Method for manufacturing a laminate having a photosensitive composition, a transfer film, and a conductive pattern.

Abstract

To provide a photosensitive composition capable of forming a resist pattern excellent in acid tolerance.SOLUTION: A photosensitive composition contains an alkali-soluble resin, a polymerizable compound having an ethylenic unsaturated group, and a photoinitiator. The polymerizable compound contains a polymerizable compound A which satisfies a requirement (X1) as follows: the requirement (X1): a contact angle of water of a film which is obtained by applying a composition comprising 100 pts.mass of the polymerizable compound A, 1.0 pt.mass of 1-[9-ethyl-6-(2- methylbenzoyl)-9H- carbazole-3-yl] ethanone-1-(O-acetyloxime), and 9 pts.mass of methyl ethyl ketone so as to form a film with 2.0 μm, and irradiating the film with i-line beams at an exposure value of 500 mJ / cm2 in a nitrogen atmosphere followed by heating at 150°C for 30 minutes is 74 degrees or more.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a photosensitive composition, a transfer film, and a method for manufacturing a laminate having a conductor pattern.

Background Art

[0002] As a method for obtaining circuit wiring or the like, it is common to use a method of performing an etching process using a resist pattern formed by a photosensitive composition. Specifically, for example, a photosensitive composition layer is formed on a substrate having a conductive layer, the photosensitive composition layer is pattern-exposed, developed to form a pattern on the conductive layer, and the conductive layer in the portion where the pattern is not formed and is exposed is etched.

[0003] For example, Patent Document 1 discloses a photosensitive resin composition containing a binder polymer, a photopolymerizable compound having an ethylenically unsaturated bond, and a photopolymerization initiator. Further, it is also disclosed that an etching process is performed using a resist pattern formed by the above photosensitive resin composition.

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0005] Here, the etching solution used for the etching process is often acidic.

[0006] The present inventors formed a resist pattern using the photosensitive composition (photosensitive resin composition) described in Patent Document 1 and etched the conductive layer. They observed modification of the conductive layer in the portion covered by the resist pattern due to the etching solution. They also found that this modification of the conductive layer occurs because the resist pattern has insufficient acid resistance. Furthermore, due to its high conductivity, a conductive layer containing silver is sometimes used. Compared to other materials used in conductive layers (e.g., copper), silver is less susceptible to etching, and the pH of the etching solution used is often lower. Therefore, further improvement in acid resistance is required for the resist patterns used to etch the conductive layer containing silver.

[0007] Therefore, the object of the present invention is to provide a photosensitive composition that can form a resist pattern with excellent acid resistance. Furthermore, the present invention aims to provide a transfer film and a method for manufacturing a laminate having a conductive pattern. [Means for solving the problem]

[0008] The inventors of this invention have diligently studied and, as a result, completed the present invention. Specifically, they have found that the above problems can be solved by the following configuration.

[0009] [1] Alkali-soluble resin and Polymerizable compounds having ethylenically unsaturated groups, It contains a photopolymerization initiator, A photosensitive composition comprising polymerizable compound A that satisfies the following requirement (X1). Requirement (X1): A composition consisting of 100 parts by mass of polymerizable compound A, 1.0 part by mass of 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]ethanone-1-(O-acetyloxime), and 9 parts by mass of methyl ethyl ketone is applied to form a 2.0 μm film, and then exposed to a nitrogen atmosphere at an exposure of 500 mJ / cm². 2The water contact angle of the film obtained by irradiating with i-line and heating at 150 °C for 30 minutes is 74 degrees or more. 〔2〕 The photosensitive composition according to 〔1〕, wherein the polymerizable compound A is a polymerizable compound A1 represented by the following formula (A). Q 1 -R 1 -Q 2 Formula (A) In formula (A), Q 1 and Q 2 each independently represents a (meth)acryloyloxy group. In formula (A), R 1 represents a chain-like divalent hydrocarbon group. 〔3〕 The photosensitive composition according to 〔1〕 or 〔2〕, wherein the polymerizable compound contains a polymerizable compound B that satisfies the following requirement (X2). Requirement (X2): After applying a composition consisting of 100 parts by mass of the polymerizable compound B, 1.0 part by mass of 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]ethanone-1-(O-acetyloxime), and 9 parts by mass of methyl ethyl ketone to form a 2.0 μm film, irradiating with i-line at an exposure amount of 500 mJ / cm 2 and heating at 150 °C for 30 minutes, the water contact angle of the resulting film is 65 degrees or less. 〔4〕 The photosensitive composition according to 〔3〕, wherein the polymerizable compound B has a bisphenol A structure. 〔5〕 The photosensitive composition according to 〔3〕 or 〔4〕, wherein the mass ratio of the content of the polymerizable compound B to the content of the polymerizable compound A is 0.50 to 4.00. 〔6〕 Content of the polymerizable compound relative to the content of the alkali-soluble resin The mass ratio of is 0.68 to 1.30, and the photosensitive composition according to any one of 〔1〕 to 〔5〕. 〔7〕 The polymerizable compound A is a polymerizable compound A1 represented by the following formula (A), The polymerizable compound satisfies the following requirement (X2) and contains a polymerizable compound B having a bisphenol A structure, and the photosensitive composition according to 〔1〕. Q 1 -R 1 -Q 2 Formula (A) In formula (A), Q 1 and Q 2 Each of these independently represents a (meth)acryloyloxy group. In formula (A), R 1 This represents a chain-like divalent hydrocarbon group. Requirement (X2): A composition consisting of 100 parts by mass of polymerizable compound B, 1.0 part by mass of 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]ethanone-1-(O-acetyloxime), and 9 parts by mass of methyl ethyl ketone is applied to form a 2.0 μm film, and then exposed to a nitrogen atmosphere at an exposure of 500 mJ / cm². 2 The water contact angle of the film obtained by irradiating it with i-rays and heating it at 150°C for 30 minutes is 65 degrees or less. [8] The polymerizable compound A mentioned above is polymerizable compound A1 represented by the following formula (A), The polymerizable compound described above contains polymerizable compound B which satisfies the following requirement (X2) and has a bisphenol A structure, The mass ratio of the content of polymerizable compound B to the content of polymerizable compound A is 0.50 to 4.00. Content of the polymerizable compound relative to the content of the alkali-soluble resin The photosensitive composition according to [1], wherein the mass ratio of is 0.68 to 1.30. Q 1 -R 1 -Q 2 Formula (A) In formula (A), Q 1 and Q 2 Each of these independently represents a (meth)acryloyloxy group. In formula (A), R 1 This represents a chain-like divalent hydrocarbon group. Requirement (X2): A composition consisting of 100 parts by mass of polymerizable compound B, 1.0 part by mass of 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]ethanone-1-(O-acetyloxime), and 9 parts by mass of methyl ethyl ketone is applied to form a 2.0 μm film, and then exposed to a nitrogen atmosphere at an exposure of 500 mJ / cm². 2 The water contact angle of the film obtained by irradiating it with i-rays and heating it at 150°C for 30 minutes is 65 degrees or less. [9] The photosensitive composition according to any one of [1] to [8], wherein the alkali-soluble resin is resin A1 that satisfies the following requirement (X3). Requirement (X3): After forming a 2.0 μm film made of the above resin A1, the water contact angle of the film obtained by heating at 150°C for 30 minutes is 65 degrees or more.

[10] The alkali-soluble resin contains constituent units derived from styrene, The photosensitive composition according to any one of [1] to [9], wherein the content of the styrene-derived constituent units is 20% by mass or more relative to the total mass of the alkali-soluble resin.

[11] The photosensitive composition according to any one of [1] to

[10] , wherein the acid value of the alkali-soluble resin is 100 mg KOH / g or more.

[12] A photosensitive composition according to any one of [1] to

[11] that satisfies the following requirement (X4). Requirement (X4): A 2.0 μm film formed using the above photosensitive composition is exposed to a nitrogen atmosphere at an exposure dose of 500 mJ / cm². 2 The water contact angle of the film obtained by irradiating it with i-rays and heating it at 150°C for 30 minutes is 60 degrees or more.

[13] Temporary support and, A transfer film having a photosensitive composition layer formed using any one of the photosensitive compositions described in [1] to

[12] .

[14] The transfer film according to

[13] , wherein the thickness of the photosensitive composition layer is 1 to 10 μm.

[15] A preparation step of preparing a laminate having a substrate, a conductive layer containing silver, and a photosensitive composition layer in this order, An exposure step of pattern exposure of the above photosensitive composition layer, A developing step involves developing an exposed photosensitive composition layer to form a resist pattern, A method for manufacturing a laminate having a conductive pattern, comprising an etching step of etching the conductive layer in a region where a resist pattern is not formed with an etching solution having a pH of less than 2.0, The above photosensitive composition layer is Alkali-soluble resin and, Polymerizable compounds having ethylenically unsaturated groups, It contains a photopolymerization initiator, A method for producing a laminate having a conductive pattern, wherein the polymerizable compound described above includes polymerizable compound A that satisfies the following requirement (X1). Requirement (X1): A composition consisting of 100 parts by mass of polymerizable compound A, 1.0 part by mass of 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]ethanone-1-(O-acetyloxime), and 9 parts by mass of methyl ethyl ketone is applied to form a 2.0 μm film, and then exposed to a nitrogen atmosphere at an exposure of 500 mJ / cm². 2 The water contact angle of the film obtained by irradiating it with i-rays and heating it at 150°C for 30 minutes is 74 degrees or higher.

[16] A method for producing a laminate having a conductive pattern as described in

[15] , wherein the polymerizable compound A is polymerizable compound A1 represented by the following formula (A). Q 1 -R 1 -Q 2 Formula (A) In formula (A), Q 1 and Q 2 Each of these independently represents a (meth)acryloyloxy group. In formula (A), R 1 This represents a chain-like divalent hydrocarbon group.

[17] A method for producing a laminate having a conductive pattern as described in

[15] or

[16] , wherein the polymerizable compound includes polymerizable compound B that satisfies the following requirement (X2). Requirement (X2): A composition consisting of 100 parts by mass of polymerizable compound B, 1.0 part by mass of 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]ethanone-1-(O-acetyloxime), and 9 parts by mass of methyl ethyl ketone is applied to form a 2.0 μm film, and then exposed to a nitrogen atmosphere at an exposure of 500 mJ / cm². 2 The water contact angle of the film obtained by irradiating it with i-rays and heating it at 150°C for 30 minutes is 65 degrees or less.

[18] A method for producing a laminate having a conductive pattern as described in

[17] , wherein the polymerizable compound B is polymerizable compound B1 having a bisphenol A structure.

[19] A method for producing a laminate having a conductive pattern according to

[17] or

[18] , wherein the mass ratio of the content of polymerizable compound B to the content of polymerizable compound A is 0.50 to 4.00.

[20] Content of the polymerizable compound relative to the content of the alkali-soluble resin A method for manufacturing a laminate having a conductive pattern according to any one of

[15] to

[19] , wherein the mass ratio of is 0.68 to 1.30.

[21] The polymerizable compound A mentioned above includes polymerizable compound A1 represented by the following formula (A), A method for producing a laminate having a conductive pattern as described in

[15] , wherein the polymerizable compound described above contains polymerizable compound B having a bisphenol A structure and satisfying the following requirement (X2). Q 1 -R 1 -Q 2 Formula (A) In formula (A), Q 1 and Q 2 Each of these independently represents a (meth)acryloyloxy group. In formula (A), R 1 This represents a chain-like divalent hydrocarbon group. Requirement (X2): A composition consisting of 100 parts by mass of polymerizable compound B, 1.0 part by mass of 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]ethanone-1-(O-acetyloxime), and 9 parts by mass of methyl ethyl ketone is applied to form a 2.0 μm film, and then exposed to a nitrogen atmosphere at an exposure of 500 mJ / cm². 2 The water contact angle of the film obtained by irradiating it with i-rays and heating it at 150°C for 30 minutes is 65 degrees or less.

[22] The polymerizable compound A mentioned above includes polymerizable compound A1 represented by the following formula (A), The above polymerizable compound satisfies the following requirement (X2) and is a photosensitive composition comprising polymerizable compound B having a bisphenol A structure, The mass ratio of the content of polymerizable compound B to the content of polymerizable compound A is 0.50 to 4.00. Content of the polymerizable compound relative to the content of the alkali-soluble resin A method for manufacturing a laminate having the conductive pattern described in

[15] , wherein the mass ratio of is 0.68 to 1.30. Q1 -R 1 -Q 2 Formula (A) In formula (A), Q 1 and Q 2 Each of these independently represents a (meth)acryloyloxy group. In formula (A), R 1 This represents a chain-like divalent hydrocarbon group. Requirement (X2): A composition consisting of 100 parts by mass of polymerizable compound B, 1.0 part by mass of 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]ethanone-1-(O-acetyloxime), and 9 parts by mass of methyl ethyl ketone is applied to form a 2.0 μm film, and then exposed to a nitrogen atmosphere at an exposure of 500 mJ / cm². 2 The water contact angle of the film obtained by irradiating it with i-rays and heating it at 150°C for 30 minutes is 65 degrees or less.

[23] A method for manufacturing a laminate having a conductive pattern according to any one of

[15] to

[22] , wherein the alkali-soluble resin is resin A1 that satisfies the following requirement (X3). Requirement (X3): After forming a 2.0 μm film made of the above resin A1, the water contact angle of the film obtained by heating at 150°C for 30 minutes is 65 degrees or more.

[24] The alkali-soluble resin contains constituent units derived from styrene, A method for manufacturing a laminate having a conductive pattern according to any one of

[15] to

[23] , wherein the constituent units derived from the styrene described above are 20% by mass or more of the total mass of the alkali-soluble resin described above.

[25] A method for producing a laminate having a conductive pattern according to any one of

[15] to

[24] , wherein the acid value of the alkali-soluble resin is 100 mg KOH / g or more. [Effects of the Invention]

[0010] According to the present invention, a photosensitive composition is available that can form a resist pattern with excellent acid resistance. Furthermore, the present invention provides a method for manufacturing a transfer film and a laminate having a conductive pattern. [Brief explanation of the drawing]

[0011] [Figure 1] This is a schematic diagram showing an example of the configuration of a transfer film used in the manufacturing method of the present invention. [Figure 2] This is a schematic diagram of the photomask used in the example. [Modes for carrying out the invention]

[0012] The present invention will be described in detail below. The following description of the constituent elements may be based on typical embodiments of the present invention, but the present invention is not limited to such embodiments.

[0013] The following definitions are used within this specification. In this specification, a numerical range represented by "~" means a range that includes the numbers written before and after "~" as the lower and upper limits, respectively. In this specification, in numerical ranges described in stages, 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 stages. Furthermore, in numerical ranges described in this specification, the upper or lower limit stated in one numerical range may be replaced with the values ​​shown in the examples.

[0014] 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.

[0015] 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. In this specification, the average transmittance of visible light is a value measured using a spectrophotometer, which can be measured using, for example, a Hitachi U-3310 spectrophotometer manufactured by Hitachi, Ltd.

[0016] In this specification, unless otherwise specified, the weight-average molecular weight (Mw) and number-average molecular weight (Mn) are calculated 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 ratios of constituent units of polymers are given by mass. 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 content of metallic elements is measured using an inductively coupled plasma (ICP) spectrometer. 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.).

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

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

[0019] In this specification, "water-soluble" means that the solubility in 100g of water at a pH of 7.0 at a liquid temperature of 22°C is 0.1g or more. Therefore, for example, a water-soluble resin refers to a resin that satisfies the above-mentioned solubility conditions.

[0020] In this specification, "pH" refers to the pH measured using a known pH meter in accordance with the method specified in JIS Z8802-1984. The pH measurement temperature shall be 25°C.

[0021] 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.

[0022] <Photosensitive composition> The photosensitive composition of the present invention comprises an alkali-soluble resin, a polymerizable compound having an ethylenically unsaturated group, and a photopolymerization initiator, wherein the polymerizable compound includes polymerizable compound A that satisfies the following requirement (X1). Requirement (X1): A composition consisting of 100 parts by mass of polymerizable compound A, 1.0 part by mass of 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]ethanone-1-(O-acetyloxime), and 9 parts by mass of methyl ethyl ketone is applied to form a 2.0 μm film, and then exposed to a nitrogen atmosphere at an exposure of 500 mJ / cm². 2 The water contact angle of the film obtained by irradiating it with i-rays and heating it at 150°C for 30 minutes is 74 degrees or higher. The details of requirement (X1) will be described in more detail later.

[0023] A resist pattern formed using the photosensitive composition of the present invention can be used as a resist pattern for etching a conductive layer on which the resist pattern is placed. When an acidic etching solution is used, the conductive layer in the area covered by the resist pattern is less likely to degrade. In other words, a resist pattern formed using the photosensitive composition of the present invention has excellent acid resistance. Furthermore, the resist pattern has acid resistance that can withstand etching solutions used for etching a conductive layer containing silver (for example, etching solutions with a pH of less than 2.0). The mechanism by which the resist pattern formed by the above photosensitive composition exhibits excellent acid resistance is not entirely clear, but the inventors speculate as follows. The resist pattern formed by the above-mentioned photosensitive composition is less susceptible to penetration by etching solutions used in the etching process because the photosensitive composition satisfies the above-mentioned characteristic points. As a result, the etching solution does not easily reach the conductive layer in the area covered by the resist pattern, and consequently, it is considered that the conductive layer in the area covered by the resist pattern is less likely to degrade. Therefore, the resist pattern formed by the above-mentioned photosensitive composition is considered to have excellent acid resistance.

[0024] Furthermore, the photosensitive composition layer formed by the photosensitive composition is preferably a negative-type photosensitive composition layer. When the photosensitive composition layer is a negative-type photosensitive composition layer, the formed pattern corresponds to the cured layer.

[0025] The following describes the components that may be included in the photosensitive composition of the present invention. Furthermore, when a resist pattern formed by the photosensitive composition of the present invention is used as a resist pattern for etching a conductive layer on which the resist pattern is placed, and an acidic etching solution is used, the fact that the conductive layer in the area covered by the resist pattern is less likely to degrade is also referred to as "excellent acid resistance."

[0026] [Alkali-soluble resin] The photosensitive composition contains an alkali-soluble resin (hereinafter also referred to as "resin A"). Examples of resin A include, but are not limited to, (meth)acrylic resins, styrene resins, epoxy resins, amide resins, amide epoxy resins, alkyd resins, phenolic resins, ester resins, urethane resins, and acid-modified epoxy acrylate resins obtained by the reaction of epoxy acrylate resins with acid anhydrides.

[0027] As resin A, (meth)acrylic resin is preferred. In this specification, (meth)acrylic resin means a resin having constituent units derived from (meth)acrylic compounds. In the (meth)acrylic resin, the content of constituent units derived from (meth)acrylic compounds is preferably 30% by mass or more, more preferably 50% by mass or more, and even more preferably 60% by mass or more, relative to the total constituent units of the (meth)acrylic resin. As resin A, polymers having structural units derived from (meth)acrylic compounds and structural units derived from styrene compounds are also preferred.

[0028] 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 viewpoint of improving the resolution of the photosensitive composition layer formed by the photosensitive composition by suppressing the swelling of the negative-type photosensitive composition by the developing solution. The lower limit of the acid value of resin A is not particularly limited, but from the viewpoint of superior developability, it is preferably 60 mg KOH / g or higher, more preferably 100 mg KOH / g or higher, even more preferably 120 mg KOH / g or higher, particularly preferably 150 mg KOH / g or higher, and most preferably 170 mg KOH / g or higher. The acid value (mgKOH / 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 acidic groups in the compound. The acid value of resin A can be adjusted by the types of constituent units that make up resin A and the content of constituent units containing acidic groups, as described later. In the following, the resolution of the photosensitive composition layer formed by the photosensitive composition will also simply be referred to as "resolution."

[0029] The weight-average molecular weight of resin A is preferably 5,000 to 500,000. A weight-average molecular weight of 500,000 or less is preferred from the viewpoint of improving resolution and developability. A weight-average molecular weight of 100,000 or less is more preferred, and 60,000 or less is even more preferred. On the other hand, a weight-average molecular weight of 5,000 or more is preferred from the viewpoint of controlling the properties of the developed aggregates and the properties of the unexposed film, such as edge fusing and cut-tip properties, when used as a negative-type photosensitive resin laminate. A weight-average molecular weight of 10,000 or more is more preferred, 20,000 or more is even more preferred, and 30,000 or more is particularly preferred. Edge fusing refers to the degree to which the negative-type photosensitive composition layer tends to protrude from the end face of the roll when wound into a roll as a negative-type photosensitive resin laminate. Cut-tip properties refer to the degree to which chips tend to fly off when the unexposed film is cut with a cutter. If this chip adheres to the upper surface of a negative-type photosensitive resin laminate, it will be transferred to the mask during subsequent exposure processes, causing defective products. The dispersion degree 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.

[0030] Furthermore, it is preferable that resin A is resin A1 that satisfies the following requirement (X3). Requirement (X3): After forming a 2.0 μm film made of resin A1, the water contact angle of the film obtained by heating at 150°C for 30 minutes is 65 degrees or greater. One method for forming a film made of resin A1 is to apply a composition in which resin A1 is dissolved in methyl ethyl ketone to form the film. If resin A1 is difficult to dissolve in methyl ethyl ketone, it is preferable to select a solvent with a boiling point of 150°C or lower in which resin A1 dissolves. The method for measuring the contact angle is the same as the measurement method for requirement (X1) described later. The water contact angle is preferably 68 degrees or higher, and more preferably 71 degrees or higher. There is no particular upper limit, but it is 180 degrees or lower, and preferably 90 degrees or lower. The above-mentioned water contact angle can be adjusted by the type of constituent units that make up resin A and the content of constituent units having carboxyl groups, as described later.

[0031] The constituent units that resin A may contain will be explained in detail below.

[0032] (Constituent units having aromatic hydrocarbon groups) Furthermore, in order to suppress line width thickening and deterioration of resolution when the focal position shifts during exposure, it is preferable that resin A contains constituent units derived from monomers having aromatic hydrocarbon groups. Examples of such aromatic hydrocarbon groups include substituted or unsubstituted phenyl groups and substituted or unsubstituted aralkyl groups. The content of constituent units derived from monomers having aromatic hydrocarbon groups in resin A is preferably 20% by mass or more, and more preferably 30% by mass or more, relative to the total mass of resin A. There is no particular upper limit, but it is preferably 95% by mass or less, and more preferably 85% by mass or less. When resin A contains multiple types, it is preferable that the average value of the content of constituent units derived from monomers having aromatic hydrocarbon groups falls within the above range.

[0033] Examples of monomers having aromatic hydrocarbon groups include monomers having aralkyl groups, styrene, and polymerizable styrene derivatives (e.g., methylstyrene, vinyltoluene, tert-butoxystyrene, acetoxystyrene, styrene dimer, and styrene trimer). Among these, monomers having aralkyl groups or styrene are preferred. When the monomer having an aromatic hydrocarbon group is styrene, the content of styrene-based constituent units is preferably 20 to 70% by mass, more preferably 25 to 65% by mass, even more preferably 30 to 60% by mass, and particularly preferably 40 to 60% by mass, relative to the total mass of resin A. If the photosensitive composition contains multiple types of resin A, the content of constituent units having an aromatic hydrocarbon group is determined as a weight average.

[0034] Examples of aralkyl groups include phenylalkyl groups which may have substituents, and a benzyl group which may have substituents is preferred.

[0035] Examples of monomers having a phenylalkyl group which may have substituents include phenylethyl (meth)acrylate.

[0036] Examples of monomers having a benzyl group, which may have substituents, include (meth)acrylates having a benzyl group, such as benzyl (meth)acrylate and chlorobenzyl (meth)acrylate; and vinyl monomers having a benzyl group, such as vinyl benzyl chloride and vinylbenzyl alcohol. (Meth)acrylates having a benzyl group are preferred, and benzyl (meth)acrylate is more preferred. When the monomer having an aromatic hydrocarbon group is benzyl (meth)acrylate, the content of the constituent units based on benzyl (meth)acrylate is preferably 50 to 95% by mass, more preferably 60 to 90% by mass, even more preferably 70 to 90% by mass, and particularly preferably 75 to 90% by mass, based on the total mass of resin A.

[0037] Furthermore, it is preferable that resin A, which contains constituent units derived from monomers having aromatic hydrocarbon groups, be obtained by polymerizing a monomer having aromatic hydrocarbon groups with at least one monomer having a carboxyl group (described later) and / or at least one non-acidic monomer (described later).

[0038] Resin A, which does not contain constituent units derived from monomers having aromatic hydrocarbon groups, is preferably obtained by polymerizing at least one monomer having a carboxyl group (described later), and more preferably by copolymerizing at least one monomer having a carboxyl group with at least one non-acidic monomer (described later).

[0039] (Constituent units containing a carboxyl group) Resin A preferably contains constituent units having a carboxyl group. The constituent units containing a carboxyl group originate from monomers that have a carboxyl group in their molecule. Examples of monomers having a carboxyl group include (meth)acrylic acid, fumaric acid, cinnamic acid, crotonic acid, itaconic acid, 4-vinylbenzoic acid, maleic anhydride, and maleic acid semiester. Among these, (meth)acrylic acid is preferred. The content of carboxyl group-containing structural units in resin A is preferably 5 to 50% by mass, more preferably 10 to 40% by mass, and even more preferably 15 to 35% by mass, based on the total mass of resin A. Setting the above content to 5% by mass or more is preferable from the viewpoint of achieving good developability and controlling edge fusing. Setting the above content to 50% by mass or less is preferable from the viewpoint of high resolution of the resist pattern, the shape of the tail, and further from the viewpoint of acid resistance.

[0040] (Non-acidic constituent units) Resin A may contain non-acidic constituent units. Non-acidic constituent units are derived from monomers that are non-acidic and have at least one polymerizable unsaturated group in their molecule. Examples of the above monomers (non-acidic monomers) include 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, isopropyl (meth)acrylate, and methacrylic acid. Examples include isobutyl, sec-butyl (meth)acrylate, tert-butyl (meth)acrylate, isoamyl (meth)acrylate, tert-amyl (meth)acrylate, sec-amyl (meth)acrylate, 2-octyl (meth)acrylate, 3-octyl (meth)acrylate, tert-octyl (meth)acrylate, and (meth)acrylates such as 2-ethylhexyl (meth)acrylate; vinyl alcohol esters such as vinyl acetate; and (meth)acrylonitrile. Among these, methyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, or n-butyl (meth)acrylate are preferred, and methyl (meth)acrylate is more preferred. The content of non-acidic constituent units in resin A is preferably 0.5 to 60% by mass, more preferably 1 to 50% by mass, and even more preferably 1 to 30% by mass, based on the total mass of resin A.

[0041] (Other constituent units) Resin A may have constituent units having 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 monomers containing groups with a linear structure in their side chains, monomers containing groups with a branched structure in their side chains, or monomers containing groups with an alicyclic structure in their side chains, a linear structure, a branched structure, or an alicyclic structure can be introduced into the side chains of resin A. The alicyclic structure may be monocyclic or polycyclic. Specific examples of monomers containing a group having a branched structure in its side chain include isopropyl (meth)acrylate, isobutyl (meth)acrylate, sec-butyl (meth)acrylate, tert-butyl (meth)acrylate, isoamyl (meth)acrylate, tert-amyl (meth)acrylate, sec-amyl (meth)acrylate, 2-octyl (meth)acrylate, 3-octyl (meth)acrylate, and tert-octyl (meth)acrylate. Among these, isopropyl (meth)acrylate, isobutyl (meth)acrylate, and tert-butyl methacrylate are preferred, and isopropyl methacrylate or tert-butyl methacrylate are more preferred. Specific examples of monomers containing a group with an alicyclic structure in its side chain include monomers having a monocyclic aliphatic hydrocarbon group and monomers having a polycyclic aliphatic hydrocarbon group. Also, (meth)acrylates having an alicyclic hydrocarbon group with 5 to 20 carbon atoms are examples. More specific examples include (meth)acrylic acid (bicyclo[2.2.1]heptyl-2), (meth)acrylic acid-1-adamantyl, (meth)acrylic acid-2-adamantyl, (meth)acrylic acid-3-methyl-1-adamantyl, (meth)acrylic acid-3,5-dimethyl-1-adamantyl, (meth)acrylic acid-3-ethyladamantyl, (meth)acrylic acid-3-methyl-5-ethyl-1-adamantyl, (meth)acrylic acid-3,5,8-triethyl-1-adamantyl, (meth)acrylic acid-3,5-dimethyl-8-ethyl-1-adamantyl, (meth)acrylic acid-2-methyl-2-adamantyl, (meth)acrylic acid-2-ethyl-2-adamantyl, (meth)acrylic acid-3-hydroxy Examples include C-1-adamantyl, octahydro-4,7-menthanoinden-5-yl (meth)acrylate, octahydro-4,7-menthanoinden-1-ylmethyl (meth)acrylate, 1-menthyl (meth)acrylate, tricyclodecane (meth)acrylate, 3-hydroxy-2,6,6-trimethyl-bicyclo[3.1.1]heptyl (meth)acrylate, 3,7,7-trimethyl-4-hydroxy-bicyclo[4.1.0]heptyl (meth)acrylate, (nor)bornyl (meth)acrylate, isobornyl (meth)acrylate, fentyl (meth)acrylate, 2,2,5-trimethylcyclohexyl (meth)acrylate, and cyclohexyl (meth)acrylate.Among these (meth)acrylic acid esters, cyclohexyl (meth)acrylate, (nor)bornyl (meth)acrylate, isobornyl (meth)acrylate, 1-adamantyl (meth)acrylate, 2-adamantyl (meth)acrylate, fentyl (meth)acrylate, 1-menthyl (meth)acrylate, or tricyclodecane (meth)acrylate are preferred, and cyclohexyl (meth)acrylate, (nor)bornyl (meth)acrylate, isobornyl (meth)acrylate, 2-adamantyl (meth)acrylate, or tricyclodecane (meth)acrylate are more preferred.

[0042] Resin A may be used alone or in combination of two or more types. When using two or more types, it is preferable to use a mixture of two types of resin A containing constituent units derived from monomers having aromatic hydrocarbon groups, or to use a mixture of resin A containing constituent units derived from monomers having aromatic hydrocarbon groups and resin A not containing constituent units derived from monomers having aromatic hydrocarbon groups. In the latter case, the proportion of resin A containing constituent units derived from monomers having aromatic hydrocarbon groups is preferably 50% by mass or more, more preferably 70% by mass or more, even more preferably 80% by mass or more, and particularly preferably 90% by mass or more, based on the total mass of resin A.

[0043] Resin A can be synthesized by polymerizing one or more of the above-mentioned monomers using a peroxide-based polymerization initiator (e.g., benzoyl peroxide) and a radical polymerization initiator such as an azo-based polymerization initiator (e.g., azobisisobutyronitrile). The polymerization method is preferably carried out by adding a monomer solution and a radical polymerization initiator solution dropwise to a heated solvent (preferably acetone, methyl ethyl ketone, cyclohexanone, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, and isopropanol) under a nitrogen stream, and then heating and stirring. After the reaction is complete, additional solvent may be added to adjust to the desired concentration. In addition to solution polymerization, bulk polymerization, suspension polymerization, or emulsion polymerization may also be used as synthesis methods.

[0044] (Properties of alkali-soluble resin (resin A)) The glass transition temperature (Tg) of resin A is preferably 30 to 135°C. By using resin A having a Tg of 135°C or lower, line width thickening and deterioration of resolution when the focal position shifts during exposure can be suppressed. From this viewpoint, the Tg of resin A is more preferably 130°C or lower, even more preferably 120°C or lower, and particularly preferably 110°C or lower. Furthermore, using resin A having a Tg of 30°C or higher is preferable from the viewpoint of improving edge fusing resistance. From this viewpoint, the Tg of resin A is more preferably 40°C or higher, even more preferably 50°C or higher, particularly preferably 60°C or higher, and most preferably 70°C or higher.

[0045] The degree of dispersion 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. In this disclosure, the degree of dispersion is the ratio of the weight-average molecular weight to the number-average molecular weight (weight-average molecular weight / number-average molecular weight). In this disclosure, the weight-average molecular weight and the number-average molecular weight are values ​​measured using gel permeation chromatography.

[0046] The photosensitive composition may also contain resins other than resin A described above. Other resins include acrylic resins, styrene-acrylic copolymers, polyurethane resins, polyvinyl alcohol, polyvinyl formal, polyester resins, epoxy resins, polyacetal resins, polybenzoxazole resins, polysiloxane resins, polyethyleneimine, polyallylamine, and polyalkylene glycols.

[0047] The content of resin A is preferably 10 to 95% by mass, more preferably 20 to 80% by mass, even more preferably 30 to 70% by mass, and particularly preferably 40 to 60% by mass, based on the total mass of the photosensitive composition. A resin A content of 95% by mass or less is preferable from the standpoint of controlling the development time. On the other hand, a resin A content of 10% by mass or more is preferable from the standpoint of improving edge fusing resistance.

[0048] [Polymerizable compound] The photosensitive composition contains a polymerizable compound having an ethylenically unsaturated group. The polymerizable compound described above includes polymerizable compound A that satisfies the requirement (X1) described later. Furthermore, it is preferable that the polymerizable compound described above includes polymerizable compound B that satisfies the requirement (X2) described later. The inclusion of polymerizable compound A and polymerizable compound B is thought to improve the peelability of the resist pattern formed by the photosensitive composition. Hereafter, the peelability of the resist pattern formed by the photosensitive composition will also be simply referred to as "peelability." In this specification, "polymerizable compound" refers to a compound that polymerizes under the action of a polymerization initiator, as described later, and is a compound different from resin A mentioned above.

[0049] Examples of ethylenically unsaturated groups found in polymerizable compounds include vinyl groups, acryloyl groups, methacryloyl groups, styryl groups, and maleimide groups, with acryloyl or methacryloyl groups being preferred.

[0050] The polymerizable compounds will be explained in detail below.

[0051] (Polymerizable compound A) Polymerizable compound A is a polymerizable compound that satisfies the following requirement (X1). Requirement (X1): A composition consisting of 100 parts by mass of polymerizable compound A, 1.0 part by mass of 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]ethanone-1-(O-acetyloxime), and 9 parts by mass of methyl ethyl ketone is applied to form a 2.0 μm film, and then exposed to a nitrogen atmosphere at an exposure of 500 mJ / cm². 2 The water contact angle of the film obtained by irradiating it with i-rays and heating it at 150°C for 30 minutes is 74 degrees or higher. A nitrogen atmosphere refers to a state where the total pressure is 1.0 atmosphere and the partial pressure of nitrogen is 0.98 atmospheres or higher. The above-mentioned water contact angle refers to the measurement taken using the tangential method with a contact angle meter (product name "FAMMS DM-701", manufactured by Kyowa Interface Science Co., Ltd.). More specifically, using the above-mentioned contact angle meter, under conditions of 23°C and 50% humidity, the amount of water dropped onto the film is 1 μL, and the contact angle is measured 20 seconds after the water is dropped onto the film. The water contact angle is preferably 76 degrees or higher, and more preferably 80 degrees or higher. There is no particular upper limit, but it is 180 degrees or lower, and preferably 90 degrees or lower.

[0052] Polymerizable compound A is not particularly limited as long as it satisfies the above requirement (X1). Polymerizable compound A is preferably a compound having two or more ethylenically unsaturated groups in one molecule, in terms of photosensitivity. Furthermore, in terms of resolution and peelability, the number of ethylenically unsaturated groups in polymerizable compound A is preferably six or less, more preferably three or less, and even more preferably two or less.

[0053] Polymerizable compound A preferably has a hydrocarbon group in terms of superior acid resistance. The hydrocarbon group is not particularly limited, but in terms of superior acid resistance, the number of carbon atoms in the hydrocarbon group is preferably 4 or more, more preferably 5 or more, and even more preferably 6 or more. There is no particular upper limit to the number of carbon atoms, but it is 20 or less. Furthermore, the hydrocarbon group may be a hydrocarbon group having a cyclic structure, or a hydrocarbon group having a chain structure. The ring structure of the hydrocarbon group may be aromatic or non-aromatic, with non-aromatic being preferred. Furthermore, the ring structure of the hydrocarbon group may be monocyclic or polycyclic, with polycyclic being preferred. Examples of ring structures in hydrocarbon groups include aromatic ring structures such as benzene rings, naphthalene rings, and fluorene rings, as well as non-aromatic ring structures such as cyclopentane rings, cyclohexane rings, norbornane rings, tetrahydrodicyclopentadiene rings, tricyclodecane rings, and adamantane rings. The chain structure of the hydrocarbon group in the chain structure may be an alkyl chain having a branched structure, or an alkyl chain without a branched structure.

[0054] In particular, polymerizable compound A is preferably polymerizable compound A1 represented by the following formula (A) because it has superior acid resistance and superior peelability. Q 1 -R 1 -Q 2 Formula (A) In formula (A), Q 1 and Q 2 Each of these independently represents a (meth)acryloyloxy group. Q 1 and Q 2 From the viewpoint of ease of synthesis, it is preferable that these be the same group. In formula (A), R 1 This represents a chain-like divalent hydrocarbon group. R 1 An example of a chain-like divalent hydrocarbon group represented by this is the alkylene group. The number of carbon atoms in the alkylene group described above is preferably 4 or more, more preferably 5 or more, and even more preferably 6 or more, in terms of superior acid resistance. There is no particular upper limit to the number of carbon atoms, but it is generally 20 or less. The alkylene group may be linear or branched. Examples of linear alkylene groups include butylene, pentylene, hexylene, heptylene, octylene, nonylene, decanylene, undecaneylene, and dodecaneylene. Examples of branched alkylene groups include iso-butylene group, tert-butylene group, neo-pentylene group, and 2-ethylhexylene group. The alkylene group described above is preferably a linear alkylene group.

[0055] Specific compounds represented by the above formula (A) include 1,3-butanediol di(meth)acrylate, tetramethylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,7-heptanediol di(meth)acrylate, 1,8-octanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, and 1,10-decanediol di(meth)acrylate. Among these, 1,6-hexanediol di(meth)acrylate, 1,7-heptanediol di(meth)acrylate, 1,8-octanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, and 1,10-decanediol di(meth)acrylate are preferred.

[0056] The polymerizable compound A may be a commercially available product. Examples of commercially available polymerizable compound A 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.), 1,10-decanediol diacrylate, and neopentyl glycol di(meth)acrylate.

[0057] The mass ratio of polymerizable compound A to the total mass of polymerizable compound is preferably 10% by mass or more, more preferably 20% by mass or more, and even more preferably 30% by mass or more, from the viewpoint of superior acid resistance. There is no particular upper limit, but for example it is 100% by mass or less, and from the viewpoint of resolution and peelability, it is preferably 99% by mass or less, more preferably 80% by mass or less, even more preferably 60% by mass or less, and particularly preferably 50% by mass or less. The mass ratio of polymerizable compound A to the total mass of solids in the photosensitive composition is preferably 5% by mass or more, and more preferably 10% by mass or more, from the viewpoint of superior acid resistance. There is no particular upper limit, but for example it is 100% by mass or less, and from the viewpoint of resolution and peelability it is preferably 50% by mass or less, more preferably 40% by mass or less, and even more preferably 20% by mass or less.

[0058] (Polymerizable compound B) Polymerizable compound B is a polymerizable compound that satisfies the following requirement (X2). Requirement (X2): A composition consisting of 100 parts by mass of polymerizable compound B, 1.0 part by mass of 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]ethanone-1-(O-acetyloxime), and 9 parts by mass of methyl ethyl ketone is applied to form a 2.0 μm film, and then exposed to a nitrogen atmosphere at an exposure of 500 mJ / cm². 2 The water contact angle of the film obtained by irradiating it with i-rays and heating it at 150°C for 30 minutes is 65 degrees or less. The above contact angle refers to the one measured using the same method as the above requirement (X1). The water contact angle is preferably 60 degrees or less, and more preferably 50 degrees or less. There is no particular lower limit, but it is 0 degrees or more, and preferably 40 degrees or more.

[0059] Polymerizable compound B is not particularly limited as long as it satisfies the above requirement (X2). Polymerizable compound B is preferably a compound having two or more ethylenically unsaturated groups in one molecule, in terms of photosensitivity. Furthermore, in terms of resolution and peelability, the number of ethylenically unsaturated groups in polymerizable compound B is preferably six or less, more preferably three or less, and even more preferably two or less. The following describes preferred polymerizable compound B1 as polymerizable compound B.

[0060] (Polymerizable compound B1) Polymerizable compound B is also preferably polymerizable compound B1 having an aromatic ring and two ethylenically unsaturated groups.

[0061] Examples of aromatic rings in polymerizable compound B1 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. Aromatic hydrocarbon rings are preferred, and benzene rings are more preferred. The above aromatic rings may have substituents. Polymerizable compound B1 may have only one aromatic ring, or it may have two or more aromatic rings.

[0062] Polymerizable compound B1 is preferably a bisphenol structure because it improves resolution by suppressing swelling of the photosensitive composition due to the developer. Examples of bisphenol structures include the bisphenol A structure derived from bisphenol A (2,2-bis(4-hydroxyphenyl)propane), the bisphenol F structure derived from bisphenol F (2,2-bis(4-hydroxyphenyl)methane), and the bisphenol B structure derived from bisphenol B (2,2-bis(4-hydroxyphenyl)butane). In terms of resolution, the bisphenol A structure is preferred. That is, polymerizable compound B is preferably a bisphenol A structure.

[0063] Examples of polymerizable compounds 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 ends of the bisphenol structure and the two polymerizable groups may be directly bonded, or they may be bonded via one or more alkylene oxy groups, and it is preferable that they are bonded via one or more alkylene oxy groups. 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 preferred. The number of alkylene oxy groups added to the bisphenol structure is not particularly limited, but 4 to 16 per molecule is preferred, and 6 to 14 is more preferred. Polymerizable compound B1 having a bisphenol structure is 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.

[0064] As polymerizable compound B1, a bifunctional ethylenically unsaturated compound having a bisphenol A structure is preferred, and 2,2-bis(4-((meth)acryloxypolyalkoxy)phenyl)propane is more preferred. Examples of 2,2-bis(4-((meth)acryloxypolyalkoxy)phenyl)propane include 2,2-bis(4-(methacryloxydiethoxy)phenyl)propane (FA-324M, manufactured by Hitachi Chemical Co., Ltd.), 2,2-bis(4-(methacryloxyethoxypropoxy)phenyl)propane, 2,2-bis(4-(methacryloxypentaethoxy)phenyl)propane (BPE-500, manufactured by Shin Nakamura Chemical Industry 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.).

[0065] As polymerizable compound B1, compounds represented by the following general formula (B1) are also preferred.

[0066] [ka]

[0067] In general formula B1, R1 and R2 each independently represent a hydrogen atom or a methyl group. A represents C2H4. B represents C3H6. n1 and n3 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 of -(AO)- and -(BO)- may be random or in a block. In the case of a block, either -(AO)- or -(BO)- may be on the bisphenyl group side. In one embodiment, n1+n2+n3+n4 is preferably 2 to 20, more preferably 2 to 16, and even more preferably 4 to 12. Also, n2+n4 is preferably 0 to 10, more preferably 0 to 4, even more preferably 0 to 2, and particularly preferably 0.

[0068] Examples of polymerizable compounds B other than polymerizable compound B1 include polymerizable compounds having an acidic group (such as a carboxyl group). The above acidic group may form an acid anhydride group. Examples of polymerizable compounds containing acidic groups 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 polymerizable compound having an acid group, for example, a polymerizable compound having an acid group described in paragraphs

[0025] to

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

[0069] Examples of polymerizable compounds B other than polymerizable compound B1 include difunctional ethylenically unsaturated compounds that do not have an aromatic ring. Examples of difunctional 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 ethylene glycol dimethacrylate. 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 commercially available polyalkylene glycol di(meth)acrylates include 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.), and Aronics® M-270 (manufactured by Toagosei Co., Ltd.). Examples of urethane di(meth)acrylates include propylene oxide-modified urethane di(meth)acrylates and ethylene oxide and propylene oxide-modified urethane di(meth)acrylates. Examples of commercially available urethane di(meth)acrylates 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.).

[0070] Polymerizable compound B1 may be used alone or in combination of two or more types. In the photosensitive composition, the mass ratio of polymerizable compound B1 to the total mass of polymerizable compounds is preferably 0% by mass or more, more preferably 50% by mass or more, even more preferably 55% by mass or more, and particularly preferably 60% by mass or more, from the viewpoint of superior resolution. There is no particular upper limit, but for example it is 100% by mass or less, and from the viewpoint of acid resistance and peelability, it is preferably 90% by mass or less, more preferably 80% by mass or less, and even more preferably 70% by mass or less.

[0071] Polymerizable compound B may be used alone or in combination of two or more types. In the photosensitive composition, the mass ratio of polymerizable compound B to the total mass of polymerizable compounds is preferably 0% by mass or more, more preferably 50% by mass or more, even more preferably 55% by mass or more, and particularly preferably 60% by mass or more, from the viewpoint of superior resolution. There is no particular upper limit, but for example it is 100% by mass or less, and from the viewpoint of acid resistance and peelability, it is preferably 90% by mass or less, more preferably 80% by mass or less, and even more preferably 70% by mass or less. The mass ratio of polymerizable compound B to the total mass of solids in the photosensitive composition is preferably 10% by mass or more, and more preferably 20% by mass or more, from the viewpoint of superior peelability. There is no particular upper limit, but for example it is 100% by mass or less, preferably 50% by mass or less, and more preferably 40% by mass or less.

[0072] (Other polymerizable compounds) The photosensitive composition may contain polymerizable compounds other than those specifically described above (other polymerizable compounds). Polymerizable compounds other than those specifically described above are not particularly limited and 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. Examples of other polymerizable compounds are given below. Note that even if a compound is listed as an example of other polymerizable compounds, if it falls under polymerizable compound A or polymerizable compound B, it will be included in the polymerizable compounds listed above.

[0073] 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.

[0074] 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.

[0075] 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, ditrimethylolpropane tetra(meth)acrylate, trimethylolethane tri(meth)acrylate, isocyanuric acid tri(meth)acrylate, glycerin tri(meth)acrylate, and alkylene oxide modified products thereof. Here, "(tri / tetra / penta / hexa)(meth)acrylate" is a concept that encompasses tri(meth)acrylate, tetra(meth)acrylate, penta(meth)acrylate, and hexa(meth)acrylate, while "(tri / tetra)(meth)acrylate" is a concept that encompasses tri(meth)acrylate and tetra(meth)acrylate. In one embodiment, the photosensitive composition may also contain the polymerizable compound B1 described above and a trifunctional or greater ethylenically unsaturated compound, and more preferably contains the polymerizable compound B1 described above and two or more trifunctional or greater ethylenically unsaturated compounds. In this case, the mass ratio of polymerizable compound B1 to trifunctional or greater ethylenically unsaturated compounds is preferably (total mass of polymerizable compound B1):(total mass of trifunctional or greater ethylenically unsaturated compounds) = 1:1 to 5:1, more preferably 1.2:1 to 4:1, and even more preferably 1.5:1 to 3:1. In one embodiment, the photosensitive composition preferably contains the polymerizable compound B1 described above and two or more trifunctional ethylenically unsaturated compounds.

[0076] 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.).

[0077] The molecular weight (or weight-average molecular weight if a molecular weight distribution exists) of the polymerizable compound (including polymerizable compounds A, B, and B1) is preferably 200 to 3000, more preferably 280 to 2200, and even more preferably 300 to 2200.

[0078] Polymerizable compounds may be used individually or in combination of two or more. The polymerizable compound content is preferably 0 to 70% by mass, more preferably 10 to 70% by mass, and even more preferably 20 to 60% by mass, based on the total mass of the solids of the photosensitive composition.

[0079] In the photosensitive composition, Content of polymerizable compounds relative to the content of alkali-soluble resin The mass ratio is preferably 0.60 to 1.50, more preferably 0.68 to 1.30, and even more preferably 0.75 to 1.20. A mass ratio of 0.68 or higher allows for a photosensitive composition with superior acid resistance, while a mass ratio of 1.30 or lower allows for a photosensitive composition with superior peelability.

[0080] In the photosensitive composition, the mass ratio of polymerizable compound B to polymerizable compound A is preferably 0.00 to 6.00, more preferably 0.50 to 4.00, even more preferably 1.00 to 3.00, and particularly preferably 1.50 to 2.00. A mass ratio of 0.50 or higher allows for a photosensitive composition with superior resolution and peelability, while a mass ratio of 4.00 or lower allows for a photosensitive composition with superior acid resistance. Furthermore, it is also preferable that the above mass ratio requirements are met in terms of acid resistance, resolution, and peelability, and that polymerizable compound A is polymerizable compound A1, and polymerizable compound B is polymerizable compound B1 having a bisphenol A structure.

[0081] [Photopolymerization initiator] The photosensitive composition contains a photopolymerization initiator. A photopolymerization initiator is a compound that initiates polymerization of a polymerizable compound upon exposure to active light such as ultraviolet light, visible light, and X-rays. There are no particular limitations on the photopolymerization initiator; known photopolymerization initiators can be used. Examples of photopolymerization initiators include photoradical polymerization initiators and photocationic polymerization initiators, with photoradical polymerization initiators being preferred.

[0082] Examples of photo-radical 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, and photopolymerization initiators having an N-phenylglycine structure.

[0083] Furthermore, the photosensitive composition preferably contains at least one selected from the group consisting of 2,4,5-triarylimidazole dimers and their derivatives as a photoradical polymerization initiator, from the viewpoint of photosensitivity, visibility of exposed and unexposed areas, and resolution. The two 2,4,5-triarylimidazole structures in the 2,4,5-triarylimidazole dimer and its derivatives may be the same or different. Examples of derivatives of the 2,4,5-triarylimidazole dimer include 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer, 2-(o-chlorophenyl)-4,5-di(methoxyphenyl)imidazole dimer, 2-(o-fluorophenyl)-4,5-diphenylimidazole dimer, 2-(o-methoxyphenyl)-4,5-diphenylimidazole dimer, and 2-(p-methoxyphenyl)-4,5-diphenylimidazole dimer.

[0084] As photoradical polymerization initiators, for example, polymerization initiators 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. 2015-14783 may be used.

[0085] Examples of photoradical polymerization initiators include ethyl dimethylaminobenzoate (DBE, CAS No. 10287-53-3), benzoin methyl ether, anisyl (p,p'-dimethoxybenzyl), TAZ-110 (trade name: manufactured by Midori Chemical Co., Ltd.), benzophenone, 4,4'-bis(diethylamino)benzophenone, TAZ-111 (trade name: manufactured by Midori Chemical Co., Ltd.), Irgacure OXE01, OXE02, OXE03, OXE04 (manufactured by BASF), Omnirad 651 and 369 (trade name: manufactured by IGM Resins BV), and 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole (manufactured by Tokyo Chemical Industry Co., Ltd.).

[0086] Examples of commercially available photoradical polymerization initiators include 1-[4-(phenylthio)]-1,2-octanedione-2-(O-benzoyl oxime) (trade name: IRGACURE® OXE-01, manufactured by BASF), 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]ethanone-1-(O-acetyl oxime) (trade name: IRGACURE OXE-02, manufactured by BASF), IRGACURE OXE-03 (manufactured by BASF), IRGACURE OXE-04 (manufactured by BASF), and 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone (trade name: Omnirad 379EG, IGM Resins). (Manufactured by BV), 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one (Trade name: Omnirad 907, manufactured by IGM Resins BV), 2-hydroxy-1-{4-[4-(2-hydroxy-2-methylpropionyl)benzyl]phenyl}-2-methylpropan-1-one (Trade name: Omnirad 127 (manufactured by IGM Resins BV), 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butanone-1 (product name: Omnirad 369, manufactured by IGM Resins BV), 2-hydroxy-2-methyl-1-phenylpropan-1-one (product name: Omnirad 1173, manufactured by IGM Resins BV), 1-hydroxycyclohexylphenyl ketone (product name: Omnirad 184, manufactured by IGM Resins BV), 2,2-dimethoxy-1,2-diphenylethane-1-one (product name: Omnirad 651, manufactured by IGM Resins BV), 2,4,6-trimethylbenzolyl-diphenylphosphine oxide (product name: Omnirad TPO H, manufactured by IGM Resins BV), bis(2,4,6-trimethylbenzolyl)phenylphosphine oxide (product name: Omnirad 819, manufactured by IGM Resins (Manufactured by BV), oxime ester-based photopolymerization initiator (product name: Lunar 6, manufactured by DKSH Japan), 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbisimidazole (2-(2-chlorophenyl)-4,5-diphenylimidazole dimer) (product name: B-CIM, manufactured by Hampford), and 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer (product name: BCTB, manufactured by Tokyo Chemical Industry Co., Ltd.), 1-[4-(phenylthio)phenyl]-3-cyclopentylpropane-1,2-dione-2-(O-benzoyloxime) (product name: TR-PBG-305, manufactured by Changzhou) Examples include 1,2-propanedione,3-cyclohexyl-1-[9-ethyl-6-(2-furanylcarbonyl)-9H-carbazole-3-yl]-,2-(O-acetyloxime) (trade name: TR-PBG-326, manufactured by Changzhou Strong Electronic Materials Co., Ltd.), and 3-cyclohexyl-1-(6-(2-(benzoyloxyimino)hexanoyl)-9-ethyl-9H-carbazole-3-yl)-propane-1,2-dione-2-(O-benzoyloxime) (trade name: TR-PBG-391, manufactured by Changzhou Strong Electronic Materials Co., Ltd.).

[0087] A photocationic polymerization initiator (photoacid generator) is a compound that generates acid upon receiving active light. While compounds that are sensitive to active light with a wavelength of 300 nm or higher, preferably 300-450 nm, and generate acid are preferred as photocationic polymerization initiators, their chemical structure is not limited. Furthermore, photocationic polymerization initiators that are not directly sensitive to active light with a wavelength of 300 nm or higher can also be preferably used in combination with a sensitizer, provided they become sensitive to active light with a wavelength of 300 nm or higher and generate acid. As the photocationic polymerization initiator, a photocationic polymerization initiator that generates an acid with a pKa of 4 or less is preferred, a photocationic polymerization initiator that generates an acid with a pKa of 3 or less is more preferred, and a photocationic polymerization initiator that generates an acid with a pKa of 2 or less is particularly preferred. There is no specific lower limit for the pKa, but for example, -10.0 or higher is preferred.

[0088] Examples of photocationic polymerization initiators include ionic photocationic polymerization initiators and nonionic photocationic polymerization initiators. Examples of ionic photocationic polymerization initiators include onium salt compounds such as diaryliodonium salts and triarylsulfonium salts, as well as quaternary ammonium salts. As the ionic photocationic polymerization initiator, the ionic photocationic polymerization initiator described in paragraphs

[0114] to

[0133] of Japanese Patent Application Publication No. 2014-085643 may be used.

[0089] Examples of nonionic photocationic polymerization initiators include trichloromethyl-s-triazines, diazomethane compounds, imidosulfonate compounds, and oximesulfonate compounds. For trichloromethyl-s-triazines, diazomethane compounds, and imidosulfonate compounds, compounds described in paragraphs

[0083] to

[0088] of Japanese Patent Publication No. 2011-221494 may be used. For oximesulfonate compounds, compounds described in paragraphs

[0084] to

[0088] of International Publication No. 2018 / 179640 may be used.

[0090] The photosensitive composition preferably contains a photoradical polymerization initiator, and more preferably contains at least one selected from the group consisting of 2,4,5-triarylimidazole dimers and their derivatives.

[0091] The photopolymerization initiator may be used alone or in combination of two or more types. The content of the photopolymerization initiator is not particularly limited, but is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and even more preferably 1.0% by mass or more, based on the total mass of the solids of the photosensitive composition. The upper limit is not particularly limited, but is preferably 20% by mass or less, more preferably 15% by mass or less, and even more preferably 10% by mass or less, based on the total mass of the photosensitive composition.

[0092] [Pigment] The photosensitive composition preferably contains a dye (also called "dye N") whose maximum absorption wavelength in the wavelength range of 400-780 nm during color development is 450 nm or higher, 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 resolution. Although the detailed mechanism is unknown, the inclusion of dye N improves adhesion to adjacent layers (e.g., water-soluble resin layers) and results in superior resolution.

[0093] In this specification, the phrase "the maximum absorption wavelength of a dye changes due to an acid, base, or radical" may mean any of the following: a dye in a colored state is decolorized by an acid, base, or radical; a dye in a decolorized state is colored by an acid, base, or radical; or a dye in a colored state changes to a colored state of another hue. Specifically, the 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 acids, bases, or radicals within the photosensitive composition 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 caused by acids, bases, or radicals. Furthermore, the dye may change its colored or decolorized state upon direct stimulation by acids, bases, or radicals without the need for exposure.

[0094] In particular, from the viewpoint of visibility and resolution of the exposed and unexposed areas, the dye N is preferably a dye whose maximum absorption wavelength changes with acid or radicals, and more preferably a dye whose maximum absorption wavelength changes with radicals. If the photosensitive composition is a negative-type photosensitive composition, it is preferable that the negative-type photosensitive composition contains both a dye N whose maximum absorption wavelength changes due to radicals, and a photoradical polymerization initiator, from the viewpoint of visibility and resolution of the exposed and unexposed areas. Furthermore, from the viewpoint of visibility between the exposed and unexposed areas, it is preferable that the dye N is a dye that develops color in response to an acid, base, or radical.

[0095] 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, 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.

[0096] 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 higher, more preferably 550 to 700 nm, and even more preferably 550 to 650 nm. Furthermore, the dye N may have only one maximum absorption wavelength in the wavelength range of 400-780 nm during color development, or it may have two or more. If the dye N has two or more maximum absorption wavelengths in the wavelength range of 400-780 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 higher.

[0097] The maximum absorption wavelength of dye N is obtained by measuring the transmission spectrum of a solution containing dye N (at a 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).

[0098] Examples of dyes that develop or decolorize upon exposure include leuco compounds. Examples of pigments that decolorize upon exposure include leuco compounds, diarylmethane-based dyes, oxazine-based dyes, xanthene-based dyes, iminonaphthoquinone-based dyes, azomethine-based dyes, and anthraquinone-based dyes. As for the dye N, a leuco compound is preferred from the viewpoint of visibility between the exposed and unexposed areas.

[0099] 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-based dyes or fluorane-based dyes are preferred, and leuco compounds having a triphenylmethane skeleton (triphenylmethane-based dyes) or fluorane-based dyes are more preferred.

[0100] 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 it is more preferable to have a lactone ring, and the lactone ring opens and develops color in response to radicals or acids.

[0101] Examples of pigment N include the following dyes and leuco compounds. Specific examples of dyes among pigment N include Brilliant Green, Ethyl Violet, Methyl Green, Crystal Violet, Basic Fuchsine, Methyl Violet 2B, Quinaldine Red, Rose Bengal, Methanyl Yellow, Thymol Sulfophthalein, Xylenol Blue, Methyl Orange, Paramethyl Red, Congofred, 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 Spiron 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-pN,N-bis(hydroxyethyl)aminophenyliminonaphthoquinone, 1-phenyl-3-methyl-4-p-diethylaminophenylimino-5-pyrazolone, and 1-β-naphthyl-4-p-diethylaminophenylimino-5-pyrazolone.

[0102] Specific examples of leuco compounds among the pigment 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-(Np-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-zaphthalide, 3-(4-diethylaminophenyl)-3-(1-ethyl-2-methylindole-3-yl)phthalide, and 3',6'-bis(diphenylamino)spiroisobenzofuran-1(3H),9'-[9H]xanthene-3-one.

[0103] From the viewpoint of visibility of exposed and unexposed areas, pattern visibility after development, and resolution, dye N is preferably a dye whose maximum absorption wavelength changes with radicals, and more preferably a dye that develops color with radicals. As the pigment N, leucocrystal violet, crystal violet lactone, brilliant green, or Victoria Pure Blue naphthalene sulfonate are preferred.

[0104] Dye N may be used alone or in combination of two or more types. The content of dye N is preferably 0.1% by mass or more, more preferably 0.1 to 10% by mass, even more preferably 0.1 to 5% by mass, and particularly preferably 0.1 to 1% by mass, based on the total mass of the photosensitive composition, from the viewpoint of visibility of exposed and unexposed areas, pattern visibility after development, and resolution.

[0105] The content of dye N refers to the amount of dye N present in the total mass of the photosensitive composition when all of the dye N is in a color-developed state. The following describes a method for quantifying the content of dye N, using a dye that develops color via radicals as an example. Solutions were prepared by dissolving 0.001 g and 0.01 g of dye in 100 mL of methyl ethyl ketone. To each of the resulting solutions, the photoradical polymerization initiator Irgacure OXE01 (trade name, BASF Japan Ltd.) was added, and radicals were generated by irradiating with 365 nm light, causing all the dyes to develop color. Subsequently, under an atmospheric environment, the absorbance of each solution at a liquid temperature of 25°C was measured using a spectrophotometer (UV3100, Shimadzu Corporation), and a calibration curve was created. Next, the absorbance of the solution in which all of the dye has developed is measured, using the same method as above, except that 3 g of the photosensitive composition is dissolved in methyl ethyl ketone instead of the dye. The amount of dye contained in the photosensitive composition is calculated from the absorbance of the obtained solution containing the photosensitive composition based on the calibration curve. Note that 3g of the photosensitive composition is equivalent to 3g of the total solids in the photosensitive composition.

[0106] [Thermal crosslinkable compound] When the photosensitive composition is a negative-type photosensitive composition, it may contain a thermally crosslinkable compound, in terms of the strength of the resulting cured film and the tackiness of the resulting uncured film. In this specification, thermally crosslinkable compounds having ethylenically unsaturated groups, as described later, will not be treated as polymerizable compounds, but as thermally crosslinkable compounds. Examples of thermally crosslinkable compounds include methylol compounds and blocked isocyanate compounds. Among these, blocked isocyanate compounds are preferred in terms of the strength of the resulting cured film and the tackiness of the resulting uncured film. Since blocked isocyanate compounds react with hydroxyl and carboxyl groups, for example, if the resin and / or polymerizable compound has at least one of a hydroxyl and a carboxyl group, the hydrophilicity of the formed film tends to decrease, and the function of the film when a cured negative-type photosensitive composition is used as a protective film tends to be enhanced. Blocked isocyanate compounds refer to "compounds having a structure in which the isocyanate group of an isocyanate is protected (so-called masked) with a blocking agent."

[0107] The dissociation temperature of the blocked isocyanate compound is not particularly limited, but is preferably 100 to 160°C, and more preferably 130 to 150°C. The dissociation temperature of blocked isocyanates refers to "the temperature of the endothermic peak associated with the deprotection reaction of blocked isocyanates, as measured by differential scanning calorimetry (DSC) analysis using a differential scanning calorimeter." As a differential scanning calorimeter, for example, a differential scanning calorimeter (model: DSC6200) manufactured by Seiko Instruments Corporation can be suitably used. However, the differential scanning calorimeter is not limited to this.

[0108] Examples of blocking agents with a dissociation temperature of 100-160°C include active methylene compounds [malonic acid diesters (dimethyl malonate, diethyl malonate, di-n-butyl malonate, di-2-ethylhexyl malonate, etc.)] and oxime compounds (compounds having a structure represented by -C(=N-OH)- in the molecule, such as formaldehyde oxime, acetaldehyde oxime, acetoxime, methyl ethyl ketoxime, and cyclohexanone oxime). Among these, as a blocking agent with a dissociation temperature of 100 to 160°C, at least one selected from oxime compounds is preferred, for example, from the viewpoint of storage stability.

[0109] Blocked isocyanate compounds are preferably configured to have an isocyanurate structure, for example, to improve the brittleness of the film and enhance adhesion to the substrate. Blocked isocyanate compounds having an isocyanurate structure can be obtained, for example, by isocyanurating and protecting hexamethylene diisocyanate. Among blocked isocyanate compounds having an isocyanurate structure, compounds having an oxime structure using an oxime compound as a blocking agent are preferred because they make it easier to set the dissociation temperature within a favorable range and reduce development residue compared to compounds without an oxime structure.

[0110] The blocked isocyanate compound may have polymerizable groups. There are no particular restrictions on the polymerizable group; known polymerizable groups can be used, and radical polymerizable groups are preferred. Polymerizable groups include ethylenically unsaturated groups such as (meth)acryloxy groups, (meth)acrylamide groups, and styryl groups, as well as epoxy groups such as glycidyl groups. Among the polymerizable groups, ethylenically unsaturated groups are preferred, (meth)acryloxy groups are more preferred, and acryloxy groups are even more preferred.

[0111] Commercially available blocked isocyanate compounds can be used. Examples of commercially available blocked isocyanate compounds include Karenz® AOI-BM, Karenz® MOI-BM, Karenz® MOI-BP, etc. (all manufactured by Showa Denko Corporation), and the block-type Duranate series (for example, Duranate® TPA-B80E, Duranate® WT32-B75P, etc., manufactured by Asahi Kasei Chemicals Corporation). Furthermore, a compound with the following structure can also be used as a blocked isocyanate compound.

[0112] [ka]

[0113] The thermally crosslinkable compound may be used alone or in combination of two or more types. If the photosensitive composition contains a thermally crosslinkable compound, the content of the thermally crosslinkable compound is preferably 1 to 50% by mass, and more preferably 5 to 30% by mass, based on the total mass of the photosensitive composition.

[0114] [Pigments] The photosensitive composition may contain a pigment. When a photosensitive composition contains a pigment, the photosensitive composition corresponds to a colored resin layer. In recent electronic devices, liquid crystal display windows may have a cover glass attached to the back edge of a transparent glass substrate or similar material to protect the liquid crystal display window. This cover glass has a black, frame-shaped light-shielding layer formed on the back edge. A colored resin layer may be used to form such a light-shielding layer. The pigment can be appropriately selected according to the desired hue, and examples include black pigment, white pigment, and pigments of other chromatic colors besides black and white. When forming a black-based pattern, black pigment is preferred as the pigment.

[0115] Examples of black pigments include known black pigments (e.g., organic pigments and inorganic pigments). In particular, from the viewpoint of optical density, carbon black, titanium oxide, titanium carbide, iron oxide, titanium oxide, or graphite are preferred as black pigments, with carbon black being more preferred. As for carbon black, from the viewpoint of surface resistance, surface-modified carbon black in which at least a portion of the surface is coated with resin is preferred.

[0116] The particle size (number-average particle size) of the black pigment is preferably 0.001 to 0.1 μm, and more preferably 0.01 to 0.08 μm, from the viewpoint of dispersion stability. "Particle size" refers to the diameter of a circle with the same area as the pigment particle, calculated from a photograph of the pigment particle taken with an electron microscope. "Number-average particle size" refers to the average value obtained by calculating the particle size for any 100 particles and averaging the calculated particle sizes of those 100 particles.

[0117] Examples of white pigments include inorganic pigments and the white pigments described in paragraphs

[0015] and

[0114] of Japanese Patent Publication No. 2005-007765. As inorganic pigments, titanium dioxide, zinc oxide, lithopone, light calcium carbonate, white carbon, aluminum oxide, aluminum hydroxide, or barium sulfate are preferred, titanium dioxide or zinc oxide is more preferred, titanium dioxide is even more preferred, rutile-type or anatase-type titanium dioxide is particularly preferred, and rutile-type titanium dioxide is most preferred. Furthermore, the surface of titanium dioxide may be treated with silica, alumina, titania, zirconia, or organic substances, or two or more of these treatments may be applied. This suppresses the catalytic activity of titanium dioxide and improves its heat resistance and fading properties. From the viewpoint of reducing the thickness of the photosensitive composition after heating, it is preferable to apply at least one of alumina treatment and zirconia treatment as a surface treatment to the surface of titanium oxide, and more preferable to apply both alumina treatment and zirconia treatment.

[0118] When the photosensitive composition is a colored resin layer, it is preferable, from the viewpoint of transferability, that the photosensitive composition also contains chromatic pigments other than black and white pigments. For chromatic pigments, the particle size (number-average particle size) is preferably 0.1 μm or less, and more preferably 0.08 μm or less, from the standpoint of superior dispersibility. The lower limit is preferably 10 nm or more. Examples of chromatic pigments include Victoria Pure Blue BO (Color Index (hereinafter also referred to as "CI") 42595), Auramine (CI 41000), Fat Black HB (CI 26150), Monolight Yellow GT (CI Pigment Yellow 12), Permanent Yellow GR (CI Pigment Yellow 17), Permanent Yellow HR (CI Pigment Yellow 83), Permanent Carmine FBB (CI Pigment Red 146), Hoster Balm Red ESB (CI Pigment Violet 19), Permanent Ruby FBH (CI Pigment Red 11), Fastel Pink B Spray (CI Pigment Red 81), and Monastral First Blue (CI Pigment Blue Examples include -15), Monolight First Black B (CI Pigment Black 1) and Carbon, CI Pigment Red 97, CI Pigment Red 122, CI Pigment Red 149, CI Pigment Red 168, CI Pigment Red 177, CI Pigment Red 180, CI Pigment Red 192, CI Pigment Red 215, CI Pigment Green 7, CI Pigment Blue 15:1, CI Pigment Blue 15:4, CI Pigment Blue 22, CI Pigment Blue 60, CI Pigment Blue 64 and CI Pigment Violet 23, with CI Pigment Red 177 being preferred.

[0119] Pigments may be used individually or in combination of two or more types. The pigment content is preferably more than 3% by mass and 40% by mass or less, more preferably more than 3% by mass and 35% by mass or less, even more preferably more than 5% by mass and 35% by mass or less, and particularly preferably 10 to 35% by mass, based on the total mass of the photosensitive composition.

[0120] When the photosensitive composition contains pigments other than black pigment (for example, white pigment and chromatic pigment), the content of pigments other than black pigment is preferably 30% by mass or less, more preferably 1 to 20% by mass, and even more preferably 3 to 15% by mass, relative to the total mass of black pigment.

[0121] When the photosensitive composition contains a black pigment, it is preferable that the black pigment (preferably carbon black) be introduced into the photosensitive composition in the form of a pigment dispersion. The dispersion may be prepared by pre-mixing a black pigment and a pigment dispersant, obtaining a mixture, and then adding it to an organic solvent (or vehicle) and dispersing it in a disperser. The pigment dispersant can be selected according to the pigment and solvent; for example, commercially available dispersants can be used. "Vehicle" refers to the medium that disperses the pigment in a pigment dispersion. The above vehicle is liquid and contains a binder component that holds the black pigment in a dispersed state, and a solvent component (organic solvent) that dissolves and dilutes the binder component.

[0122] Examples of known dispersers include kneaders, roll mills, attritors, super mills, dissolvers, homomixers, and sand mills. Alternatively, the material may be finely ground using frictional force through mechanical grinding. Examples of dispersers and fine grinders can be found in, for example, the "Dictionary of Pigments" (by Kunizo Asakura, 1st edition, Asakura Shoten, 2000, pp. 438, 310).

[0123] [solvent] The photosensitive composition may contain a solvent. Any commonly used solvent can be used without any particular restrictions. Organic solvents are preferred as the solvent. Examples of organic solvents include methyl ethyl ketone, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate (also known as 1-methoxy-2-propyl acetate), diethylene glycol ethyl methyl ether, cyclohexanone, methyl isobutyl ketone, ethyl lactate, methyl lactate, caprolactam, methanol, ethanol, n-propanol, 2-propanol, N,N-dimethylformamide, N,N-dimethylacetamide, and mixtures thereof. Preferred solvents include a mixed solvent of methyl ethyl ketone and propylene glycol monomethyl ether acetate, a mixed solvent of methyl ethyl ketone, propylene glycol monomethyl ether acetate and methanol, a mixed solvent of diethylene glycol ethyl methyl ether and propylene glycol monomethyl ether acetate, or a mixed solvent of methyl ethyl ketone, propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate.

[0124] The solvent may be used individually or in combination of two or more types. When the photosensitive composition contains a solvent, the solids content of the photosensitive composition is preferably 5 to 80% by mass, more preferably 8 to 40% by mass, and even more preferably 10 to 30% by mass. In other words, when the photosensitive composition contains a solvent, the solvent content is preferably 20 to 95% by mass, more preferably 60 to 95% by mass, and even more preferably 70 to 95% by mass, relative to the total solids content of the photosensitive composition.

[0125] When the photosensitive composition contains a solvent, the viscosity (at 25°C) of the photosensitive composition is preferably 1 to 50 mPa·s, more preferably 2 to 40 mPa·s, and even more preferably 3 to 30 mPa·s, from the viewpoint of coatability. Viscosity is measured using, for example, a VISCOMETER TV-22 (manufactured by TOKI SANGYO CO.LTD). When the photosensitive composition contains a solvent, the surface tension (at 25°C) of the photosensitive composition is preferably 5 to 100 mN / m, more preferably 10 to 80 mN / m, and even more preferably 15 to 40 mN / m, from the viewpoint of coatability. Surface tension is measured by, for example, an automatic surface tensile. Measurements are performed using CBVP-Z (manufactured by Kyowa Interface Science Co., Ltd.).

[0126] As a solvent, the Solvent described in paragraphs 0054 and 0055 of U.S. Patent Publication No. 2005 / 282073 may also be used, and the contents of that specification are incorporated herein by reference. Additionally, organic solvents with a boiling point of 180-250°C (high-boiling point solvents) can be used as solvents if necessary.

[0127] [Other additives] The photosensitive composition may contain, as necessary, known additives in addition to the above-mentioned components. Examples of additives include radical polymerization inhibitors, antioxidants (e.g., phenidone), rust inhibitors (e.g., benzotriazoles and carboxybenzotriazoles), sensitizers, surfactants, plasticizers, heterocyclic compounds (e.g., triazoles), pyridines (e.g., isonicotinamides), and purine bases (e.g., adenine). Other additives include, for example, metal oxide particles, chain transfer agents, antioxidants, dispersants, acid growth agents, development accelerators, conductive fibers, ultraviolet absorbers, thickeners, crosslinking agents, organic or inorganic precipitation inhibitors, and paragraphs

[0165] to

[0184] of Japanese Patent Publication No. 2014-085643, the contents of which are incorporated herein by reference. Each additive may be used individually or in combination of two or more.

[0128] The photosensitive composition may contain a radical polymerization inhibitor. Examples of radical polymerization inhibitors include the thermal polymerization inhibitors described in paragraph

[0018] of Japanese Patent No. 4502784. Among these, phenothiazine, phenoxazine, 1-phenyl-3-pyrazolidone, or 4-methoxyphenol are preferred. Other radical polymerization inhibitors include naphthylamine, cuprous chloride, nitrosophenylhydroxyamine aluminum salt, and diphenylnitrosamine. In order not to impair the sensitivity of the photosensitive composition, it is preferable to use nitrosophenylhydroxyamine aluminum salt as a radical polymerization inhibitor. The content of the radical polymerization inhibitor is preferably 0.005 to 5.0% by mass, more preferably 0.01 to 3.0% by mass, and even more preferably 0.01 to 1.0% by mass, relative to the total mass of the polymerizable compound.

[0129] Examples of benzotriazoles include 1,2,3-benzotriazole, 1-chloro-1,2,3-benzotriazole, bis(N-2-ethylhexyl)aminomethylene-1,2,3-benzotriazole, bis(N-2-ethylhexyl)aminomethylene-1,2,3-tolyltriazole, and bis(N-2-hydroxyethyl)aminomethylene-1,2,3-benzotriazole.

[0130] Examples of carboxybenzotriazoles include 4-carboxy-1,2,3-benzotriazole, 5-carboxy-1,2,3-benzotriazole, N-(N,N-di-2-ethylhexyl)aminomethylenecarboxybenzotriazole, N-(N,N-di-2-hydroxyethyl)aminomethylenecarboxybenzotriazole, and N-(N,N-di-2-ethylhexyl)aminoethylenecarboxybenzotriazole. Commercially available carboxybenzotriazoles such as CBT-1 (Johoku Chemical Industry Co., Ltd., trade name) can be used.

[0131] The total content of benzotriazoles and carboxybenzotriazoles is preferably 0.01 to 3% by mass, and more preferably 0.05 to 1% by mass, relative to the total mass of the photosensitive composition. When the content is 0.01% by mass or more, the storage stability of the photosensitive composition is better. On the other hand, when the content is 3% by mass or less, the maintenance of sensitivity and suppression of dye decolorization are better.

[0132] The photosensitive composition may contain a sensitizer. The sensitizer is not particularly limited, and known sensitizers, dyes, and pigments can be used. Examples of sensitizers include dialkylaminobenzophenone compounds, pyrazoline 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.

[0133] The sensitizer may be used alone or in combination of two or more types. When a photosensitive composition contains a sensitizer, the amount of sensitizer can be appropriately selected depending on the purpose, but from the viewpoint of improving sensitivity to a light source and improving the curing speed by balancing polymerization rate and chain transfer, 0.01 to 5% by mass and more preferably 0.05 to 1% by mass is preferred based on the total mass of the photosensitive composition.

[0134] The photosensitive composition may also contain a surfactant. Examples of surfactants include anionic surfactants, cationic surfactants, nonionic surfactants, and amphoteric surfactants, with nonionic surfactants being preferred. Examples of nonionic surfactants include polyoxyethylene higher alkyl ethers, polyoxyethylene higher alkylphenyl ethers, polyoxyethylene glycol higher fatty acid diesters, silicone-based surfactants, and fluorine-based surfactants. As surfactants, for example, those described in paragraphs 0120 to 0125 of International Publication No. 2018 / 179640 can also be used. Furthermore, surfactants described in paragraph 0017 of Japanese Patent No. 4502784 and paragraphs 0060 to 0071 of Japanese Unexamined Patent Publication No. 2009-237362 can also be used as surfactants. 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, F-551-A, F-552, F-554, F-555-A, F-556, F-557, F-558, F-559, F-560, F-561, and F-56. 5, F-563, F-568, F-575, F-780, EXP, MFS-330, MFS-578, MFS-579, MFS-586, MFS-587, R-41, R-41-LM, R-01, R-40, R-40-LM, RS-43, TF-1956, RS-90, R-94, RS-72-K, DS-21 (all manufactured by DIC Corporation), Florard FC430, FC431, FC171 (all manufactured by Sumitomo 3M Co., Ltd.), Surflon S-382, SC-101, SC-103, SC-104, SC-105, SC-1068, SC-381, SC-383, S-393, KH-40 (all manufactured by AGC Inc.), PolyFox PF636, PF656, PF6320, PF6520, PF7002 (all manufactured by OMNOVA), Futegent Examples include 710FL, 710FM, 610FM, 601AD, 601ADH2, 602A, 215M, 245F, 251, 212M, 250, 209F, 222F, 208G, 710LA, 710FS, 730LM, 650AC, 681, 683 (all manufactured by NEOS Corporation), and U-120E (Unichem Corporation). Furthermore, acrylic compounds having a molecular structure with a functional group containing a fluorine atom, in which the fluorine atom-containing functional group is cleaved and the fluorine atom volatilizes when heat is applied, can also be suitably used as fluorine-based surfactants. Examples of such fluorine-based surfactants include the Megafac DS series manufactured by DIC Corporation (Chemical Daily (February 22, 2016), Nikkei Sangyo Shimbun (February 23, 2016)), such as Megafac DS-21. Furthermore, as a fluorine-based surfactant, it is also preferable to use a polymer of a fluorine atom-containing vinyl ether compound having a fluorinated alkyl group or a fluorinated alkylene ether group and a hydrophilic vinyl ether compound. In addition, block polymers can also be used as fluorine-based surfactants. Furthermore, as a fluorine-based surfactant, a fluorine-containing polymer compound can also be preferably used, which includes a structural unit derived from a (meth)acrylate compound having a fluorine atom and a structural unit derived from a (meth)acrylate compound having two or more (preferably five or more) alkylene oxy groups (preferably ethylene oxy groups, propylene oxy groups). Furthermore, fluorine-containing polymers having ethylenically unsaturated bond-containing groups in their side chains can also be used as fluorine-based surfactants. Examples include Megafac RS-101, RS-102, RS-718K, and RS-72-K (all manufactured by DIC Corporation).

[0135] As for fluorine-based surfactants, from the viewpoint of improving environmental suitability, it is preferable that the surfactant is derived from a substitute material for compounds having a linear perfluoroalkyl group with 7 or more carbon atoms, such as perfluorooctanoic acid (PFOA) and perfluorooctanesulfonic acid (PFOS). Nonionic surfactants include glycerol, trimethylolpropane, trimethylolethane and their ethoxylates and propoxylates (e.g., glycerol propoxylate, glycerol ethoxylate, etc.), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid esters, Pluronic® L10, L31, L61, L62, 10R5, 17R2, 25R2 (all manufactured by BASF), Tetronic 304, 701, 704, 901, 904, 150R1 (all manufactured by BASF), and Solspers. Examples include 20000 (manufactured by Lubrizol Nippon Co., Ltd.), NCW-101, NCW-1001, NCW-1002 (manufactured by Fujifilm Wako Pure Chemical Industries Ltd.), Paionin D-6112, D-6112-W, D-6315 (manufactured by Takemoto Oil & Fat Co., Ltd.), Orfin E1010, Surfinol 104, 400, 440 (manufactured by Nisshin Chemical Industry Co., Ltd.), etc.

[0136] Examples of silicone-based surfactants include linear polymers composed of siloxane bonds, and modified siloxane polymers in which organic groups have been introduced into the side chains or terminals.

[0137] Specific examples of surfactants include DOWSIL 8032 ADDITIVE, Toray Silicone DC3PA, Toray Silicone SH7PA, Toray Silicone DC11PA, Toray Silicone SH21PA, Toray Silicone SH28PA, Toray Silicone SH29PA, Toray Silicone SH30PA, Toray Silicone SH8400 (all manufactured by Toray Dow Corning Co., Ltd.), as well as 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, KP-341 , KF-6001, KF-6002, KP-101KP-103, KP-104, KP-105, KP-106, KP-109, KP-109, KP-112, KP-120, KP-121, KP -124, KP-125, 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, KP-652 (all manufactured by Shin-Etsu Silicone Co., Ltd.), F-4440, TSF-4300, TSF-4445, TSF-4460, TSF-4452 (all manufactured by Momentum Examples include BYK300, BYK306, BYK307, BYK310, BYK320, BYK323, BYK330, BYK313, BYK315N, BYK331, BYK333, BYK345, BYK347, BYK348, BYK349, BYK370, BYK377, BYK378, and BYK323 (all manufactured by BIC Chemie), etc.

[0138] Surfactants can be used individually or in combination of two or more types. If the photosensitive composition contains a surfactant, the surfactant content is preferably 0.01 to 3.0% by mass, more preferably 0.01 to 1.0% by mass, and even more preferably 0.05 to 0.80% by mass, based on the total mass of the photosensitive composition.

[0139] [Impurities etc.] The photosensitive composition may contain impurities. Examples of impurities include metal impurities or their ions, halide ions, residual organic solvents, residual monomers, and water.

[0140] Examples of metallic impurities include sodium, potassium, magnesium, calcium, iron, manganese, copper, aluminum, titanium, chromium, cobalt, nickel, zinc, tin, and their ions, as well as halide ions. In particular, sodium ions, potassium ions, and halide ions are easily mixed in, so it is preferable to have the following concentrations. Metallic impurities are compounds different from the aforementioned particles (e.g., metal oxide particles) that may be present in the transfer film.

[0141] The content of metal impurities is preferably 80 ppm by mass or less, more preferably 10 ppm by mass or less, and even more preferably 2 ppm by mass or less, relative to the total mass of the photosensitive composition. The lower limit is preferably 1 ppb by mass or more, and more preferably 0.1 ppm by mass or more, relative to the total mass of the photosensitive composition.

[0142] Methods for adjusting the impurity content include, for example, selecting raw materials with a low impurity content for the photosensitive composition, as well as methods for preventing the inclusion of impurities during the formation of the photosensitive composition and methods for removing them by washing. The impurity content can be quantified by known methods such as ICP emission spectroscopy, atomic absorption spectroscopy, and ion chromatography.

[0143] Examples of residual organic solvents include benzene, formaldehyde, trichloroethylene, 1,3-butadiene, carbon tetrachloride, chloroform, N,N-dimethylformamide, N,N-dimethylacetamide, and hexane. The residual organic solvent content is preferably 100 ppm by mass or less, more preferably 20 ppm by mass or less, and even more preferably 4 ppm by mass or less, relative to the total mass of the photosensitive composition. The lower limit is preferably 10 ppb by mass or more, and more preferably 100 ppb by mass or more, relative to the total mass of the photosensitive composition. One method for adjusting the residual organic solvent content is to adjust the drying conditions in the transfer film manufacturing method described later. Furthermore, the residual organic solvent content can be quantified by known methods such as gas chromatography analysis.

[0144] The water content in the photosensitive composition is preferably 0.01 to 1.0% by mass, and more preferably 0.05 to 0.5% by mass, relative to the total mass of the photosensitive composition, in order to improve reliability and lamination properties.

[0145] Furthermore, the photosensitive composition is preferably one that satisfies requirement (X4) in terms of acid resistance. Requirement (X4): A 2.0 μm film formed using a photosensitive composition is exposed to a nitrogen atmosphere at an exposure dose of 500 mJ / cm². 2 The water contact angle of the film obtained by irradiating it with i-rays and heating it at 150°C for 30 minutes is 60 degrees or more. One method for forming a film using the above-mentioned photosensitive composition is to form the film on a glass substrate or the like using a transfer film, which will be described later. The above contact angle refers to the one measured using the same method as the above requirement (X1). The water contact angle is preferably 63 degrees or higher, and more preferably 66 degrees or higher. There is no particular upper limit, but it is 180 degrees or lower, and preferably 90 degrees or lower.

[0146] <Transfer film> The transfer film used in the method for manufacturing a laminate having a conductive pattern of the present invention comprises a temporary support and a photosensitive composition layer, the photosensitive composition layer containing solid components contained in the above-mentioned photosensitive composition (specifically, alkali-soluble resin, polymerizable compound having an ethylenically unsaturated group, and photopolymerization initiator, etc.). The transfer film may have other layers besides the temporary support and the photosensitive composition layer. Other layers include, for example, the intermediate layer described later. The transfer film may also have other components (for example, a protective film, etc.) described later.

[0147] Examples of the transfer film include the following configurations (1) or (2), with configuration (2) being preferred. (1) "Temporary support / photosensitive composition layer / protective film" (2) "Temporary support / intermediate layer / photosensitive composition layer / protective film" The transfer film preferably has an intermediate layer. In each of the above configurations, the photosensitive composition layer is preferably a negative-type photosensitive composition layer or a colored resin layer, as described later.

[0148] From the viewpoint of suppressing the generation of air bubbles in the lamination process described above, the maximum width of the waviness of the transfer film is preferably 300 μm or less, more preferably 200 μm or less, and even more preferably 60 μm or less. The lower limit of the maximum width of the waviness is 0 μm or more, preferably 0.1 μm or more, and more preferably 1 μm or more. The maximum width of the transfer film's waviness is measured using the following procedure. First, the transfer film is cut perpendicular to the main surface to a size of 20 cm x 20 cm to prepare a test sample. If the transfer film has a protective film, the protective film is removed. Next, the test sample is placed on a smooth and horizontal stage with the surface of the temporary support facing the stage. After placement, a 3D surface image is obtained by scanning the surface of the test sample within a 10 cm square area in the center of the test sample using a laser microscope (e.g., VK-9700SP manufactured by Keyence Corporation), and the minimum concave height is subtracted from the maximum convex height observed in the obtained 3D surface image. The above operation is performed for 10 test samples, and the arithmetic mean is defined as the "maximum waviness width of the transfer film".

[0149] In the photosensitive composition layer of the transfer film, if there is an additional composition layer on the surface opposite to the temporary support of the photosensitive composition layer, the total thickness of the additional composition layer is preferably 0.1 to 30%, and more preferably 0.1 to 20%, of the total thickness of the photosensitive composition layer.

[0150] For superior adhesion, the transmittance of the photosensitive composition layer at a wavelength of 365 nm is preferably 10% or more, more preferably 30% or more, and even more preferably 50% or more. The upper limit is preferably 99.9% or less, and more preferably 99.0% or less.

[0151] An example of an embodiment of the transfer film will be described. The transfer film 10 shown in Figure 1 comprises, in this order, a temporary support 11, a composition layer 17 including an intermediate layer 13 and a photosensitive composition layer 15, and a protective film 19. The transfer film 10 shown in Figure 1 has an intermediate layer 13 and a protective film 19, but it does not necessarily have to have an intermediate layer 13 and a protective film 19. In Figure 1, each layer (e.g., the photosensitive composition layer and the intermediate layer, etc.) other than the protective film 19 that can be placed on the temporary support 11 is also referred to as a "composition layer".

[0152] The following provides a detailed description of each component and part of the transfer film.

[0153] [Temporary support] The transfer film has a temporary support. The temporary support is a component that supports the photosensitive composition layer and is ultimately removed by a peeling process.

[0154] The temporary support may have either a single-layer or multi-layer structure. A film is preferred as the temporary support, and a resin film is more preferred. Furthermore, a film that is flexible and does not undergo significant deformation, shrinkage, or stretching under pressure or under pressure and / or heating is also preferred as the temporary support, and a film that is free from deformation such as wrinkles and scratches is also preferred. Examples of films include polyethylene terephthalate 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.

[0155] The temporary support is preferably highly transparent so that pattern exposure can be performed through it. The transmittance at 313nm, 365nm, 313nm, 405nm, and 436nm is preferably 60% or higher, more preferably 70% or higher, even more preferably 80% or higher, and most preferably 90% or higher. Preferred transmittance values ​​include, for example, 82%, 91%, and 97%. From the viewpoint of pattern formation during pattern exposure via the temporary support and the transparency of the temporary support, it is preferable that the haze of the temporary support be small. Specifically, the haze value of the temporary support is preferably 2% or less, more preferably 1.0% or less, and even more preferably 0.1% or less. There is no particular lower limit, but 0.01% is an example. From the standpoint of pattern formation during pattern exposure via a temporary support and the transparency of the temporary support, it is preferable to have a small number of fine particles, foreign matter, and defects in the temporary support. The number of fine particles, foreign matter, and defects with a diameter of 1 μm or more in the temporary support is 50 per 10 mm. 2 The following is preferable: 10 pieces / 10mm 2 The following is more preferable: 3 pieces / 10mm 2 The following is even more preferable: 0 pieces / 10mm 2 That is particularly preferable.

[0156] The thickness of the temporary support is preferably 5 μm or more, and more preferably 6 μm or more. The upper limit is preferably 200 μm or less, more preferably 150 μm or less, even more preferably 50 μm or less, particularly preferably 25 μm or less, and most preferably 16 μm or less, from the viewpoint of ease of handling and versatility. The thickness of the temporary support is calculated as the average value of any five points measured by cross-sectional observation using a SEM (Scanning Electron Microscope).

[0157] From the viewpoint of handling properties, the temporary support may have a layer containing fine particles (lubricant layer) on one or both sides of the temporary support. The diameter of the fine particles contained in the lubricant layer is preferably 0.05 to 0.8 μm. The thickness of the lubricant layer is preferably 0.05 to 1.0 μm.

[0158] From the viewpoint of improving the adhesion between the temporary support and the photosensitive composition layer, the surface of the temporary support that contacts the photosensitive composition layer may be surface-modified. Examples of the surface modification treatment include treatments using UV irradiation, corona discharge, plasma, and the like. The exposure amount in UV irradiation is preferably 10 to 2000 mJ / cm 2 and more preferably 50 to 1000 mJ / cm 2 If the exposure amount is within the above range, the lamp output and illuminance are not particularly limited. Examples of the light source in UV irradiation include low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, carbon arc lamps, metal halide lamps, xenon lamps, chemical lamps, electrodeless discharge lamps, and light-emitting diodes (LEDs) that emit light in the wavelength band of 150 to 450 nm. Examples of the temporary support include biaxially stretched polyethylene terephthalate films with a film thickness of 16 μm, biaxially stretched polyethylene terephthalate films with a film thickness of 12 μm, and biaxially stretched polyethylene terephthalate films with a film thickness of 9 μm.

[0159] ​Examples of the temporary support include paragraphs

[0017] to

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

[0019] to

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

[0041] to

[0057] of WO 2012 / 081680, and paragraphs

[0029] to

[0040] of WO 2018 / 179370, and the contents thereof are incorporated herein. Examples of commercially available products of the temporary support include registered trademark Lumirror 16KS40 and registered trademark Lumirror 16FB40 (both manufactured by Toray Industries, Inc.); Cosmo Shine A4100, Cosmo Shine A4300, and Cosmo Shine A8300 (all manufactured by Toyobo Co., Ltd.).

[0160] [Photosensitive composition layer] The transfer film has a photosensitive composition layer. As the photosensitive composition layer, a negative photosensitive composition layer is preferable. When the photosensitive composition layer is a negative photosensitive composition layer, the formed resist pattern corresponds to a cured film. The photosensitive composition layer is preferably formed by the above photosensitive composition. Therefore, the photosensitive composition layer preferably contains the solid content in the photosensitive composition. The components contained in the photosensitive composition layer (specifically, an alkali-soluble resin, a polymerizable compound having an ethylenically unsaturated group, a photopolymerization initiator, etc.) are as described above. The method for forming the photosensitive composition layer will be described later. The layer thickness (film thickness) of the photosensitive composition is generally 0.1 to 300 μm, preferably 0.2 to 100 μm, more preferably 0.5 to 50 μm, still more preferably 0.5 to 15 μm, particularly preferably 1 to 10 μm, and most preferably 1 to 8 μm. Thereby, the developability of the photosensitive composition layer is improved, and the resolution can be improved. Specific examples of the preferable film thickness include, for example, 1.2 μm, 2.5 μm, 3.5 μm, 5.0 μm, 6.0 μm, and 7.0 μm.

[0161] (Transmittance of the photosensitive composition layer) The visible light transmittance per 1.0 μm of film thickness of the photosensitive composition layer is preferably 80% or higher, more preferably 90% or higher, and most preferably 95% or higher. Regarding the transmittance of visible light, it is preferable that the average transmittance at wavelengths of 400 to 800 nm, the minimum transmittance at wavelengths of 400 to 800 nm, and the transmittance at a wavelength of 400 nm all satisfy the above requirements. Preferred values ​​for transmittance include, for example, 87%, 92%, and 98%. The transmittance per 1.0 μm of film thickness of the cured film obtained by curing the photosensitive composition layer is preferably the same as the transmittance described above.

[0162] (Dissolution rate of the photosensitive composition layer) The dissolution rate of the photosensitive composition layer in a 1.0% aqueous sodium carbonate solution is preferably 0.01 μm / sec or higher, more preferably 0.10 μm / sec or higher, and even more preferably 0.20 μm / sec or higher, from the viewpoint of suppressing residue during development. There is no particular upper limit to the dissolution rate, but from the viewpoint of the pattern edge shape, it is preferably 5.0 μm / sec or lower, more preferably 4.0 μm / sec or lower, and even more preferably 3.0 μm / sec or lower. Specific preferred values ​​include, for example, 1.8 μm / sec, 1.0 μm / sec, and 0.7 μm / sec. The dissolution rate per unit time of the photosensitive composition layer in a 1.0% by mass sodium carbonate aqueous solution shall be measured as follows. A photosensitive composition layer with a thickness of 1.0 to 10 μm, formed on a glass substrate and with the solvent thoroughly removed, is subjected to shower development using a 1.0% by mass sodium carbonate aqueous solution at a liquid temperature of 25°C, for a maximum time of 2 minutes until the photosensitive composition layer is completely dissolved. The dissolution rate is determined by dividing the thickness of the photosensitive composition layer by the time required for the photosensitive composition layer to completely dissolve. If the layer does not completely dissolve in 2 minutes, the dissolution rate is determined by dividing the amount of change in film thickness up to that point by the above time. The above shower development will use a 1 / 4 MIN JJX030PP shower nozzle manufactured by Ikeuchi Co., Ltd., with a shower spray pressure of 0.08 MPa. Under the above conditions, the shower flow rate per unit time will be 1800 mL / min.

[0163] Furthermore, the dissolution rate of the cured film of the photosensitive composition layer (film thickness in the range of 1.0 to 10 μm) in a 1.0% aqueous sodium carbonate solution is preferably 3.0 μm / second or less, more preferably 2.0 μm / second or less, even more preferably 1.0 μm / second or less, and most preferably 0.2 μm / second or less. The cured film of the photosensitive composition layer is exposed to an i-line at an exposure dose of 300 mJ / cm². 2 This film is obtained by exposure using [a specific method]. Specific preferred values ​​include, for example, 0.8 μm / sec, 0.2 μm / sec, and 0.001 μm / sec.

[0164] (Swelling rate of the photosensitive composition layer after exposure) From the viewpoint of improving pattern formation, the swelling rate of the photosensitive composition layer with respect to a 1.0% by mass aqueous solution of sodium carbonate after exposure is preferably 100% or less, more preferably 50% or less, and even more preferably 30% or less. The swelling rate of the photosensitive composition layer after exposure relative to a 1.0% by mass sodium carbonate aqueous solution shall be measured as follows. A photosensitive composition layer (with a film thickness in the range of 1.0 to 10 μm) formed on a glass substrate, with the solvent thoroughly removed, is subjected to a high-pressure mercury lamp at 500 mJ / cm². 2 Exposure is performed (measured with the i-line). The glass substrate is immersed in a 1.0 mass% sodium carbonate aqueous solution at 25°C, and the film thickness is measured after 30 seconds. Then, the percentage increase in film thickness after immersion compared to the film thickness before immersion is calculated. Specific preferred values ​​include, for example, 4%, 13%, and 25%.

[0165] (Foreign matter in the photosensitive composition layer) From the viewpoint of pattern formation, the number of foreign particles with a diameter of 1.0 μm or more in the photosensitive composition layer is 10 particles / mm². 2 The following is preferable: 5 pieces / mm 2 The following are preferable. The number of foreign objects shall be measured as follows: Using an optical microscope, five arbitrary regions (1 mm × 1 mm) on the surface of the photosensitive composition layer are observed from the direction normal to the surface of the photosensitive composition layer. The number of foreign objects with a diameter of 1.0 μm or more in each region is measured, and the total number of foreign objects is calculated by arithmetic mean. A specific desirable value would be, for example, 0 pieces / mm 2 , 1 piece / mm 2 , 4 pieces / mm 2 , and 8 pieces / mm 2 Examples include:

[0166] (Haze of dissolved material in the photosensitive composition layer) From the perspective of suppressing the formation of aggregates during development, 1.0 cm³ of 1.0% sodium carbonate aqueous solution at 30°C is added to 1.0 L. 3 The haze of the solution obtained by dissolving the photosensitive resin layer is preferably 60% or less, more preferably 30% or less, even more preferably 10% or less, and most preferably 1% or less. The haze will be measured using the following procedure. First, prepare a 1.0% by mass sodium carbonate aqueous solution and adjust the liquid temperature to 30°C. Add 1.0 cm to 1.0 L of sodium carbonate aqueous solution. 3 Add the photosensitive composition layer. Stir at 30°C for 4 hours, taking care not to introduce air bubbles. After stirring, measure the haze of the solution in which the photosensitive composition layer has dissolved. The haze is measured using a haze meter (product name "NDH4000", manufactured by Nippon Denshoku Industries Co., Ltd.) with a liquid measurement unit and a liquid measurement cell with an optical path length of 20 mm. Specific preferred haze values ​​include, for example, 0.4%, 1.0%, 9.0%, and 24%.

[0167] [Thermoplastic resin layer] The transfer film may have a thermoplastic resin layer. The thermoplastic resin layer is typically placed between the temporary support and the photosensitive composition layer. The inclusion of a thermoplastic resin layer in the transfer film improves its conformability to the substrate during the lamination process, suppressing the inclusion of air bubbles between the substrate and the transfer film. As a result, adhesion between the thermoplastic resin layer and adjacent layers (e.g., the temporary support) can be ensured. The thermoplastic resin layer contains a resin. The resin contains a thermoplastic resin as part or all of it. In other words, in one embodiment, it is preferable that the resin of the thermoplastic resin layer is a thermoplastic resin.

[0168] (Alkali-soluble resin (thermoplastic resin)) The thermoplastic resin is preferably an alkali-soluble resin. Examples of alkali-soluble resins include acrylic resins, polystyrene resins, styrene-acrylic copolymers, polyurethane resins, polyvinyl alcohol, polyvinyl formal, polyamide resins, polyester resins, polyamide resins, epoxy resins, polyacetal resins, polyhydroxystyrene resins, polyimide resins, polybenzoxazole resins, polysiloxane resins, polyethyleneimine, polyallylamine, and polyalkylene glycols.

[0169] As the alkali-soluble resin, acrylic resin is preferred from the viewpoint of developability and adhesion to adjacent layers. Here, 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. Preferably, the acrylic resin contains a total content of 50% by mass or more of constituent units derived from (meth)acrylic acid, (meth)acrylic acid ester, and (meth)acrylamide, relative to the total mass of the acrylic resin. Among them, the total content of the structural units derived from (meth)acrylic acid and the structural units derived from (meth)acrylate is preferably 30 to 100% by mass, more preferably 50 to 100% by mass, based on the total mass of the acrylic resin.

[0170] Further, the alkali-soluble resin is preferably a polymer having an acid group. Examples of the acid group include a carboxy group, a sulfo group, a phosphoric acid group, and a phosphonic acid group, and a carboxy group is preferred. From the viewpoint of developability, the alkali-soluble resin is more preferably an alkali-soluble resin having an acid value of 60 mgKOH / g or more, and even more preferably a carboxy group-containing acrylic resin having an acid value of 60 mgKOH / g or more. The upper limit of the acid value of the alkali-soluble resin is not particularly limited, but is preferably 300 mgKOH / g or less, more preferably 250 mgKOH / g or less, even more preferably 200 mgKOH / g or less, and particularly preferably 150 mgKOH / g or less.

[0171] The carboxy group-containing acrylic resin having an acid value of 60 mgKOH / g or more is not particularly limited and can be appropriately selected from known resins for use. For example, an alkali-soluble resin which is a carboxy group-containing acrylic resin having an acid value of 60 mgKOH / g or more among the polymers described in paragraph 0025 of JP-A-2011-095716, a carboxy group-containing acrylic resin having an acid value of 60 mgKOH / g or more among the polymers described in paragraphs 0033 to 0052 of JP-A-2010-237589, and a carboxy group-containing acrylic resin having an acid value of 60 mgKOH / g or more among the binder polymers described in paragraphs 0053 to 0068 of JP-A-2016-224162 can be mentioned. The copolymerization ratio of the structural unit having a carboxy group in the above carboxy group-containing acrylic resin is preferably 5 to 50% by mass, more preferably 10 to 40% by mass, and even more preferably 12 to 30% by mass, based on the total mass of the acrylic resin. From the viewpoints of developability and adhesion to an adjacent layer, an acrylic resin having a structural unit derived from (meth)acrylic acid is particularly preferred as the alkali-soluble resin.

[0172] Alkali-soluble resins may have reactive groups. Reactive groups can be any groups capable of addition polymerization, including ethylenically unsaturated groups; polycondensable groups such as hydroxyl and carboxyl groups; and polyaddition reactive groups such as epoxy groups and (blocked) isocyanate groups.

[0173] The weight-average molecular weight (Mw) of the alkali-soluble resin is preferably 1,000 or more, more preferably 10,000 to 100,000, and even more preferably 20,000 to 50,000.

[0174] Alkali-soluble resins may be used individually or in combination of two or more types. From the viewpoint of developability and adhesion to adjacent layers, the content of alkali-soluble resin is preferably 10 to 99% by mass, more preferably 20 to 90% by mass, even more preferably 40 to 80% by mass, and particularly preferably 50 to 75% by mass, relative to the total mass of the thermoplastic resin layer.

[0175] (dye) The thermoplastic resin layer preferably contains a dye (also simply called "dye B") whose maximum absorption wavelength in the wavelength range of 400 to 780 nm during color development is 450 nm or higher, and whose maximum absorption wavelength changes with the presence of an acid, base, or radical. A preferred embodiment of dye B is the same as that of the preferred embodiment of dye N described above, except for the points described later.

[0176] From the viewpoint of visibility and resolution of exposed and unexposed areas, dye B is preferably a dye whose maximum absorption wavelength changes with acid or radicals, and more preferably a dye whose maximum absorption wavelength changes with acid. From the viewpoint of visibility and resolution of the exposed and unexposed areas, the thermoplastic resin layer preferably contains both a dye whose maximum absorption wavelength changes with an acid as dye B, and a compound that generates an acid when exposed to light, as described later.

[0177] Dye B may be used alone or in combination of two or more types. From the viewpoint of visibility of the exposed and unexposed areas, the content of dye B is preferably 0.2% by mass or more, more preferably 0.2 to 6% by mass, even more preferably 0.2 to 5% by mass, and particularly preferably 0.25 to 3.0% by mass, relative to the total mass of the thermoplastic resin layer.

[0178] Here, the content of pigment B refers to the amount of pigment B present in the thermoplastic resin layer when all of the pigment B is in a colored state. Below, we will explain how to quantify the content of pigment B using a pigment that develops color through radicals as an example. Solutions were prepared by dissolving 0.001 g and 0.01 g of dye in 100 mL of methyl ethyl ketone. To each of the resulting solutions, the photoradical polymerization initiator Irgacure OXE01 (trade name, BASF Japan Ltd.) was added, and radicals were generated by irradiating with 365 nm light, causing all the dyes to develop color. Subsequently, under an atmospheric environment, the absorbance of each solution at a liquid temperature of 25°C was measured using a spectrophotometer (UV3100, Shimadzu Corporation), and a calibration curve was created. Next, the absorbance of the solution in which all of the dye has developed is measured, using the same method as above, except that 0.1 g of the thermoplastic resin layer is dissolved in methyl ethyl ketone instead of the dye. From the absorbance of the obtained solution containing the thermoplastic resin layer, the amount of dye contained in the thermoplastic resin layer is calculated based on the calibration curve. Note that 3g of the thermoplastic resin layer is equivalent to 3g of the solid content of the composition.

[0179] (Compounds that generate acids, bases, or radicals upon exposure to light) The thermoplastic resin layer may contain a compound (also simply called "compound C") that generates an acid, base, or radical upon exposure to light. As compound C, a compound that generates an acid, base, or radical upon exposure to active light such as ultraviolet light and visible light is preferred. As compound C, known photoacid generators, photobase generators, and photoradical polymerization initiators (photoradical generators) can be used.

[0180] -Photoacid Generator- The thermoplastic resin layer may contain a photoacid generator from the viewpoint of resolution. Examples of photoacid generators include photocationic polymerization initiators that may be included in the negative-type photosensitive composition layer described above, and the preferred embodiments are the same except for the points described later.

[0181] From the viewpoint of sensitivity and resolution, the photoacid generator preferably contains at least one compound selected from the group consisting of onium salt compounds and oxime sulfonate compounds, and from the viewpoint of sensitivity, resolution, and adhesion, it is more preferable to contain an oxime sulfonate compound. Furthermore, photoacid generators having the following structure are also preferred as photoacid generators.

[0182] [ka]

[0183] -Photoradical polymerization initiator- The thermoplastic resin layer may contain a photoradical polymerization initiator. Examples of photoradical polymerization initiators include photoradical polymerization initiators that may be included in the negative-type photosensitive composition layer described above, and the preferred embodiments are the same.

[0184] -Photobase Generator- The thermoplastic resin composition may contain a photobase generator. The photobase generator is not particularly limited as long as it is a known photobase generator, for example, 2-nitrobenzylcyclohexylcarbamate, triphenylmethanol, O-carbamoylhydroxylamide, O-carbamoyloxime, [[(2,6-dinitrobenzyl)oxy]carbonyl]cyclohexylamine, bis[[(2-nitrobenzyl)oxy]carbonyl]hexane1,6-diamine, 4-(methylthiobenzoyl)-1-methyl-1-morpholinoethane, (4-morpholinobenzoyl)- Examples include 1-benzyl-1-dimethylaminopropane, N-(2-nitrobenzyloxycarbonyl)pyrrolidine, hexaamminecobalt(III)tris(triphenylmethylborate), 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone, 2,6-dimethyl-3,5-diacetyl-4-(2-nitrophenyl)-1,4-dihydropyridine, and 2,6-dimethyl-3,5-diacetyl-4-(2,4-dinitrophenyl)-1,4-dihydropyridine.

[0185] Compound C may be used alone or in combination of two or more types. From the viewpoint of visibility and resolution of the exposed and unexposed areas, the content of compound C is preferably 0.1 to 10% by mass, and more preferably 0.5 to 5% by mass, relative to the total mass of the thermoplastic resin layer.

[0186] (Plasticizer) The thermoplastic resin layer preferably contains a plasticizer from the viewpoint of resolution, adhesion to adjacent layers, and developability. The plasticizer is preferably smaller in molecular weight (or weight-average molecular weight if it is an oligomer or polymer with a molecular weight distribution) than the alkali-soluble resin. The molecular weight (weight-average molecular weight) of the plasticizer is preferably 200 to 2,000. The plasticizer is not particularly limited as long as it is a compound that is compatible with alkali-soluble resins and exhibits plasticity. However, from the viewpoint of imparting plasticity, the plasticizer preferably has an alkylene oxy group in its molecule, and polyalkylene glycol compounds are more preferred. The alkylene oxy group contained in the plasticizer is more preferably a polyethylene oxy structure or a polypropylene oxy structure.

[0187] Furthermore, from the viewpoint of resolution and storage stability, it is preferable that the plasticizer contains a (meth)acrylate compound. From the viewpoint of compatibility, resolution, and adhesion to adjacent layers, it is more preferable that the alkali-soluble resin is an acrylic resin and the plasticizer contains a (meth)acrylate compound. Examples of (meth)acrylate compounds used as plasticizers include the polymerizable compounds described above as being included in the negative-type photosensitive composition layer. In transfer films, when a thermoplastic resin layer and a negative-type photosensitive composition layer are laminated in direct contact, it is preferable that both the thermoplastic resin layer and the negative-type photosensitive composition layer contain the same (meth)acrylate compound. This is because the inclusion of the same (meth)acrylate compound in both the thermoplastic resin layer and the negative-type photosensitive composition layer suppresses the diffusion of components between layers, thereby improving storage stability.

[0188] When a thermoplastic resin layer contains a (meth)acrylate compound as a plasticizer, it is preferable that the (meth)acrylate compound does not polymerize in the exposed area after exposure, from the viewpoint of adhesion between the thermoplastic resin layer and adjacent layers. Furthermore, as a (meth)acrylate compound used as a plasticizer, a polyfunctional (meth)acrylate compound having two or more (meth)acryloyl groups in one molecule is preferred from the viewpoint of resolution of the thermoplastic resin layer, adhesion to adjacent layers, and developability. Furthermore, as the (meth)acrylate compound used as a plasticizer, (meth)acrylate compounds having an acid group or urethane (meth)acrylate compounds are also preferred.

[0189] The plasticizer may be used alone or in combination of two or more types. From the viewpoint of resolution of the thermoplastic resin layer, adhesion to adjacent layers, and developability, the plasticizer content is preferably 1 to 70% by mass, more preferably 10 to 60% by mass, and even more preferably 20 to 50% by mass, relative to the total mass of the thermoplastic resin layer.

[0190] (Sensitizer) The thermoplastic resin layer may contain a sensitizer. The sensitizer is not particularly limited and may include the negative-type photosensitive composition layer described above.

[0191] The sensitizer may be used alone or in combination of two or more types. The amount of sensitizer can be appropriately selected depending on the purpose, but from the viewpoint of improving sensitivity to the light source and visibility of the exposed and unexposed areas, it is preferably 0.01 to 5% by mass, and more preferably 0.05 to 1% by mass, relative to the total mass of the thermoplastic resin layer.

[0192] (Additives, etc.) The thermoplastic resin layer may contain known additives such as surfactants, in addition to the above components, as needed. Furthermore, the thermoplastic resin layer is described in paragraphs 0189 to 0193 of Japanese Patent Publication No. 2014-085643, and the contents described in this publication are incorporated herein by reference.

[0193] The thickness of the thermoplastic resin layer is not particularly limited, but from the viewpoint of adhesion to adjacent layers, it is preferably 1 μm or more, and more preferably 2 μm or more. There is no particular upper limit, but from the viewpoint of developability and resolution, it is preferably 20 μm or less, more preferably 10 μm or less, and even more preferably 8 μm or less.

[0194] [Middle class] The transfer film may also preferably have an intermediate layer between the temporary support and the photosensitive composition layer. Examples of intermediate layers include a water-soluble resin layer and an oxygen-blocking layer with oxygen-blocking function, as described as a "separation layer" in Japanese Patent Publication No. 5-072724. As an intermediate layer, an oxygen barrier layer is preferred because it improves sensitivity during exposure, reduces the time load on the exposure machine, and improves productivity. More preferably, an oxygen barrier layer exhibiting low oxygen permeability is dispersed or dissolved in water or an alkaline aqueous solution (a 1% by mass aqueous solution of sodium carbonate at 22°C). The following describes the various components that the water-soluble resin layer (intermediate layer) may contain.

[0195] The water-soluble resin layer (intermediate layer) contains resin. The above resin preferably contains a water-soluble resin as part or all of it. Examples of resins that can be used as water-soluble resins include polyvinyl alcohol-based resins, polyvinylpyrrolidone-based resins, cellulose-based resins, acrylamide-based resins, polyethylene oxide-based resins, gelatin, vinyl ether-based resins, polyamide resins, and copolymers thereof. Furthermore, as the water-soluble resin, copolymers of (meth)acrylic acid / vinyl compounds can also be used. Among the copolymers of (meth)acrylic acid / vinyl compounds, copolymers of (meth)acrylic acid / (meth)acrylate are preferred, and copolymers of methacrylic acid / methacrylate are more preferred. When the water-soluble resin is a copolymer of (meth)acrylic acid / vinyl compound, the composition ratio (mol%) is preferably, for example, 90 / 10 to 20 / 80, and more preferably 80 / 20 to 30 / 70.

[0196] The lower limit of the weight-average molecular weight of the water-soluble resin is preferably 5000 or more, more preferably 7000 or more, and even more preferably 10000 or more. The upper limit is preferably 200000 or less, more preferably 100000 or less, and even more preferably 50000 or less. The dispersion degree (Mw / Mn) of the water-soluble resin is preferably 1 to 10, and more preferably 1 to 5.

[0197] Water-soluble resins may be used individually or in combination of two or more types. The content of the water-soluble resin is not particularly limited, but in terms of further improving oxygen barrier properties and interlayer mixing suppression ability, it is preferably 50% by mass or more, more preferably 70% by mass or more, even more preferably 80% by mass or more, and particularly preferably 90% by mass or more, based on the total mass of the water-soluble resin layer (intermediate layer). There is no particular upper limit, but for example, it is preferably 99.9% by mass or less, and even more preferably 99.8% by mass or less.

[0198] The intermediate layer may contain other components in addition to the water-soluble resin mentioned above. Other preferred components include polyhydric alcohols, alkylene oxide adducts of polyhydric alcohols, phenol derivatives, or amide compounds, with polyhydric alcohols, phenol derivatives, or amide compounds being more preferred. Other ingredients include, for example, well-known surfactants.

[0199] Examples of polyhydric alcohols include glycerin, diglycerin, and diethylene glycol. The number of hydroxyl groups in polyhydric alcohols is preferably 2 to 10. Examples of alkylene oxide adducts of polyhydric alcohols include compounds obtained by adding ethyleneoxy groups and propyleneoxy groups to the above-mentioned polyhydric alcohols. The average number of alkylene oxy groups added is preferably 1 to 100, preferably 2 to 50, and more preferably 2 to 20. Examples of phenol derivatives include bisphenol A and bisphenol S. An example of an amide compound is N-methylpyrrolidone.

[0200] The intermediate layer preferably contains at least one selected from the group consisting of water-soluble cellulose derivatives, polyhydric alcohols, oxide adducts of polyhydric alcohols, polyether resins, phenol derivatives, and amide compounds.

[0201] The molecular weight of the other components is preferably less than 5000, more preferably 4000 or less, even more preferably 3000 or less, particularly preferably 2000 or less, and most preferably 1500 or less. The lower limit is preferably 60 or more.

[0202] Other ingredients may be used individually or in combination of two or more. The content of other components is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and even more preferably 1% by mass or more, relative to the total mass of the intermediate layer. The upper limit is preferably less than 30% by mass, more preferably 10% by mass or less, and even more preferably 5% by mass or less.

[0203] The intermediate layer may contain impurities. Examples of impurities include those contained in the above-mentioned photosensitive composition layer.

[0204] The thickness of the water-soluble resin layer (interlayer) is not particularly limited, but is preferably 0.1 to 5 μm, and more preferably 0.5 to 3 μm. When the thickness of the water-soluble resin layer (interlayer) is within the above range, the oxygen barrier properties are not reduced, and the ability to suppress interlayer mixing is excellent. Furthermore, the increase in the time required to remove the water-soluble resin layer (interlayer) during development can also be suppressed.

[0205] [Protective film] The transfer film may have a protective film on the photosensitive composition layer. As protective films, resin films having heat resistance and solvent resistance can be used. Examples include 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.

[0206] The thickness of the protective film is preferably 1 to 100 μm, more preferably 5 to 50 μm, even more preferably 5 to 40 μm, and particularly preferably 15 to 30 μm. The thickness of the protective film is preferably 1 μm or more for superior mechanical strength, and 100 μm or less for relatively low cost.

[0207] 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 square meter. 2 The following is preferable: "Fish eyes" refer to foreign matter, undissolved material, and oxidatively degraded materials that are incorporated into the film during the manufacturing process, such as by heat melting, kneading, extrusion, biaxial stretching, and casting.

[0208] 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 conductive layer.

[0209] From the standpoint 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 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.

[0210] [Method for manufacturing transfer film] There are no particular limitations on the method for manufacturing the transfer film, and known methods can be used. Examples of methods for manufacturing the transfer film 10 include a method comprising the steps of: applying an intermediate layer forming composition to the surface of a temporary support 11 to form a coating film, and further drying this coating film to form an intermediate layer 13; applying a photosensitive composition to the surface of the intermediate layer 13 to form a coating film, and further drying this coating film to form a photosensitive composition layer 15; and a method comprising the steps of applying a photosensitive composition to the surface of a temporary support 11 to form a coating film, and further drying this coating film to form a photosensitive composition layer 15.

[0211] If the transfer film 10 has a protective film 19, the protective film 19 may be pressed onto the composition layer 17 of the transfer film 10 manufactured by the above manufacturing method. As a method for manufacturing the transfer film 10, it is preferable to include a step of providing a protective film 19 so as to contact the side of the composition layer 17 opposite to the side of the temporary support 11, thereby manufacturing a transfer film 10 comprising a temporary support 11, an intermediate layer 13, a photosensitive composition layer 15, and a protective film 19. After manufacturing the transfer film 10 using the above manufacturing method, the transfer film 10 may be wound up to produce and store a roll of transfer film. The roll of transfer film 10 can be provided in its original form for the lamination process with the substrate using the roll-to-roll method described later.

[0212] Furthermore, the method for manufacturing the transfer film 10 may also be a method of forming a composition layer 17 on the protective film 19.

[0213] (Composition for forming a thermoplastic resin layer and method for forming a thermoplastic resin layer) When the transfer film has a thermoplastic resin layer, there are no particular limitations on the method for forming the thermoplastic resin layer on the temporary support, and known methods can be used. For example, it can be formed by applying a thermoplastic resin layer-forming composition onto the 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 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 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 any known solvent can be used. Examples of solvents include those similar to those 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 solids content of the composition.

[0214] (Water-soluble resin composition and method for forming an intermediate layer (water-soluble resin layer)) The water-soluble resin composition preferably contains the various components that form the intermediate layer (water-soluble resin layer) described above, as well as a solvent. In the water-soluble resin 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 water-soluble resin layer described above. The solvent is not particularly limited as long as it can dissolve or disperse the water-soluble resin, but 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 individually or in combination of two or more types. The solvent content is preferably 50 to 2500 parts by mass, more preferably 50 to 1900 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.

[0215] The method for forming the water-soluble resin layer is not particularly limited as long as it is a method capable of forming a layer containing the above components, and examples include known coating methods (slit coating, spin coating, curtain coating, and inkjet coating, etc.).

[0216] (Photosensitive composition and method for forming a photosensitive composition layer) In terms of superior productivity, it is desirable to form the photosensitive composition by a coating method using the photosensitive composition comprising the components of the photosensitive composition described above (e.g., resin A, polymerizable compound, and polymerization initiator, etc.) 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. A preferred method for manufacturing a transfer film is to apply a photosensitive composition onto an intermediate layer to form a coating film, and then dry this coating film at a predetermined temperature to form a photosensitive composition layer.

[0217] 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).

[0218] Preferred drying methods for photosensitive composition coatings include heat drying and vacuum drying. In this specification, "drying" means removing at least a portion of the solvent contained in the composition. Examples of drying methods include natural drying, heat drying, and vacuum drying. These methods can be applied individually or in combination. The drying temperature is preferably 80°C or higher, and more preferably 90°C or higher. Furthermore, 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. Furthermore, the drying time is preferably 20 seconds or more, more preferably 40 seconds or more, and even more preferably 60 seconds or more. There is no particular upper limit to the drying time, but it is preferably 600 seconds or less, and more preferably 300 seconds or less.

[0219] 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 includes known methods. Examples of devices for laminating a protective film onto a photosensitive composition layer include known laminators such as vacuum laminators and auto-cut laminators. The laminator is preferably equipped with a heat-sensitive roller, such as a rubber roller, and capable of applying pressure and heating.

[0220] <Application> The photosensitive composition and transfer film of the present invention can be applied to a variety of uses. For example, they 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 members. 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, and etching resists for wiring formation.

[0221] <Method for manufacturing a laminate having a conductive pattern> The above photosensitive composition and the above transfer film can be suitably used in the manufacture of laminates having a conductive pattern. In particular, the above photosensitive composition and the above transfer film can be suitably used in the manufacture of laminates having a conductive pattern that includes silver in the conductive pattern. More specifically, the method for manufacturing a laminate having a conductive pattern according to the present invention is: A preparation step of preparing a laminate having a substrate, a conductive layer containing silver, and a photosensitive composition layer in this order, An exposure step in which a photosensitive composition layer is pattern-exposed, A developing step involves developing an exposed photosensitive composition layer to form a resist pattern, It is preferable to have an etching step in which the conductive layer in the region where the resist pattern is not formed is etched with an etching solution having a pH of less than 2.0. The photosensitive composition layer comprises an alkali-soluble resin, a polymerizable compound having an ethylenically unsaturated group, and a photopolymerization initiator, wherein the polymerizable compound includes polymerizable compound A that satisfies the following requirement (X1). Requirement (X1): A composition consisting of 100 parts by mass of polymerizable compound A, 1.0 part by mass of 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]ethanone-1-(O-acetyloxime), and 9 parts by mass of methyl ethyl ketone is applied to form a 2.0 μm film, and then exposed to a nitrogen atmosphere at an exposure of 500 mJ / cm². 2 The water contact angle of the film obtained by irradiating it with i-rays and heating it at 150°C for 30 minutes is 74 degrees or higher. The above contact angle is the same as requirement (X1) above, so the explanation is omitted. The following describes each step. We will also describe any steps that may be performed in the manufacturing of laminates having a conductive pattern.

[0222] [Preparation process] The preparation step is to prepare a laminate having, in this order, a substrate, a conductive layer containing silver, and a photosensitive composition layer. The photosensitive composition layer contains an alkali-soluble resin, a polymerizable compound having an ethylenically unsaturated group, and a photopolymerization initiator, wherein the polymerizable compound contains polymerizable compound A that satisfies the above requirement (X1). That is, it is preferable that the photosensitive composition layer is formed using the above photosensitive composition. The preparation step preferably involves forming a conductive layer containing silver on a substrate, and then forming a photosensitive composition layer on the conductive layer containing silver. The photosensitive composition layer may be formed on the conductive layer containing silver using the photosensitive composition, or it may be formed using the transfer film. When forming a photosensitive composition layer using the above-mentioned photosensitive composition, it is preferable to form the photosensitive composition layer on a silver-containing conductive material by coating the photosensitive composition, in accordance with the method for manufacturing a transfer film. When forming a photosensitive composition layer on a conductive layer containing silver using a transfer film, it is preferable to form the photosensitive composition layer by a lamination process described later. In addition, the laminate prepared in the preparation step may be one in which a conductive layer containing silver and a photosensitive composition layer are formed on one side of the substrate in this order from the substrate side, or it may be one in which a conductive layer containing silver and a photosensitive composition layer are formed on both sides of the substrate in this order from the substrate side.

[0223] (substrate) The substrate is not particularly limited, but examples include resin substrates, glass substrates, ceramic substrates and semiconductor substrates, with the substrate described in paragraph

[0140] of International Publication No. 2018 / 155193 being preferred. As the material for the resin substrate, polyethylene terephthalate, cycloolefin polymer, or polyimide are preferred. The thickness of the resin substrate is preferably 5 to 200 μm, and more preferably 10 to 100 μm.

[0224] (Conductive layer) The conductive layer contains silver and is positioned on the surface of the substrate. Examples of conductive layers containing silver include conductive layers formed from silver conductive materials such as silver mesh and silver nanowires, and metallic layers (conductive layers) made of silver or a silver alloy. Furthermore, the substrate may have only one conductive layer, or it may have two or more conductive layers. When two or more conductive layers are arranged, it is preferable that the conductive layers be made of different materials. As a conductive layer other than the silver-containing conductive layer, it is preferable that the conductive layer is 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. Preferred embodiments of the conductive layer are described, for example, in paragraph

[0141] of International Publication No. 2018 / 155193, which are incorporated herein by reference.

[0225] A substrate on which a conductive layer is arranged is preferably one having at least one of transparent electrodes and routing wiring. Such a substrate can be suitably used as a substrate for a touch panel. Transparent electrodes can function suitably as electrodes for touch panels. Preferred transparent electrodes include metal oxide films such as ITO (indium tin oxide) and IZO (indium zinc oxide), as well as metal meshes and metal nanowires. It is also preferable that a conductive layer containing silver be used as the transparent electrode, and that the transparent electrode be formed from a silver mesh or silver nanowire.

[0226] Metal is preferred as the material for routing the wiring. Examples of metals used for wiring include gold, silver, copper, molybdenum, aluminum, titanium, chromium, zinc, and manganese, as well as alloys composed of two or more of these metallic elements. Silver, copper, molybdenum, aluminum, or titanium are preferred materials for wiring, with silver or copper being particularly preferred.

[0227] (Photosensitive composition layer) The method for forming a photosensitive composition layer on a silver-containing conductive layer is not particularly limited, but examples include a method involving a step of coating a photosensitive composition onto a silver-containing conductive layer (coating step), and a method involving lamination of the photosensitive composition layer of a transfer film with the silver-containing conductive layer (lamination step).

[0228] -Coating process- The coating process involves applying a photosensitive composition onto a conductive layer containing silver to form a photosensitive composition layer. The coating process is preferably carried out by a coating method using a photosensitive composition containing the components constituting the photosensitive composition described above (e.g., resin A, polymerizable compound, and polymerization initiator, etc.) 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.

[0229] 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).

[0230] Preferred drying methods for photosensitive composition coatings include heat drying and vacuum drying. In this specification, "drying" means removing at least a portion of the solvent contained in the composition. Examples of drying methods include natural drying, heat drying, and vacuum drying. These methods can be applied individually or in combination. The drying temperature is preferably 80°C or higher, and more preferably 90°C or higher. Furthermore, 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. Furthermore, the drying time is preferably 20 seconds or more, more preferably 40 seconds or more, and even more preferably 60 seconds or more. There is no particular upper limit to the drying time, but it is preferably 600 seconds or less, and more preferably 300 seconds or less.

[0231] -Lamination process- The lamination process involves bonding a transfer film, which has a temporary support and a photosensitive composition layer, to a substrate such that the surface of the transfer film opposite to the temporary support is in contact with the conductive layer of the substrate, which has a conductive layer on its surface. By performing the lamination process, a substrate with a photosensitive composition layer is obtained, having the substrate, conductive layer, photosensitive composition layer, and temporary support in this order. If the transfer film has a protective film, the protective film should be removed before proceeding with the lamination process.

[0232] In the above bonding process, it is preferable to bring the photosensitive composition layer side of the transfer film (the surface opposite to the temporary support side) into contact with the metal layer on the substrate and press it down. There are no particular restrictions on the method of pressing as described above, 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 part and apply pressure and heat using a roll or the like. For lamination, known laminators such as vacuum laminators and auto-cut laminators can be used. The lamination temperature is not particularly limited, but it is preferably, for example, 70 to 130°C.

[0233] [Synthesis process] The exposure process involves pattern exposure of the photosensitive composition layer. By performing an exposure process and a development process described later, a resist pattern that protects at least a portion of the conductive layer is formed on the conductive layer on the substrate. "Pattern exposure" refers to a method of exposure that involves a pattern of exposure, resulting in a form of exposure where exposed and unexposed areas exist. The positional relationship between the exposed area (exposed region) and the unexposed area (unexposed region) in pattern exposure can be adjusted as appropriate. Exposure may be performed from the side opposite to the substrate of the photosensitive composition, or from the side of the photosensitive composition layer.

[0234] Examples of exposure methods in the exposure process include mask exposure, direct imaging exposure, and projection exposure. When a composition layer is formed by the above bonding process, the exposure process may be performed after peeling off the temporary support or without peeling it off. The method for peeling off the temporary support 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.

[0235] In the exposure process for pattern exposure, a curing reaction of components contained in the photosensitive composition layer may occur in the exposed region of the photosensitive composition layer (the region corresponding to the opening of the photomask). After exposure, a development process is performed to remove the unexposed region of the photosensitive composition layer, forming a resist pattern.

[0236] As a light source for pattern exposure, any light source capable of irradiating with light in a wavelength range sufficient to cure the photosensitive composition layer (for example, 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.

[0237] 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 5-200 mJ / cm². 2 Preferably, 10-200 mJ / cm² 2 This is preferable.

[0238] Preferred embodiments of the light source, exposure amount, and exposure method used for exposure are described, for example, in paragraphs

[0146] to

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

[0239] [Development process] The development process involves performing a development treatment on the exposed photosensitive composition layer to form a resist pattern. Furthermore, when a photosensitive composition layer is formed using the transfer film described above, a step of removing the temporary support is performed before carrying out the development step. The step of removing the temporary support may be performed before the exposure step or between the exposure step and the development step. The above photosensitive composition layer can be developed using a developing solution. An alkaline aqueous solution is preferred as the developing solution. Examples of alkaline compounds that may be included in the alkaline aqueous solution include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, and choline (2-hydroxyethyltrimethylammonium hydroxide).

[0240] The temperature of the developing solution during the developing process is preferably 10 to 50°C, more preferably 15 to 40°C, and even more preferably 20 to 35°C. The pH of the developer solution used in the developing process is preferably 9 or higher, more preferably 10 or higher, and even more preferably 11 or higher. The upper limit is preferably 14 or lower, and more preferably less than 13.

[0241] The water content in the developer is preferably 50% by mass or more and less than 100% by mass, and more preferably 90% by mass or more and less than 100% by mass, relative to the total mass of the developer. The content of alkaline compounds in the developer is preferably 0.01 to 20% by mass, and more preferably 0.1 to 10% by mass, relative to the total mass of the developer.

[0242] Examples of development methods include paddle development, shower development, spin development, and dip development.

[0243] 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.

[0244] After development, it is also 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 developing and / or rinsing, a drying process may be performed to remove any excess liquid from the substrate with the metal layer.

[0245] The position and size of the resist pattern formed on the metal layer substrate are not particularly limited, but it is preferable that it includes a fine line shape. Specifically, the line width of the resist pattern is preferably 20 μm or less, more preferably 15 μm or less, even more preferably 10 μm or less, and particularly preferably 5 μm or less. The lower limit is often 1.0 μm or more.

[0246] [Etching process] The etching process involves etching the conductive layer in areas where a resist pattern has not been formed using an etching solution with a pH of less than 2.0. By performing the etching process, the conductive layer is removed at the openings in the resist pattern, and the conductive layer ends up having a pattern shape similar to that of the resist pattern. Therefore, the etching process yields a laminate having a conductive pattern. As for the etching process, known methods can be applied, for example, the method described in paragraphs

[0209] to

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

[0048] to

[0054] of Japanese Patent Publication No. 2010-152155, etc., and a wet etching method involving immersion in an etching solution. The pH of the etching solution is less than 2.0. Etching solutions with a pH of less than 2.0 include ferric nitrate aqueous solution, a mixed acid of ferric nitrate and sulfuric acid, phosphoric acid, nitric acid, acetic acid and water, and a mixed acid of chromic acid, sulfuric acid and water. It is preferable that the etching solution does not dissolve the resist pattern. Furthermore, since the resist pattern is acid-resistant, even if the pH of the etching solution is less than 2.0, the conductive layer containing silver coated on the resist pattern is less susceptible to modification or etching by the etching solution. The developer used in the development process may also serve as the etching solution used in the etching process. In this case, the development and etching processes may be carried out simultaneously.

[0247] After the etching process, it is also preferable to perform a rinsing process to remove any remaining etching solution from the conductive layer substrate before proceeding to the next step. Water or the like can be used for the rinsing process. After etching and / or rinsing, a drying process may be performed to remove any excess liquid from the conductive layer substrate.

[0248] [Peeling process] The method for manufacturing a laminate having a conductive pattern according to the present invention may include a peeling step. The stripping process is the process of removing the resist pattern that remains after the etching process described above. There are no particular limitations on the method for removing the remaining resist pattern, but one method is to remove it by chemical treatment, and a method using a stripping solution is preferred. Alternatively, the material may be removed using a stripping solution by known methods such as the spray method, shower method, and paddle method.

[0249] Examples of stripping solutions include those obtained by dissolving an inorganic or 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. Tetramethylammonium hydroxide or alkanolamine compounds are preferred as alkaline organic compounds. It is also preferable that the stripping solution does not dissolve the metal layer.

[0250] A method for removing the resist pattern involves immersing a substrate having the remaining resist pattern in a stirring stripping solution, preferably at a liquid temperature of 30 to 80°C, more preferably 50 to 80°C, for 1 to 30 minutes.

[0251] The pH of the stripping solution used in the stripping process is preferably 11 or higher, more preferably 12 or higher, and even more preferably 13 or higher. The upper limit is preferably 14 or lower, and more preferably 13.8 or lower. The temperature of the stripping solution used during the stripping process is preferably higher than the temperature of the developing solution used during the developing process. Specifically, the value obtained by subtracting the temperature of the developing solution from the temperature of the stripping solution (temperature of the stripping solution - temperature of the developing solution) is preferably 10°C or higher, and more preferably 20°C or higher. The upper limit is preferably 100°C or lower, and more preferably 80°C or lower. The pH of the stripping solution used in the stripping process is preferably higher than the pH of the developing solution used in the developing process. Specifically, the value obtained by subtracting the pH of the developing solution from the pH of the stripping solution (pH of the stripping solution - pH of the developing solution) is preferably 1 or higher, and more preferably 1.5 or higher. The upper limit is preferably 5 or lower, and more preferably 4 or lower.

[0252] After removing the resist pattern with a stripping solution, it is also preferable to perform a rinsing process to remove any remaining stripping solution from the substrate. Water or the like can be used for the rinsing process. After stripping the resist pattern with a stripping solution and / or rinsing, a drying process may be performed to remove any excess solution from the substrate.

[0253] [Other processes] The method for manufacturing a laminate having a conductive pattern may include any steps other than those described above (other steps). Examples include, but are not limited to, the steps described in paragraph

[0172] of International Publication No. 2019 / 022089 for reducing the visible light reflectance, and the steps described in paragraph

[0172] of International Publication No. 2019 / 022089 for forming a new metal layer on an insulating film.

[0254] (A process to reduce the reflectance of visible light) 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 metal layers having a substrate. One treatment that reduces visible light reflectivity is oxidation. If the substrate has a metal layer containing copper, the copper can be oxidized to copper oxide, which blackens the metal layer and reduces its visible light reflectivity. Treatments for reducing visible light reflectance are described in paragraphs

[0017] to

[0025] of Japanese Patent Publication No. 2014-150118, and in paragraphs

[0041] ,

[0042] ,

[0048] and

[0058] of Japanese Patent Publication No. 2013-206315, and the contents described in these publications are incorporated herein by reference.

[0255] (Steps to form an insulating film, steps to form a new conductive layer on the surface of the insulating film) A method for manufacturing a laminate having a conductor pattern may also preferably include the steps of forming an insulating film on the surface of the circuit wiring and forming a new conductive layer on the surface of the insulating film. Through the above process, a second electrode pattern insulated from the first electrode pattern can be formed. The process for forming the insulating film is not particularly limited and includes known methods for forming permanent films. Alternatively, an insulating film with a desired pattern may be formed by photolithography using an insulating photosensitive material. The process of forming a new conductive layer on an insulating film is not particularly limited, and for example, a new conductive layer with a desired pattern may be formed by photolithography using a conductive photosensitive material.

[0256] 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, it is possible to form a touch panel circuit wiring 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 touch panel circuit wiring from both sides of the substrate using a roll-to-roll method.

[0257] <Applications of laminates with conductive patterns> The method for manufacturing laminates having conductive patterns is not limited to specific applications and can be applied to, for example, the manufacture of conductive films such as touch panels, transparent heaters, transparent antennas, electromagnetic shielding materials, and dimmable films; the manufacture of printed circuit boards and semiconductor packages; the manufacture of pillars and pins for interconnects between semiconductor chips and packages; the manufacture of metal masks; the manufacture of tape substrates such as COF (Chip on Film) and TAB (Tape Automated Bonding); and the like. Furthermore, the above-mentioned touch panel can be a capacitive touch panel. The method for manufacturing the laminate according to the present invention can be used to form conductive films and peripheral circuit wiring in the touch panel. The above-mentioned touch panel can be applied to display devices such as organic EL (electro-luminescence) display devices and liquid crystal display devices. [Examples]

[0258] The present invention will be described in more detail below based on examples. The materials, quantities, proportions, processing details, 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. Unless otherwise specified, "parts" and "%" are based on mass. Furthermore, in the following examples, the weight-average molecular weight of the resin is the weight-average molecular weight obtained by gel permeation chromatography (GPC) on a polystyrene basis. In addition, the acid value of the resin is the theoretical acid value derived from the ratio of the resin's constituent units.

[0259] <Transfer film> Transfer films used in each example and comparative example were prepared using the components shown in Table 1 below. A photosensitive composition having the composition described in Table 1 was applied to a temporary support (polyethylene terephthalate film, thickness: 16 μm, haze: 0.12%) using a slit nozzle. The amount applied was adjusted so that the thickness of the formed photosensitive composition layer was as described in Table 1. The photosensitive composition on the temporary support was dried in a 100°C convection oven for 2 minutes to form a photosensitive composition layer. A protective film (polypropylene film, thickness: 12 μm, haze: 0.2%) was laminated onto the photosensitive composition layer to prepare a transfer film. The units of the amounts (addition amounts) of each component listed in Table 1 are parts by mass. The details of each component in the table are as follows:

[0260] [Alkali-soluble resin (Resin A)] • Polymer 1: Styrene / methacrylic acid / methyl methacrylate copolymer (mass ratio of constituent units: 52 / 29 / 19, acid value: 189 mg KOH / g, contact angle: 75 degrees, corresponds to resin A1 above) • Polymer 2: Styrene / methacrylic acid / methyl methacrylate copolymer (mass ratio of constituent units: 52 / 15 / 33, acid value: 99 mgKOH / g, contact angle: 78 degrees, corresponds to resin A1 above) • Polymer 3: Benzyl methacrylate / methacrylic acid / acrylic acid copolymer (mass ratio of constituent units: 74.5 / 10 / 15.5, acid value: 186 mg KOH / g, contact angle: 62 degrees, does not correspond to resin A1 above) • Polymer 4: Benzyl methacrylate / methacrylic acid copolymer (mass ratio of constituent units: 82.7 / 17.3, acid value: 113 mg KOH / g, contact angle: 72 degrees, corresponds to resin A1 above) Furthermore, whether or not resin A corresponds to resin A1 was determined by measuring the contact angle using the method described in requirement (X3) above. The film used for measuring the contact angle was prepared by the following method. Resin A was spin-coated onto glass under conditions that allowed for the formation of a 2.0 μm thick film, and dried at 100°C for 2 minutes using a hot plate to obtain a 2.0 μm film. For resins with high viscosity that could not be obtained to form a 2.0 μm film, the resin was diluted with methyl ethyl ketone until a suitable viscosity was achieved, and then spin-coated. If the resin did not dissolve in methyl ethyl ketone, a solvent with a boiling point of 150°C or lower in which the resin dissolves was used. The obtained films were heated in an oven at 150°C for 30 minutes to obtain films for contact angle measurement.

[0261] [Polymerizable compound] • BPE500: Ethoxylated bisphenol A dimethacrylate (average number of -CH2CH2O- groups per molecule: 10), manufactured by Shin Nakamura Chemical Industry Co., Ltd. (contact angle: 44 degrees, polymerizable compound B having a bisphenol A structure) Products containing (Applies to) • BPE900: Ethoxylated bisphenol A dimethacrylate (average number of -CH2CH2O- groups per molecule: 17), manufactured by Shin-Nakamura Chemical Industry Co., Ltd. (contact angle: 34 degrees, corresponds to polymerizable compound B above which has a bisphenol A structure) • HD-N: 1,6-Hexanediol dimethacrylate, manufactured by Shin-Nakamura Chemical Industry Co., Ltd. (Contact angle: 77 degrees, corresponds to polymerizable compound A1 above) • A-NOD-N: 1,9-nonanediol diacrylate, manufactured by Shin-Nakamura Chemical Industry Co., Ltd. (contact angle: 86 degrees, corresponds to polymerizable compound A1 above) • NOD-N: 1,9-nonanediol dimethacrylate, manufactured by Shin-Nakamura Chemical Industry Co., Ltd. (contact angle: 87 degrees, corresponds to polymerizable compound A1 above) • A-HD-N: 1,6-Hexanediol diacrylate, manufactured by Shin-Nakamura Chemical Industry Co., Ltd. (Contact angle: 76 degrees, corresponds to polymerizable compound A1 above) • A-DOD-N: 1,10-decanediol diacrylate, manufactured by Shin-Nakamura Chemical Industry Co., Ltd. (contact angle: 89 degrees, corresponds to polymerizable compound A1 above) • A-DCP: Tricyclodencanedimethanol diacrylate, manufactured by Shin-Nakamura Chemical Industry Co., Ltd. (Contact angle: 90 degrees, corresponds to polymerizable compound A above) • TO2349: Aronix (registered trademark) TO-2349, manufactured by Toagosei Co., Ltd. (contact angle: 58 degrees, polymerizable compound B mentioned above) Products containing (Applies to) Furthermore, whether the polymerizable compound falls under polymerizable compound A and polymerizable compound B was determined by measuring the contact angle using the methods described in requirements (X1) and (X2) above. The film used for measuring the contact angle was prepared by the following method. A coating composition was prepared by mixing 100 parts by mass of polymerizable compound with 1.0 part by mass of 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]ethanone-1-(O-acetyloxime) and 9 parts by mass of methyl ethyl ketone. The above coating solution was spin-coated onto glass under conditions that would allow for the formation of a 2.0 μm thick film after drying. The film was then dried at room temperature for 10 minutes to obtain a 2.0 μm thick film. This film was placed in a nitrogen purge box (MUVPBQ-150×135×33, manufactured by ITEC Systems Co., Ltd.) and nitrogen purged until the partial pressure of nitrogen reached 0.99 atmospheres. After purging, exposure was performed using a high-pressure mercury lamp at an exposure dose of 500 mJ / cm². 2 The film was exposed by irradiating it with i-ray light. The exposed film was heated in a 150°C oven for 30 minutes to obtain a cured film for contact angle measurement.

[0262] [Photopolymerization initiator] • BCIM: 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer

[0263] [Sensitizer] • EAB-F: 4,4'-bis(diethylamino)benzophenone

[0264] [Polymerization inhibitor] • Seriously contraindicated drug 1: Phenothiazine • Seriously prohibited substance 2: 1-phenyl-3-pyrazolidone

[0265] [Additives] • LCV: Leucocrystal violet, manufactured by Tokyo Chemical Industry Co., Ltd. • Chain transfer agent A: N-phenylcarbamoylmethyl-N-carboxymethylaniline, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. • CBT-1: Carboxybenzotriazole, manufactured by Johoku Chemical Co., Ltd. • F-552: Megafuck (registered trademark) F-552, manufactured by DIC Corporation. • BYK-330: BYK-330, manufactured by Big Chemie.

[0266] [solvent] • MEK: Methyl ethyl ketone • PGMEA: Propylene glycol monomethyl ether acetate • MeOH: methanol

[0267] <Measurement> [Photosensitive composition water contact angle] For each example and comparative example of a photosensitive composition, a film of the photosensitive composition was prepared using the following method for measuring the water contact angle, and the water contact angle of the film was measured. Each photosensitive composition was applied to the above temporary support using a slit-shaped nozzle and dried in a 100°C convection oven for 2 minutes to form a photosensitive composition layer with a thickness of 2.0 μm. The above protective film was laminated onto the photosensitive composition layer to prepare a transfer film for water contact angle measurement. The protective film of the transfer film used for measuring the water contact angle was peeled off to expose the photosensitive composition layer, and the photosensitive composition layer was bonded to the glass substrate. The bonding was performed by lamination under the conditions of a roll temperature of 90°C, a linear pressure of 0.8 MPa, and a linear speed of 3.0 m / min. By the above procedure, a laminate having a glass substrate, a photosensitive composition layer, and a temporary support in that order was obtained. The temporary support of the above laminate is peeled off, and the polymerized compound is cured under the same conditions as when the cured film was prepared, in a nitrogen atmosphere with an exposure dose of 500 mJ / cm². 2 The i-ray was irradiated onto the material, and the material was heated in a 150°C oven for 30 minutes to obtain a cured film for contact angle measurement. The water contact angle of the above-mentioned cured film was measured under the same conditions as the water contact angle of polymerizable compounds.

[0268] <Rating> [Resolution] The protective film of the transfer film described above was peeled off to expose the photosensitive composition layer, and the photosensitive composition layer was laminated to substrate 1 (polyethylene terephthalate film, thickness: 40 μm). Lamination was performed by lamination under the conditions of roll temperature 90°C, linear pressure 0.8 MPa, and linear speed 3.0 m / min. By the above procedure, a laminate having substrate 1, photosensitive composition layer, and temporary support in this order was obtained. Without removing the temporary support of the laminate described above, the temporary support was brought into close contact with a glass mask (duty cycle 1:1) having a line and space pattern with a line width of 3.0 to 50 μm, and the laminate was exposed from the temporary support side with an ultra-high pressure mercury lamp (USH-2004MB, manufactured by Ushio Inc.). The exposure amount for the above exposure was determined as follows: Exposure was performed using an ultra-high pressure mercury lamp (USH-2004MB, manufactured by Ushio Inc.) while changing the exposure amount according to the procedure described above. After leaving the exposure for 1 hour, the exposure amount was determined such that, when developed under the conditions described later, the remaining pattern width in the 50 μm line / 50 μm space pattern area was in the range of 49.0 microns to 51.0 microns, and this was used as the exposure amount in the procedure described above.

[0269] After exposure, the temporary support was left for one hour, and then a resist pattern was formed by development. Development was performed using a 1.0% potassium carbonate aqueous solution (developer) at 30°C for 30 seconds using a shower development method. The line width of the pattern corresponding to the mask with the narrowest line width among the resist patterns formed after development was defined as the achieved resolution. Based on the above achieved resolution, the resolution of the photosensitive composition layer was evaluated according to the following criteria. Furthermore, if there was significant roughness on the sidewalls of the pattern, or if the bottom edge was noticeably blurred and connected to the adjacent line pattern, it was considered that the pattern was not resolved. In terms of resolution evaluation, A to C are within a range that is practically acceptable, B is preferable, and A is particularly preferable.

[0270] (Resolution evaluation criteria) A: Achievable resolution of 10 μm or less B: Achievable resolution greater than 10 μm and less than or equal to 15 μm C: Achievable resolution greater than 15 μm and less than or equal to 20 μm. D: Achievable resolution greater than 20 μm and less than or equal to 30 μm E: Resolution exceeds 30 μm, or resolution is not achieved.

[0271] [Acid resistance] The protective film of the above transfer film was peeled off to expose the photosensitive composition layer, and the photosensitive composition layer was laminated to the conductive layer of substrate 2 (a substrate having a 50 nm thick silver nanowire layer (conductive layer) on the surface of a 40 μm PET film) so that they faced each other. The lamination was performed by lamination under the conditions of a roll temperature of 90°C, a linear pressure of 0.8 MPa, and a linear speed of 3.0 m / min. By the above procedure, a laminate having substrate 2 (PET film, conductive layer), photosensitive composition layer, and temporary support in this order was obtained. Furthermore, when the surface resistance of the conductive layer in the above laminate was measured using a non-destructive sheet resistance meter (Napson EC-80P), the surface resistance (resistance before treatment) was found to be 60 Ω / □.

[0272] Exposure and development were performed using the same procedure as for the high-resolution exposure described above, except that the entire surface was exposed without using a mask. As a result of the above process, a laminate was obtained in which a cured film (resist film) derived from the photosensitive composition layer was formed on the entire surface of the conductive layer of the substrate 2. A 30 wt% aqueous solution of ferric nitrate (pH: 0.6) at 40°C was supplied to the resist film side surface of the above laminate using a shower method for 120 seconds. Next, the surface resistance value (resistance value after treatment) was measured using the non-destructive sheet resistance measuring instrument described above, and the change from the resistance value before treatment was determined. The percentage change in resistance was calculated using the following formula. However, if the percentage change in resistance calculated using the following formula was negative, its absolute value was used as the percentage change in resistance. (Formula) (Change in resistance) = {(Resistance after treatment) - (Resistance before treatment)} × 100 / (Resistance before treatment) Based on this change, the acid resistance of the resist film formed by the photosensitive composition was evaluated according to the following criteria. In terms of acid resistance, A to C are within a range that is practically acceptable, B is preferred, and A is particularly preferred.

[0273] (Acid resistance evaluation criteria) A: Resistance change is 2% or less B: Resistance change of more than 2% and less than or equal to 5% C: Resistance change of more than 5%, 10% or less D: Resistance change of more than 10% and less than or equal to 20% E: Resistance change exceeds 20%, or the resistance value after processing exceeds the measurement limit.

[0274] [Peelability] Except for using a glass mask with a line-and-space pattern having a line width of 50 μm (duty cycle 1:1), a resist pattern for peelability evaluation was formed using the same procedure as for resolution evaluation. The resist pattern was immersed in a 3 wt% NaOH aqueous solution at 50°C, and the time it took for the resist pattern to peel off was measured. Based on the time it took for the resist pattern to peel off (peeling time), the peelability of the resist pattern formed by the photosensitive composition was evaluated according to the following criteria. In terms of evaluation, A to C are within a range that is practically acceptable, B is preferable, and A is particularly preferable.

[0275] (Peelability evaluation criteria) A: Peeling time is 30 seconds or less. B: Peeling time is more than 30 seconds and 45 seconds or less. C: Peeling time is more than 45 seconds and 60 seconds or less. D: Peeling time is more than 60 seconds and 80 seconds or less. E: Peeling time exceeds 80 seconds, or the resist pattern cannot be peeled off.

[0276] <Result> Table 1 shows the composition of the photosensitive compositions for each example and comparative example, the thickness of the photosensitive composition layer, the water contact angle of the photosensitive composition, and the evaluation results for resolution, acid resistance, and peelability. Table 1 is divided into Table 1-1 and Table 1-2. The components of the photosensitive composition in Table 1 are as described above. In Table 1, the content of each component is expressed in parts by mass. In Table 1, the notation "Polymerizable compound / Resin A" represents the mass ratio of the total polymerizable compound content to the resin content. In Table 1, the notation "Polymerizable compound B / Polymerizable compound A" represents the mass ratio of polymerizable compound B to polymerizable compound A.

[0277] [Table 1]

[0278] [Table 2]

[0279] The results in Table 1 confirm that the photosensitive composition of the present invention produces the desired effect. From a comparison of Examples 11 and 13 with other examples, it was confirmed that when polymerizable compound A is polymerizable compound A1 represented by the above formula (A), the resolution is superior. From a comparison of Examples 10 and 11 with other examples, it was confirmed that when the polymerizable compound contains polymerizable compound B that satisfies the above requirement (X2), it exhibits superior peelability. From a comparison of Examples 5-7 and 10-12 with other examples, it was confirmed that polymerizable compound B exhibits superior resolution when it has a bisphenol A structure. From a comparison of Examples 6, 7, and 10-12 with other examples, it was confirmed that when the mass ratio of polymerizable compound B to polymerizable compound A is 0.50-4.00, one or more of the following properties—resolution, acid resistance, and peelability—are superior. From a comparison of Examples 8 and 9 with the other examples, Content of polymerizable compounds relative to the content of alkali-soluble resin It was confirmed that when the mass ratio was between 0.68 and 1.30, at least one of the following properties—acid resistance and peelability—was superior. From a comparison of Examples 1, 3, 4 and 15-24 with other examples, it was found that polymerizable compound A is polymerizable compound A1 represented by the above formula (A), the polymerizable compound satisfies the above requirement (X2) and contains polymerizable compound B having a bisphenol A structure, and the mass ratio of the content of polymerizable compound B to the content of polymerizable compound A is 0.50 to 4.00. Content of polymerizable compounds relative to the content of alkali-soluble resin It was confirmed that when the mass ratio is between 0.68 and 1.30, one or more of the following properties—resolution, acid resistance, and peelability—are superior. From a comparison between Example 1 and Example 4, it was confirmed that when the alkali-soluble resin is resin A1 that satisfies the above requirement (X3), at least one of the following is superior: acid resistance and release properties. From a comparison between Example 1 and Example 3, and between Example 7 and Example 12, it was confirmed that when the acid value of the alkali-soluble resin is 100 mg KOH / g or higher, at least one of the following is superior: acid resistance and / or peelability. A comparison of Example 2 with other examples confirmed that when the thickness of the photosensitive composition layer in the transfer film is 1 to 10 μm, resolution is superior.

[0280] <Formation of a photosensitive composition layer using a photosensitive composition> [Example 1B] The photosensitive composition used to prepare the transfer film in Example 1, as described in Table 1, was spin-coated onto the substrate 1 to form a coating film. The amount of coating was adjusted so that the resulting photosensitive composition layer would have the thickness described in Table 1. The coating film on the substrate 1 was dried on a hot plate at 90°C for 2 minutes to form a photosensitive composition layer on the substrate 1. Next, the surface of the photosensitive composition layer was bonded to the temporary support used to prepare the transfer film. By following the above procedure, a laminate having the substrate 1, the photosensitive composition layer, and the temporary support in that order was obtained. When the above laminate was subjected to exposure and development processing using the same procedure as for the resolution evaluation above, and the resolution was evaluated using the same criteria as above, the same resolution evaluation was obtained as in Example 1.

[0281] Furthermore, a photosensitive composition layer was formed on the substrate 2 in the same manner as the resolution evaluation procedure of Example 1B, and a laminate was obtained having the substrate 2, the photosensitive composition layer, and the temporary support in this order. The laminate was subjected to exposure and development treatment in the same manner as the acid resistance evaluation procedure, and the acid resistance was evaluated using the same criteria as above, and the acid resistance evaluation was the same as in Example 1. Furthermore, when the laminate used in the resolution evaluation of Example 1B, which has the substrate 1, photosensitive composition layer, and temporary support in this order, was evaluated for peelability using the same procedure and evaluation criteria as above, the peelability evaluation was the same as that of Example 1.

[0282] [Examples 2B to 24B] In the same manner as in Example 1B, the photosensitive compositions used to prepare the transfer films of Examples 2 to 24, as described in Table 1, were evaluated for resolution, acid resistance, and peelability, and the evaluations were the same as those for each example.

[0283] <Changes to temporary support and protective film> [Examples 1C to 24C] In the preparation of the transfer film, the only differences were that the temporary support was changed to a 16 μm thick biaxially oriented polyethylene terephthalate film (Lumirror 16FB40, manufactured by Toray Industries, Inc.) and the protective film was changed to a 30 μm thick biaxially oriented polypropylene film (Alfan E-201F, manufactured by Oji F-Tex Corporation). Otherwise, the resolution, acid resistance, and peelability were evaluated in the same manner as in Examples 1 to 24, and the evaluations were the same as in each example.

[0284] [Examples 1D to 24D] In the preparation of the transfer film, the only differences were that the temporary support was changed to a 38 μm thick biaxially oriented polyethylene terephthalate film (Lumirror #38-U48, manufactured by Toray Industries, Inc.) and the protective film was changed to a 30 μm thick biaxially oriented polypropylene film (Alfan FG-201, manufactured by Oji F-Tex Corporation). The resolution, acid resistance, and peelability were evaluated in the same manner as in Examples 1 to 24, and the evaluations were the same as in each example.

[0285] [Examples 1E to 24E] In the preparation of the transfer film, the only differences were that the temporary support was changed to a 16 μm thick biaxially oriented polyethylene terephthalate film (Lumirror 16KS40, manufactured by Toray Industries, Inc.) and the protective film was changed to a 30 μm thick biaxially oriented polypropylene film (Alfan FG-201, manufactured by Oji F-Tex Corporation). Otherwise, the resolution, acid resistance, and peelability were evaluated in the same manner as in Examples 1 to 24, and the evaluations were the same as in each example.

[0286] [Examples 1F to 24F] In the preparation of the transfer film, the only differences were that the temporary support was changed to a 38 μm thick biaxially oriented polyethylene terephthalate film (Cosmoshine A4160, manufactured by Toyobo Co., Ltd.) and the protective film was changed to a 30 μm thick biaxially oriented polypropylene film (Alfan FG-201, manufactured by Oji F-Tex Co., Ltd.). The resolution, acid resistance, and peelability were evaluated in the same manner as in Examples 1 to 24, and the evaluations were the same as in each example.

[0287] <Fabrication of circuit boards> [Example 101] A laminate having substrate 2 (PET film, conductive layer), photosensitive composition layer, and temporary support in the same manner as the acid resistance evaluation procedure described above was obtained. Without removing the temporary support, the resulting laminate was pattern-exposed by bringing the temporary support and the photomask into contact using a photomask with the pattern shown in Figure 2 (hereinafter also referred to as "Pattern A"), in which conductive layer pads are connected in one direction. A high-pressure mercury lamp with i-line (365 nm) as the main exposure wavelength was used for exposure. In Figure 2, Pattern A is a pattern in which the solid and shaded areas are exposed, and the rest is shielded, and the dotted line DL virtually represents an alignment frame. Subsequently, the temporary support was peeled off, and development and washing were performed to obtain a resist (cured film of photosensitive composition) pattern in the shape of pattern A. Next, a 30 wt% aqueous solution of ferric nitrate (pH: 0.6) at 40°C was supplied in a shower manner for 120 seconds. After that, the resist was removed by immersion in a 3 wt% NaOH aqueous solution at 50°C. Using a 30 wt% aqueous solution of ferric nitrate at 40°C, the conductive layer (silver nanowire layer) could be etched, and a circuit wiring substrate was obtained in which the silver nanowires were formed in a shape corresponding to pattern A. When the obtained circuit wiring board was examined under a microscope, it was found to have a clean pattern with no peeling or chipping.

[0288] [Examples 102-124] In Example 101, circuit wiring boards were fabricated in the same manner as in Example 101, except that the transfer film used was changed to the transfer film used in Examples 2 to 24. When the obtained circuit wiring boards were observed under a microscope, none of the circuit wiring boards showed any peeling or chipping, and all had clean patterns.

[0289] [Example 101B] In Example 101, the photosensitive composition layer was formed on substrate 2 in the same manner as in Example 1B. Otherwise, the circuit wiring board was fabricated in the same manner as in Example 101. When the obtained circuit wiring board was observed under a microscope, there were no peeling or chipping, and the pattern was clean.

[0290] [Examples 101B~124B] In Example 101B, a circuit wiring board was fabricated in the same manner as in Example 101B, except that the photosensitive composition used was changed to one of the photosensitive compositions used in Examples 2 to 24. When the obtained circuit wiring boards were observed under a microscope, none of the circuit wiring boards showed any peeling or chipping, and all had clean patterns. [Explanation of symbols]

[0291] 10 Transfer film 11 Temporary support 13. Middle Class 15 Photosensitive composition layer 17 Composition layer 19 Protective film SL Non-image section G Non-image area DL alignment frame

Claims

1. Alkali-soluble resin and, Polymerizable compounds having ethylenically unsaturated groups, It contains a photopolymerization initiator, The polymerizable compound includes polymerizable compound A that satisfies the following requirement (X1): A photosensitive composition wherein the content of the polymerizable compound A is 10% by mass or more relative to the total mass of the polymerizable compound, The following requirements (X4) must be met, The content of the polymerizable compound is 20 to 60% by mass relative to the total solid content of the photosensitive composition. A photosensitive composition in which the mass ratio of the polymerizable compound to the alkali-soluble resin is 0.68 to 1.

30. Requirement (X1): A composition comprising 100 parts by mass of polymerizable compound A, 1.0 part by mass of 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]ethanone-1-(O-acetyloxime), and 9 parts by mass of methyl ethyl ketone is applied to form a 2.0 μm film, and then exposed to a nitrogen atmosphere at an exposure of 500 mJ / cm². ２ The water contact angle of the film obtained by irradiating it with i-rays and heating it at 150°C for 30 minutes is 74 degrees or higher. Requirement (X4): A 2.0 μm film formed using the photosensitive composition is irradiated with i-rays at an exposure dose of 500 mJ / cm² under a nitrogen atmosphere and heated at 150°C for 30 minutes, and the resulting film has a water contact angle of 63 degrees or more.

2. The photosensitive composition according to claim 1, wherein the polymerizable compound A is polymerizable compound A1 represented by the following formula (A). Q １ -R １ -Q ２ Formula (A) In formula (A), Q １ and Q ２ Each of these independently represents a (meth)acryloyloxy group. In formula (A), R １ This represents a chain-like divalent hydrocarbon group.

3. The photosensitive composition according to claim 1 or 2, wherein the polymerizable compound comprises polymerizable compound B that satisfies the following requirement (X2). Requirement (X2): A composition comprising 100 parts by mass of polymerizable compound B, 1.0 part by mass of 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]ethanone-1-(O-acetyloxime), and 9 parts by mass of methyl ethyl ketone is applied to form a 2.0 μm film, and then exposed to a nitrogen atmosphere at an exposure of 500 mJ / cm². ２ The water contact angle of the film obtained by irradiating it with i-rays and heating it at 150°C for 30 minutes is 65 degrees or less.

4. The photosensitive composition according to claim 3, wherein the polymerizable compound B has a bisphenol A structure.

5. The photosensitive composition according to claim 3 or 4, wherein the mass ratio of the content of polymerizable compound B to the content of polymerizable compound A is 0.50 to 4.

00.

6. The polymerizable compound A is polymerizable compound A1 represented by the following formula (A), The photosensitive composition according to claim 1, wherein the polymerizable compound comprises polymerizable compound B having a bisphenol A structure and satisfying the following requirement (X2). Q １ -R １ -Q ２ Formula (A) In formula (A), Q １ and Q ２ Each of these independently represents a (meth)acryloyloxy group. In formula (A), R １ This represents a chain-like divalent hydrocarbon group. Requirement (X2): A composition comprising 100 parts by mass of polymerizable compound B, 1.0 part by mass of 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]ethanone-1-(O-acetyloxime), and 9 parts by mass of methyl ethyl ketone is applied to form a 2.0 μm film, and then exposed to a nitrogen atmosphere at an exposure of 500 mJ / cm². ２ The water contact angle of the film obtained by irradiating it with i-rays and heating it at 150°C for 30 minutes is 65 degrees or less.

7. The polymerizable compound A is polymerizable compound A1 represented by the following formula (A), The polymerizable compound includes polymerizable compound B having a bisphenol A structure and satisfying the following requirement (X2): The photosensitive composition according to claim 1, wherein the mass ratio of the content of polymerizable compound B to the content of polymerizable compound A is 0.50 to 4.

00. Q １ -R １ -Q ２ Formula (A) In formula (A), Q １ and Q ２ Each of these independently represents a (meth)acryloyloxy group. In formula (A), R １ This represents a chain-like divalent hydrocarbon group. Requirement (X2): A composition comprising 100 parts by mass of polymerizable compound B, 1.0 part by mass of 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]ethanone-1-(O-acetyloxime), and 9 parts by mass of methyl ethyl ketone is applied to form a 2.0 μm film, and then exposed to a nitrogen atmosphere at an exposure of 500 mJ / cm². ２ The water contact angle of the film obtained by irradiating it with i-rays and heating it at 150°C for 30 minutes is 65 degrees or less.

8. The photosensitive composition according to any one of claims 1 to 7, wherein the alkali-soluble resin is resin A1 that satisfies the following requirement (X3). Requirement (X3): After forming a 2.0 μm film made of the resin A1, the water contact angle of the film obtained by heating at 150°C for 30 minutes is 65 degrees or more.

9. The alkali-soluble resin contains constituent units derived from styrene, The photosensitive composition according to any one of claims 1 to 8, wherein the content of the styrene-derived constituent units is 20% by mass or more with respect to the total mass of the alkali-soluble resin.

10. The photosensitive composition according to any one of claims 1 to 9, wherein the acid value of the alkali-soluble resin is 100 mg KOH / g or more.

11. The photosensitive composition according to any one of claims 1 to 10, wherein the content of the polymerizable compound A is 10 to 50% by mass with respect to the total solid content of the photosensitive composition.

12. A photosensitive composition according to any one of claims 1 to 11, used to form an etching resist used when performing an etching process with an acidic etching solution.

13. Temporary support and A transfer film having a photosensitive composition layer formed using the photosensitive composition according to any one of claims 1 to 12.

14. The transfer film according to claim 13, wherein the thickness of the photosensitive composition layer is 1 to 10 μm.

15. A transfer film according to claim 13 or 14, used to form an etching resist used when performing an etching treatment with an acidic etching solution.

16. A preparation step of preparing a laminate having a substrate, a conductive layer containing silver, and a photosensitive composition layer in this order, An exposure step of pattern exposure of the photosensitive composition layer, A developing step involves developing an exposed photosensitive composition layer to form a resist pattern, A method for manufacturing a laminate having a conductive pattern, comprising an etching step of etching the conductive layer in a region where a resist pattern is not formed with an etching solution having a pH of less than 2.0, The photosensitive composition layer is Alkali-soluble resin and, Polymerizable compounds having ethylenically unsaturated groups, It contains a photopolymerization initiator, The polymerizable compound includes polymerizable compound A that satisfies the following requirement (X1): A method for producing a laminate having a conductive pattern, wherein the content of the polymerizable compound A is 10% by mass or more relative to the total mass of the polymerizable compound. Requirement (X1): A composition comprising 100 parts by mass of polymerizable compound A, 1.0 part by mass of 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]ethanone-1-(O-acetyloxime), and 9 parts by mass of methyl ethyl ketone is applied to form a 2.0 μm film, and then exposed to a nitrogen atmosphere at an exposure of 500 mJ / cm². ２ The water contact angle of the film obtained by irradiating it with i-rays and heating it at 150°C for 30 minutes is 74 degrees or higher.

17. A method for producing a laminate having a conductive pattern according to claim 16, wherein the polymerizable compound A is polymerizable compound A1 represented by the following formula (A). Q １ -R １ -Q ２ Formula (A) In formula (A), Q １ and Q ２ Each of these independently represents a (meth)acryloyloxy group. In formula (A), R １ This represents a chain-like divalent hydrocarbon group.

18. A method for producing a laminate having a conductive pattern according to claim 16 or 17, wherein the polymerizable compound comprises polymerizable compound B that satisfies the following requirement (X2). Requirement (X2): A composition comprising 100 parts by mass of polymerizable compound B, 1.0 part by mass of 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]ethanone-1-(O-acetyloxime), and 9 parts by mass of methyl ethyl ketone is applied to form a 2.0 μm film, and then exposed to a nitrogen atmosphere at an exposure of 500 mJ / cm². ２ The water contact angle of the film obtained by irradiating it with i-rays and heating it at 150°C for 30 minutes is 65 degrees or less.

19. The method for producing a laminate having a conductive pattern according to claim 18, wherein the polymerizable compound B is polymerizable compound B1 having a bisphenol A structure.

20. A method for manufacturing a laminate having a conductive pattern according to claim 18 or 19, wherein the mass ratio of the content of polymerizable compound B to the content of polymerizable compound A is 0.50 to 4.

00.

21. A method for manufacturing a laminate having a conductive pattern according to any one of claims 16 to 20, wherein the mass ratio of the content of the polymerizable compound to the content of the alkali-soluble resin is 0.68 to 1.

30.

22. The polymerizable compound A includes polymerizable compound A1 represented by the following formula (A), A method for producing a laminate having a conductive pattern according to claim 16, wherein the polymerizable compound includes polymerizable compound B having a bisphenol A structure and satisfying the following requirement (X2). Q １ -R １ -Q ２ Formula (A) In formula (A), Q １ and Q ２ Each of these independently represents a (meth)acryloyloxy group. In formula (A), R １ This represents a chain-like divalent hydrocarbon group. Requirement (X2): A composition comprising 100 parts by mass of polymerizable compound B, 1.0 part by mass of 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]ethanone-1-(O-acetyloxime), and 9 parts by mass of methyl ethyl ketone is applied to form a 2.0 μm film, and then exposed to a nitrogen atmosphere at an exposure of 500 mJ / cm². ２ The water contact angle of the film obtained by irradiating it with i-rays and heating it at 150°C for 30 minutes is 65 degrees or less.

23. The polymerizable compound A includes polymerizable compound A1 represented by the following formula (A), The polymerizable compound satisfies the following requirement (X2) and comprises a photosensitive composition containing polymerizable compound B having a bisphenol A structure, The mass ratio of the content of polymerizable compound B to the content of polymerizable compound A is 0.50 to 4.

00. A method for manufacturing a laminate having a conductive pattern according to claim 16, wherein the mass ratio of the content of the polymerizable compound to the content of the alkali-soluble resin is 0.68 to 1.

30. Q １ -R １ -Q ２ Formula (A) In formula (A), Q １ and Q ２ Each of these independently represents a (meth)acryloyloxy group. In formula (A), R １ This represents a chain-like divalent hydrocarbon group. Requirement (X2): A composition comprising 100 parts by mass of polymerizable compound B, 1.0 part by mass of 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]ethanone-1-(O-acetyloxime), and 9 parts by mass of methyl ethyl ketone is applied to form a 2.0 μm film, and then exposed to a nitrogen atmosphere at an exposure of 500 mJ / cm². ２ The water contact angle of the film obtained by irradiating it with i-rays and heating it at 150°C for 30 minutes is 65 degrees or less.

24. A method for manufacturing a laminate having a conductive pattern according to any one of claims 16 to 23, wherein the alkali-soluble resin is resin A1 that satisfies the following requirement (X3). Requirement (X3): After forming a 2.0 μm film made of the resin A1, the water contact angle of the film obtained by heating at 150°C for 30 minutes is 65 degrees or more.

25. The alkali-soluble resin contains constituent units derived from styrene, A method for manufacturing a laminate having a conductive pattern according to any one of claims 16 to 24, wherein the constituent units derived from styrene constitute 20% by mass or more of the total mass of the alkali-soluble resin.

26. A method for producing a laminate having a conductive pattern according to any one of claims 16 to 25, wherein the acid value of the alkali-soluble resin is 100 mg KOH / g or more.

Images