).

[0113] The surfactant may be used alone or in combination of two or more types. The surfactant content is preferably 0.01 to 5.00% by mass, and more preferably 0.05 to 1.00% by mass, relative to the total mass of the thermoplastic resin layer.

[0114] (Rust Inhibitor) The thermoplastic resin layer may also preferably contain a rust inhibitor. Examples of rust inhibitors include heterocyclic compounds. 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, pyrimidine compounds, and pyridine compounds, with triazole compounds, benzotriazole compounds, or tetrazole compounds being preferred. Examples of heterocyclic compounds include compounds described in International Publication No. 2022 / 039027.

[0115] The rust inhibitor may be used alone or in combination of two or more types. The rust inhibitor content is preferably 0.01 to 5.00% by mass, and more preferably 0.05 to 1.00% by mass, relative to the total mass of the thermoplastic resin layer.

[0116] It is also preferable that the thermoplastic resin layer is substantially free of polymerization initiators, as this makes it easier to remove during the developing process. Here, "substantially free" means that the polymerization initiator content is less than 0.01% by mass of the total mass of the thermoplastic resin layer, and preferably 0.001% by mass or less.

[0117] <Properties of the Thermoplastic Resin Layer> (Film Thickness) The film thickness of the thermoplastic resin layer is preferably 1 to 15 μm in terms of development speed and resolution. Among these, the lower limit of the film thickness is more preferably 2 μm or more, even more preferably 3 μm or more, particularly preferably 6 μm or more, and most preferably 10 μm or more. The upper limit of the film thickness is more preferably 13 μm or less.

[0118] (Unsaturated double bond value of thermoplastic resin layer) The unsaturated double bond value of the thermoplastic resin layer is 2.50 mmol / g or less, preferably 2.30 mmol / g or less, and more preferably 1.00 mmol / g or less, in terms of superior effects of the present invention. The lower limit is preferably 0.00 mmol / g or more, and more preferably greater than 0.00 mmol / g, in terms of superior step-following ability on the transferred material. The unsaturated double bond value of the thermoplastic resin layer is the number of unsaturated double bonds (mol / g) contained per gram of thermoplastic resin layer. The unsaturated double bond value of the thermoplastic resin layer can be adjusted to the above numerical range by adjusting the content of components containing unsaturated double bond groups in the thermoplastic resin layer (for example, alkali-soluble thermoplastic resin having unsaturated double bond groups, and plasticizer having unsaturated double bond groups, etc.).

[0119] The unsaturated double bond value of the thermoplastic resin layer is obtained by measuring the iodine value (g / 100g) of the thermoplastic resin layer in accordance with the test method for "iodine value" described in JIS K 0070-1992, and calculating the number of unsaturated double bonds contained per gram (mol / g). The specific procedure for iodine titration performed when measuring the iodine value is preferably as follows: Weigh 0.30 to 0.20 g of the thermoplastic resin layer into a stoppered Erlenmeyer flask to three significant figures. Then, add approximately 10 ml of carbon tetrachloride to dissolve the sample. Using a full-length pipette, add 25 ml of iodine monochloride solution and shake. Stopper the flask and leave it in the dark at room temperature for 30 minutes. Add approximately 20 ml of potassium iodide solution (100 g / l) and approximately 100 ml of water. Titrate with 0.1 mol / l sodium thiosulfate solution. When the solution turns pale yellow, add a few drops of starch solution (10 g / l) and titrate until the blue color disappears.

[0120] <Acid Value of Thermoplastic Resin Layer> The acid value of the thermoplastic resin layer is 20.0 to 100.0 mgKOH / g, and is preferably 20.0 to 95.0 mgKOH / g, and more preferably 20.0 to 85.0 mgKOH / g, in terms of superior effects of the present invention. The above acid value (mgKOH / g) is the mass [mg] of potassium hydroxide required to neutralize 1 g of the thermoplastic resin layer. The acid value of the thermoplastic resin layer can be adjusted to the above numerical range by adjusting the content of acid group-containing components in the thermoplastic resin layer (for example, alkali-soluble thermoplastic resin having acid groups, and plasticizer having acid groups, etc.). The acid value of the thermoplastic resin layer can be measured, for example, using a 0.1 N KOH aqueous solution as the titrant with an automatic titrator (for example, a product manufactured by Hiranuma Sangyo Co., Ltd., product name "COM-555").

[0121] In terms of having superior effects, an example of a preferred embodiment of the thermoplastic resin layer is an embodiment that satisfies at least one of the following requirements A and B. Requirement A: The unsaturated double bond value of the thermoplastic resin layer is 2.30 mmol / g or less. Requirement B: The acid value of the thermoplastic resin layer is 20.0 to 95.0 mgKOH / g. Another example of a preferred embodiment of the thermoplastic resin layer is an embodiment in which the unsaturated double bond value of the thermoplastic resin layer is 1.00 mmol / g or less.

[0122] [Intermediate Layer] The transfer film preferably has an intermediate layer. The presence of an intermediate layer in the transfer film suppresses the mixing of components between the thermoplastic resin layer and the photosensitive composition layer. A water-soluble resin layer containing a water-soluble resin is preferred as the intermediate layer. Alternatively, an oxygen-blocking layer with oxygen-blocking function, as described as a "separation layer" in Japanese Patent Publication No. 5-072724, can also be used as the intermediate layer. An oxygen-blocking layer is preferred because it improves sensitivity during exposure, reduces the time load on the exposure machine, and improves productivity. The oxygen-blocking layer used as the intermediate layer can be appropriately selected from known layers described in the above publication, etc. Among these, 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.

[0123] <Water-soluble resin> Examples of water-soluble resins included in the above-mentioned water-soluble resin layer include polyvinyl alcohol-based resins, polyvinylpyrrolidone-based resins, cellulose-based resins, (meth)acrylamide-based resins, polyethylene oxide-based resins, gelatin, vinyl ether-based resins, polyamide resins, and copolymers thereof. The water-soluble resin preferably contains polyvinyl alcohol, and more preferably contains both polyvinyl alcohol and polyvinylpyrrolidone, in order to further improve oxygen barrier properties and interlayer mixing inhibition ability.

[0124] 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. The upper limit is preferably 200,000 or less, more preferably 100,000 or less, and even more preferably 50,000 or less. The polydispersity of the water-soluble resin is preferably 1.0 to 10.0, and more preferably 1.0 to 5.0.

[0125] The water-soluble resin may be used alone or in combination of two or more types. The content of the water-soluble resin is preferably 50.00% by mass or more, more preferably 70.00% by mass or more, and even more preferably 80.00% by mass or more, relative to the total mass of the intermediate layer. There is no particular upper limit to the content of the water-soluble resin, but it is often 99.90% by mass or less, and preferably 99.80% by mass or less, relative to the total mass of the intermediate layer.

[0126] <Photocatalytically Decolorizing Compounds> For superior resolution, the intermediate layer may also preferably contain a photocatalytically decolorizing compound. By including a photocatalytically decolorizing compound in the intermediate layer, the intermediate layer also functions as a CEL, resulting in superior resolution. A photocatalytically decolorizing compound is a compound whose absorption at the exposure wavelength decreases and its transmittance increases (i.e., it becomes decolorized) upon exposure. The photocatalytically decolorizing compound should be decolorized by the exposure light used in pattern exposure. Specifically, it is preferable to decolorize with light with a wavelength of 190 to 500 nm, more preferably with light with a wavelength of 365 nm or 405 nm, and even more preferably with light with a wavelength of 365 nm.

[0127] The molar extinction coefficient of a photocatalytic compound at a wavelength of 365 nm is 5,000 L·mol. －１ ・cm －１ The above is preferable, and 8,000 L·mol －１ ・cm －１ The above is more preferable, 15,000 L·mol －１ ・cm －１ The above is even more preferable. The upper limit of the above molar extinction coefficient is not particularly limited, but 40,000 L·mol －１ ・cm －１ The following is often the case: The molar extinction coefficient at the above wavelength of 365 nm is the value before exposure (i.e., before decolorization). The molar extinction coefficient at the above wavelength of 365 nm can be measured using a spectrophotometer (for example, Shimadzu UV-3100). The difference in the molar extinction coefficient at the wavelength of 365 nm before and after decolorization of a photodecolorizable compound ((molar extinction coefficient at 365 nm before decolorization) - (molar extinction coefficient at 365 nm after decolorization)) is 5,000 L·mol －１ ・cm －１ The above is preferable, and 8,000 L·mol －１ ・cm －１ The above is more preferable, 10,000 L·mol －１ ・cm －１ The above is even more preferable. There is no particular upper limit, up to 40,000 L·mol. －１ ・cm －１ The following are common cases.

[0128] Examples of photocatalytic compounds include diazonium salts, oxime sulfonate compounds, oxime ester compounds, acylphosphine oxide compounds, stilbazolium salts, and nitrone compounds. When the intermediate layer contains a photocatalytic compound, the photocatalytic compound in the intermediate layer may be the same as or different from the nitrone compound in the thermoplastic resin layer.

[0129] The photocatalytic compound may be used alone or in combination of two or more types. The content of the photocatalytic compound is preferably 1.00 to 50.00% by mass, and more preferably 5.00 to 20.00% by mass, relative to the total mass of the intermediate layer.

[0130] The intermediate layer may contain other known components, such as surfactants, in addition to the components mentioned above. Examples of surfactants that may be included in the intermediate layer include those that may be included in the thermoplastic resin layer described above. The surfactant may be used alone or in combination of two or more types. The surfactant content is preferably 0.01 to 10.00% by mass, and more preferably 0.10 to 1.00% by mass, relative to the total mass of the intermediate layer.

[0131] <Properties of the intermediate layer> The thickness of the intermediate layer is preferably 0.01 to 5 μm, and more preferably 0.1 to 3 μm.

[0132] [Photosensitive Composition Layer] The transfer film has a photosensitive composition layer. The photosensitive composition layer is preferably a negative-type photosensitive composition layer because it offers superior resolution. When the photosensitive composition layer is a negative-type photosensitive composition layer, the pattern formed by exposure corresponds to the cured layer.

[0133] The negative-type photosensitive composition layer preferably contains resin A, a polymerizable monomer (a compound having a polymerizable group), and a polymerization initiator.

[0134] <Resin A> Resin A is preferably an alkali-soluble resin. Examples of resin A include (meth)acrylic resin, polystyrene resin, styrene-(meth)acrylic copolymer, polyurethane resin, polyvinyl alcohol, polyvinyl formal, polyamide resin, polyester resin, epoxy resin, polyacetal resin, polyhydroxystyrene resin, polyimide resin, polybenzoxazole resin, polysiloxane resin, polyethyleneimine, polyallylamine, and polyalkylene glycol.

[0135] Resin A is preferably a (meth)acrylic resin. In other words, it is preferably one or more polymers selected from the group consisting of acrylic resins and methacrylic resins. (Meth)acrylic resin means a resin having at least one constituent unit selected from the group consisting of constituent units derived from (meth)acrylic acid, constituent units derived from (meth)acrylic acid esters, and constituent units derived from (meth)acrylamide. As for the (meth)acrylic resin, it is preferable that the total content of constituent units derived from (meth)acrylic acid, constituent units derived from (meth)acrylic acid esters, and constituent units derived from (meth)acrylamide is 50% by mass or more of the total mass of the (meth)acrylic resin. In particular, the total content of constituent units derived from (meth)acrylic acid and constituent units derived from (meth)acrylic acid esters is preferably 30 to 100% by mass, and more preferably 50 to 100% by mass, of the total mass of the (meth)acrylic resin.

[0136] The acid value of resin A is preferably 220 mg KOH / g or less, more preferably less than 200 mg KOH / g, and even more preferably less than 190 mg KOH / g, from the standpoint of suppressing swelling of the photosensitive composition layer by alkaline developer and thus improving resolution. The lower limit of the above acid value is not particularly limited, but from the standpoint of improving developability, it is more preferably 120 mg KOH / g or more, and even more preferably 150 mg KOH / g or more.

[0137] The weight-average molecular weight of resin A is not particularly limited, but from the viewpoint of developability and resolution, it is preferably 500,000 or less, more preferably 100,000 or less, and even more preferably 60,000 or less. Furthermore, from the viewpoint of edge fusing and cut-tip properties of the transfer film, it is preferably 5,000 or more, more preferably 10,000 or more, and even more preferably 20,000 or more. Edge fusing refers to the degree to which the photosensitive composition layer tends to protrude from the end face of the roll when the transfer film is wound into a roll. Cut-tip properties refer to the degree to which chips tend to fly off when the unexposed film is cut with a cutter. If these chips adhere to the upper surface of the photosensitive composition layer, they will be transferred to the mask in subsequent exposure processes, causing defective products. The polydispersity of resin A 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.

[0138] Resin A preferably contains constituent units based on monomers having aromatic hydrocarbon groups, as this provides superior resolution. Examples of monomers having aromatic hydrocarbon groups include monomers having aralkyl groups, styrene, and polymerizable styrene derivatives (e.g., methylstyrene, vinyltoluene, tert-butoxystyrene, acetoxystyrene, 4-vinylbenzoic acid, styrene dimer, and styrene trimer, etc.), with monomers having aralkyl groups or styrene being preferred. Examples of aralkyl groups include optionally substituted phenylalkyl groups, and optionally substituted benzyl groups are preferred. Examples of monomers having aralkyl groups include (meth)acrylates having benzyl groups, such as benzyl (meth)acrylate and chlorobenzyl (meth)acrylate; vinyl monomers having benzyl groups, such as vinylbenzyl chloride and vinylbenzyl alcohol; and (meth)acrylates having phenylalkyl groups other than benzyl groups, such as phenylethyl (meth)acrylate. Among the monomers having aralkyl groups, benzyl (meth)acrylate is particularly preferred.

[0139] Resin A may have one or more constituent units based on monomers having aromatic hydrocarbon groups. The content of constituent units based on monomers having aromatic hydrocarbon groups is preferably 20 to 80% by mass, more preferably 25 to 70% by mass, and even more preferably 30 to 65% by mass, relative to the total constituent units of resin A.

[0140] Resin A is preferably composed of constituent units having acidic groups from the viewpoint of alkali developability. Examples of acidic groups include carboxyl groups, sulfol groups, phosphoric acid groups, and phosphonic acid groups, with carboxyl groups being preferred. The monomer that gives the constituent units having acidic groups is preferably (meth)acrylate or (meth)acrylic acid having a carboxyl group, and (meth)acrylic acid is more preferred.

[0141] Resin A may have one or more constituent units having acidic groups. The content of constituent units having acidic groups (preferably constituent units derived from (meth)acrylic acid) is preferably 10 to 50% by mass, and more preferably 15 to 40% by mass, relative to the total constituent units of resin A, in terms of developability and resolution.

[0142] Resin A is preferably composed of reactive groups, and more preferably of constituent units having reactive groups, in that it exhibits superior resolution. The reactive groups are preferably radical polymerizable groups, and more preferably ethylenically unsaturated groups. The ethylenically unsaturated groups are more preferably allyl groups or (meth)acryloxy groups. Examples of constituent units having reactive groups are, but are not limited to, those listed below.

[0143]

[0144] Resin A may have one type of reactive group-containing structural unit, or two or more types. The content of the reactive group-containing structural unit is preferably 5 to 70% by mass, more preferably 10 to 50% by mass, and even more preferably 20 to 40% by mass, relative to the total structural units of resin A, in terms of superior resolution.

[0145] As a means of introducing reactive groups into resin A, one method involves reacting functional groups such as hydroxyl groups, carboxyl groups, primary amino groups, secondary amino groups, acetoacetyl groups, and sulfo groups with compounds such as epoxy compounds, blocked isocyanate compounds, isocyanate compounds, vinyl sulfone compounds, aldehyde compounds, methylol compounds, and carboxylic acid anhydrides. A preferred example of a means of introducing reactive groups into resin A is to synthesize a polymer having carboxyl groups by polymerization, and then, by polymer reaction, react a portion of the carboxyl groups of the obtained polymer with glycidyl (meth)acrylate to introduce (meth)acryloxy groups into the polymer. By this means, a resin having (meth)acryloxy groups in its side chains can be obtained.

[0146] Resin A may contain constituent units derived from non-acidic monomers. Examples of the non-acidic monomers 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; esters of vinyl alcohols such as vinyl acetate; and (meth)acrylonitrile. Among these, methyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, or n-butyl (meth)acrylate are preferred, and methyl (meth)acrylate is more preferred. The content of constituent units derived from non-acidic monomers in resin A is preferably 0.5 to 60% by mass, more preferably 1 to 50% by mass, and even more preferably 1 to 40% by mass, relative to the total constituent units of resin A.

[0147] Resin A may have a linear structure, a branched structure, or an alicyclic structure in its side chains. In this specification, "main chain" refers to the relatively longest bonding chain in the polymer compound molecule constituting the resin, and "side chain" refers to an atomic group branching off from the main chain. By using a monomer containing a group having a branched structure or an alicyclic structure in its side chains, a branched structure or an alicyclic structure can be introduced into the side chains of resin A. The group having an alicyclic structure may be monocyclic or fused. Examples of monomers containing a group having a branched structure in its side chains include the monomer described in paragraph

[0064] of International Publication No. 2021 / 166719, the contents of which are incorporated herein by reference.

[0148] Resin A may be used alone or in combination of two or more types. The content of resin A is preferably 20.00 to 80.00% by mass, more preferably 30.00 to 70.00% by mass, and even more preferably 40.00 to 65.00% by mass, based on the total mass of the photosensitive composition layer.

[0149] The photosensitive composition layer may also contain resins other than resin A described above.

[0150] <Polymerizable Monomer> The photosensitive composition layer preferably contains a polymerizable monomer. The polymerizable monomer is a different compound from resin A described above, and its molecular weight (weight-average molecular weight) is preferably 200 to 2,000. A polyfunctional polymerizable monomer having two or more polymerizable groups in one molecule is preferred in terms of superior resolution. The number of polymerizable groups in one molecule of the polymerizable monomer is preferably 6 or less, and more preferably 3 or less. The polymerizable groups of the polymerizable monomer are preferably radical polymerizable groups. The radical polymerizable groups are preferably ethylenically unsaturated groups such as vinyl groups, (meth)acryloyl groups, styryl groups, and maleimide groups, and more preferably (meth)acryloyl groups.

[0151] Polymerizable monomers are preferably those that include monomers having radical polymerizable groups (hereinafter also referred to as "radical polymerizable monomers").

[0152] (Radical Polymerizable Monomer B1) The radical polymerizable monomer preferably includes radical polymerizable monomer B1 having an aromatic ring and two ethylenically unsaturated groups. Examples of the aromatic ring include aromatic hydrocarbon rings such as benzene rings, naphthalene rings, and anthracene rings, aromatic heterocycles such as thiophene rings, furan rings, pyrrole rings, imidazole rings, triazole rings, and pyridine rings, and fused rings thereof, with aromatic hydrocarbon rings being preferred and benzene rings being more preferred. The aromatic ring may have substituents. Radical polymerizable monomer B1 may have only one aromatic ring or may have two or more aromatic rings.

[0153] The radical polymerizable monomer B1 is preferably a bisphenol structure because it suppresses swelling of the photosensitive composition layer by the developer and provides superior resolution. Examples of bisphenol structures 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.

[0154] Examples of radical polymerizable monomers B1 having a bisphenol structure include compounds 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 directly bonded to both ends of the bisphenol structure or bonded via one or more alkylene oxy groups, and it is preferable that they are bonded via one or more alkylene oxy groups. That is, it is preferable that radical polymerizable monomer B1 has an alkylene oxide-modified bisphenol structure. The alkylene oxy groups added to both ends of the bisphenol structure are preferably ethylene oxy groups or propylene oxy groups, with ethylene oxy groups being more preferable. The number of alkylene oxy groups added to the bisphenol structure is not particularly limited, but it is preferably 4 to 16 per molecule, and more preferably 6 to 14. Radical polymerizable monomers B1 having a bisphenol structure are described in paragraphs

[0072] to

[0080] of Japanese Patent Application Publication No. 2016-224162, and the contents described in this publication are incorporated herein by reference.

[0155] As the radical polymerizable monomer 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-(methacryloxydodecaethoxytetrapropoxy)phenyl)propane Examples include (FA-3200MY, manufactured by Hitachi Chemical Co., Ltd.), 2,2-bis(4-(methacryloxypentadecaethoxy)phenyl)propane (BPE-1300, manufactured by Shin Nakamura Chemical Industry Co., Ltd.), 2,2-bis(4-(methacryloxydiethoxy)phenyl)propane (BPE-200, manufactured by Shin Nakamura Chemical Industry Co., Ltd.), ethoxylated (10)bisphenol A diacrylate (NK ester A-BPE-10, manufactured by Shin Nakamura Chemical Industry Co., Ltd.), and ethoxylated bisphenol A dimethacrylate (BPE-100, manufactured by Shin Nakamura Chemical Industry Co., Ltd.).

[0156] As the radical polymerizable monomer B1, compounds represented by the following general formula (B1) are also preferred.

[0157]

[0158] In general formula (B1), R １ and R ２ Each of these independently represents either a hydrogen atom or a methyl group. A is C ２ H ４ This represents B is C ３ H ６This represents the following: n1 and n3 are each independently integers from 1 to 39, and n1 + n3 is an integer from 2 to 40. n2 and n4 are each independently integers from 0 to 29, and n2 + n4 is an integer from 0 to 30. The arrangement of the constituent units -(A-O)- and -(B-O)- may be random or in blocks. In the case of blocks, either -(A-O)- or -(B-O)- 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. Also, n2 + n4 is preferably 0 to 10, more preferably 0 to 4, even more preferably 0 to 2, and particularly preferably 0.

[0159] Radical polymerizable monomer B1 may be used alone or in combination of two or more types. The content of radical polymerizable monomer B1 is preferably 10.00 to 70.00% by mass, more preferably 20.00 to 60.00% or more by mass, and even more preferably 25.00 to 50.00% by mass, relative to the total mass of the photosensitive composition layer, in terms of superior resolution.

[0160] The radical polymerizable monomer may include radical polymerizable monomers other than radical polymerizable monomer B1. The polymerizable monomers other than radical polymerizable monomer B1 can be appropriately selected from known compounds. Examples include compounds having one ethylenically unsaturated group in one molecule (monofunctional ethylenically unsaturated compounds), difunctional ethylenically unsaturated compounds without aromatic rings, and trifunctional or more ethylenically unsaturated compounds.

[0161] 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.

[0162] Examples of bifunctional ethylenically unsaturated compounds that do not have an 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 tricyclodecanedimethanol diacrylate (A-DCP, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), tricyclodecanedimethanol dimethacrylate (DCP, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), 1,9-nonanediol diacrylate (A-NOD-N, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), 1,6-hexanediol diacrylate (A-HD-N, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), polyethylene glycol dimethacrylate (4G, 9G, 14G, and 23G, etc., manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), Aronics® M-220 (manufactured by Toagosei Co., Ltd.), Aronics® M-240 (manufactured by Toagosei Co., Ltd.), Aronics® M-270 (manufactured by Toagosei 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)acrylate and ethylene oxide and propylene oxide-modified urethane di(meth)acrylate. Examples of commercially available products include 8UX-015A (manufactured by Taisei Fine Chemical Co., Ltd.), UA-32P (manufactured by Shin Nakamura Chemical Industry Co., Ltd.), and UA-1100H (manufactured by Shin Nakamura Chemical Industry Co., Ltd.).

[0163] Examples of ethylenically unsaturated compounds with three or more functions include dipentaerythritol (tri / tetra / penta / hexa)(meth)acrylate, pentaerythritol (tri / tetra)(meth)acrylate, trimethylolpropane tri(meth)acrylate, ditrimethylolpropanetetra(meth)acrylate, trimethylolethane tri(meth)acrylate, isocyanuric acid tri(meth)acrylate, glycerin tri(meth)acrylate, and alkylene oxide modified products thereof.

[0164] Examples of alkylene oxide-modified ethylenically unsaturated compounds with three or more functions include caprolactone-modified (meth)acrylate compounds (such as KAYARAD® DPCA-20 from Nippon Kayaku Co., Ltd., and A-9300-1CL from Shin Nakamura Chemical Industry Co., Ltd.), ethoxylated trimethylolpropane triacrylate (such as SR454, SR499, and SR502 from Tomoe Industries Co., Ltd.), and alkylene oxide-modified (meth)acrylate compounds (such as KAYARAD RP-1040 from Nippon Kayaku Co., Ltd., ATM-35E and A-9300 from Shin Nakamura Chemical Industry Co., Ltd., and EBECRYL® from Daicel Ornex Co., Ltd.). Examples include 135, ethoxylated glycerin triacrylate (such as A-GLY-9E manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), Arronix (registered trademark) TO-2349 (manufactured by Toagosei Co., Ltd.), Arronix M-520 (manufactured by Toagosei Co., Ltd.), and Arronix M-510 (manufactured by Toagosei Co., Ltd.).

[0165] Furthermore, polymerizable monomers having an acidic group (such as a carboxyl group) may be used as radical polymerizable monomers. The acidic group may form an acid anhydride group. Examples of radical polymerizable monomers having an acidic group include Arronix® TO-2349 (manufactured by Toagosei Co., Ltd.), Arronix® M-520 (manufactured by Toagosei Co., Ltd.), and Arronix® M-510 (manufactured by Toagosei Co., Ltd.). As radical polymerizable monomers having an acidic group, for example, polymerizable monomers having an acidic group described in paragraphs

[0025] to

[0030] of Japanese Patent Application Publication No. 2004-239942 may be used.

[0166] The polymerizable monomer (preferably a radical polymerizable monomer) may be used alone or in combination of two or more. The polymerizable monomer (preferably a radical polymerizable monomer) is preferably present in an amount of 10.00 to 70.00% by mass, more preferably 20.00 to 60.00% by mass, and even more preferably 30.00 to 50.00% by mass, based on the total mass of the photosensitive composition layer.

[0167] <Polymerization Initiator> The photosensitive composition layer preferably contains a polymerization initiator. A radical polymerization initiator is preferred, and a photoradical polymerization initiator is more preferred. A photoradical polymerization initiator is a polymerization initiator that generates radicals when exposed to active light such as ultraviolet light, visible light, and X-rays, but a compound that generates radicals when exposed to ultraviolet light is preferred. Examples of photoradical polymerization initiators include photopolymerization initiators having an oxime ester structure, photopolymerization initiators having an α-aminoalkylphenone structure, photopolymerization initiators having an α-hydroxyalkylphenone structure, photopolymerization initiators having an acylphosphine oxide structure, photopolymerization initiators having an N-phenylglycine structure, and photopolymerization initiators having a bistriarylimidazole structure. Photopolymerization initiators having an oxime ester structure, photopolymerization initiators having an α-aminoalkylphenone structure, photopolymerization initiators having an N-phenylglycine structure, or photopolymerization initiators having a triarylbiimidazole structure are preferred, and photopolymerization initiators having a triarylbiimidazole structure are more preferred. Preferred photopolymerization initiators having a triarylbiimidazole structure include 2,4,5-triarylimidazole dimers and their derivatives, specifically, for example, 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. Alternatively, as photopolymerization initiators, for example, those described in paragraphs

[0031] to

[0042] of Japanese Patent Application Publication No. 2011-95716 and paragraphs

[0064] to

[0081] of Japanese Patent Application Publication No. 2015-014783 may be used.

[0168] Specifically, examples of photoradical polymerization initiators include ethyl dimethylaminobenzoate (DBE), benzoin methyl ether, anisyl (p,p'-dimethoxybenzyl), TAZ-110 (manufactured by Midori Chemical Co., Ltd.), benzophenone, 4,4'-bis(diethylamino)benzophenone, TAZ-111 (manufactured by Midori Chemical Co., Ltd.), 1-[4-(phenylthio)]phenyl-1,2-octanedione-2-(O-benzoyl oxime) (IRGACURE® OXE-01, manufactured by BASF), 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]ethanone-1-(O-acetyl oxime) (IRGACURE OXE-02, manufactured by BASF), IRGACURE OXE-03 (manufactured by BASF), IRGACURE OXE-04 (BASF), 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone (Omnirad 379EG, IGM Resins B.V.), 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one (Omnirad 907, IGM Resins B.V.), 2-hydroxy-1-{4-[4-(2-hydroxy-2-methylpropionyl)benzyl]phenyl}-2-methylpropan-1-one (Omnirad 127, IGM Resins B.V.), 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butanone-1 (Omnirad 369, manufactured by IGM Resins B.V., 2-hydroxy-2-methyl-1-phenylpropan-1-one (Omnirad 1173, manufactured by IGM Resins B.V.), 1-hydroxycyclohexylphenyl ketone (Omnirad 184, manufactured by IGM Resins B.V.), 2,2-dimethoxy-1,2-diphenylethane-1-one (Omnirad 651, manufactured by IGM Resins B.V.), 2,4,6-trimethylbenzoyl-diphenylphosphine oxide (Omnirad TPO H, manufactured by IGM Resins B.V.), bis(2,4,6-Trimethylbenzoyl)phenylphosphine oxide (Omnirad 819, IGM Resins B.V.), oxime ester-based photopolymerization initiator (Lunar 6, DKSH Japan), 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbisimidazole (2-(2-chlorophenyl)-4,5-diphenylimidazole dimer) (B-CIM, Hampford), 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer (BCTB, Tokyo Chemical Industries), 1-[4-(phenylthio)phenyl]-3-cyclopentylpropane-1,2-dione-2-(o-benzoyl oxime) (TR-PBG-305, Changzhou Strong Power). Examples include 1,2-propanedione,3-cyclohexyl-1-[9-ethyl-6-(2-furanylcarbonyl)-9H-carbazole-3-yl]-,2-(O-acetyloxime) (TR-PBG-326, manufactured by Changzhou Strong Electronic New Materials Co., Ltd.) and 3-cyclohexyl-1-(6-(2-(benzoyloxyimino)hexanoyl)-9-ethyl-9H-carbazole-3-yl)-propane-1,2-dione-2-(O-benzoyloxime) (TR-PBG-391, manufactured by Changzhou Strong Electronic New Materials Co., Ltd.).

[0169] The polymerization initiator (preferably a radical polymerization initiator) may be used alone or in combination of two or more. The content of the polymerization initiator (preferably a radical polymerization initiator) is preferably 1.00 to 15.00% by mass, and more preferably 3.00 to 10.00% by mass, based on the total mass of the photosensitive composition layer.

[0170] The photosensitive composition layer may contain other components besides those mentioned above.

[0171] <Sensitizer> The photosensitive composition layer may also preferably contain a sensitizer, as this provides superior resolution. Examples of sensitizers 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. Dialkylaminobenzophenone compounds, anthracene compounds, distylylbenzene compounds, or styrylpyridine compounds are preferred, and dialkylaminobenzophenone compounds are more preferred.

[0172] The sensitizer may be used alone or in combination of two or more types. The sensitizer content is preferably 0.001 to 5.00% by mass, more preferably 0.01 to 1.00% by mass, and even more preferably 0.01 to 0.50% by mass, based on the total mass of the photosensitive composition layer.

[0173] <Dye> The photosensitive composition layer may also preferably contain a dye (also called "dye N") whose maximum absorption wavelength in the wavelength range of 400 to 780 nm at the time of color development is 450 nm or more, and whose maximum absorption wavelength changes with the presence of an acid, base, or radical, from the viewpoint of visibility of the exposed and unexposed areas, pattern visibility after development, and superior resolution. Although the detailed mechanism is unknown, the presence of dye N improves adhesion to adjacent layers and provides superior resolution.

[0174] In this specification, the phrase "the maximum absorption wavelength of a dye changes in response to an acid, base, or radical" may mean any of the following: a dye in a colored state becomes decolorized by an acid, base, or radical; a dye in a decolorized state becomes colored by an acid, base, or radical; or 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 decolorized state upon exposure. In this case, the dye may change its colored or decolorized state due to the generation and action of an acid, base, or radical within the photosensitive composition layer upon exposure, or it may be a dye that changes its colored or decolorized state due to a change in the state (e.g., pH) within the photosensitive composition layer due to an acid, base, or radical. Furthermore, the dye may change its colored or decolorized state upon direct stimulation by an acid, base, or radical without exposure.

[0175] In particular, from the viewpoint of visibility between exposed and unexposed areas, and from the viewpoint of superior resolution, the dye N 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 a radical. If the photosensitive composition layer is a negative-type photosensitive composition layer, the negative-type photosensitive composition layer preferably contains both a dye whose maximum absorption wavelength changes in response to a radical and a photoradical polymerization initiator as the dye N, from the viewpoint of visibility between exposed and unexposed areas, and from the viewpoint of superior resolution. Furthermore, from the viewpoint of visibility between exposed and unexposed areas, the dye N is preferably a dye that develops color in response to an acid, base, or radical.

[0176] An example of the color development mechanism of dye N is a configuration in which a photoradical polymerization initiator, a photocationic polymerization initiator (photoacid generator), or a photobase generator is added to a photosensitive composition layer, and after exposure, radicals, acids, or bases generated from the photoradical polymerization initiator, photocationic polymerization initiator, or photobase generator cause a radical-reactive dye, an acid-reactive dye, or a base-reactive dye (e.g., a leuco dye) to develop color.

[0177] From the viewpoint of visibility of the exposed and unexposed areas, the maximum absorption wavelength of dye N in the wavelength range of 400 to 780 nm during color development is preferably 550 nm or more, more preferably 550 to 700 nm, and even more preferably 550 to 650 nm. Furthermore, dye N may have only one maximum absorption wavelength in the wavelength range of 400 to 780 nm during color development, or it may have two or more. If dye N has two or more maximum absorption wavelengths in the wavelength range of 400 to 780 nm during color development, the maximum absorption wavelength with the highest absorbance among the two or more maximum absorption wavelengths should be 450 nm or more.

[0178] The maximum absorption wavelength of dye N is obtained by measuring the transmission spectrum of a solution containing dye N (at a liquid temperature of 25°C) in the range of 400 to 780 nm using a spectrophotometer: UV3100 (manufactured by Shimadzu Corporation) in an atmospheric environment, and detecting the wavelength at which the light intensity is minimum (maximum absorption wavelength).

[0179] Examples of dyes that develop or decolorize upon exposure include leuco compounds. Examples of dyes that decolorize upon exposure include leuco compounds, diarylmethane dyes, oxazine dyes, xanthene dyes, iminonaphthoquinone dyes, azomethine dyes, and anthraquinone dyes.

[0180] As for the dye N, a leuco compound is preferred from the viewpoint of visibility between the exposed and unexposed areas. Examples of leuco compounds include leuco compounds having a triarylmethane skeleton (triarylmethane dyes), leuco compounds having a spiropyran skeleton (spiropyran dyes), leuco compounds having a fluorane skeleton (fluorane dyes), leuco compounds having a diarylmethane skeleton (diarylmethane dyes), leuco compounds having a rhodamine lactam skeleton (rhodamine lactam dyes), leuco compounds having an indolylphthalide skeleton (indolylphthalide dyes), and leuco compounds having a leucoauramine skeleton (leucoauramine dyes). Among these, triarylmethane dyes or fluorane dyes are preferred, and leuco compounds having a triphenylmethane skeleton (triphenylmethane dyes) or fluorane dyes are more preferred.

[0181] As a leuco compound, it is preferable to have a lactone ring, sultine ring, or sultone ring from the viewpoint of visibility between the exposed and unexposed areas. This allows the lactone ring, sultine ring, or sultone ring of the leuco compound to react with radicals generated from a photoradical polymerization initiator or acids generated from a photocationic polymerization initiator, thereby changing the leuco compound to a closed state and decolorizing it, or changing the leuco compound to an open state and developing color. As a leuco compound, it is preferable to have a lactone ring, sultine ring, or sultone ring, and the lactone ring, sultine ring, or sultone ring opens and develops color in response to radicals or acids, and more preferably a lactone ring, and the lactone ring opens and develops color in response to radicals or acids.

[0182] Examples of dyes N include the following dyes and leuco compounds. Specific examples of dyes among dyes N include: Brilliant Green, Ethyl Violet, Methyl Green, Crystal Violet, Basic Fuchsine, Methyl Violet 2B, Quinaldine Red, Rose Bengal, Methanyl Yellow, Thymol Sulfonphthalein, Xylenol Blue, Methyl Orange, Paramethyl Red, Congo Red, Benzopulpurine 4B, α-Naphthyl Red, Nile Blue 2B, Nile Blue A, Methyl Violet, Malachite Green, Parafuchsine, 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.), Oil Scarlet #308 (manufactured by Orient Chemical Co., Ltd.) Examples include Orient Chemical Industries Co., Ltd.'s Oil Red OG, Orient Chemical Industries Co., Ltd.'s Oil Red RR, Orient Chemical Industries Co., Ltd.'s Oil Green #502, Orient Chemical Industries Co., Ltd.'s Spilon Red BEH Special, Hodogaya Chemical Co., Ltd.'s m-Cresol Purple, Cresol Red, Rhodamine B, Rhodamine 6G, Sulforhodamine B, Auramine, 4-p-diethylaminophenyliminonaphthoquinone, 2-carboxyanilino-4-p-diethylaminophenyliminonaphthoquinone, 2-carboxystearylamino-4-p-N,N-bis(hydroxyethyl)aminophenyliminonaphthoquinone, 1-phenyl-3-methyl-4-p-diethylaminophenylimino-5-pyrazolone, and 1-β-naphthyl-4-p-diethylaminophenylimino-5-pyrazolone.

[0183] Specific examples of leuco compounds among the dye N include p,p',p''-hexamethyltriaminotriphenylmethane (leucocrystal violet), Pergascript Blue SRB (manufactured by Ciba-Geigy), crystal violet lactone, malachite green lactone, benzoylleucomethylene blue, 2-(N-phenyl-N-methylamino)-6-(N-p-tolyl-N-ethyl)aminofluorane, 2-anilino-3-methyl-6-(N-ethyl-p-toluidino)fluorane, 3,6-dimethoxyfluorane, 3-(N,N-diethylamino)-5-methyl-7-(N,N-dibenzylamino)fluorane, 3-(N-cyclohexyl-N-methylamino)- 6-methyl-7-anilinofluorane, 3-(N,N-diethylamino)-6-methyl-7-anilinofluorane, 3-(N,N-diethylamino)-6-methyl-7-xylidinofluorane, 3-(N,N-diethylamino)-6-methyl-7-chlorofluorane, 3-(N,N-diethylamino)-6-methoxy-7-aminofluorane, 3-(N,N-diethylamino)-7-(4-chloroanilino)fluorane, 3-(N,N-diethylamino)-7-chlorofluorane, 3-(N,N-di Ethylamino)-7-benzylaminofluorane, 3-(N,N-diethylamino)-7,8-benzofluorane, 3-(N,N-dibutylamino)-6-methyl-7-anilinofluorane, 3-(N,N-dibutylamino)-6-methyl-7-xylidinofluorane, 3-piperidino-6-methyl-7-anilinofluorane, 3-pyrrolidino-6-methyl-7-anilinofluorane, 3,3-bis(1-ethyl-2-methylindole-3-yl)phthalide, 3,3-bis(1-n-butyl-2- Examples include methylindole-3-yl)phthalide, 3,3-bis(p-dimethylaminophenyl)-6-dimethylaminophthalide, 3-(4-diethylamino-2-ethoxyphenyl)-3-(1-ethyl-2-methylindole-3-yl)-4-azaphthalide, 3-(4-diethylaminophenyl)-3-(1-ethyl-2-methylindole-3-yl)phthalide, and 3',6'-bis(diphenylamino)spiroisobenzofuran-1(3H),9'-[9H]xanthene-3-one.

[0184] From the viewpoint of visibility of exposed and unexposed areas, pattern visibility after development, and superior resolution, dye N is preferably a dye whose maximum absorption wavelength changes due to radicals, and more preferably a dye that develops color due to radicals. As dye N, leucocrystal violet, crystal violet lactone, brilliant green, or Victoria Pure Blue naphthalene sulfonate are preferred.

[0185] Dye N may be used alone or in combination of two or more types. From the viewpoint of visibility of exposed and unexposed areas, pattern visibility after development, and superior resolution, the content of dye N is preferably 0.10 to 10.00% by mass, more preferably 0.10 to 5.00% by mass, and even more preferably 0.10 to 1.00% by mass, relative to the total mass of the photosensitive composition layer. The content of dye N refers to the amount of dye when all of the dye N contained in the total mass of the photosensitive composition layer is brought into a colored state. The following describes a method for quantifying the content of dye N using a dye that develops color by radicals as an example. Prepare a solution by dissolving 0.001 g and 0.01 g of dye in 100 mL of methyl ethyl ketone. To each of the obtained solutions, the photoradical polymerization initiator Irgacure OXE01 (trade name, BASF Japan Co., Ltd.) is added, and radicals are generated by irradiating with 365 nm light, causing all the dyes to develop color. Then, under an atmospheric environment, the absorbance of each solution at a liquid temperature of 25°C is measured using a spectrophotometer (UV3100, Shimadzu Corporation) to create a calibration curve. Next, the absorbance of the solution in which all the dyes have developed color is measured using the same method as above, except that 3 g of the photosensitive composition layer is dissolved in methyl ethyl ketone instead of the dye. From the absorbance of the obtained solution containing the photosensitive composition layer, the amount of dye contained in the photosensitive composition layer is calculated based on the calibration curve.

[0186] <Rust Inhibitor> The photosensitive composition layer may also preferably contain a rust inhibitor. Examples of rust inhibitors include those that may be contained in the thermoplastic resin layer described above. The rust inhibitor may be used alone or in combination of two or more types. The content of the rust inhibitor is preferably 0.001 to 5.00% by mass, more preferably 0.01 to 1.00% by mass, and even more preferably 0.01 to 0.50% by mass, based on the total mass of the photosensitive composition layer.

[0187] <Polymerization Inhibitor> The photosensitive composition layer may also preferably contain a polymerization inhibitor. Examples of polymerization inhibitors include those that may be included in the thermoplastic resin layer described above. The polymerization inhibitor may be used alone or in combination of two or more types. The content of the polymerization inhibitor is preferably 0.001 to 5.00% by mass, more preferably 0.01 to 1.00% by mass, and even more preferably 0.01 to 0.50% by mass, based on the total mass of the photosensitive composition layer.

[0188] <Surfactants> The photosensitive composition layer may also preferably contain surfactants. Examples of surfactants include those that may be contained in the thermoplastic resin layer described above. Surfactants may be used alone or in combination of two or more. The surfactant content is preferably 0.001 to 5.00% by mass, more preferably 0.01 to 1.00% by mass, and even more preferably 0.01 to 0.50% by mass, based on the total mass of the photosensitive composition layer.

[0189] <Hydrogen-donating compounds> The photosensitive composition layer may contain hydrogen-donating compounds. Hydrogen-donating compounds have effects such as further improving the sensitivity of photopolymerization initiators to active light and suppressing polymerization inhibition of polymerizable monomers by oxygen.

[0190] Examples of hydrogen-donating compounds include amines and amino acid compounds.

[0191] Examples of amines include compounds described in M. R. Sander et al., "Journal of Polymer Society," Vol. 10, p. 3173 (1972), Japanese Patent Publication No. 44-020189, Japanese Unexamined Patent Publication No. 51-082102, Japanese Unexamined Patent Publication No. 52-134692, Japanese Unexamined Patent Publication No. 59-138205, Japanese Unexamined Patent Publication No. 60-084305, Japanese Unexamined Patent Publication No. 62-018537, Japanese Unexamined Patent Publication No. 64-033104, and Research Disclosure No. 33825, etc. More specifically, examples include 4,4'-bis(diethylamino)benzophenone, tris(4-dimethylaminophenyl)methane (also known as leucocrystal violet), triethanolamine, p-dimethylaminobenzoate 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 in terms of superior effects of the present invention.

[0192] Examples of amino acid compounds include N-phenylglycine, N-methyl-N-phenylglycine, and N-ethyl-N-phenylglycine. Among these, N-phenylglycine is preferred as the amino acid compound because it exhibits superior effects compared to the present invention.

[0193] Examples of hydrogen-donating compounds include organometallic compounds (such as tributyltin acetate) described in Japanese Patent Publication No. 48-042965, hydrogen donors described in Japanese Patent Publication No. 55-034414, and sulfur compounds (such as trithiane) described in Japanese Patent Application Publication No. 6-308727.

[0194] The hydrogen-donating compound may be used alone or in combination of two or more. The content of the hydrogen-donating compound is preferably 0.01 to 10.00% by mass, more preferably 0.01 to 8.00% by mass, and even more preferably 0.03 to 5.00% by mass, relative to the total mass of the photosensitive composition layer, in order to improve the curing speed by balancing the polymerization growth rate and chain transfer.

[0195] The photosensitive composition layer may contain known additives in addition to the above components, as needed. Examples of additives include chain transfer agents, polymerization inhibitors, antioxidants (e.g., phenidone), plasticizers, and particles (e.g., metal oxide particles). Other components include other additives described in paragraphs

[0058] to

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

[0196] <Properties of the photosensitive composition layer> The thickness of the photosensitive composition layer is preferably 1 to 30 μm, more preferably 1 to 15 μm, even more preferably 1 to 8 μm, particularly preferably 1 to 4 μm, and most preferably 1 to 3 μm, in terms of superior resolution.

[0197] [Protective Film] The transfer film may have a protective film on the photosensitive composition layer. As the protective film, a resin film having heat resistance and solvent resistance can be used, for example, polyolefin films such as polypropylene film and polyethylene film, polyester films such as polyethylene terephthalate film, polycarbonate film, and polystyrene film. Alternatively, a resin film made of the same material as the temporary support described above may be used as the protective film. Among these, polyolefin film is preferred as the protective film, polypropylene film or polyethylene film is more preferred, and polyethylene film is even more preferred.

[0198] The thickness of the protective film is preferably 1 to 100 μm, more preferably 5 to 50 μm, even more preferably 5 to 40 μm, and particularly preferably 15 to 30 μm, from the viewpoint of mechanical strength and economic considerations.

[0199] Furthermore, in the case of protective films, the number of fisheyes with a diameter of 80 μm or more contained in the protective film is 5 per meter. ２ The following is preferable: "Fish eyes" refer to foreign matter, undissolved material, and oxidatively degraded materials incorporated into the film during the manufacturing process of a film by methods such as thermal melting, kneading, extrusion, biaxial stretching, and casting.

[0200] The number of particles with a diameter of 3 μm or larger contained in the protective film is 30 particles / mm². ２ The following is preferable: 10 pieces / mm ２ The following is more preferable: 5 pieces / mm ２ The following is even more preferable: This makes it possible to suppress defects caused by the transfer of irregularities resulting from particles contained in the protective film to the photosensitive composition layer or metal layer.

[0201] From the viewpoint of providing windability, the arithmetic mean roughness Ra of the surface of the protective film opposite to the surface in contact with the photosensitive composition layer is preferably 0.01 μm or more, more preferably 0.02 μm or more, and even more preferably 0.03 μm or more. On the other hand, it is preferably less than 0.50 μm, more preferably 0.40 μm or less, and even more preferably 0.30 μm or less. From the viewpoint of suppressing defects during transfer, the surface roughness Ra of the surface of the protective film in contact with the photosensitive composition layer is preferably 0.01 μm or more, more preferably 0.02 μm or more, and even more preferably 0.03 μm or more. On the other hand, it is preferably less than 0.50 μm, more preferably 0.40 μm or less, and even more preferably 0.30 μm or less.

[0202] [Method for Manufacturing Transfer Film] There are no particular limitations on the method for manufacturing the transfer film, and known methods can be used. For example, a method for manufacturing the transfer film 10 shown in Figure 1 includes the steps of: applying a thermoplastic resin layer-forming composition to the surface of a temporary support 12 to form a coating film, and then drying this coating film to form a thermoplastic resin layer 14; applying an intermediate layer-forming composition to form a coating film, and then drying this coating film to form an intermediate layer 16; applying a photosensitive composition to the surface of the intermediate layer 16 to form a coating film, and then drying this coating film to form a photosensitive composition layer 18; and placing a protective film 20 on the photosensitive composition layer 18. By the above steps, a transfer film 10 can be manufactured in which the temporary support 12, the thermoplastic resin layer 14, the intermediate layer 16, the photosensitive composition layer 18, and the protective film 20 are laminated in this order. After manufacturing the transfer film 10 by the above manufacturing method, the transfer film 10 may be wound up to produce and store a transfer film in roll form. The roll-type transfer film 10 can be supplied in its original form for the lamination process with the substrate using the roll-to-roll method described later.

[0203] <Composition for forming a thermoplastic resin layer and method for forming a thermoplastic resin layer> The method for forming a thermoplastic resin layer on a temporary support is not particularly limited, and known methods can be used. For example, it can be formed by applying the composition for forming a thermoplastic resin layer to a temporary support and drying it as necessary. The composition for forming a thermoplastic resin layer preferably contains the various components for forming the thermoplastic resin layer described above and a solvent. In the composition for forming a thermoplastic resin 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 thermoplastic resin layer described above. The solvent is not particularly limited as long as it can dissolve or disperse each component other than the solvent, and known solvents can be used. Examples of solvents include those similar to the solvents contained in the photosensitive composition described later, and the preferred embodiments are also the same. The solvent content is preferably 50 to 1,900 parts by mass, and more preferably 100 to 900 parts by mass, per 100 parts by mass of the total solid content of the composition.

[0204] 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 include known coating methods (slit coating, spin coating, curtain coating, and inkjet coating, etc.).

[0205] <Composition for forming an intermediate layer and method for forming an intermediate layer> The intermediate layer formation composition preferably contains the various components for forming the intermediate layer described above and a solvent. In the intermediate layer formation composition, the preferred range for the content of each component relative to the total solid content of the composition is the same as the preferred range for the content of each component relative to the total mass of the intermediate layer described above. The solvent is not particularly limited as long as it can dissolve or disperse each component other than the solvent, 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 C1-C3 alcohols, acetone, ethylene glycol, and glycerin, with C1-C3 alcohols being preferred, and methanol or ethanol being more preferred. The solvent may be used alone or in combination of two or more. The solvent content 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, per 100 parts by mass of the total solid content of the composition.

[0206] The method for forming the intermediate layer composition is not particularly limited as long as it is a method capable of forming a layer containing the above components, and examples include known coating methods (slit coating, spin coating, curtain coating, and inkjet coating, etc.).

[0207] <Photosensitive composition (composition for forming a photosensitive composition layer) and method for forming a photosensitive composition layer> In terms of excellent productivity and ease of forming the above-mentioned photosensitive composition layer, it is desirable that the photosensitive composition layer be formed by a coating method using a photosensitive composition (composition for forming a photosensitive composition layer) containing the above-mentioned components constituting the photosensitive composition layer (for example, alkali-soluble resin, polymerizable monomer, and polymerization initiator, etc.) and a solvent.

[0208] The photosensitive composition preferably contains various components that form the photosensitive composition layer described above, and a solvent. In the photosensitive composition, the preferred range of content of each component relative to the total solid content of the composition is the same as the preferred range of content of each component relative to the total mass of the photosensitive composition layer described above. The solvent is not particularly limited as long as it can dissolve or disperse each component other than the solvent, and known solvents can be used. Specifically, examples include alkylene glycol ether solvents, alkylene glycol ether acetate solvents, alcohol solvents (methanol and ethanol, etc.), ketone solvents (acetone and 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.

[0209] The solvent preferably contains at least one selected from the group consisting of alkylene glycol ether solvents and alkylene glycol ether acetate solvents. More preferably, 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 preferred, and even more preferably, a mixed solvent containing at least three types: 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.

[0210] Examples of alkylene glycol ether solvents include ethylene glycol monoalkyl ether, ethylene glycol dialkyl ether, propylene glycol monoalkyl ether (such as propylene glycol monomethyl ether acetate), propylene glycol dialkyl ether, diethylene glycol dialkyl ether, dipropylene glycol monoalkyl ether, and dipropylene glycol dialkyl ether. Examples of alkylene glycol ether acetate solvents include ethylene glycol monoalkyl ether acetate, propylene glycol monoalkyl ether acetate, diethylene glycol monoalkyl ether acetate, and dipropylene glycol monoalkyl ether acetate. As solvents, solvents described in paragraphs 0092 to 0094 of International Publication No. 2018 / 179640 and solvents described in paragraph 0014 of Japanese Patent Application Publication No. 2018-177889 may be used, and these contents are incorporated herein. Solvents may be used individually or in combination of two or more. The solvent content 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, per 100 parts by mass of the total solids content of the composition.

[0211] Methods for applying the photosensitive composition include, for example, printing, spraying, roll coating, bar coating, curtain coating, spin coating, and die coating (i.e., slit coating).

[0212] For drying the coating film of the photosensitive composition, heat drying and vacuum drying are preferred. The drying temperature is preferably 80°C or higher, and more preferably 90°C or higher. The upper limit is preferably 130°C or lower, and more preferably 120°C or lower. Drying can also be performed by continuously changing the temperature. The drying time is preferably 20 seconds or higher, more preferably 40 seconds or higher, and even more preferably 60 seconds or higher. There is no particular upper limit to the drying time, but it is preferably 600 seconds or lower, and more preferably 300 seconds or lower.

[0213] Furthermore, a transfer film can be manufactured by laminating a protective film onto a photosensitive composition layer. The method for laminating the protective film onto the photosensitive composition layer is not particularly limited and known methods can be used. Examples of equipment for laminating the protective film onto the photosensitive composition layer include known laminators such as vacuum laminators and auto-cut laminators. It is preferable that the laminator is equipped with any heatable roller, such as a rubber roller, and is capable of applying pressure and heating.

[0214] [Properties of the Transfer Film] <Transmittance of the Transfer Film> The transfer film is subjected to ultraviolet light, including light with a wavelength of 365 nm, when the irradiation dose at a wavelength of 365 nm is 2000 mJ / cm². ２ When irradiation is performed from the thermoplastic resin layer side, and the transmittance of the laminate at a wavelength of 365 nm before irradiation is T0, and the transmittance of the laminate at a wavelength of 365 nm after irradiation is T2000, the value of T2000 / T0 is preferably 250 or more, more preferably 500 or more, and even more preferably 1000 or more, in terms of superior effects of the present invention. The upper limit is typically 15,000 or less, and preferably 12,000 or less.

[0215] Specifically, T2000 and T0 can be measured using a laminate T obtained by laminating a transfer film to glass such that the photosensitive composition layer of the transfer film is in contact with the glass, and then peeling off the temporary support. If the transfer film comprises, for example, a temporary support, a thermoplastic resin layer, and a photosensitive composition layer, the laminate T has a glass / photosensitive composition layer / thermoplastic resin layer configuration. If the transfer film comprises, for example, a temporary support, a thermoplastic resin layer, an intermediate layer, and a photosensitive composition layer, the laminate T has a glass / photosensitive composition layer / intermediate layer / thermoplastic resin layer configuration. T2000 and T0 of the laminate (the laminate obtained by peeling off the temporary support from the transfer film of the present invention) can be obtained by excluding the transmittance of the glass from the transmittance measured for the laminate T before and after ultraviolet light irradiation. The light irradiated onto the laminate is ultraviolet light including light with a wavelength of 365 nm. As the irradiation method, a method can be used in which light emitted from a light source is irradiated through a bandpass filter with a wavelength of 365 nm. The above light source is not particularly limited as long as it is a light source capable of emitting ultraviolet light including light with a wavelength of 365 nm. Examples include low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, carbon arc lamps, metal halide lamps, xenon lamps, chemical lamps, electrodeless discharge lamps, and light-emitting diodes (LEDs) that emit light in the 150-450 nm wavelength range. The exposure time, etc., is based on an irradiation dose of 2000 mJ / cm² at a wavelength of 365 nm. ２ The parameters can be adjusted as needed to achieve the above result. The transmittance before and after irradiation can be measured using a spectrophotometer (for example, a Shimadzu UV-1800). The irradiation dose at a wavelength of 365 nm can be measured using a known illuminometer.

[0216] The T2000 / T0 value can be adjusted by adjusting the composition (especially the type and content of the nitrone compound) and layer thickness of each layer in the transfer film.

[0217] T0 is preferably 10% or less, more preferably 1% or less, and even more preferably 0.1% or less. The lower limit of T0 is 0% or more, and is often 0.0001% or more. T2000 is preferably 30% or more, more preferably 40% or more, even more preferably 45% or more, and particularly preferably 50% or more. The upper limit of T2000 is 100% or less, is often 95% or less, and is more often 90% or less.

[0218] In the present invention, it is preferable that the transfer film satisfies the above-mentioned requirements when ultraviolet light including light with a wavelength of 405 nm is used instead of ultraviolet light including light with a wavelength of 365 nm, and the ratio of transmittance measured at a wavelength of 405 nm also satisfies the above-mentioned requirements. That is, the transfer film is obtained by peeling off a temporary support and irradiating the laminate with ultraviolet light including light with a wavelength of 405 nm with an irradiation dose of 2000 mJ / cm² at a wavelength of 405 nm. ２ When irradiated in such a manner, and the transmittance of the laminate at a wavelength of 405 nm before irradiation is T0' and the transmittance of the laminate at a wavelength of 405 nm after irradiation is T2000', the value of T2000' / T0' is preferably 250 or more, more preferably 500 or more, and even more preferably 1000 or more, in terms of superior effects of the present invention. The upper limit is typically 15000 or less, and preferably 12000 or less.

[0219] <Transmittance of the photosensitive composition layer> The photosensitive composition layer of the transfer film has a transmittance of 2000 mJ / cm² relative to the photosensitive composition layer. ２ The photosensitive composition layer is irradiated with ultraviolet light including light with a wavelength of 365 nm, and the transmittance at the above wavelength of 365 nm after irradiation is measured. Ｔ２０００ In that case, the above Re Ｔ２０００ It is preferable that the percentage is 75% or more. Ｔ２０００ The lower limit is more preferably 80% or more, even more preferably 85% or more, and particularly preferably 90% or more. Ｔ２０００ The upper limit is 100% or less, and is often 95% or less.

[0220] The above Re Ｔ２０００This is determined by excluding the transmittance of glass from the transmittance measured for the laminate TP (glass / photosensitive composition layer after light irradiation) obtained by removing the thermoplastic resin layer and intermediate layer from the laminate T after light irradiation used for measuring T2000 and T2000' described above. Methods for removing the thermoplastic resin layer and intermediate layer include removal by applying a developer solution (e.g., applying an alkaline developer solution) and removal by peeling off tape. The method of irradiation with ultraviolet light and the method of measuring the transmittance described above can be the same as the method for measuring T2000 / T0 of the transfer film described above.

[0221] It is preferable that the photosensitive composition layer of the transfer film also satisfies the above requirements when the transmittance measured at a wavelength of 405 nm is obtained using ultraviolet light including light with a wavelength of 405 nm, instead of ultraviolet light including light with a wavelength of 365 nm. That is, the photosensitive composition layer of the transfer film should have a transmittance of 2000 mJ / cm² relative to the photosensitive composition layer. ２ The photosensitive composition layer is irradiated with ultraviolet light including light with a wavelength of 405 nm, and the transmittance at the above wavelength of 405 nm after irradiation is measured. Ｔ２０００ ' と When that happens, the above Re Ｔ２０００ It is preferable that ' is 75% or more. Ｔ２０００ The lower limit of ' is more preferably 80% or more, even more preferably 85% or more, and particularly preferably 90% or more. Ｔ２０００ The upper limit for ' is 100% or less, and is often 95% or less.

[0222] [Applications] The transfer film of the present invention can be applied to a variety of applications. For example, it can be applied to electrode protective films, insulating films, planarization films, overcoat films, hardcoat films, passivation films, partitions, spacers, microlenses, optical filters, anti-reflective films, etching resists, and plated components. More specific examples include protective films or insulating films for touch panel electrodes, protective films or insulating films for printed circuit boards, protective films or insulating films for TFT substrates, color filters, overcoat films for color filters, etching resists and plating resists for wiring formation, and metal masks with minute through-holes used in the manufacture of OLEDs (Organic Light Emitting Diodes), etc.

[0223] The transfer film of the present invention is preferably used in the manufacture of a laminate having a conductive pattern, and more specifically, it is preferably used in the formation of an etching resist or plating resist for the formation of a conductive pattern.

[0224] [Method for Manufacturing a Laminate Having a Conductor Pattern] The method for manufacturing a laminate having a conductor pattern is not particularly limited as long as it uses the transfer film of the present invention, but the following method is preferred. The method includes: a bonding step of bonding the transfer film of the present invention described above so that the photosensitive composition layer side is in contact with the metal layer of a substrate having a metal layer on its surface; an exposure step of pattern-exposing the photosensitive composition layer from the side opposite to the substrate side; a developing step of developing the exposed photosensitive composition layer using an alkaline developer to form a resist pattern; an etching step of etching the metal layer in an area where the resist pattern is not arranged to form a conductor pattern, and a plating step of plating the metal layer; a resist peeling step of peeling off the resist pattern; and, if the plating step is included, a removal step of removing the metal layer exposed by the resist peeling step to form a conductor pattern on the substrate. The specific steps of the above manufacturing method will be described in detail below.

[0225] [Peeling Step] If the transfer film has a protective film, the above manufacturing method preferably includes a peeling step to peel the protective film from the transfer film before the lamination step. When the peeling step is performed, the surface of the photosensitive composition layer of the transfer film is exposed. The method of peeling the protective film is not particularly limited and can be carried out by known methods. For example, the protective film can be peeled off while being wound into a roll.

[0226] [Lamination Process] The lamination process involves laminating the transfer film so that the photosensitive composition layer side is in contact with the metal layer of a substrate having a metal layer on its surface. After performing the lamination process, a laminate (substrate with photosensitive composition layer) is obtained having the substrate, conductive layer, thermoplastic resin layer, intermediate layer, photosensitive composition layer, and temporary support in this order.

[0227] The substrate having the conductive layer described above has a conductive layer on the substrate, and any additional layers may be formed as needed. In other words, the substrate having a conductive layer is a conductive substrate having at least a substrate and a conductive layer disposed on the substrate.

[0228] Examples of substrates include resin substrates, glass substrates, and semiconductor substrates. Preferred embodiments of the substrate are described, for example, in paragraph

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

[0229] 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, from the viewpoint of conductivity and fine wire formation. Furthermore, only one conductive layer may be arranged on the substrate, or two or more layers may be arranged. When two or more conductive layers are arranged, it is preferable that the conductive layers be made of different materials. Preferred embodiments of the conductive layer are described, for example, in paragraph

[0141] of International Publication No. 2018 / 155193, and this content is incorporated herein by reference.

[0230] The conductive layer may be a transparent conductive layer capable of forming a transparent electrode through a process described later. The transparent conductive layer is preferably composed of a metal oxide film such as ITO (indium tin oxide) and IZO (indium zinc oxide), as well as metal wires such as metal mesh and metal nanowires. Examples of metal wires include silver and copper wires. Among these, silver conductive materials such as silver mesh and silver nanowires are preferred.

[0231] The thickness of the conductive layer is not particularly limited, but is preferably 50 nm or more, and more preferably 100 nm or more. The upper limit is preferably 10 μm or less, and more preferably 2 μm or less.

[0232] In the above bonding process, it is preferable to press the conductive layer and the surface of the photosensitive composition layer together so that they are in contact. There are no particular restrictions on the method of pressing, and known transfer methods and lamination methods can be used. In particular, it is preferable to place the surface of the photosensitive composition layer on a substrate having a conductive portion and apply pressure and heat using a roll or the like. Known laminators such as vacuum laminators and auto-cut laminators can be used for bonding. There are no particular restrictions on the lamination temperature, but for example, 70 to 130°C is preferred.

[0233] [Exposure Process] The exposure process is a process of pattern-exposing the photosensitive composition layer from the side opposite to the substrate. By performing the exposure process and the development process described later, a resist pattern that protects at least a part of the conductive layer is formed on the conductive layer on the substrate. Here, "pattern exposure" refers to exposure in a patterned manner, that is, exposure in a manner in which exposed areas and unexposed areas exist. The positional relationship between the exposed and unexposed areas in pattern exposure is not particularly limited and can be adjusted as appropriate.

[0234] As a light source for pattern exposure, any light source capable of irradiating light in a wavelength range sufficient to cure the photosensitive composition layer (e.g., 365 nm or 405 nm) can be appropriately selected and used. Among these, 365 nm is preferred as the dominant wavelength of the exposure light for pattern exposure. The dominant wavelength is the wavelength with the highest intensity. 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 / cm². ２ Preferably, 10 to 200 mJ / cm² ２ This is preferable.

[0235] Examples of exposure methods include mask exposure, direct imaging exposure, and projection exposure, with projection exposure being preferred. A preferred embodiment of the light source, exposure amount, and exposure method used for exposure is described, for example, in paragraphs

[0146] to

[0147] of International Publication No. 2018 / 155193, which are incorporated herein by reference.

[0236] [Temporary support peeling step] The above manufacturing method preferably includes a temporary support peeling step for peeling off the temporary support. The temporary support peeling step is performed between the lamination step and the exposure step, or between the exposure step and the development step described later, and is preferably performed before the exposure step (specifically, between the lamination step and the exposure step). The peeling method is not particularly limited, and a mechanism similar to the cover film peeling mechanism described in paragraphs

[0161] to

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

[0237] [Development Process] The development process is a process of developing the exposed photosensitive composition layer using an alkaline developer to form a resist pattern. When the photosensitive composition layer is a negative-type photosensitive composition layer, the unexposed portion of the photosensitive composition layer is removed by the alkaline developer, and the exposed photosensitive composition layer is formed as a resist pattern. It is also preferable that the thermoplastic resin layer and the intermediate layer are removed in the development process. An alkaline aqueous solution is preferred for the alkaline developer. Examples of alkaline compounds that may be included in the alkaline developer include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, and choline (2-hydroxyethyltrimethylammonium hydroxide).

[0238] Examples of development methods include paddle development, shower development, spin development, and dip development.

[0239] Examples of developers preferred in this specification include the developer described in paragraph

[0194] of International Publication No. 2015 / 093271, and examples of development methods preferred in this specification include the development method described in paragraph

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

[0240] After development, it is preferable to perform a rinsing process to remove any remaining developer solution from the conductive layer substrate before proceeding to the next step. Water or the like can be used for the rinsing process. After development and / or rinsing, a drying process may be performed to remove any excess liquid from the conductive layer substrate.

[0241] In the method for manufacturing a laminate having a conductive pattern, either an etching step or a plating step is performed.

[0242] [Etching Process] The etching process is a process of forming a conductive pattern by applying an etching process to the metal layer in the area where the resist pattern is not placed. Known methods can be applied as etching methods, for example, the method described in paragraphs

[0209] to

[0210] of Japanese Patent Application Publication No. 2017-120435, the method described in paragraphs

[0048] to

[0054] of Japanese Patent Application Publication No. 2010-152155, a wet etching method involving immersion in an etching solution, and a dry etching method such as plasma etching.

[0243] For wet etching, the etching solution used should be appropriately selected as either acidic or alkaline depending on the material to be etched. Examples of acidic etching solutions include aqueous solutions of a single acidic component selected from hydrochloric acid, sulfuric acid, nitric acid, acetic acid, hydrofluoric acid, oxalic acid, and phosphoric acid, as well as aqueous solutions 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 a single alkaline component selected from sodium hydroxide, potassium hydroxide, ammonia, organic amines, and salts of organic amines (such as tetramethylammonium hydroxide), as well as aqueous solutions of an alkaline component and a salt (such as potassium permanganate). The alkaline component may be a combination of multiple alkaline components.

[0244] [Plating Process] The plating process is a process of applying a plating treatment to the conductive layer in areas where a resist pattern is not placed. Examples of plating methods include electrolytic plating and electroless plating, and electrolytic plating is preferred from the viewpoint of productivity. When the plating process is carried out, a plated layer having a pattern shape similar to the areas where a resist pattern is not placed (openings of the resist pattern) is obtained on the substrate with the conductive layer. When carrying out the plating process, it is preferable that the conductive layer is a metal layer.

[0245] Examples of metals that can be included in the plating layer include known metals. Specifically, these include metals such as copper, chromium, lead, nickel, gold, silver, tin, and zinc, as well as alloys of these metals. Among these, the plating layer preferably contains copper or an alloy thereof, as this provides superior conductivity of the conductor pattern. Furthermore, the plating layer preferably contains copper as its main component, as this provides superior conductivity of the conductor pattern.

[0246] The thickness of the plating layer is preferably 0.1 μm or more, and more preferably 1 μm or more. The upper limit is preferably 20 μm or less.

[0247] [Resist Stripping Step] In the method for manufacturing a laminate having the conductive pattern described above, a resist stripping step is included after the etching step or the plating step. The resist stripping step is a step of stripping off the remaining resist pattern. There are no particular limitations on the method of removing the resist pattern, but a method of removal by chemical treatment is one example, and a method of removal using a removal solution is preferred. As a removal method, one example is to immerse a substrate having the remaining resist pattern in a stirring removal solution, preferably at a liquid temperature of 30 to 80°C, more preferably 50 to 80°C, for 1 to 30 minutes. Examples of removal solutions include a removal solution obtained by dissolving an inorganic alkaline component or an organic alkaline component in water, dimethyl sulfoxide, N-methylpyrrolidone, or a mixture thereof. Examples of inorganic alkaline components include sodium hydroxide and potassium hydroxide. Examples of organic alkaline components include primary amine compounds, secondary amine compounds, tertiary amine compounds, and quaternary ammonium salt compounds. Alternatively, the removal may be carried out using a known method such as a spray method, a shower method, or a paddle method with the removal solution.

[0248] [Removal step] In the method for manufacturing a laminate, if a plating process is performed, the method includes a removal step to remove the metal layer exposed by the resist peeling step and form a conductive pattern on the substrate.

[0249] There are no particular limitations on the method for removing a portion of the conductive layer, but it is preferable to use a known etching solution. Examples of known etching solutions include ferric chloride solution, cupric chloride solution, ammonia alkali solution, sulfuric acid-hydrogen peroxide mixture, and phosphoric acid-hydrogen peroxide mixture.

[0250] When the removal process is performed, the conductive layer exposed on the surface of the substrate is removed, while the plated layer with a pattern shape (conductor pattern) remains, resulting in a laminate having a conductor pattern.

[0251] The upper limit of the line width of the formed conductor pattern is preferably 8 μm or less, and more preferably 6 μm or less. There is no particular limit to the lower limit, but it is often 1 μm or more.

[0252] [Other steps] The method for manufacturing a laminate having a conductive pattern may include any steps other than those described above (other steps). For example, these may include, but are not limited to, the steps of reducing the visible light reflectance as described in paragraph

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

[0172] of International Publication No. 2019 / 022089.

[0253] <Step to reduce visible light reflectance> A method for manufacturing 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 multiple conductive layers having a substrate. An example of a treatment to reduce visible light reflectance is oxidation treatment. If 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 to reduce visible light reflectance are described in paragraphs 0017 to 0025 of Japanese Patent Application Publication No. 2014-150118 and in paragraphs 0041, 0042, 0048 and 0058 of Japanese Patent Application Publication No. 2013-206315, and the contents described in these publications are incorporated herein by reference.

[0254] <Steps for forming an insulating film and forming a new conductive layer on the surface of the insulating film> The method for manufacturing a laminate having a conductive pattern may also preferably include 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 for forming the insulating film is not particularly limited and includes known methods for forming a permanent film. Alternatively, an insulating photosensitive material may be used to form an insulating film with a desired pattern by photolithography. The step for forming a new conductive layer on the insulating film is not particularly limited and, for example, a conductive photosensitive material may be used to form a new conductive layer with a desired pattern by photolithography.

[0255] In the manufacturing method of a laminate having a conductive pattern, it is preferable to use a substrate having multiple conductive layers on both surfaces of the substrate, and to sequentially or simultaneously form circuits on the conductive layers formed on both surfaces of the substrate. With such a configuration, a laminate having a conductive pattern for a touch panel can be formed in which a first conductive pattern is formed on one surface of the substrate and a second conductive pattern is formed on the other surface. It is also preferable to form such a laminate having a conductive pattern for a touch panel from both sides of the substrate using a roll-to-roll method.

[0256] [Applications of Laminates Having Conductive Patterns] Laminates having conductive patterns manufactured by the above manufacturing method can be applied to various devices. Examples of devices equipped with laminates having conductive patterns manufactured by the above manufacturing method include display devices, printed circuit boards, semiconductor packages, and input devices (e.g., touch panels), with printed circuit boards or semiconductor packages being preferred. Furthermore, the above input devices can be applied to display devices such as organic EL displays and liquid crystal displays.

[0257] The present invention will be described in more detail below based on the following examples. The materials, amounts used, proportions, processing content, and processing procedures shown in the following examples can be modified as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be interpreted as being limited by the following examples.

[0258] In the following examples, unless otherwise specified, "parts" and "%" are based on mass. Also, in the following examples, unless otherwise specified, the theoretical acid value was used.

[0259] [Manufacturing of Transfer Film] The composition and components of each layer used in the production of the transfer film are described below.

[0260] [Photosensitive Composition Layer] Table 1 shows the composition of each photosensitive composition layer in each transfer film described later. The numerical values ​​for each component represent the amount (parts by mass) used for each component.

[0261]

[0262] Details of each component are as follows:

[0263] <Resin (Alkali-Soluble Resin)> Resin A1 was synthesized using the method described later. Table 2 below shows the types and mass ratios (mass%) of each monomer used to synthesize resin A1, as well as the weight-average molecular weight. The weight-average molecular weight (Mw) of the synthesized resin A1 was measured by gel permeation chromatography (GPC) under the following conditions.

[0264] - GPC Conditions - Equipment: Tosoh Corporation, Tosoh High-Speed ​​GPC System HLC-8420GPC (product name) Guard column: Tosoh Corporation, HZ-L Separation column: Tosoh Corporation, three TSK gel Super HZM-N (product name) columns connected in series Measurement temperature: 40°C Eluent: THF (tetrahydrofuran) Flow rate: Sample pump 0.35 mL / min, reference pump 0.175 mL / min Injection volume: 10 μL Detector: Differential refractometer GPC column calibration standard solution: Tosoh Corporation standard polystyrene

[0265]

[0266] The abbreviations in the table represent the following compounds: St: Styrene (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) MAA: Methacrylic acid (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) MMA: Methyl methacrylate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) MAA-GMA: A structure in which glycidyl methacrylate is added to a structural unit derived from methacrylic acid.

[0267] -Synthesis of Resin A1- 67 g of propylene glycol monomethyl ether was placed in a flask and heated to 90°C under a nitrogen stream. To this solution, 45.0 g of styrene, 5.0 g of methyl methacrylate, 50.0 g of methacrylic acid, and 4 g of polymerization initiator V-601 (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) were dissolved in 33 g of propylene glycol monomethyl ether and added dropwise over 3 hours. After the dropwise addition was complete, 1 g of V-601 was added three times at 1-hour intervals. The reaction was then allowed to proceed for another 3 hours. After the reaction, the reaction solution was diluted with 33 g of propylene glycol monomethyl ether acetate and 100 g of propylene glycol monomethyl ether. Under an air stream, the diluted reaction solution was heated to 100°C, and 0.53 g of tetraethylammonium bromide and 0.26 g of p-methoxyphenol were added. 30 g of glycidyl methacrylate (Bremmer G, manufactured by NOF Corporation) was added dropwise to this solution over 20 minutes. After reacting this solution at 100°C for 7 hours, it was diluted with propylene glycol monomethyl ether acetate to obtain a solution of resin A1 with a solid content of 30%.

[0268] The above resin A1 solution was used in the preparation of the photosensitive composition layer-forming composition described later. The resin content in Table 1 above refers to the amount of solids.

[0269] <Other Components> Details of each component other than the resin in Table 1 are as follows: (Polymerizable Compounds (Radical Polymerizable Monomers)) ・BPE-500: 2,2-bis(4-(methacryloxypentaethoxy)phenyl)propane, manufactured by Shin Nakamura Chemical Industry Co., Ltd. ・BPE-100: 2,2-bis(4-(methacryloylethoxy)phenyl)propane, manufactured by Shin Nakamura Chemical Industry Co., Ltd. ・Arronix M-270: Polypropylene glycol diacrylate (n≒12), manufactured by Toagosei Co., Ltd., listed as "M-270" in the table (Polymerization Initiator) ・B-CIM: 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, manufactured by Hampford (Sensitizer) ・SB-PI 701: 4,4'-bis(diethylamino)benzophenone, manufactured by Sanyo Trading Co., Ltd. (Chain Transfer Agent) • N-phenylcarbamoylmethyl-N-carboxymethylaniline: Manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. (Dye) • LCV: Leucocrystal violet, manufactured by Tokyo Chemical Industry Co., Ltd. (Rust inhibitor) • CBT-1: Carboxybenzotriazole, manufactured by Johoku Chemical Co., Ltd. (Polymerization inhibitor) • TDP-G: Phenothiazine, manufactured by Kawaguchi Chemical Co., Ltd.

[0270] (Surfactants) ・Polymer W1: A polymer synthesized by the following method (indicated as "W1" in the table).

[0271] A 300 mL three-necked flask equipped with a condenser, thermometer, stirring blade, and nitrogen inlet tube was heated to 80°C with 14.0 g of cyclopentanone. A mixed solution of 18.00 g (42.6 mmol) of Cyraprene™-0701T (JNC), 12.00 g (30.2 mmol) of compound (a) below, 0.25 g (1.1 mmol) of V-601 (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), and 56.00 g of cyclopentanone was added dropwise over 120 minutes. After aging for 1 hour, a mixed solution of 0.17 g (0.7 mmol) of V-601 and 1.40 g of cyclopentanone was added and aged for another hour. A further mixed solution of 0.17 g (0.7 mmol) of V-601 and 1.40 g of cyclopentanone was added and aged for 3 hours to obtain 98.5 g of the target polymer W1 solution. The weight-average molecular weight Mw of the obtained polymer W1 was 24,700, and the Mw / Mn ratio was 2.8. The progress of the reaction was also confirmed by NMR.

[0272]

[0273] The structure of polymer W1 is as follows. The numerical values ​​for each structural unit indicate the mass ratio.

[0274]

[0275] The solution of polymer W1 obtained in the upper section was used to prepare the photosensitive composition layer-forming composition described later. Note that the amount of surfactant W1 in Table 1 above represents the amount of solids.

[0276] <Preparation of photosensitive composition for forming a photosensitive layer> After mixing the above-mentioned components to obtain the composition shown in Table 1, methyl ethyl ketone (MEK) was added to prepare a photosensitive composition for forming a photosensitive layer with a solid content of 15% by mass.

[0277] [Intermediate Layer] Table 3 shows the composition of each intermediate layer in each transfer film described later. The values ​​for each component represent the amount (parts by mass) used for each component.

[0278]

[0279] Details of each component are as follows: <Resin> ・PVA: Polyvinyl alcohol, product name "Kuraray Poval PVA-205", manufactured by Kuraray Co., Ltd. ・PVP: Polyvinylpyrrolidone, product name "Polyvinylpyrrolidone K-30", manufactured by Nippon Shokubai Co., Ltd. ・HPMC: Hydroxypropyl methylcellulose, product name "Metrol 60SH-03", manufactured by Shin-Etsu Chemical Co., Ltd.

[0280] <Surfactants> ・Silicone-based surfactant, product name "BYK-345", manufactured by Bic Chemie Japan Co., Ltd.

[0281] <Photocatalytically extinct compounds> • 4-(N,N-dimethylamino)benzenediazonium tetrafluoroborate, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. (Molar extinction coefficient at a wavelength of 360 nm before quenching: 10,000 L・mol) －１ ・cm －１ Molar extinction coefficient at a wavelength of 360 nm after quenching: 1,500 L·mol －１ ・cm －１ )

[0282] <Preparation of Intermediate Layer Forming Composition> After mixing each component to obtain the composition shown in Table 3, a solvent (a mixed solvent prepared by mixing ion-exchanged water and methanol (manufactured by Mitsubishi Gas Chemical Co., Ltd.) in a mixing ratio (ion-exchanged water / methanol [mass ratio]) of 40 / 60) was added to prepare an intermediate layer forming composition with a solid content of 5% by mass.

[0283] [Thermoplastic Resin Layer] Table 4 shows the composition of each thermoplastic resin layer in each transfer film described later. The values ​​for each component represent the amount (parts by mass) used for each component.

[0284]

[0285]

[0286] Details of each component are as follows:

[0287] <Resins (Alkali-Soluble Thermoplastic Resins)> Resins A2 to A4 were synthesized according to the synthesis method of resin A1. Table 5 shows the types and mass ratios (mass%) of each monomer used to synthesize resins A2 to A4, as well as the weight-average molecular weight. The weight-average molecular weight was measured using the same method as described above for resin A1.

[0288]

[0289] The abbreviations in the table represent the following compounds: BzMA: Benzyl methacrylate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) MAA: Methacrylic acid (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) AA: Acrylic acid (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) BA: Butyl acrylate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.)

[0290] <Plasticizers> ・A-DCP: Tricyclodecanedimethanol diacrylate, manufactured by Shin-Nakamura Chemical Industry Co., Ltd. ・8UX-015A: Urethane acrylate, manufactured by Taisei Fine Chemical Co., Ltd. ・Aronics TO-2349: Polyfunctional acrylate containing carboxyl groups, manufactured by Toagosei Co., Ltd. ・DCP: Tricyclodecanedimethanol dimethacrylate, manufactured by Shin-Nakamura Chemical Industry Co., Ltd. ・BPE-500: 2,2-bis(4-(methacryloxypentaethoxy)phenyl)propane, manufactured by Shin-Nakamura Chemical Industry Co., Ltd. ・ARFON UC3510: Acrylic polymer containing carboxylic acid groups, manufactured by Toagosei Co., Ltd.

[0291] <Rust Inhibitor> ・CBT-1: Carboxybenzotriazole, manufactured by Johoku Chemical Co., Ltd.

[0292] <Polymerization inhibitor> ・TDP-G: Phenothiazine, manufactured by Kawaguchi Chemical Co., Ltd.

[0293] <Nitron Compounds> Compounds (A) to (H): Compounds synthesized by the synthesis methods described later were used. Compounds (A) to (H) are as follows.

[0294]

[0295] <Surfactants> ・EXP. S-315: Manufactured by DIC Corporation ・Megafac F552: Manufactured by DIC Corporation

[0296] <<Synthesis of Compounds (A) to (H)>> ・Synthesis example of Compound (A):

[0297]

[0298] To a mixed methanol / water solution (volume ratio methanol 10 / water 1, 550 mL) of 2-formylpyrrole (47.5 g, 1 eq.), 4-ethylnitrobenzene (75.6 g, 1 eq.) and zinc (68.6 g, 2.1 eq.), acetic acid (150 g, 5 eq.) was added dropwise at 0° C. over 30 minutes. After completion of the dropwise addition, the reaction solution was warmed to room temperature, stirred for 2 hours, ethyl acetate was added, and the resulting precipitate was separated by filtration (ethyl acetate was used to wash the precipitate). Water was added to the obtained filtrate, followed by stirring, extraction was performed with ethyl acetate, the obtained organic layer was washed with saturated aqueous sodium bicarbonate and saturated brine, then dried over magnesium sulfate. The organic solvent was distilled off from the obtained organic layer using a rotary evaporator, tert-butyl methyl ether was added to the residue, and the resulting solid was collected by filtration (tert-butyl methyl ether was also used to wash the solid), to give Compound (A) (89.2 g, 83%) as a gray solid.

[0299] For Compound (A) 1 H NMR (400MHz,CDCl3) δ12.19(brs,1H),7.92(s,1H),7.68(d,2H,J=4.0Hz),7.29(d,2H,J=4.0Hz),7.06(d,1H,J=4.0Hz),6.68(d,1H,J=4.0Hz),6.40(d,1H,J=4.0Hz),2.71(q,2H,J=8.0Hz),1.26(t,3H,J=8.0Hz).

[0300] ・Synthesis examples of Compounds (B) to (H): Compounds (B) to (H) were synthesized according to the synthesis procedure for Compound (A), except that the types of the aldehyde compound and nitro compound were changed.

[0301] ・・Synthesis example of Compound (B)

[0302]

[0303] For Compound (B) 1H NMR (400MHz, CDCl3) δ8.33(s,1H),7.73(d,2H,J=4.0Hz),7.43(d,1H,J=4.0Hz),7.29(d,2H,J=4 .0Hz),6.90(d,1H,J=4.0Hz),2.71(q,2H,J=8.0Hz),1.26(t,3H,J=8.0Hz).

[0304] ・・Synthesis example of compound (C)

[0305]

[0306] Compound (C) 1 H NMR (400MHz, CDCl3) δ8.24(s,1H),7.72(d,2H,J=4.0Hz),7.33(d,1H,J=4.0Hz),7.28(d,2H,J=4 .0Hz),6.42(d,1H,J=4.0Hz),2.70(q,2H,J=8.0Hz),1.26(t,3H,J=8.0Hz).

[0307] ・・Synthesis example of compound (D)

[0308]

[0309] Compound (D) 1 H NMR (400MHz, CDCl3) δ12.15(brs,1H),7.84(s,1H),7.38(s,2H),7.33-7.25(m,5H),7.04(d,1H,J=4.0Hz),6.65(d,1H,J =4.0Hz),6.38(d,1H,J=4.0Hz),3.99(t,2H,J=8.0Hz),3.12(t,2H,J=8.0Hz),2.22(s,6H).(several signals are overlapped)

[0310] ・・Synthesis example of compound (E)

[0311]

[0312] Compound (E) 1H NMR (400MHz, CDCl3) δ8.81(s,1H),8.14(d,1H,J=4.0Hz),7.80(d,2H,J=8.0Hz),7.56(d,1H,J=4 .0Hz),7.35(d,2H,J=8.0Hz),2.74(q,2H,J=8.0Hz),1.28(t,3H,J=8.0Hz).

[0313] ・・Synthetic example of compound (F)

[0314]

[0315] Compound (F) 1 H NMR (400 MHz, CDCl3) δ9.14(d,1H,J=4.0Hz),8.04(s,1H),7.70(d,2H,J=8.0Hz),7.45-7.28(m,4H),2.72(q,2H,J=8.0Hz),1.27(t,3H,J=8.0Hz).(several signals are overlapped).

[0316] ・・Synthesis example of compound (G)

[0317]

[0318] Compound (G) 1 H NMR (400MHz, CDCl3) δ8.66(s,1H), 8.01(d, 2H, J=4.0Hz)), 7.87(d,2H, J=4.0Hz), 7.71(d, 1H, J=4.0Hz), 7.63(d, 1H, J=4.0Hz).

[0319] ・・Synthetic example of compound (H)

[0320]

[0321] Compound (H) 1H NMR (400MHz,CDCl3) δ8.59 (s,1H),8.19(d,2H,J=4.0Hz),7.93(d,1H,J=4.0Hz),7.88(d,2H,J=4.0Hz),7.58(d,1H,J=4.0Hz),5.29 (septet,1H,J=8.0Hz), 4.39 (q, 2H, J=8.0Hz), 1.42-1.39 (m,9H). (several signals are overlapped)

[0322] The following shows the molar extinction coefficients at a wavelength of 365 nm before and after quenching for each of compounds (A) to (H). Compound (A): Molar extinction coefficient before quenching: 12,754 L·mol －１ ・cm －１ Molar extinction coefficient after quenching: 398 L·mol －１ ・cm －１ Compound (B): Molar extinction coefficient before quenching: 13,961 L·mol －１ ・cm －１ Molar extinction coefficient after quenching: 456 L·mol －１ ・cm －１ Compound (C): Molar extinction coefficient before quenching: 14,871 L·mol －１ ・cm －１ Molar extinction coefficient after quenching: 602 L·mol －１ ・cm －１ Compound (D): Molar extinction coefficient before quenching: 19,030 L·mol －１ ・cm －１ Molar extinction coefficient after quenching: 622 L·mol －１ ・cm －１ Compound (E): Molar extinction coefficient before quenching: 11,411 L·mol －１ ・cm －１ Molar extinction coefficient after quenching: 1,199 L·mol －１ ・cm －１ Compound (F): Molar extinction coefficient before quenching: 12,126 L·mol －１ ・cm －１ Molar extinction coefficient after quenching: 644 L·mol －１ ・cm －１Compound (G): Molar extinction coefficient before quenching: 23,318 L·mol －１ ・cm －１ Molar extinction coefficient after quenching: 466 L·mol －１ ・cm －１ Compound (H): Molar extinction coefficient before quenching: 23,994 L·mol －１ ・cm －１ Molar extinction coefficient after quenching: 480 L·mol －１ ・cm －１

[0323] <Preparation of composition for forming thermoplastic resin layer> After mixing each component to obtain the composition shown in Table 4, a composition for forming a thermoplastic resin layer with a solid content of 25% by mass was prepared by adding solvents (MEK, PGMEA).

[0324] [Manufacturing of Transfer Films] Transfer films consisting of a temporary support, a thermoplastic resin layer, an intermediate layer, and a photosensitive composition layer were prepared to have the configurations shown in Tables 6 to 8 below. The specific procedure is as follows: First, a thermoplastic resin layer-forming composition for forming the thermoplastic resin layer shown in Tables 6 to 8 was applied to the temporary support (polyethylene terephthalate film, thickness: 16 μm, haze: 0.12%) using a slit nozzle with a coating width of 1.0 m and a film thickness after drying that matches the values ​​listed in Tables 6 to 8. Next, the obtained coating was dried at 80°C for 40 seconds to form a thermoplastic resin layer. Next, an intermediate layer-forming composition for forming the intermediate layer shown in Tables 6 to 8 was applied to the thermoplastic resin layer using a slit nozzle with a coating width of 1.0 m and a film thickness after drying that matches the values ​​listed in Tables 6 to 8. Next, the obtained coating was dried at 80°C for 40 seconds to form an intermediate layer. Next, a photosensitive composition layer-forming composition (photosensitive composition) shown in Tables 6 to 8 is applied to the intermediate layer using a slit nozzle with a coating width of 1.0 m and with a film thickness after drying that matches the values ​​listed in Tables 6 to 8. The photosensitive composition layer is then formed by drying in a 100°C convection oven for 2 minutes. A protective film (polypropylene film, thickness: 12 μm, haze: 0.2%) is laminated onto the photosensitive composition layer to produce a transfer film.

[0325] [Measurement of physical properties of transfer film] [Measurement of unsaturated double bond value of thermoplastic resin layer] The protective film of the transfer film is peeled off. Next, the transfer film after peeling off the protective film is laminated to glass, and the temporary support is peeled off to obtain a laminate T of glass / photosensitive composition layer / intermediate layer / thermoplastic resin layer. Next, the thermoplastic resin layer is peeled off from the laminate T using tape. Next, the iodine value (g / 100g) of the thermoplastic resin layer peeled off with tape is measured in accordance with the test method for "iodine value" described in JIS K 0070-1992, and the number of unsaturated double bonds contained per gram (mol / g) is determined. The specific procedure for iodine titration is as follows. Weigh out 0.30 to 0.20 g of the thermoplastic resin layer to three significant figures into a stoppered Erlenmeyer flask. Next, add about 10 ml of carbon tetrachloride to dissolve the sample. Add 25 ml of iodine monochloride solution using a full-length pipette and shake. Stopper the bottle and leave it in the dark at room temperature for 30 minutes. Add approximately 20 ml of potassium iodide solution (100 g / l) and approximately 100 ml of water. Titrate with 0.1 mol / l sodium thiosulfate solution, and when the solution turns pale yellow, add a few drops of starch solution (10 g / l) and titrate until the blue color disappears.

[0326] [Measurement of the acid value of the thermoplastic resin layer] The protective film is peeled off the transfer film. Next, the transfer film after the protective film has been peeled off is laminated to glass, and the temporary support is peeled off to obtain a laminate T of glass / photosensitive composition layer / intermediate layer / thermoplastic resin layer. Next, the thermoplastic resin layer is peeled off from the laminate T using tape. Next, 0.5 g is accurately weighed as a sample from the thermoplastic resin layer peeled off with tape, dissolved in a mixed solvent of 30 g of acetone and 5 g of pure water, and titrated with a 0.1 N KOH aqueous solution. The titration is performed using an automatic titrator (product name: COM-555, manufactured by Hiranuma Sangyo Co., Ltd.) to determine the acid value of the thermoplastic resin layer (mg KOH / g).

[0327] [Evaluation of Transfer Film] Evaluation is performed using each of the produced transfer films of the examples and comparative examples. [Evaluation Item 1: Resolution of transfer film immediately after production] A silicon wafer having a seed layer formed thereon is prepared as a substrate. The produced transfer film was laminated on the substrate (lamination step). Pressure bonding is performed using a heat roll at 100°C at a pressure of 0.7 MPa and a speed of 2 m / min. Next, after peeling off the temporary support (temporary support peeling step), pattern exposure is performed using a mask including a wiring pattern (L = 1 to 2 µm, in 0.1 µm increments, 10 lines) such that line (L) / space (S) = 1 / 1 (width ratio), using a projection exposure apparatus with a theoretical resolution of 1.5 µm using a high-pressure mercury lamp as the light source (exposure step). The exposure amount is defined as the exposure amount at which the number of remaining step stages becomes 13 when exposed using a 41-step tablet manufactured by Stouffer and developed in a time that is 2.0 times the minimum development time. Note that the minimum development time refers to the time required for the photosensitive composition layer to completely disappear when development is performed in an unexposed state. Using an aqueous sodium carbonate solution at 30°C (sodium carbonate content is 1% by mass relative to the total mass of the aqueous sodium carbonate solution) as the developer, spray development is performed for a time 2.0 times the minimum development time, unexposed areas are removed, and a resist pattern is formed on the substrate surface to obtain a patterned laminate. After the above development, the L / S (µm / µm) of the smallest pattern free of residue and peeling is taken as the resolution of the resist. For practical purposes, the minimum L / S is preferably 1.2 / 1.2 (µm / µm) or less, more preferably 1.1 / 1.1 (µm / µm) or less. The results are shown in the "Resolution immediately after production" column of Tables 6 to 8.

[0328] [Evaluation Item 2: Resolution of Transfer Film After Time] The prepared transfer films of the examples and comparative examples are stored for 120 days at 25°C and 50% humidity. The transfer films stored for the above predetermined period are used to perform the same evaluation as in Evaluation Item 1 above. In practical terms, the minimum L / S is preferably 1.5 / 1.5 (μm / μm) or less, more preferably 1.4 / 1.4 (μm / μm) or less, even more preferably 1.3 / 1.3 (μm / μm) or less, and particularly preferably 1.2 / 1.2 (μm / μm) or less. The results are shown in the "Resolution After Time" column of Tables 6 to 8.

[0329] [Evaluation Item 3: Stability over Time] Stability over time is evaluated based on the change in resolution between the evaluation value of the transfer film immediately after preparation (Evaluation Item 1) and the evaluation value of the transfer film after time (Evaluation Item 2) (|Evaluation value of the transfer film after time - Evaluation Item 1: Evaluation value of the transfer film immediately after preparation|). The results are shown in the "Stability over Time" column of Tables 6 to 8. (Evaluation Criteria) A: No change B: Change of 0.2 μm or less C: Change of 0.3 μm or less D: Change greater than 0.3 μm

[0330] [Evaluation Item 4: Sensitivity Evaluation] Sensitivity evaluation was performed according to the following procedure. A 0.7 mm thick silicon wafer was subjected to Cu sputtering to a thickness of 200 nm to obtain a substrate having a metal layer. The transfer film for each example was laminated to the above substrate so that the photosensitive composition layer side was in contact with the conductive layer. The films were pressed together at a pressure of 0.7 MPa and a speed of 2 m / min using a 100°C heat roll (lamination process). Next, the temporary support was peeled off and 2000 mJ / cm² was applied using a Stuffer 41-step tablet. ２The images were exposed to light and developed for 2.0 times the minimum development time. A 30°C sodium carbonate aqueous solution (sodium carbonate content: 1% by mass relative to the total mass of the sodium carbonate aqueous solution) was used as the developer, and spray development was performed for 2.0 times the minimum development time. The number of remaining steps after removing the unexposed areas and the sensitivity were evaluated according to the evaluation criteria below. The results are shown in the "Sensitivity" column of Tables 6 to 8. (Evaluation Criteria) A: 11 or more remaining steps B: 6 to 10 remaining steps C: 5 or fewer remaining steps

[0331] Tables 6 to 8 are shown below. In Tables 6 to 8, the values ​​in the "Photosensitive Composition Layer," "Intermediate Layer," and "Thermoplastic Resin Layer" columns indicate the types of each layer shown in Tables 1, 3, and 4 in the upper section. For example, in Example 1 in Table 6, "1" for the photosensitive composition layer represents the photosensitive composition layer 1 shown in Table 1 in the upper section, "1" for the intermediate layer represents the intermediate layer 1 shown in Table 3 in the upper section, and "1" for the thermoplastic resin layer represents the thermoplastic resin layer 1 shown in Table 4 in the upper section.

[0332]

[0333]

[0334]

[0335] The results shown in Tables 6 to 8 above confirm that the transfer film of the present invention exhibits excellent stability over time.

[0336] From a comparison of Examples 1 to 7, it is clear that when the unsaturated double bond value of the thermoplastic resin layer is 2.30 mmol / g or less, and the acid value of the thermoplastic resin layer is 20.0 to 95.0 mgKOH / g, at least one of these conditions is met, the stability over time is superior. Furthermore, from a comparison of Examples 1 to 7, it is clear that when the unsaturated double bond value of the thermoplastic resin layer is 1.00 mmol / g or less, the stability over time is remarkably superior. Furthermore, from a comparison of Examples 1 to 7, it is clear that when the unsaturated double bond value of the thermoplastic resin layer is 1.00 mmol / g or less, and the acid value of the thermoplastic resin layer is 20.0 to 95.0 mgKOH / g, the stability over time is remarkably superior. From a comparison of Example 3 and Example 13, it is confirmed that when the intermediate layer contains a photodecolorizable compound, the transfer film can form a pattern with superior resolution, and also exhibits superior stability over time. In addition, from a comparison of Examples 6, 8 to 12, and 14 to 15, it is confirmed that in compound (1), Ar １ and Ar ２ However, when each independently represents an aromatic ring group having one or more electron-withdrawing groups as substituents, it has been confirmed that the sensitivity characteristics of the transfer film are excellent (see the comparison between Examples 6 and 8-12 and Examples 14-15. Note that in compound (1) used in the transfer films of Examples 6 and 8-12, Ar １ and Ar ２ At least one of them does not fall under the category of an aromatic ring group having one or more electron-withdrawing groups as substituents. In contrast, in compound (1) used in the transfer films of Examples 14-15, Ar １ and Ar ２ (However, all of these are aromatic ring groups that have one or more electron-withdrawing groups as substituents.)

[0337] [Manufacturing of Laminates Having Conductor Patterns] Laminates having conductor patterns are manufactured using the transfer films of each embodiment by the following method. A substrate having a metal layer is obtained by performing Cu sputtering to a thickness of 200 nm on the surface of a 0.7 mm thick silicon wafer. The transfer film of each example is laminated to the above substrate so that the photosensitive composition layer side is in contact with the conductor layer. The substrates are pressed together at a pressure of 0.7 MPa and a speed of 2 m / min using a heat roll at 100°C (lamination step). Pattern exposure is performed using a projection exposure apparatus with a high-pressure mercury lamp as the light source, with the following exposure amount, using a mask having a predetermined pattern (exposure step). The exposure amount is such that when exposed using a 41-step tablet manufactured by Stouffer and developed for 2.0 times the shortest development time, the number of remaining step stages is 13. Spray development is performed using a 1% by mass aqueous sodium carbonate solution at 30°C for 2.0 times the shortest development time, removing the unexposed areas to form a resist pattern (development step). Electroplating is performed on the conductive layer in areas where no resist pattern is formed, using a copper sulfate plating solution to form a copper plating layer with a thickness of 2 μm (plating process). Subsequently, the resist pattern is removed using a stripping solution (resist stripping process). The conductive layer exposed by the stripping of the resist pattern is then etched (removal process) to form a conductive pattern layer.

[0338] Furthermore, a laminate having a conductive pattern is manufactured using the transfer film of Example 3 in the same manner as above, except that a step of peeling off the temporary support is added between the bonding step and the exposure step.

[0339] 10 Transfer film 12 Temporary support 14 Thermoplastic resin layer 16 Intermediate layer 18 Photosensitive composition layer 20 Protective film

Claims

1. A transfer film having a temporary support, a thermoplastic resin layer, and a photosensitive composition layer, wherein the thermoplastic resin layer contains an alkali-soluble thermoplastic resin, a plasticizer, and a nitrone compound, the unsaturated double bond value of the thermoplastic resin layer is 2.50 mmol / g or less, and the acid value of the thermoplastic resin layer is 20.0 to 100.0 mg KOH / g.

2. The transfer film according to claim 1, wherein the content of the plasticizer is 10.0 to 60.0% by mass with respect to the total mass of the thermoplastic resin layer.

3. The transfer film according to claim 1 or 2, wherein the thickness of the thermoplastic resin layer is 3 to 15 μm.

4. The transfer film according to claim 1 or 2, further comprising an intermediate layer between the photosensitive composition layer and the thermoplastic resin layer.

5. The transfer film according to claim 4, wherein the intermediate layer contains a photodecolorizing compound.

6. A transfer film according to claim 1 or 2, satisfying at least one of the following requirements A and B: Requirement A: The unsaturated double bond value of the thermoplastic resin layer is 2.30 mmol / g or less. Requirement B: The acid value of the thermoplastic resin layer is 20.0 to 95.0 mgKOH / g.

7. The transfer film according to claim 1 or 2, wherein the unsaturated double bond value of the thermoplastic resin layer is 1.00 mmol / g or less.

8. A method for manufacturing a laminate having a conductive pattern, comprising: a bonding step of bonding the transfer film according to claim 1 or 2 such that the photosensitive composition layer side is in contact with the metal layer of a substrate having a metal layer on its surface; an exposure step of pattern-exposing the photosensitive composition layer from the side opposite to the substrate side; a developing step of developing the exposed photosensitive composition layer using an alkaline developer to form a resist pattern; an etching step of etching the metal layer in an area where the resist pattern is not arranged to form a conductive pattern, and a plating step of plating the metal layer; a resist peeling step of peeling off the resist pattern; and, if the plating step is included, a removal step of removing the metal layer exposed by the resist peeling step to form a conductive pattern on the substrate.

9. A method for manufacturing a laminate having a conductive pattern according to claim 8, comprising the step of peeling off the temporary support before the exposure step.

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