Photosensitive resin composition, transfer film, method for manufacturing resin patterns, method for manufacturing conductive patterns, and polymer

Abstract

To provide a photosensitive resin composition, etc., capable of forming a resin pattern with excellent adhesion. [Solution] A photosensitive resin composition, etc., comprising a polymer containing a structural unit having a group represented by the following formula (1), and a structural unit having at least one selected from the group consisting of a silyl group and a fluoro group, an alkali-soluble resin, a polymerizable compound, and a photopolymerization initiator. JPEG2026061802000041.jpg2167 In formula (1), R 1 and R 2 * represents a hydrogen atom or substituent, and * represents a bonding site with another structure.

Description

Technical Field

[0001] The present disclosure relates to a photosensitive resin composition, a transfer film, a method for manufacturing a resin pattern, a method for manufacturing a conductive pattern, and a polymer.

Background Art

[0002] In the production of printed circuit boards and the like, photosensitive resin compositions are widely used as resist materials.

[0003] For example, Patent Document 1 describes a resin composition containing a coloring material A and a resin B. The coloring material A contains a pigment, and the resin B contains a repeating unit b1-1 having an acid group, a repeating unit b1-2 having a functional group b selected from a group containing two or more aromatic rings, a group containing a heterocyclic group, and a group containing a condensed ring, and a repeating unit b1-3 other than the repeating unit b1-1 and the repeating unit b1-2. A resin composition is described in which the content of the coloring material A in the total solid content of the resin composition is 55% by mass or more.

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0005] When forming a resin pattern on a substrate using a photosensitive resin composition, pattern collapse may occur. This is presumed to be due to low adhesion between the substrate and the resin pattern.

[0006] The problem to be solved by one embodiment of the present disclosure is to provide a photosensitive resin composition capable of forming a resin pattern with excellent adhesion. Another problem to be solved by other embodiments of the present disclosure is to provide a transfer film using the above photosensitive resin composition, a method for producing a resin pattern, and a method for producing a conductive pattern. Another problem to be solved by other embodiments of the present disclosure is to provide a novel polymer.

Means for Solving the Problems

[0007] The means for solving the above problems include the following aspects. <1> A photosensitive resin composition comprising a polymer containing a structural unit having a group represented by the following formula (1) and a structural unit having at least one selected from the group consisting of a silyl group and a fluoro group, an alkali-soluble resin, a polymerizable compound, and a photoinitiator.

Chemical formula

Chemical formula

Chemical formula

Chemical formula

Chemical formula

Chemical formula

[0008] According to one embodiment of the present disclosure, a photosensitive resin composition capable of forming a resin pattern with excellent adhesion is provided. Furthermore, other embodiments of this disclosure provide a method for manufacturing a transfer film, a resin pattern, and a conductive pattern using the above-mentioned photosensitive resin composition. Furthermore, other embodiments of the present disclosure provide novel polymers. [Brief explanation of the drawing]

[0009] [Figure 1] This is a schematic cross-sectional view showing an example of a transfer film relating to this disclosure. [Modes for carrying out the invention]

[0010] The contents of this disclosure are described in detail below. The descriptions of the constituent elements described below may be based on representative embodiments of this disclosure, but this disclosure is not limited to such embodiments. In this disclosure, the "~" symbol indicating a numerical range is used to mean that the numbers before and after it are included as the lower and upper limits, respectively. In numerical ranges described stepwise within this specification, the upper or lower limit of one numerical range may be replaced with the upper or lower limit of another numerical range described stepwise. Furthermore, in numerical ranges described within this specification, the upper or lower limit of that range may be replaced with the values ​​shown in the examples. Furthermore, in the notation of groups (atomic groups) in this disclosure, notations that do not specify whether they are substituted or unsubstituted include both those with and without substituents. For example, "alkyl group" includes not only alkyl groups without substituents (unsubstituted alkyl groups) but also alkyl groups with substituents (substituted alkyl groups). Furthermore, in this disclosure, a combination of two or more preferred embodiments is a more preferred embodiment. In this disclosure, the amount of each component in the composition means the total amount of any multiple substances present in the composition, unless otherwise specified, if there are multiple substances corresponding to each component in the composition. In this disclosure, the term "process" includes not only independent processes but also any process that cannot be clearly distinguished from other processes, as long as its intended purpose is achieved. In this disclosure, "(meth)acrylic acid" is a concept that encompasses both acrylic acid and methacrylic acid, "(meth)acrylate" is a concept that encompasses both acrylate and methacrylate, and "(meth)acryloyl group" is a concept that encompasses both acryloyl group and methacryloyl group. Furthermore, unless otherwise specified, the weight-average molecular weight (Mw) and number-average molecular weight (Mn) in this disclosure are molecular weights obtained by detecting the molecules using a differential refractometer with THF (tetrahydrofuran) as the solvent, using a gel permeation chromatography (GPC) analyzer with TSKgel GMHxL, TSKgel G4000HxL, or TSKgel G2000HxL columns (all product names of Tosoh Corporation), and then converting them using polystyrene as the standard substance. In this disclosure, unless otherwise specified, the molecular weight of a compound with a molecular weight distribution is the weight-average molecular weight. In this disclosure, unless otherwise specified, the ratios of the constituent units of the polymer are given by mass ratio. In this disclosure, "solids" means components other than solvents contained in the composition. The details of this disclosure are described below.

[0011] [Photosensitive resin composition] The photosensitive resin composition of this disclosure comprises a polymer (hereinafter also referred to as "specific polymer") containing a structural unit having a group represented by the following formula (1), and a structural unit having at least one selected from the group consisting of a silyl group and a fluoro group, an alkali-soluble resin, a polymerizable compound, and a photopolymerization initiator.

[0012] [ka]

[0013] In formula (1), R 1 and R 2 Each of these independently represents a hydrogen atom or a substituent, and * represents a bonding site with another structure.

[0014] As a result of diligent research by the present inventors, it has been found that by adopting the above configuration, a resin pattern with excellent adhesion can be formed, and for example, it is effective in suppressing the collapse of the formed resin pattern. The mechanism by which this produces excellent effects is not clear, but it is hypothesized as follows.

[0015] The specific polymer contains a structural unit having a group represented by formula (1), so that the group represented by formula (1) interacts with the substrate (or metal layer). In particular, the inclusion of a structural unit having at least one selected from the group consisting of silyl groups and fluoro groups in the specific polymer makes it easier for the polymer to segregate on the surface of the photosensitive resin composition. As a result, the group represented by formula (1) interacts more easily with the substrate (or metal layer), further improving adhesion. In other words, the combination of a structural unit having a group represented by the following formula (1) and a structural unit having at least one selected from the group consisting of silyl groups and fluoro groups results in excellent adhesion. Furthermore, the photosensitive resin composition of this disclosure includes an alkali-soluble resin and a polymerizable compound. This makes it possible to freely adjust the strength and flexibility of the photosensitive resin layer and obtain a resin pattern with suitable bendability.

[0016] On the other hand, Patent Document 1 does not contain any description of combinations of specific polymers, alkali-soluble resins, polymerizable compounds, and photopolymerization initiators.

[0017] <Specific polymers> The photosensitive resin composition of this disclosure comprises a polymer containing a structural unit having a group represented by formula (1), and a structural unit having at least one selected from the group consisting of a silyl group and a fluoro group.

[0018] [ka]

[0019] In formula (1), R 1 and R 2 Each of these independently represents a hydrogen atom or a substituent, and * represents a bonding site with another structure.

[0020] R 1 and R 2Examples of substituents represented by include halogen atoms, alkyl groups, aryl groups, alkenyl groups, alkoxy groups, ester groups, carbonyl groups, sulfonyl groups, amino groups, amide groups, and combinations thereof.

[0021] R 1 and R 2 These elements may be linked to each other to form a ring. The formed ring may be monocyclic or polycyclic. The ring may also have substituents. Examples of the formed ring include a benzene ring, a naphthalene ring, a pyridine ring, a furan ring, and a thiophene ring. In particular, from the perspective of adhesion, R 1 and R 2 Preferably, the elements are linked to each other to form a ring, and the formed ring is preferably a benzene ring.

[0022] From the viewpoint of adhesion, the structural unit having the group represented by formula (1) is preferably a structural unit having the group represented by the following formula (1A).

[0023] [ka]

[0024] In formula (1A), R 11 , R 12 , R 13 , and R 14 Each of these independently represents a hydrogen atom or a substituent, and * represents a bonding site with another structure.

[0025] R 11 , R 12 , R 13 , and R 14 The substituent represented by the above R is 1 and R 2 Examples of substituents similar to those represented by include

[0026] In particular, from the perspective of adhesion, R 11 , R 12 , R 13 , and R14 It is preferable that it is a hydrogen atom.

[0027] From the viewpoint of adhesion, the structural unit having the group represented by formula (1) is preferably a structural unit having the group represented by the following formula (1B). [ka]

[0028] In equation (1B), * represents a bonding site with another structure.

[0029] From the viewpoint of adhesion, the structural unit having the group represented by formula (1) is preferably a structural unit having the group represented by the following formula (1C). [ka]

[0030] In addition to the substructure of the group represented by formula (1B), the presence of the -CH2-C(=O)O- structure ensures a certain distance between the substructure of the group represented by formula (1B) and the main chain. This increases the degrees of freedom of molecular motion of the substructure of the group represented by formula (1B), improving adhesion.

[0031] In this disclosure, "polymer" means a compound with a weight-average molecular weight of 1000 or more.

[0032] It is preferable that the structural unit having the group represented by formula (1) is introduced into the polymer by polymerization using a polymerizable monomer having the group represented by formula (1). In other words, the specific polymer preferably contains structural units derived from a polymerizable monomer having a group represented by formula (1), more preferably contains structural units derived from a polymerizable monomer having a group represented by formula (1A), even more preferably contains structural units derived from a polymerizable monomer having a group represented by formula (1B), and particularly preferably contains structural units derived from a polymerizable monomer having a group represented by formula (1C).

[0033] In this disclosure, "polymerizable monomer" means a monomer having a polymerizable group. The polymerizable group is preferably a photopolymerizable group, and more preferably a photoradical polymerizable group.

[0034] From the viewpoint of reactivity, the polymerizable group is preferably a group containing an ethylenic double bond, more preferably a (meth)acryloyl group, vinylphenyl group, vinyl ether group, styryl group, or allyl group, even more preferably a (meth)acryloyl group (i.e., CH2=CH-C(=O)- or CH2=C(CH3)-C(=O)-), and particularly preferably a (meth)acryloyloxy group or a (meth)acryloylamino group.

[0035] Examples of polymerizable monomers having a group represented by formula (1) include the following polymerizable monomers.

[0036] [ka]

[0037] From the viewpoint of surface segregation, the content of structural units having the group represented by formula (1) is preferably 1% to 70% by mass, more preferably 5% to 60% by mass, and even more preferably 10% to 50% by mass, relative to the total amount of the specific polymer.

[0038] Furthermore, the specific polymer includes a structural unit having at least one selected from the group consisting of silyl groups and fluoro groups.

[0039] A structural unit having at least one selected from the group consisting of silyl groups and fluoro groups is preferably introduced into a polymer by polymerization using a polymerizable monomer having at least one selected from the group consisting of silyl groups and fluoro groups. In other words, it is preferable that the specific polymer contains structural units derived from polymerizable monomers having at least one selected from the group consisting of silyl groups and fluoro groups.

[0040] In a polymerizable monomer having at least one selected from the group consisting of a silyl group and a fluoro group, the polymerizable group is the same as the polymerizable group in a polymerizable monomer having a group represented by formula (1).

[0041] Examples of polymerizable monomers having a silyl group include -Si(OR 21 Examples include polymerizable monomers having a group represented by )3, and polymerizable monomers having an organosiloxane structure. 21 Each is independently an alkyl group or -Si(R 22 )3, R 22 Each of these is an alkyl group, independently of the others.

[0042] R 21 and R 22 The alkyl group represented by R may be a linear alkyl group, a branched alkyl group, or a cyclic alkyl group. 21 and R 22 The alkyl group represented by preferably has 1 to 6 carbon atoms, and more preferably a methyl group or an ethyl group.

[0043] -Si(OR 21 Polymerizable monomers having a group represented by )3 are -Si(OSi(R 22 It is preferable that the polymerizable monomer has a group represented by )3)3, and more preferably that the polymerizable monomer has a group represented by -Si(OSi(CH3)3.

[0044] The organosiloxane structure is, for example, -[Si(R 23 )2O] n -Si(R 23 ) is represented as 2-. 23 Each of these is an alkyl group, independently of the others. n is an integer greater than or equal to 1.

[0045] R 23 The alkyl group represented by R may be a linear alkyl group, a branched alkyl group, or a cyclic alkyl group. 23 The alkyl group represented by preferably has 1 to 6 carbon atoms, and more preferably a methyl group or an ethyl group.

[0046] n is preferably between 1 and 65, and more preferably between 1 and 10.

[0047] Examples of polymerizable monomers having a fluorogroup include polymerizable monomers having a fluoroalkyl group. The fluoroalkyl group preferably has 1 to 8 carbon atoms, and more preferably 2 to 6 carbon atoms.

[0048] Fluoroalkyl groups are used to enhance the surface segregation of polymers, such as *-(CF2) n R (where R represents a hydrogen atom or a fluorine atom, n represents 1 to 8 (preferably 2 to 6), and * represents a bonding site with other structures) is preferred, and a perfluoroalkyl group is more preferred.

[0049] Examples of polymerizable monomers having at least one selected from the group consisting of silyl groups and fluoro groups include the following compounds.

[0050] [ka]

[0051] From the viewpoint of surface segregation, the content of structural units having at least one selected from the group consisting of silyl groups and fluoro groups is preferably 30% to 99% by mass, more preferably 40% to 95% by mass, and even more preferably 50% to 90% by mass, relative to the total amount of the specific polymer. When the content of structural units having at least one selected from the group consisting of silyl groups and fluoro groups is within the above range, a good planar photosensitive resin layer can be obtained with less film thickness unevenness and less prone to defects such as bright spots.

[0052] The specific polymer may contain structural units having a group represented by formula (1), and structural units having at least one selected from the group consisting of silyl groups and fluoro groups. Other structures are not particularly limited, but it is preferable to have crosslinkable functional groups from the viewpoint of further improving adhesion.

[0053] Because the specific polymer has crosslinkable functional groups, it can crosslink with polymerizable compounds, thereby linking the photosensitive resin layer formed from the photosensitive resin composition with the substrate, and thus improving adhesion.

[0054] The number of crosslinkable functional groups may be one or two or more. Furthermore, if there are two or more crosslinkable functional groups, there may be only one type or two or more types.

[0055] Examples of crosslinkable functional groups include polymerizable groups, isocyanate groups, acid anhydride groups, and amino groups.

[0056] In particular, from the viewpoint of further improving adhesion, it is preferable that the crosslinkable functional group be a polymerizable group.

[0057] The polymerizable group may be a thermally polymerizable group or a photopolymerizable group. Examples of thermopolymerizable groups include epoxy groups and oxetane groups.

[0058] The polymerizable group is preferably a photopolymerizable group, and more preferably a photoradical polymerizable group.

[0059] From the viewpoint of reactivity, the photopolymerizable group is preferably a group containing an ethylenic double bond, more preferably a (meth)acryloyl group, vinylphenyl group, vinyl ether group, styryl group, or allyl group, even more preferably a (meth)acryloyl group (i.e., CH2=CH-C(=O)- or CH2=C(CH3)-C(=O)-), and particularly preferably a (meth)acryloyloxy group or a (meth)acryloylamino group.

[0060] The crosslinkable functional group has an ethylenically double bond, and it is preferable that the shortest linking chain connecting the ethylenically double bond to the polymer's main chain has 3 to 8 atoms.

[0061] The shortest linking chain has 3 to 8 atoms, which facilitates crosslinking with polymerizable compounds and improves adhesion.

[0062] The specific polymer preferably further contains structural units having crosslinkable functional groups.

[0063] Methods for introducing crosslinkable functional groups into a polymer include direct introduction during the polymerization process, or introduction by reacting with a low-molecular-weight compound after the polymerization process. For example, an intermediate polymer may be synthesized by first introducing structural units having a carboxylic acid such as (meth)acrylic acid into the polymer, and then methacrylic groups may be introduced into the polymer by reacting with glycidyl methacrylate.

[0064] From the viewpoint of adhesion, the content of structural units having crosslinkable functional groups is preferably 1% to 40% by mass, more preferably 3% to 30% by mass, and even more preferably 5% to 20% by mass, based on the total amount of the specific polymer.

[0065] The specific polymer may contain structural units other than those described above.

[0066] Other structural units can be appropriately selected from structural units derived from commonly known polymerizable monomers.

[0067] The weight-average molecular weight of the specific polymer is preferably 1,500 to 300,000, preferably 5,000 to 200,000, and most preferably 10,000 to 150,000. When the weight-average molecular weight is within the above range, it can efficiently exhibit adhesion and has excellent solubility in solvents.

[0068] The content of the specific polymer is preferably 0.01% to 3% by mass, more preferably 0.05% to 1% by mass, and even more preferably 0.1% to 0.5% by mass, relative to the solid content of the photosensitive resin composition. Certain polymers can provide adhesion benefits even in relatively small amounts.

[0069] <Alkali-soluble resin> The photosensitive resin composition of this disclosure comprises an alkali-soluble resin. 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. There are no particular restrictions on the alkali-soluble resin; for example, known alkali-soluble resins used in etching resists are preferred. Furthermore, the alkali-soluble resin is preferably a binder polymer. The alkali-soluble resin is preferably an alkali-soluble resin having an acidic group. Among these, polymer A, described later, is preferred as the alkali-soluble resin.

[0070] -polymerizationA- The alkali-soluble resin preferably contains polymer A. The acid value of polymer 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, in order to suppress swelling of the photosensitive resin layer by the developer and thereby improve resolution. The lower limit of the acid value of polymer A is not particularly limited, but it is preferably 60 mg KOH / g or higher, and more preferably 120 mg KOH / g or higher, from the standpoint of superior developability.

[0071] The acid value is the mass [mg] of potassium hydroxide required to neutralize 1 g of the sample, and in this specification, the unit is expressed as mgKOH / g. The acid value can be calculated, for example, from the average content of acid groups in the compound. The acid value of polymer A can be adjusted by the types of constituent units that make up polymer A and the content of constituent units that contain acid groups.

[0072] The weight-average molecular weight of polymer A is preferably 5,000 to 500,000. A weight-average molecular weight of 500,000 or less is preferable because it improves resolution and developability. A weight-average molecular weight of 100,000 or less is more preferable, and 60,000 or less is even more preferable. On the other hand, if the weight-average molecular weight is 5,000 or more, it is possible to control the properties of the developed aggregates, as well as the properties of the unexposed film, such as edge fusing and cut-tip properties, when used as a transfer film. The weight-average molecular weight is more preferably 10,000 or less, even more preferably 20,000 or more, and particularly preferably 30,000 or more.

[0073] Edge fusing refers to the degree to which the photosensitive resin layer tends to protrude from the edge of the roll when the transfer film is wound into a roll. Cut-tip properties refer to the degree to which chips tend to fly off when the unexposed film is cut with a cutter. If these chips adhere to the upper surface of the transfer film, they will be transferred to the mask in subsequent exposure processes, causing defective products. The dispersion degree of polymer 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. The dispersion degree is the ratio of the weight-average molecular weight to the number-average molecular weight (weight-average molecular weight / number-average molecular weight).

[0074] From the viewpoint of suppressing line width thickening and resolution deterioration when the focal position shifts during exposure, polymer A preferably contains structural units derived from polymerizable monomers having aromatic hydrocarbon groups. Examples of aromatic hydrocarbon groups include substituted or unsubstituted phenyl groups and substituted or unsubstituted aralkyl groups. The content of structural units derived from polymerizable monomers having aromatic hydrocarbon groups is preferably 10% to 95% by mass, and more preferably 20% to 80% by mass, relative to the total amount of polymer A.

[0075] Examples of polymerizable monomers having aromatic hydrocarbon groups include monomers having aralkyl groups, styrene, and styrene derivatives (e.g., methylstyrene, vinyltoluene, tert-butoxystyrene, acetoxystyrene, 4-vinylbenzoic acid, styrene dimer, styrene trimer, etc.).

[0076] Among these, polymerizable monomers having aromatic hydrocarbon groups are preferably polymerizable monomers having aralkyl groups or styrene. In one embodiment, when the polymerizable monomer having aromatic hydrocarbon groups in polymer A is styrene, the content of structural units derived from styrene is preferably 10% to 50% by mass, more preferably 15% to 45% by mass, and even more preferably 20% to 40% by mass, based on the total amount of polymer A.

[0077] Examples of aralkyl groups include substituted or unsubstituted phenylalkyl groups (excluding benzyl groups), substituted or unsubstituted benzyl groups, etc., with substituted or unsubstituted benzyl groups being preferred.

[0078] Examples of polymerizable monomers having a phenylalkyl group include phenylethyl (meth)acrylate.

[0079] Examples of polymerizable monomers having a benzyl group include (meth)acrylates having a benzyl group, such as benzyl (meth)acrylate and chlorobenzyl (meth)acrylate; and vinyl monomers having a benzyl group, such as vinylbenzyl chloride and vinylbenzyl alcohol. Among these, benzyl (meth)acrylate is preferred as the polymerizable monomer having an aralkyl group. In one embodiment, when the polymerizable monomer having an aromatic hydrocarbon group in polymer A is benzyl (meth)acrylate, the content of structural units derived from 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 amount of polymer A.

[0080] Polymer A, which contains a polymerizable monomer having an aromatic hydrocarbon group, is preferably obtained by polymerizing the polymerizable monomer having an aromatic hydrocarbon group with at least one selected from the group consisting of a first monomer and a second monomer, as described later.

[0081] Polymer A, which does not contain polymerizable monomers having aromatic hydrocarbon groups, is preferably obtained by polymerizing a first monomer, and more preferably by copolymerizing a first monomer with a second monomer.

[0082] The first monomer is a polymerizable monomer having a carboxyl group in its molecule. Examples of the first monomer include (meth)acrylic acid, fumaric acid, cinnamic acid, crotonic acid, itaconic acid, 4-vinylbenzoic acid, maleic anhydride, and maleic acid semiester. Among these, (meth)acrylic acid is preferred as the first monomer. The content of structural units derived from the first monomer is preferably 5% to 50% by mass, more preferably 10% to 40% by mass, and even more preferably 15% to 30% by mass, relative to the total amount of polymer A.

[0083] The second monomer is a non-acidic polymerizable monomer. Examples of the second monomer include (meth)acrylates such as methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, cyclohexyl (meth)acrylate, and 2-ethylhexyl (meth)acrylate; vinyl alcohol esters such as vinyl acetate; and (meth)acrylonitrile. Among these, the second monomer is preferably methyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, or n-butyl (meth)acrylate, with methyl (meth)acrylate being particularly preferred. The content of structural units derived from the second monomer is preferably 5% to 60% by mass, more preferably 15% to 50% by mass, and even more preferably 20% to 45% by mass, relative to the total amount of polymer A.

[0084] Polymer A is preferable from the viewpoint of suppressing line width thickening and deterioration of resolution when the focal position shifts during exposure, if it contains structural units derived from polymerizable monomers having aralkyl groups and / or structural units derived from styrene. For example, polymer A is preferably a copolymer containing structural units derived from methacrylic acid, structural units derived from methyl methacrylate and structural units derived from styrene; or a copolymer containing structural units derived from methacrylic acid and structural units derived from benzyl methacrylate.

[0085] In one embodiment, polymer A is preferably a polymer containing 25% to 40% by mass of structural units derived from a polymerizable monomer having an aromatic hydrocarbon group, 20% to 35% by mass of structural units derived from a first monomer, and 30% to 45% by mass of structural units derived from a second monomer. In another embodiment, polymer A is preferably a copolymer containing 70% to 90% by mass of structural units derived from a polymerizable monomer having an aromatic hydrocarbon group, and 10% to 25% by mass of structural units derived from a first monomer.

[0086] The polymer A contained in the photosensitive resin composition of this disclosure may be one type or two or more types. If there are two or more types, it is preferable to combine two types of polymer A containing structural units derived from polymerizable monomers having aromatic hydrocarbon groups, or to combine polymer A containing structural units derived from polymerizable monomers having aromatic hydrocarbon groups with polymer A not containing structural units derived from polymerizable monomers having aromatic hydrocarbon groups. In the latter case, the proportion of polymer A containing structural units derived from polymerizable 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 amount of polymer A.

[0087] Polymer A may have a branched or alicyclic structure in its side chains. Alternatively, Polymer A may have a linear structure in its side chains. For example, a branched or alicyclic structure can be introduced into the side chains of Polymer A by using a polymerizable monomer containing a group having a branched structure in its side chains, or a polymerizable monomer containing a group having an alicyclic structure in its side chains. The group having an alicyclic structure may be monocyclic or polycyclic.

[0088] Examples of polymerizable monomers containing a group with 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, polymerizable monomers containing a group having a branched structure in its side chain are preferably isopropyl (meth)acrylate, isobutyl (meth)acrylate, and tert-butyl methacrylate, and more preferably isopropyl methacrylate or tert-butyl methacrylate.

[0089] Specific examples of polymerizable 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. Polymerizable monomers containing a group with an alicyclic structure in its side chain include, for example, (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 Examples include 3-hydroxy-1-adamantyl acrylate, octahydro-4,7-menthanoinden-5-yl (meth)acrylate, octahydro-4,7-menthanoinden-1-ylmethyl (meth)acrylate, 1-menthyl (meth)acrylate, tricyclodecane (meth)acrylate, 3-hydroxy-2,6,6-trimethyl-bicyclo[3.1.1]heptyl (meth)acrylate, 3,7,7-trimethyl-4-hydroxy-bicyclo[4.1.0]heptyl (meth)acrylate, (nor)bornyl (meth)acrylate, isobornyl (meth)acrylate, fentyl (meth)acrylate, 2,2,5-trimethylcyclohexyl (meth)acrylate, and cyclohexyl (meth)acrylate.Among the above, 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, and tricyclodecane (meth)acrylate are preferred, and cyclohexyl (meth)acrylate, (nor)bornyl (meth)acrylate, isobornyl (meth)acrylate, 2-adamantyl (meth)acrylate, and tricyclodecane (meth)acrylate are more preferred.

[0090] The synthesis of polymer A is preferably carried out by diluting one or more monomers described above with a solvent such as acetone, methyl ethyl ketone, or isopropanol, adding an appropriate amount of a radical polymerization initiator such as benzoyl peroxide or azoisobutyronitrile to the solution, and then heating and stirring. In some cases, the synthesis may be carried out by adding a portion of the mixture dropwise to the reaction solution. After the reaction is complete, the solvent may be further added to adjust the concentration to the desired level. In addition to solution polymerization, bulk polymerization, suspension polymerization, or emulsion polymerization may also be used as synthesis methods.

[0091] The glass transition temperature (Tg) of polymer A is preferably 30°C or higher and 135°C or lower. By using polymer A having a Tg of 135°C or lower in a photosensitive resin composition, line width thickening and deterioration of resolution when the focal position shifts during exposure can be suppressed. From this viewpoint, the Tg of polymer A is more preferably 130°C or lower, even more preferably 120°C or lower, and particularly preferably 110°C or lower. Furthermore, using polymer 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 polymer 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.

[0092] The photosensitive resin composition may contain resins other than alkali-soluble resins. Examples of resins other than alkali-soluble resins include acrylic resins, styrene-acrylic copolymers (provided that the styrene content is 40% by mass or less), 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.

[0093] The alkali-soluble resin contained in the photosensitive resin composition of this disclosure may be one type or two or more types.

[0094] The alkali-soluble resin content is preferably in the range of 10% to 90% by mass, more preferably 30% to 70% by mass, and even more preferably 40% to 60% by mass, relative to the solid content of the photosensitive resin composition. A ratio of 90% by mass or less of alkali-soluble resin to the photosensitive resin composition is preferable from the viewpoint of controlling the development time. On the other hand, a ratio of 10% by mass or more of alkali-soluble resin to the photosensitive resin composition is preferable from the viewpoint of improving edge fusing resistance.

[0095] <Polymerizable compound> The photosensitive resin composition of this disclosure contains a polymerizable compound. In this disclosure, "polymerizable compound" means a compound having a polymerizable group. The specific polymer may have polymerizable groups, but the photosensitive resin composition of this disclosure includes polymerizable compounds in addition to the specific polymer.

[0096] Furthermore, the alkali-soluble resin may have polymerizable groups, but the photosensitive resin composition of this disclosure contains a polymerizable compound in addition to the alkali-soluble resin.

[0097] The preferred embodiments of the polymerizable groups in a polymerizable compound are the same as the preferred embodiments of the polymerizable groups that a particular polymer may have.

[0098] As polymerizable compounds, compounds having one or more ethylenically unsaturated groups (i.e., ethylenically unsaturated compounds) are preferred in that they provide superior photosensitivity of the photosensitive resin layer, and compounds having two or more ethylenically unsaturated groups in one molecule (i.e., polyfunctional ethylenically unsaturated compounds) are more preferred.

[0099] Furthermore, in terms of superior resolution and exfoliation properties, the number of ethylenically unsaturated groups in one molecule of an ethylenically unsaturated compound is preferably 6 or less, more preferably 3 or less, and even more preferably 2 or less.

[0100] The photosensitive resin composition preferably contains a difunctional ethylenically unsaturated compound having two ethylenically unsaturated groups in one molecule, or a trifunctional ethylenically unsaturated compound having three ethylenically unsaturated groups, and more preferably contains a difunctional ethylenically unsaturated compound, in that it provides a better balance between the photosensitivity, resolution, and peelability of the photosensitive resin layer.

[0101] The content of the difunctional ethylenically unsaturated compound is preferably 60% by mass or more, more preferably over 70% by mass, and even more preferably 90% by mass or more, based on the total amount of polymerizable compounds, from the viewpoint of excellent release properties. The upper limit of the content of the difunctional ethylenically unsaturated compound is not particularly limited and may be 100% by mass. In other words, all polymerizable compounds contained in the photosensitive resin composition may be difunctional ethylenically unsaturated compounds.

[0102] Furthermore, (meth)acrylate compounds are preferred as the ethylenically unsaturated compound.

[0103] -Polymerizable compound B1- The photosensitive resin composition preferably contains polymerizable compound B1 having at least one aromatic ring and two ethylenically unsaturated groups in one molecule.

[0104] The content of polymerizable compound B1 is preferably 40% by mass or more, more preferably 50% by mass or more, even more preferably 55% by mass or more, and particularly preferably 60% by mass or more, based on the total amount of polymerizable compound, from the viewpoint of superior resolution. There is no particular upper limit on the content of polymerizable compound B1. From the viewpoint of peelability, the content of polymerizable compound B1 is preferably 99% by mass or less, more preferably 95% by mass or less, even more preferably 90% by mass or less, and particularly preferably 85% by mass or less, based on the total amount of polymerizable compound.

[0105] 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. The aromatic ring in polymerizable compound B1 is preferably an aromatic hydrocarbon ring, and more preferably a benzene ring. The aromatic ring may have substituents.

[0106] From the viewpoint of suppressing swelling of the photosensitive resin layer by the developer and improving resolution, polymerizable compound B1 preferably has a bisphenol skeleton.

[0107] Examples of bisphenol skeletons include the bisphenol A skeleton derived from bisphenol A (2,2-bis(4-hydroxyphenyl)propane), the bisphenol F skeleton derived from bisphenol F (2,2-bis(4-hydroxyphenyl)methane), and the bisphenol B skeleton derived from bisphenol B (2,2-bis(4-hydroxyphenyl)butane). Among these, the bisphenol A skeleton is preferred.

[0108] Examples of polymerizable compounds B1 having a bisphenol skeleton include compounds having a bisphenol skeleton and two polymerizable groups (preferably (meth)acryloyl groups) bonded to both ends of the bisphenol skeleton.

[0109] The bisphenol skeleton and the polymerizable group may be directly bonded, or they may be bonded via one or more alkylene oxy groups. The alkylene oxy group bonded to the bisphenol skeleton is preferably an ethylene oxy group or a propylene oxy group, and more preferably an ethylene oxy group. The number of alkylene oxy groups added to the bisphenol skeleton is not particularly limited. The number of added alkylene oxy groups is preferably 4 to 16 per molecule, and more preferably 6 to 14.

[0110] Polymerizable compound B1 having a bisphenol skeleton is described in paragraphs 0072 to 0080 of Japanese Patent Publication No. 2016-224162, and the contents described in this publication are incorporated herein by reference.

[0111] Polymerizable compound B1 is preferably a bifunctional ethylenically unsaturated compound having a bisphenol A skeleton, and more preferably 2,2-bis(4-((meth)acryloxypolyalkoxy)phenyl)propane.

[0112] Examples of 2,2-bis(4-((meth)acryloxypolyalkoxy)phenyl)propane include 2,2-bis(4-(methacryloxydiethoxy)phenyl)propane (FA-324M, manufactured by Hitachi Chemical Co., Ltd.), 2,2-bis(4-(methacryloxyethoxypropoxy)phenyl)propane, 2,2-bis(4-(methacryloxypentaethoxy)phenyl)propane (BPE-500, manufactured by Shin Nakamura Chemical Co., Ltd.), and 2,2-bis(4-(methacryloxydodecaethoxytetrapropoxy)phenyl)propane (FA-3 Examples include 200MY (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.), 2,2-bis(4-(methacryloxyethoxy)phenyl)propane (BPE-100, manufactured by Shin Nakamura Chemical Industry Co., Ltd.), and ethoxylated (10)bisphenol A diacrylate (NK ester A-BPE-10, manufactured by Shin Nakamura Chemical Industry Co., Ltd.).

[0113] Examples of polymerizable compound B1 include compounds represented by the following formula (P1). From the viewpoint of transferability and resolution, polymerizable compounds are preferably those that include a compound represented by the following formula (P1).

[0114] [ka]

[0115] In formula (P1), R 21 and R 22 Each of the following independently represents either a hydrogen atom or a methyl group: A independently represents -C2H4-, B independently represents -C3H6-, n1 and n3 independently represent integers from 1 to 39, and n1+n3 is an integer from 2 to 40, and n2 and n4 independently represent integers from 0 to 29, and n2+n4 is an integer from 0 to 30. The sequence of the repeating units -(AO)- and -(BO)- may be random or blocky. If the sequence is blocky, either -(AO)- or -(BO)- may be on the bisphenyl group side.

[0116] n1+n2+n3+n4 is preferably between 2 and 20, more preferably between 2 and 16, and even more preferably between 2 and 8.

[0117] Furthermore, n2+n4 is preferably between 0 and 10, more preferably between 0 and 4, even more preferably between 0 and 2, and particularly preferably 0.

[0118] The polymerizable compound B1 contained in the photosensitive resin composition may be one type or two or more types.

[0119] The content of polymerizable compound B1 is preferably 10% by mass or more, and more preferably 20% by mass or more, relative to the solid content of the photosensitive resin composition, from the viewpoint of superior resolution. There is no particular upper limit to the content of polymerizable compound B1. From the viewpoint of improving transferability and edge fusing resistance, the content of polymerizable compound B1 is preferably 70% by mass or less, and more preferably 60% by mass or less.

[0120] The photosensitive resin composition may contain polymerizable compounds other than polymerizable compound B1. Polymerizable compounds other than polymerizable compound B1 are not particularly limited and can be appropriately selected from known compounds. For example, polymerizable compounds other than polymerizable compound B1 include compounds having one ethylenically unsaturated group in one molecule (i.e., monofunctional ethylenically unsaturated compounds), difunctional ethylenically unsaturated compounds without aromatic rings, and trifunctional or more ethylenically unsaturated compounds.

[0121] 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.

[0122] 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.

[0123] Examples of alkylene glycol di(meth)acrylates include tricyclodecanedimethanol diacrylate (A-DCP, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), tricyclodecanedimethanol dimethacrylate (DCP, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), 1,9-nonanediol diacrylate (A-NOD-N, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), 1,6-hexanediol diacrylate (A-HD-N, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), ethylene glycol dimethacrylate, 1,10-decanediol diacrylate, and neopentyl glycol di(meth)acrylate.

[0124] 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.

[0125] 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. A commercially available example is 8UX-0. Examples include 15A (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.).

[0126] 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, and trimethylolethane tri(meth)acrylate. Examples include acrylates, isocyanuric acid tri(meth)acrylate, glycerin tri(meth)acrylate, and alkylene oxide modified products thereof.

[0127] 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.

[0128] Examples of alkylene oxide modified products of ethylenically unsaturated compounds with three or more functions include caprolactone-modified (meth)acrylate compounds (KAYARAD® DPCA-20, manufactured by Nippon Kayaku Co., Ltd.; A-9300-1CL, manufactured by Shin Nakamura Chemical Industry Co., Ltd.), alkylene oxide-modified (meth)acrylate compounds (KAYARAD RP-1040, manufactured by Nippon Kayaku Co., Ltd.; ATM-35E and A-9300, manufactured by Shin Nakamura Chemical Industry Co., Ltd.; EBECRYL® 135, manufactured by Daicel Ornex Co., Ltd.), ethoxylated glycerin triacrylate (A-GLY-9E, manufactured by Shin Nakamura Chemical Industry Co., Ltd.), 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.).

[0129] Furthermore, polymerizable compounds other than polymerizable compound B1 may be polymerizable compounds having an acid group as described in paragraphs 0025 to 0030 of Japanese Patent Application Publication No. 2004-239942.

[0130] The polymerizable compound contained in the photosensitive resin composition may be one type or two or more types.

[0131] The polymerizable compound content is preferably 10% to 70% by mass, more preferably 20% to 60% by mass, and even more preferably 20% to 50% by mass, relative to the solid content of the photosensitive resin composition.

[0132] The weight-average molecular weight (Mw) of the polymerizable compound containing polymerizable compound B1 is preferably 200 to 3,000, more preferably 280 to 2,200, and even more preferably 300 to 2,200.

[0133] <Photopolymerization initiator> The photosensitive resin composition of this disclosure contains a photopolymerization initiator.

[0134] A photopolymerization initiator is a compound that initiates the polymerization of a polymerizable compound when exposed to active light such as ultraviolet light, visible light, or X-rays. The photopolymerization initiator is not particularly limited, and known photopolymerization initiators can be used.

[0135] Examples of photopolymerization initiators include photoradical polymerization initiators and photocationic polymerization initiators. Among these, photoradical polymerization initiators are preferred.

[0136] Examples of photoradical polymerization initiators include photopolymerization initiators having an oxime ester skeleton, photopolymerization initiators having an α-aminoalkylphenone skeleton, photopolymerization initiators having an α-hydroxyalkylphenone skeleton, photopolymerization initiators having an acylphosphine oxide skeleton, and photopolymerization initiators having an N-phenylglycine skeleton.

[0137] Furthermore, from the viewpoint of photosensitivity, visibility of exposed and unexposed areas, and resolution, the photosensitive resin 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. The two 2,4,5-triarylimidazole skeletons 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.

[0138] The photoradical polymerization initiator may be the polymerization initiator described in paragraphs 0031 to 0042 of Japanese Patent Publication No. 2011-95716 and paragraphs 0064 to 0081 of Japanese Patent Publication No. 2015-14783.

[0139] Examples of photoradical polymerization initiators include ethyl dimethylaminobenzoate (DBE, CAS No. 10287-53-3), benzoin methyl ether, anisyl (p,p'-dimethoxybenzyl), and benzophenone.

[0140] Examples of commercially available photoradical polymerization initiators include 2,4-bis(trichloromethyl)-6-[2-(4-methylphenyl)ethenyl]-1,3,5-triazine (product name: TAZ-110, manufactured by Midori Chemical Co., Ltd.), (product name: TAZ-111, manufactured by Midori Chemical Co., Ltd.), 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole (manufactured by Tokyo Chemical Industry Co., Ltd.), 1-[4-(phenylthio)phenyl]-1,2-octanedione-2-(O-benzoyl oxime) (product name: Irgacure® OXE-01, manufactured by BASF Japan), and 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]ethanone-1-(O-acetyl oxime) (product name: Irgacure OXE-02 (manufactured by BASF Japan), Irgacure OXE-03 (manufactured by BASF Japan), OXE-04 (manufactured by BASF Japan), 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone (product name: Omnirad 379EG, manufactured by IGM Resins BV), 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one (product name: Omnirad 907, manufactured by IGM Resins BV), 2-hydroxy-1-{4-[4-(2-hydroxy-2-methylpropionyl)benzyl]phenyl}-2-methylpropan-1-one (product name: Omnirad 127, manufactured by IGM Resins (Manufactured by IGM Resins BV), 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butanone-1 (Trade name: Omnirad 369, manufactured by IGM Resins BV), 2-hydroxy-2-methyl-1-phenylpropan-1-one (Trade name: Omnirad 1173, manufactured by IGM Resins BV), 1-hydroxycyclohexylphenyl ketone (Trade name: Omnirad 184, manufactured by IGM Resins BV), 2,2-dimethoxy-1,2-diphenylethane-1-one (Trade name: Omnirad 651, manufactured by IGM Resins BV), 2,4,6-trimethylbenzoyl-diphenylphosphine oxide (Trade name: Omnirad TPO H, manufactured by IGM Resins BV)Examples include bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide (trade name: Omnirad 819, manufactured by IGM Resins BV), oxime ester-based photopolymerization initiators (trade name: Lunar 6, manufactured by DKSH Japan Co., Ltd.), 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbisimidazole (2-(2-chlorophenyl)-4,5-diphenylimidazole dimer) (trade name: B-CIM, manufactured by Hampford), and 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer (trade name: BCTB, manufactured by Tokyo Chemical Industry Co., Ltd.).

[0141] A photocationic polymerization initiator (photoacid generator) is a compound that generates acid upon receiving active light. While the photocationic polymerization initiator is not particularly limited, it is preferable that it is a compound that reacts to active light with a wavelength of 300 nm or higher, preferably 300 nm to 450 nm, and generates acid. Furthermore, even compounds that do not directly react to active light with a wavelength of 300 nm or higher can be preferably used in combination with a sensitizer if they react to such light and generate acid when used in combination with a sensitizer.

[0142] The photocationic polymerization initiator is preferably one that generates an acid with a pKa of 4 or less, more preferably one that generates an acid with a pKa of 3 or less, and particularly preferably one that generates an acid with a pKa of 2 or less. The lower limit of the pKa is not particularly limited, for example, -10.0 is preferred.

[0143] Examples of photocationic polymerization initiators include ionic photocationic polymerization initiators and nonionic photocationic polymerization initiators.

[0144] Examples of ionic photocationic polymerization initiators include onium salt compounds such as diaryliodonium salts and triarylsulfonium salts, and quaternary ammonium salts.

[0145] The ionic photocationic polymerization initiator may be the ionic photocationic polymerization initiator described in paragraphs 0114 to 0133 of Japanese Patent Application Publication No. 2014-85643.

[0146] Examples of nonionic photocationic polymerization initiators include trichloromethyl-s-triazine compounds, diazomethane compounds, imidosulfonate compounds, and oximesulfonate compounds. The trichloromethyl-s-triazine compounds, diazomethane compounds, and imidosulfonate compounds may be those described in paragraphs 0083 to 0088 of Japanese Patent Publication No. 2011-221494. The oximesulfonate compounds may be those described in paragraphs 0084 to 0088 of International Publication No. 2018 / 179640.

[0147] The photopolymerization initiator contained in the photosensitive resin composition may be one type or two or more types.

[0148] The content of the photopolymerization initiator is not particularly limited, but is preferably 0.5% by mass or more, more preferably 1% by mass or more, and even more preferably 3% by mass or more, relative to the solid content of the photosensitive resin composition. The upper limit of the photopolymerization initiator content is not particularly limited. The content of the photopolymerization initiator is preferably 10% by mass or less, and more preferably 8% by mass or less, relative to the solid content of the photosensitive resin composition.

[0149] <Sensitizer> The photosensitive resin composition of this disclosure may contain a sensitizer.

[0150] The sensitizer is not particularly limited, and known sensitizers, dyes, and pigments can be used. Examples of sensitizers include dialkylaminobenzophenone compounds, pyrazoline compounds, anthracene compounds, coumarin compounds, xanthone compounds, thioxanthone compounds, acridone compounds, oxazole compounds, benzoxazole compounds, thiazole compounds, benzothiazole compounds, triazole compounds (e.g., 1,2,4-triazole), stilbene compounds, triazine compounds, thiophene compounds, naphthalimide compounds, triarylamine compounds, and aminoacridine compounds.

[0151] The photosensitive resin composition may contain only one type of sensitizer, or two or more types.

[0152] When a photosensitive resin composition contains a sensitizer, the amount of sensitizer can be appropriately selected depending on the purpose. From the viewpoint of improving sensitivity to light sources and improving curing speed by balancing polymerization rate and chain transfer, the amount of sensitizer is preferably 0.01% to 5% by mass, and more preferably 0.05% to 1% by mass, relative to the solid content of the photosensitive resin composition.

[0153] <Polymerization inhibitors> The photosensitive resin composition of this disclosure may contain a polymerization inhibitor.

[0154] Examples of polymerization inhibitors include the thermal polymerization inhibitor described in paragraph 0018 of Japanese Patent No. 4502784. Other examples of polymerization inhibitors include phenothiazine, phenoxazine, 4-methoxyphenol, naphthylamine, cuprous chloride, nitrosophenylhydroxyamine aluminum salt, and diphenylnitrosamine. Among these, the radical polymerization inhibitor is preferably phenothiazine, phenoxazine, 4-methoxyphenol, or nitrosophenylhydroxyamine aluminum salt.

[0155] If the photosensitive resin composition contains a polymerization inhibitor, the amount of polymerization inhibitor is preferably 0.01% to 5% by mass, and more preferably 0.05% to 1% by mass, relative to the solid content of the photosensitive resin composition, from the viewpoint of storage stability of the photosensitive resin composition.

[0156] <Antioxidant> The photosensitive resin composition of this disclosure may contain an antioxidant.

[0157] Examples of antioxidants include 3-pyrazolidones such as 1-phenyl-3-pyrazolidone (also known as phenidone), 1-phenyl-4,4-dimethyl-3-pyrazolidone, and 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone; polyhydroxybenzenes such as hydroquinone, catechol, pyrogallol, methylhydroquinone, and chlorhydroquinone; and paramethylaminophenol, paraaminophenol, parahydroxyphenylglycine, and paraphenylenediamine. In particular, 3-pyrazolidones are preferred as antioxidants, and 1-phenyl-3-pyrazolidone is more preferred, as they exhibit superior effects in this disclosure.

[0158] When the photosensitive resin composition contains an antioxidant, the antioxidant content is preferably 0.001% by mass or more, more preferably 0.005% by mass or more, and even more preferably 0.01% by mass or more, relative to the solid content of the photosensitive resin composition. There is no particular upper limit to the antioxidant content, but 1% by mass or less is preferred.

[0159] <Chain movement agent> The photosensitive resin composition of this disclosure may contain a chain transfer agent.

[0160] Examples of chain transfer agents include N-phenylcarbamoylmethyl-N-carboxymethylaniline and N,N-tetraethyl-4,4-diaminobenzophenone.

[0161] When the photosensitive resin composition contains a chain transfer agent, the antioxidant content is preferably 0.01% to 5% by mass, and more preferably 0.05% to 1% by mass, relative to the solid content of the photosensitive resin composition.

[0162] <Dye> The photosensitive resin composition of this disclosure may contain a dye. The photosensitive resin composition of this disclosure preferably contains a dye (hereinafter also simply referred to as "dye N") whose maximum absorption wavelength in the wavelength range of 400 nm to 780 nm during color development is 450 nm or more, and whose maximum absorption wavelength changes with the presence of an acid, base, or radical, from the viewpoint of visibility of the exposed and unexposed areas, pattern visibility after development, and resolution. When dye N is included, although the detailed mechanism is unknown, adhesion to adjacent layers (e.g., temporary support and intermediate layer) is improved and resolution is further enhanced.

[0163] 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 becomes decolorized due to an acid, base, or radical; a dye in a decolorized state becomes colored due to an acid, base, or radical; or a dye in a colored state changes to a colored state of another hue.

[0164] Specifically, the dye 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 of acids, bases, or radicals within the photosensitive resin layer upon exposure, or the dye may change its colored or decolorized state due to a change in the state (e.g., pH) within the photosensitive resin layer caused by acids, bases, or radicals. Furthermore, dye N may be a dye that does not undergo exposure but changes its colored or decolorized state upon direct stimulation by acids, bases, or radicals.

[0165] In particular, from the viewpoint of visibility of exposed and unexposed areas, as well as resolution, the dye is preferably one whose maximum absorption wavelength changes with acid or radicals, and more preferably one whose maximum absorption wavelength changes with radicals.

[0166] From the viewpoint of visibility of the exposed and unexposed areas, as well as resolution, the photosensitive resin composition preferably contains both a dye N whose maximum absorption wavelength changes due to radicals, and a photoradical polymerization initiator.

[0167] Furthermore, from the viewpoint of visibility between the exposed and unexposed areas, the dye is preferably a dye that develops color in response to an acid, base, or radical.

[0168] An example of a dye color development mechanism is a method in which a photoradical polymerization initiator, a photocationic polymerization initiator (photoacid generator), or a photobase generator is added to a photosensitive resin composition, and after exposure, the radicals, acids, or bases generated from the photoradical polymerization initiator, photocationic polymerization initiator, or photobase generator cause color development.

[0169] From the viewpoint of visibility of the exposed and unexposed areas, the maximum absorption wavelength of the dye in the wavelength range of 400 nm to 780 nm during color development is preferably 550 nm or higher, more preferably 550 nm to 700 nm, and even more preferably 550 nm to 650 nm.

[0170] Furthermore, a dye may have only one maximum absorption wavelength in the wavelength range of 400 nm to 780 nm during color development, or it may have two or more. If dye N has two or more maximum absorption wavelengths in the wavelength range of 400 nm to 780 nm during color development, the maximum absorption wavelength with the highest absorbance among the two or more maximum absorption wavelengths should be 450 nm or higher.

[0171] The maximum absorption wavelength of a dye is obtained by measuring the transmission spectrum of a solution containing the dye (at a temperature of 25°C) in the range of 400 nm 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 (i.e., the maximum absorption wavelength).

[0172] Examples of dyes that develop or decolorize upon exposure include leuco compounds. Examples of dyes that decolorize upon exposure include leuco compounds, diarylmethane dyes, oxazine dyes, xanthene dyes, iminonaphthoquinone dyes, azomethine dyes, and anthraquinone dyes. Among these, leuco compounds are preferred as the dye from the viewpoint of visibility between the exposed and unexposed areas.

[0173] 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).

[0174] In particular, the leuco compound is preferably a triarylmethane-based dye or a fluorane-based dye, and more preferably a leuco compound (triphenylmethane-based dye) or fluorane-based dye having a triphenylmethane skeleton.

[0175] From the viewpoint of visibility between the exposed and unexposed areas, the leuco compound preferably has a lactone ring, a sultine ring, or a sultone ring. The lactone ring, sultine ring, or sultone ring of the leuco compound reacts with radicals generated from a photoradical polymerization initiator or acids generated from a photocationic polymerization initiator to change from a closed ring state to an open ring state and develop color, or to change from an open ring state to a closed ring state and decolorize. The leuco compound preferably has a lactone ring, a sultine ring, or a sultone ring and develops color upon ring opening by a radical or acid, and more preferably has a lactone ring and develops color upon ring opening by a radical or acid.

[0176] Examples of pigments include the following dyes and leuco compounds. The dyes 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, Congo Red, Benzopulpurine 4B, α-Naphthyl Red, Nile Blue 2B, Nile Blue A, Methyl Violet, Malachite Green, Parafuchsine, Victoria Pure Blue - Naphthalene Sulfonate, Victoria Pure Blue BOH (manufactured by Hodogaya Chemical Co., Ltd.), Oil Blue #603 (manufactured by Orient Chemical Co., Ltd.), Oil Pink #312 (manufactured by Orient Chemical Co., Ltd.), Oil Red 5B (manufactured by Orient Chemical Co., Ltd.), Oil Scarlet #308 (manufactured by Orient Chemical Co., Ltd.) Examples include: Oil Red OG (manufactured by Orient Chemical Industry Co., Ltd.), Oil Red RR (manufactured by Orient Chemical Industry Co., Ltd.), Oil Green #502 (manufactured by Orient Chemical Industry Co., Ltd.), Spiron Red BEH Special (manufactured by Hodogaya Chemical Industry Co., Ltd.), m-Cresol Purple, Cresol Red, Rhodamine B, Rhodamine 6G, Sulforhodamine B, Auramine, 4-p-diethylaminophenyliminonaphthoquinone, 2-carboxyanilino-4-p-diethylaminophenyliminonaphthoquinone, 2-carboxystearylamino-4-pN,N-bis(hydroxyethyl)aminophenyliminonaphthoquinone, 1-phenyl-3-methyl-4-p-diethylaminophenylimino-5-pyrazolone, and 1-β-naphthyl-4-p-diethylaminophenylimino-5-pyrazolone.

[0177] Examples of leuco compounds 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, and 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-diethylamino) (Tylamino)-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-methylindole-3-yl)phthalide Examples include cylindole-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.

[0178] From the viewpoint of visibility of exposed and unexposed areas, pattern visibility after development, and resolution, the dye is preferably a dye whose maximum absorption wavelength changes due to radicals, and more preferably a dye that develops color due to radicals.

[0179] The dye is preferably Leucocrystal violet, crystal violet lactone, brilliant green, or Victoria pure blue naphthalene sulfonate.

[0180] From the viewpoint of visibility of exposed and unexposed areas, pattern visibility after development, and resolution, the dye content 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, relative to the solid content of the photosensitive resin composition.

[0181] <Surfactants> The photosensitive resin composition of this disclosure may contain a surfactant from the viewpoint of uniform thickness.

[0182] In the photosensitive resin composition of this disclosure, a surfactant is not required because a specific polymer has surfactant properties.

[0183] <Solvent> The photosensitive resin composition of this disclosure preferably contains a solvent. When the photosensitive resin composition of this disclosure contains a solvent, the formation of a photosensitive resin layer by coating tends to become easier.

[0184] Examples of solvents include alkylene glycol ethers, alkylene glycol ether acetates, alcohols (e.g., methanol and ethanol), ketones (e.g., acetone and methyl ethyl ketone), aromatic hydrocarbons (e.g., toluene), aprotic polar solvents (e.g., N,N-dimethylformamide), cyclic ethers (e.g., tetrahydrofuran), esters, amides, lactones, and mixed solvents containing two or more of these.

[0185] When preparing a transfer film comprising a temporary support, a thermoplastic resin layer, an intermediate layer, and a photosensitive resin layer, the photosensitive resin composition preferably contains at least one selected from the group consisting of alkylene glycol ethers and alkylene glycol ether acetates. In particular, the solvent is more preferably a mixed solvent containing at least one selected from the group consisting of alkylene glycol ethers and alkylene glycol ether acetate solvents, and at least one selected from the group consisting of ketones and cyclic ethers, and even more preferably a mixed solvent containing at least one selected from the group consisting of alkylene glycol ethers and alkylene glycol ether acetates, a ketone, and a cyclic ether.

[0186] Examples of alkylene glycol ethers include ethylene glycol monoalkyl ether, ethylene glycol dialkyl ether, propylene glycol monoalkyl ether, propylene glycol dialkyl ether, diethylene glycol dialkyl ether, dipropylene glycol monoalkyl ether, and dipropylene glycol dialkyl ether.

[0187] Examples of alkylene glycol ether acetates include ethylene glycol monoalkyl ether acetate, propylene glycol monoalkyl ether acetate, diethylene glycol monoalkyl ether acetate, and dipropylene glycol monoalkyl ether acetate.

[0188] The solvent may be one of the solvents described in paragraphs 0092-0094 of International Publication No. 2018 / 179640 and one of the solvents described in paragraph 0014 of Japanese Patent Application Publication No. 2018-177889, the contents of which are incorporated herein by reference.

[0189] The photosensitive resin composition may contain only one solvent or two or more solvents. 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 solids in the photosensitive resin composition.

[0190] <Other ingredients> The photosensitive resin composition of this disclosure may further contain known additives such as metal oxide particles, dispersants, acid builders, development accelerators, conductive fibers, thermoacid generators, ultraviolet absorbers, thickeners, crosslinking agents, and organic or inorganic precipitation inhibitors.

[0191] The method for preparing the photosensitive resin composition is not particularly limited. For example, one method involves preparing a solution in which each component is dissolved in the solvent, and then mixing the resulting solutions in a predetermined ratio.

[0192] [Transfer film] The transfer film of this disclosure includes a temporary support and a photosensitive resin layer disposed on the temporary support and formed from the photosensitive resin composition. The photosensitive resin layer formed from the photosensitive resin composition may be a photosensitive resin layer containing solid components of the photosensitive resin composition.

[0193] The following describes a specific embodiment of the transfer film.

[0194] The transfer film 20 shown in Figure 1 comprises, in this order, a temporary support 11, a transfer layer 12 including a thermoplastic resin layer 13, an intermediate layer 15, and a photosensitive resin layer 17, and a protective film 19.

[0195] Although the transfer film 20 shown in Figure 1 has a protective film 19 placed on it, the protective film 19 does not necessarily have to be placed on it.

[0196] Furthermore, although the transfer film 20 shown in Figure 1 has a thermoplastic resin layer 13 and an intermediate layer 15 arranged therein, the thermoplastic resin layer 13 or the intermediate layer 15, or the thermoplastic resin layer 13 and the intermediate layer 15, may not be arranged.

[0197] Hereinafter, each element constituting the transfer film will be described.

[0198] <Temporary support> The temporary support supports the photosensitive resin layer and is a peelable support.

[0199] The temporary support may be a single layer or a laminate in which two or more layers are laminated. Examples of the temporary support include those consisting only of a base material; a laminate including a base material and a particle-containing layer disposed on one surface of the base material; and a laminate including a base material and particle-containing layers disposed on both surfaces of the base material.

[0200] Examples of the base material constituting the temporary support include glass, resin film, and paper. From the viewpoints of strength, flexibility, and light transmittance, the base material constituting the temporary support is preferably a resin film.

[0201] Examples of the resin film include polyethylene terephthalate (PET) film, cellulose triacetate film, polystyrene film, and polycarbonate film. Among them, the resin film is preferably a PET film, and more preferably a biaxially stretched PET film.

[0202] When the particle-containing layer is disposed on one surface or both surfaces of the base material, the particle-containing layer may be a single layer or two or more layers.

[0203] The particle-containing layer is formed, for example, by applying a composition for the particle-containing layer onto a substrate and drying it. Also, the particle-containing layer can be disposed by a coextrusion method when forming a resin film. The composition for the particle-containing layer preferably contains a binder polymer and particles. The type of the binder polymer is not particularly limited and can be appropriately selected according to the purpose. Examples of the binder polymer include acrylic resin, urethane resin, olefin resin, styrene-butadiene resin, ester resin, vinyl chloride resin, and vinylidene chloride resin. When the particle-containing layer is disposed by the coextrusion method, it is preferable to use PET as the binder polymer.

[0204] The particle-containing layer may contain each of the binder polymer and the particles alone or may contain two or more of them.

[0205] The particles contained in the particle-containing layer are not particularly limited and can be appropriately selected according to the purpose. The content of the particles in the particle-containing layer can be appropriately adjusted depending on the amount of particles added to the composition for the particle-containing layer. In this specification, the particles contained in the particle-containing layer are referred to as "added particles".

[0206] The added particles are distinguished from impurities that are unexpectedly mixed during the manufacturing process of the temporary support and particles formed during the manufacturing process of the temporary support. The added particles are preferably particles having the property of not melting at 200°C.

[0207] In the temporary support, whether it is an added particle or not can be determined, for example, by the following method. Since the added particles usually have uniformity in shape and distribution, they can be determined by observing with an optical microscope.

[0208] Examples of the added particles include inorganic particles and organic particles.

[0209] Examples of inorganic particles include inorganic oxide particles such as silicon dioxide (silica), titanium dioxide (titania), zirconium oxide (zirconia), magnesium oxide (magnesia), and aluminum oxide (alumina).

[0210] Examples of organic particles include acrylic resin, polyester, polyurethane, and polycarbonate. Examples include polymer particles such as nitrates, polyolefins, and polystyrene.

[0211] If the temporary support has a particle-containing layer, it is preferable that the added particles contained in the particle-containing layer are inorganic oxide particles.

[0212] The average particle size of the added particles is not particularly limited, but is, for example, 0.1 μm to 10 μm. The average particle size is measured using a TEM (transmission electron microscope) after cutting a 100 nm thick section with an ultramicrotome.

[0213] The thickness of the temporary support is preferably 25 μm or more, more preferably 50 μm or more, and even more preferably 75 μm or more, from the viewpoint of suppressing deformation of the circuit board to be bonded with the transfer film. The upper limit of the thickness is not particularly limited, for example, 200 μm.

[0214] The temporary support may be made from recycled materials. Examples of recycled materials include used film, which has been washed, chipped, and then used as raw material to make film. A specific example of recycled materials is Toray's Ecouse series.

[0215] <Photosensitive resin layer> The photosensitive resin layer is formed from the photosensitive resin composition of this disclosure. The photosensitive resin layer preferably contains the solid content of the photosensitive resin composition of this disclosure. If the photosensitive resin composition contains a solvent, the photosensitive resin layer in the transfer film contains at least components other than the solvent of the photosensitive resin composition (i.e., solids). In this case, the photosensitive resin layer may further contain the solvent. An example of a case where the photosensitive resin layer contains a solvent is when a photosensitive resin composition containing a solvent is applied and dried to form a photosensitive resin layer, and the solvent remains in the photosensitive resin layer even after drying.

[0216] The photosensitive resin layer is preferably a negative-type photosensitive resin layer in which the solubility of the exposed area in the developer decreases upon exposure, and the unexposed area is removed by development.

[0217] The average thickness of the photosensitive resin layer is preferably 0.5 μm to 30 μm, more preferably 1 μm to 10 μm, and even more preferably 1 μm to 5 μm, from the viewpoint of pattern shape, surface roughness, and resolution.

[0218] <Middle class> The transfer film preferably includes an intermediate layer between the temporary support and the photosensitive resin layer.

[0219] By incorporating an intermediate layer, mixing of components can be suppressed when applying multiple layer-forming compositions and during storage after application.

[0220] The intermediate layer is preferably a water-soluble resin layer containing a water-soluble resin. Furthermore, as an intermediate layer, an oxygen-blocking layer with oxygen-blocking function, as described as a "separation layer" in Japanese Patent Publication No. 5-072724, can also be used. Using an oxygen-blocking layer as the intermediate layer is preferable because it improves sensitivity during exposure, reduces the time load on the exposure machine, and improves productivity.

[0221] The oxygen barrier layer used as the intermediate layer may be appropriately selected from known layers described in the above publications, etc. Among these, an oxygen barrier layer that exhibits low oxygen permeability and is dispersed or dissolved in water or an alkaline aqueous solution (a 1% by mass aqueous solution of sodium carbonate at 22°C) is preferred.

[0222] Hereinafter, each component that the intermediate layer may contain will be described.

[0223] The intermediate layer preferably contains a resin.

[0224] Preferably, a part or all of the above resin contains a water-soluble resin.

[0225] Examples of resins that can be used as the water-soluble resin include resins such as polyvinyl alcohol-based resins, polyvinyl pyrrolidone-based resins, cellulose-based resins, acrylamide-based resins, polyethylene oxide-based resins, gelatin, vinyl ether-based resins, polyamide resins, and copolymers thereof.

[0226] In addition, as the water-soluble resin, a copolymer of (meth)acrylic acid / vinyl compound can also be used. As the copolymer of (meth)acrylic acid / vinyl compound, a copolymer of (meth)acrylic acid / (meth)allyl acrylate is preferable, and a copolymer of methacrylic acid / methacrylic acid allyl is more preferable.

[0227] When the water-soluble resin is a copolymer of (meth)acrylic acid / vinyl compound, as each composition ratio (mol%), for example, 90 / 10 to 20 / 80 is preferable, and 80 / 20 to 30 / 70 is more preferable.

[0228] The lower limit value of the weight average molecular weight of the water-soluble resin is preferably 5,000 or more, more preferably 7,000 or more, and even more preferably 10,000 or more. Also, the upper limit value is preferably 200,000 or less, more preferably 100,000 or less, and even more preferably 50,000 or less. The dispersity (Mw / Mn) of the water-soluble resin is preferably 1 to 10, and more preferably 1 to 5.

[0229] Furthermore, in order to further improve the ability to suppress interlayer mixing of the intermediate layer, it is preferable that the resin contained in the intermediate layer is different from the resin contained in the layer located on one side of the intermediate layer and the resin contained in the layer located on the other side. For example, if polymer A is contained in the photosensitive resin layer and a thermoplastic resin (alkali-soluble resin) is contained in the thermoplastic resin layer described later, it is preferable that the resin contained in the intermediate layer is different from polymer A and the thermoplastic resin (alkali-soluble resin).

[0230] The water-soluble resin preferably contains polyvinyl alcohol, and more preferably contains both polyvinyl alcohol and polyvinylpyrrolidone, in order to further improve oxygen barrier properties and interlayer mixing inhibition ability.

[0231] The water-soluble resin contained in the intermediate layer may be one type or two or more types.

[0232] 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.

[0233] The intermediate layer may contain known additives such as surfactants, as needed.

[0234] The thickness of the intermediate layer is not particularly limited, but is preferably 0.1 μm to 5 μm, and more preferably 0.5 to 3 μm. When the thickness of the water-soluble resin layer (intermediate layer) is within the above range, the oxygen barrier properties are not reduced, and the ability to suppress interlayer mixing is excellent. Furthermore, the increase in the time required to remove the intermediate layer during development can also be suppressed.

[0235] <Thermoplastic resin layer> The transfer film preferably includes a thermoplastic resin layer between the temporary support and the intermediate layer. The inclusion of a thermoplastic resin layer in the transfer film improves its conformability to the substrate during the bonding process, thereby 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.

[0236] 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.

[0237] (Alkali-soluble resin (thermoplastic resin)) The thermoplastic resin is preferably an alkali-soluble resin.

[0238] 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.

[0239] As the alkali-soluble resin, acrylic resin is preferred from the viewpoint of developability and adhesion to adjacent layers.

[0240] 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.

[0241] 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.

[0242] In particular, the total content of constituent units derived from (meth)acrylic acid and constituent units derived from (meth)acrylic acid esters is preferably 30% to 100% by mass, and more preferably 50% to 100% by mass, relative to the total mass of the acrylic resin.

[0243] Furthermore, the alkali-soluble resin is preferably a polymer having acidic groups.

[0244] Examples of acidic groups include carboxyl groups, sulfol groups, phosphate groups, and phosphonic acid groups, with carboxyl groups being preferred.

[0245] From the viewpoint of developability, alkali-soluble resins with an acid value of 60 mg KOH / g or higher are more preferred, and carboxyl group-containing acrylic resins with an acid value of 60 mg KOH / g or higher are even more preferred.

[0246] The upper limit of the acid value of the alkali-soluble resin is not particularly limited, but it is preferably 300 mg KOH / g or less, more preferably 250 mg KOH / g or less, even more preferably 200 mg KOH / g or less, and particularly preferably 150 mg KOH / g or less.

[0247] The carboxyl group-containing acrylic resin with an acid value of 60 mgKOH / g or higher is not particularly limited and can be appropriately selected from known resins.

[0248] For example, examples include an alkali-soluble resin which is a carboxyl group-containing acrylic resin with an acid value of 60 mg KOH / g or more among the polymers described in paragraph

[0025] of Japanese Patent Publication No. 2011-095716, a carboxyl group-containing acrylic resin with an acid value of 60 mg KOH / g or more among the polymers described in paragraphs

[0033] to

[0052] of Japanese Patent Publication No. 2010-237589, and a carboxyl group-containing acrylic resin with an acid value of 60 mg KOH / g or more among the binder polymers described in paragraphs

[0053] to

[0068] of Japanese Patent Publication No. 2016-224162.

[0249] The copolymerization ratio of the carboxyl group-containing structural units in the above-mentioned carboxyl 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.

[0250] As for the alkali-soluble resin, an acrylic resin having constituent units derived from (meth)acrylic acid is particularly preferred from the viewpoint of developability and adhesion to adjacent layers.

[0251] 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.

[0252] 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.

[0253] The alkali-soluble resin contained in the thermoplastic resin layer may be one type or two or more types.

[0254] 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, based on the total mass of the thermoplastic resin layer.

[0255] (dye) The thermoplastic resin layer preferably contains a dye (also simply called "dye B") whose maximum absorption wavelength in the wavelength range of 400 nm 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.

[0256] 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.

[0257] 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.

[0258] 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.

[0259] The dye B contained in the thermoplastic resin layer may be one type or two or more types.

[0260] 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.

[0261] 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 for forming the thermoplastic resin layer.

[0262] (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.

[0263] 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.

[0264] As compound C, known photoacid generators, photobase generators, and photoradical polymerization initiators (photoradical generators) can be used.

[0265] (Photoacid generator) The thermoplastic resin layer may contain a photoacid generator from the viewpoint of resolution.

[0266] Examples of photoacid generators include photocationic polymerization initiators that may be included in the photosensitive resin layer described above, and the preferred embodiments are the same except for the points described later.

[0267] 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.

[0268] [ka]

[0269] (Photoradical polymerization initiator) The thermoplastic resin layer may contain a photoradical polymerization initiator.

[0270] Examples of photoradical polymerization initiators include photoradical polymerization initiators that may be included in the photosensitive resin layer described above, and the preferred embodiments are the same.

[0271] (Photobase Generator) The thermoplastic resin composition may contain a photobase generator.

[0272] 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.

[0273] The compound C contained in the thermoplastic resin layer may be one type or two or more types.

[0274] 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.

[0275] (Plasticizer) The thermoplastic resin layer preferably contains a plasticizer from the viewpoint of resolution, adhesion to adjacent layers, and developability.

[0276] 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.

[0277] 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.

[0278] 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.

[0279] Examples of (meth)acrylate compounds used as plasticizers include the polymerizable compounds described above as being included in the photosensitive resin layer.

[0280] In transfer films, when a thermoplastic resin layer and a photosensitive resin layer are laminated in direct contact, it is preferable that both the thermoplastic resin layer and the negative-type photosensitive resin 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 photosensitive resin layer suppresses the diffusion of components between layers, thereby improving storage stability.

[0281] 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.

[0282] 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.

[0283] 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.

[0284] The plasticizer contained in the thermoplastic resin layer may be one type or two or more types.

[0285] 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.

[0286] (Sensitizer) The thermoplastic resin layer may contain a sensitizer.

[0287] The sensitizer is not particularly limited, and examples include sensitizers that may contain the negative-type photosensitive resin layer described above.

[0288] The thermoplastic resin layer may contain one type of sensitizer or two or more types.

[0289] The sensitizer content 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, 0.01% to 5% by mass, and more preferably 0.05% to 1% by mass, is preferred based on the total mass of the thermoplastic resin layer.

[0290] (Additives, etc.) The thermoplastic resin layer may contain known additives such as surfactants, in addition to the above components, as needed.

[0291] 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.

[0292] 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.

[0293] <Protective film> The transfer film of this disclosure may have a protective film on the surface opposite to the intermediate layer side of the photosensitive resin layer.

[0294] A resin film can be used as the protective film. Examples of the above-mentioned resin films include polyolefin films such as polypropylene film and polyethylene film, polyester films such as polyethylene terephthalate film, polycarbonate film, and polystyrene film. Among these, from the viewpoint of heat resistance and other factors, the protective film is preferably a polyolefin film, more preferably a polypropylene film or polyethylene film, and even more preferably a polyethylene film.

[0295] The average thickness of the protective film is not particularly limited, but from the viewpoint of mechanical strength, it is preferably 1.0 μm to 100.0 μm, more preferably 5.0 μm to 50.0 μm, and even more preferably 5.0 μm to 40.0 μm.

[0296] <Application> The transfer film of this disclosure is preferably used for forming circuit wiring that is placed on a support substrate such as a sheet, metal substrate, ceramic substrate, and glass in the manufacturing process film for semiconductor packages, printed circuit boards, flexible printed wiring boards, and interposer rewiring layers.

[0297] <Method for manufacturing transfer film> The method for manufacturing the transfer film of this disclosure is not particularly limited, but it is preferable to include in this order: a step of forming a thermoplastic resin layer with a thickness of 1 μm to 10 μm on one side of a temporary support by coating (hereinafter also referred to as the "thermoplastic resin layer formation step"), a step of forming the intermediate layer on the side of the thermoplastic resin layer opposite to the side in contact with the temporary support by coating (hereinafter also referred to as the "intermediate layer formation step"), and a step of forming the photosensitive resin layer on the side of the intermediate layer opposite to the side in contact with the thermoplastic resin layer by coating (hereinafter also referred to as the "photosensitive resin layer formation step"). Furthermore, the method for manufacturing the transfer film of this disclosure may include a step of providing a protective film on the surface of the photosensitive resin layer (hereinafter referred to as the protective film placement step). 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.

[0298] (Thermoplastic resin layer formation process) A thermoplastic resin layer forming composition used in the thermoplastic resin layer forming process can be prepared by dissolving or dispersing the material to be contained in the thermoplastic resin layer in a solvent. Examples of solvents include the aforementioned water-soluble solvents, alkylene glycol ethers, alkylene glycol ether acetates, ketone solvents (such as methyl ethyl ketone), aromatic hydrocarbon solvents (such as toluene), aprotic polar solvents (such as N,N-dimethylformamide), ether solvents (such as diethyl ether), ester solvents (such as n-propyl acetate), amide solvents, and lactone solvents. Methods for applying thermoplastic resin layer-forming compositions include printing, spraying, roll coating, bar coating, curtain coating, spin coating, and die coating (i.e., slit coating). The drying temperature can be 80°C to 130°C. Note that the drying temperature refers to the temperature of the environment in which the thermoplastic resin layer-forming composition is dried. The drying time can be between 20 and 600 seconds.

[0299] (Intermediate layer formation process) The intermediate layer forming composition used in the intermediate layer forming process can be prepared by dissolving or dispersing the materials to be contained in the intermediate layer (such as surfactants) in a solvent. Examples of solvents include water and the aforementioned water-soluble solvents. The application method, drying temperature, and drying time for the intermediate layer-forming composition are the same as those for the thermoplastic resin layer-forming process, and are therefore omitted from this description.

[0300] (Photosensitive resin layer formation process) The application method, drying temperature, and drying time for the photosensitive resin composition are the same as those for the thermoplastic resin layer formation process, and are therefore omitted from this description.

[0301] (Protective film placement process) The protective film placement step may include laminating a protective film onto the surface of the photosensitive resin layer. The protective film can be applied using a known laminator such as a vacuum laminator or an auto-cut laminator. Preferably, the laminator is equipped with a heat-sensitive roller, such as a rubber roller, and is capable of applying pressure and heating.

[0302] [Method for manufacturing resin patterns] The method for manufacturing a resin pattern according to the present disclosure comprises, in this order, a step of laminating a transfer film and a substrate so that the photosensitive resin layer in the transfer film according to the present disclosure is in contact with the substrate (hereinafter also referred to as the "lamination step"), a step of pattern exposure to the photosensitive resin layer (hereinafter also referred to as the "exposure step"), and a step of developing the photosensitive resin layer after exposure to form a resin pattern (hereinafter also referred to as the "development step"). Preferably, the method includes a step of peeling off a temporary support (hereinafter also referred to as the "temporary support peeling step") after the lamination step and before the development step.

[0303] (Lamination process) In the lamination process, it is preferable to bring the surface of the transfer film with the photosensitive resin layer into contact with the substrate and press it down. If the substrate is a conductive substrate as described later, it is preferable to bring the photosensitive resin layer into contact with the conductive layer and press it down. If the transfer film has a protective film as described later, it is preferable to perform the lamination process after peeling off the protective film.

[0304] Examples of bonding methods include known transfer methods and lamination methods. In particular, it is preferable to place the transfer film on the circuit board and apply pressure and heat using a roll or the like.

[0305] The transfer film and substrate can be bonded together using a known laminator such as a vacuum laminator or an auto-cut laminator.

[0306] The lamination temperature is not particularly limited. The lamination temperature is preferably, for example, 80°C to 150°C, more preferably 90°C to 150°C, and even more preferably 100°C to 150°C. When using a laminator equipped with rubber rollers, the lamination temperature refers to the temperature of the rubber rollers.

[0307] The substrate is preferably a conductive substrate (wiring substrate) having a support substrate and a conductive layer disposed on the support substrate.

[0308] Examples of support substrates include resin substrates, glass substrates, and semiconductor substrates. Preferred embodiments of the support substrate are described, for example, in paragraph 0140 of International Publication No. 2018 / 155193, which are incorporated herein by reference. Furthermore, if the support substrate is a resin substrate, it is preferable that the resin substrate material is a substrate containing a cycloolefin polymer, polyethylene terephthalate, or polyimide. The average thickness of the support substrate is not particularly limited and can range from 5.0 μm to 200.0 μm.

[0309] The conductive layer is preferably at least one layer selected from the group consisting of a metal layer, a conductive metal oxide layer, a graphene layer, a carbon nanotube layer, and a conductive polymer layer, from the viewpoint of conductivity and fine wire formation. Furthermore, the support substrate may have only one conductive layer or 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. 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.

[0310] A conductive substrate having at least one of transparent electrodes and routing wiring is preferred. A conductive substrate with such a configuration can be suitably used as a substrate for a touch panel. Transparent electrodes can function suitably as electrodes for touch panels. Preferably, transparent electrodes are composed of metal oxide films such as ITO (indium tin oxide) and IZO (indium zinc oxide), metal meshes, and metal nanowires. Examples of metal wires include those made of silver and copper. Among these, silver conductive materials such as silver mesh and silver nanowires are preferred.

[0311] 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, manganese, and alloys composed of two or more of these metal elements. Copper, molybdenum, aluminum, or titanium are preferred materials for wiring, with copper being particularly preferred.

[0312] The substrate may be a substrate into which elements that connect semiconductor elements to each other are incorporated. Examples of elements that connect semiconductor elements to each other include elements on which wiring patterns for interconnecting semiconductor elements are formed on a silicon substrate.

[0313] The substrate may have a seed layer on its surface. Examples of materials constituting the seed layer include copper, chromium, lead, nickel, gold, silver, tin, and zinc. The average thickness of the seed layer is not particularly limited and can be 50 nm to 2 μm. There are no particular limitations on the method of forming the seed layer, and examples include coating a dispersion of metal nanoparticles and sintering the coating film, sputtering, and vapor deposition.

[0314] From the viewpoint of reducing transmission loss, the dielectric loss tangent of the substrate at 24 GHz is preferably 0.05 or less, and more preferably 0.03 or less.

[0315] (Exposure process) The exposure process involves pattern exposure of the photosensitive resin layer. "Pattern exposure" refers to a form of exposure that is patterned, resulting in areas that are exposed and areas that are not.

[0316] The positional relationship between the exposed and unexposed areas in pattern exposure is not particularly limited and can be adjusted as appropriate.

[0317] Exposure may be performed from the photosensitive resin layer side or from the circuit board side.

[0318] The exposure method may also be contact exposure, which involves bringing a mask (also called a "photomask") into contact with a photosensitive resin layer.

[0319] Furthermore, the exposure method may be proximity exposure, lens projection exposure, mirror projection exposure, or direct exposure using an exposure laser, etc., in addition to contact exposure. In the case of lens projection exposure, an exposure machine with an appropriate numerical aperture (NA) of the lens can be used depending on the required resolution and depth of field. In the case of direct exposure, drawing may be performed directly on the photosensitive resin layer, or reduction projection exposure may be performed on the photosensitive resin layer via a lens.

[0320] Furthermore, exposure may be performed in the atmosphere, under reduced pressure, or under vacuum. During exposure, a liquid such as water may be interposed between the light source and the photosensitive resin layer.

[0321] In particular, from the viewpoint of further improving resolution, projection exposure is preferred, and lens projection exposure is more preferred.

[0322] The detailed arrangement and specific size of the pattern in pattern exposure are not particularly limited.

[0323] From the viewpoint of achieving high resolution, in pattern exposure, the pattern width is preferably 5 μm or less, and more preferably 2.5 μm or less. The lower limit of the pattern width is not particularly limited, and is, for example, 1.0 μm.

[0324] The light source for exposure is not particularly limited. Examples of light sources include those capable of irradiating light in a wavelength range that can harden the exposed area (e.g., 365 nm or 405 nm). Specific examples of light sources include various lasers; semiconductor light sources such as light-emitting diodes (LEDs); and discharge lamps such as ultra-high pressure mercury lamps, high-pressure mercury lamps, and metal halide lamps.

[0325] The amount of exposure is not particularly limited. The exposure dose is 5 mJ / cm². 2 ~200 mJ / cm 2 Preferably, it is 10 mJ / cm 2 ~200 mJ / cm 2 It is preferable that it be so.

[0326] (Developing process) In the development process, the exposed photosensitive resin layer is developed to form a resin pattern.

[0327] The exposed photosensitive resin layer can be developed using a developing solution.

[0328] The developer is not particularly limited, and any known developer can be used. Examples of developing solutions include the developing solution described in Japanese Patent Publication No. 5-72724.

[0329] The developing solution is preferably an alkaline aqueous solution. Examples of alkaline compounds that may be contained in alkaline aqueous solutions 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).

[0330] The pH of the alkaline aqueous solution is not particularly limited. The pH of the alkaline aqueous solution at 25°C is preferably, for example, 8 to 13, more preferably 9 to 12, and even more preferably 10 to 12.

[0331] The content of the alkaline compound in the alkaline aqueous solution is not particularly limited, but is preferably 0.1% to 5% by mass, and more preferably 0.1% to 3% by mass, relative to the total mass of the alkaline aqueous solution.

[0332] The temperature of the developing solution is not particularly limited. The developer solution temperature is preferably, for example, 20°C to 40°C.

[0333] Examples of development methods include paddle development, shower development, spray development, shower and spin development, and dip development.

[0334] As for the development method, the development method described in paragraph

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

[0335] After the developing process, a rinsing treatment may be performed to remove the developer solution. Water or similar substances can be used for the rinsing treatment.

[0336] After the developing process and / or rinsing process, a drying process may be performed to remove excess liquid.

[0337] (Temporary support removal process) In the temporary support peeling step, the temporary support is peeled off the transfer film. 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.

[0338] The temporary support peeling step is preferably performed after the bonding step and before the developing step. The temporary support peeling step may also be performed after the bonding step and before the exposure step, or after the exposure step. From the viewpoint of suppressing radical polymerization inhibition by oxygen during exposure and preventing mask contamination, it is preferable that the temporary support peeling process be performed after the lamination process and the exposure process, and before the development process. From the viewpoint of improving the resolution of the resin pattern and suppressing defects in the resin pattern, it is preferable that the temporary support peeling process be performed after the bonding process and before the exposure process.

[0339] The method for manufacturing a resin pattern according to this disclosure may include a step of further exposing the formed resin pattern (hereinafter also referred to as the "post-exposure step") and / or a step of further heating the formed resist pattern (hereinafter also referred to as the "post-bake step").

[0340] If the process includes both a post-exposure step and a post-bake step, it is preferable to perform the post-exposure step first, followed by the post-bake step.

[0341] The exposure dose in the post-exposure process is 100 mJ / cm². 2 ~5000 mJ / cm 2 Preferably, 200 mJ / cm² 2~3000 mJ / cm 2 This is preferable.

[0342] The heating temperature in the post-baking process is preferably 80°C to 250°C, and more preferably 90°C to 160°C. The heating time in the post-baking process is preferably 1 to 180 minutes, and more preferably 10 to 60 minutes.

[0343] [Method for manufacturing conductive patterns] In the first embodiment, the method for manufacturing a conductive pattern of the present disclosure preferably comprises, in this order, the steps of: forming a resin pattern on a substrate using the method for manufacturing a resin pattern of the present disclosure; performing a plating process on areas of the substrate where the resin pattern is not formed (hereinafter also referred to as the "plating step"); and removing the resin pattern (hereinafter also referred to as the "pattern removal step").

[0344] The details of the process for forming a resin pattern on the substrate are as described above.

[0345] (Plating process) Examples of plating methods include electroplating and electroless plating. Of these, electroplating is preferred from the standpoint of productivity.

[0346] The metal used in the plating process is not particularly limited, and any known metal can be used. Examples of usable metals include copper, chromium, lead, nickel, gold, silver, tin, zinc, and alloys of these metals. From the viewpoint of electrical conductivity, copper or its alloys are preferred.

[0347] The average thickness of the plating layer formed by the plating process is not particularly limited and can be between 0.1 μm and 20.0 μm.

[0348] (Pattern removal process) There are no particular limitations on the method for removing the resin pattern, but one method is removal by chemical treatment, and a method using a removal solution is preferred. Examples of removal solutions include those in which an inorganic alkaline component or an organic alkaline component is dissolved in water, dimethyl sulfoxide, N-methylpyrrolidone, or a mixture thereof. Examples of inorganic alkaline components include sodium hydroxide and potassium hydroxide. Examples of organic alkali components include primary amine compounds, secondary amine compounds, tertiary amine compounds, and quaternary ammonium salt compounds.

[0349] The temperature of the removal solution is preferably 30°C to 80°C, and more preferably 50°C to 80°C. A preferred method of removal involves immersing a laminate having the pattern to be removed in a removal solution that is being stirred and has a liquid temperature of 50°C to 80°C for 1 to 30 minutes. Alternatively, the pattern may be removed using a removal solution and known methods such as the spray method, shower method, or paddle method.

[0350] (Protective layer formation process) The method for manufacturing a conductive pattern according to this disclosure may include a step of forming a protective layer on the surface of the plating layer after forming the resin pattern and before the pattern removal step (hereinafter also referred to as the "protective layer formation step"). The material constituting the protective layer is preferably one that does not dissolve in the removal solution or etching solution used in the pattern removal process or seed layer removal process. Examples of materials constituting the protective layer include nickel, chromium, tin, zinc, magnesium, gold, silver, alloys thereof, and resins. Nickel or chromium are preferred as materials constituting the protective layer.

[0351] Methods for forming the protective layer include electroless plating and electroplating, with electroplating being preferred.

[0352] The average thickness of the protective layer is not particularly limited and can be between 0.3 μm and 3.0 μm.

[0353] (Seed layer removal process) If the substrate has a seed layer on its surface, the method for manufacturing a conductive pattern according to this disclosure may include a step of removing the seed layer (hereinafter also referred to as the "seed layer removal step"). The seed layer removal step is a step of removing the exposed seed layer to obtain conductive nanowires.

[0354] The method for removing the seed layer is not particularly limited and may be carried out by using a known etching solution. Examples of etching solutions include ferric chloride solution, cupric chloride solution, ammonia-alkali solution, sulfuric acid-hydrogen peroxide mixture, and phosphoric acid-hydrogen peroxide mixture.

[0355] In a second embodiment, the method for manufacturing a conductive pattern of the present disclosure preferably comprises, in this order, the steps of: forming a resin pattern on a conductive layer of a conductive substrate (a substrate having a conductive layer) using the method for manufacturing a resin pattern of the present disclosure; etching areas of the substrate where the resin pattern is not formed (hereinafter also referred to as the "etching step"); and removing the resin pattern (hereinafter also referred to as the "pattern removal step").

[0356] The details of the process for forming a resin pattern on the substrate are as described above. A preferred embodiment of the substrate having a conductive layer is as described above. Furthermore, the preferred embodiment of the pattern removal process in the second embodiment is the same as the preferred embodiment of the pattern removal process in the first embodiment.

[0357] (Etching process) Known etching methods can be used as etching procedures. Specifically, examples include the methods described in paragraphs

[0209] to

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

[0048] to

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

[0358] For wet etching, the etching solution used can be appropriately selected as either acidic or alkaline depending on the object being etched.

[0359] Examples of acidic etching solutions include acidic aqueous solutions containing at least one acidic compound, and acidic mixed aqueous solutions of an acidic compound and at least one selected from the group consisting of ferric chloride, ammonium fluoride, and potassium permanganate.

[0360] The acidic compound (a compound that dissolves in water and exhibits acidity) contained in the acidic aqueous solution is preferably at least one selected from the group consisting of hydrochloric acid, sulfuric acid, nitric acid, acetic acid, hydrofluoric acid, oxalic acid, and phosphoric acid.

[0361] Examples of alkaline etching solutions include alkaline aqueous solutions containing at least one alkaline compound, and alkaline aqueous mixed solutions of an alkaline compound and a salt (e.g., potassium permanganate).

[0362] The alkaline compound (a compound that dissolves in water and exhibits alkalinity) contained in the alkaline aqueous solution is preferably at least one selected from the group consisting of sodium hydroxide, potassium hydroxide, ammonia, organic amines, and salts of organic amines (e.g., tetramethylammonium hydroxide).

[0363] It is preferable that the etching solution does not dissolve the resist pattern.

[0364] The developing solution used in the development process may also serve as the etching solution used in the etching process. In this case, the developing and etching processes may be performed simultaneously.

[0365] After the etching process, a rinsing process may be performed to remove the etching solution. Water or similar substances can be used for the rinsing process.

[0366] After the etching and / or rinsing process, a drying process may be performed to remove any excess liquid.

[0367] Furthermore, a circuit wiring board may be manufactured using the transfer film of this disclosure. A method for manufacturing a circuit wiring board may include a step of forming a solder resist layer having openings on the surface of a substrate from which the seed layer has been removed, using solder resist (hereinafter also referred to as the "solder resist layer formation step"). The opening is preferably designed to expose the conductive pattern formed on the surface of the substrate. Conventional known solder resists can be used. Examples of solder resists include azide-cyclized polyisoprene resins, azide-phenol resins, and chloromethyl polystyrene resins. The average thickness of the solder resist layer is not particularly limited and can be between 5 μm and 50 μm. The method for forming the solder resist layer is not particularly limited and can be carried out by conventionally known methods.

[0368] A method for manufacturing a circuit wiring board may include a step of forming bump electrodes in the openings of the solder resist layer. Preferably, the bump electrodes are connected to the conductor patterns exposed at the openings.

[0369] A method for manufacturing a circuit wiring board may include a step of mounting semiconductor elements that connect to bump electrodes. The semiconductor to be mounted preferably has electrodes, and it is preferable to connect these electrodes to the bump electrodes. After mounting the semiconductor, it is preferable to seal the semiconductor using a conventionally known sealing material.

[0370] [polymer] The polymers of this disclosure include structural units having a group represented by formula (1), and structural units having at least one selected from the group consisting of a silyl group and a fluoro group. Preferred embodiments of structural units having a group represented by formula (1), and structural units having at least one selected from the group consisting of a silyl group and a fluoro group, are as described above.

[0371] In other words, a structural unit having a group represented by formula (1) is preferably a structural unit having a group represented by formula (1A), more preferably a structural unit having a group represented by formula (1B), and even more preferably a structural unit having a group represented by formula (1C). Furthermore, the polymers of this disclosure preferably contain crosslinkable functional groups. Preferred embodiments of the crosslinkable functional groups are as described above.

[0372] The polymers of this disclosure may contain structural units other than those described above.

[0373] By incorporating the polymer of this disclosure into a photosensitive resin composition, a resin pattern with excellent adhesion can be formed. [Examples]

[0374] The present disclosure will be further described in detail below with reference to examples. The materials, quantities, proportions, processing details, and processing procedures shown in the following examples may be modified as appropriate, provided that they do not deviate from the spirit of this disclosure. Therefore, the scope of this disclosure is not limited to the specific examples shown below.

[0375] (Synthesis of polymer P1) A 300 mL three-necked flask equipped with a condenser, stirrer, nitrogen inlet tube, and thermometer was placed in a flask containing 6.0 g of PGMEA and heated to 90°C. A mixed solution of 15.7 g (37.1 mmol) of X-22-2404, 2.0 g (6.2 mmol) of compound M1, 2.4 g (10.7 mmol) of compound M14, 0.06 g (0.3 mmol) of V-601, and 24.0 g of PGMEA was added dropwise over 150 minutes. After aging for 1 hour, a mixed solution of 0.1 g of V-601 and 2.4 g of PGMEA was added. After aging for another 1 hour, a mixed solution of 0.1 g of V-601 and 2.4 g of PGMEA was added. The mixture was heated to 100°C and aged for 3 hours to obtain an intermediate polymer. After cutting off the nitrogen supply, 2.0 g (20.1 mmol) of triethylamine, 13.3 mg (0.1 mmol) of 4-methoxyphenol, and 11.6 g of PGMEA were added to the intermediate polymer solution and stirred at 60°C for 4 hours. The resulting solution was reprecipitated and purified with a mixed solution of 50 mL of 0.1 N hydrochloric acid and 300 mL of methanol under ice cooling to obtain the target polymer P1. The weight-average molecular weight (Mw) of polymer P1 was 58600.

[0376] [ka]

[0377] Polymers P2 and P3 were synthesized using the same method as polymer P1. Polymers P4 to P19 can be synthesized in the same manner as polymer P1.

[0378] (Compounds that do not fall under the category of specific polymers) Polymers PP1 and PP2 can be synthesized using the same method as polymer P1. Polymer PP3 (surfactant): F-552 (manufactured by DIC Corporation)

[0379] [Table 1]

[0380] [Table 2]

[0381] [Table 3]

[0382] [Table 4]

[0383] [Table 5]

[0384] [Table 6]

[0385] [Table 7]

[0386] [Table 8]

[0387] The components used in the preparation of the photosensitive resin composition, other than the compounds mentioned above, are as follows:

[0388] (Alkali-soluble resin) Polymer A-1 was synthesized using a known method. The weight-average molecular weight (Mw) of the synthesized polymer was measured by gel permeation chromatography (GPC) under the following conditions.

[0389] -GPC conditions- Equipment: Tosoh Corporation, Tosoh High-Speed ​​GPC System HLC-8420GPC (product name) Guard column: Tosoh Corporation, HZ-L Separation column: A column consisting of three TSK gel Super HZM-N (product name) columns manufactured by Tosoh Corporation, connected in series. Measurement temperature: 40℃ Eluent: THF (tetrahydrofuran) Flow rate: Sample pump 0.35 mL / min, Reference pump 0.175 mL / min Injection volume: 10μL Detector: Differential refractometer GPC column calibration standard solution: Standard polystyrene manufactured by Tosoh Corporation

[0390] -Synthesis of polymers- The monomers used in the synthesis of the polymer are listed below. St: Styrene (manufactured by Fujifilm Wako Pure Chemical Corporation) MAA: Methacrylic acid (manufactured by Fujifilm Wako Pure Chemical Corporation) MMA: Methyl methacrylate (manufactured by Fujifilm Wako Pure Chemical Corporation) MAA-GMA: A structural unit in which glycidyl methacrylate is added to a structural unit derived from methacrylic acid. BzMA: Benzyl methacrylate (manufactured by Fujifilm Wako Pure Chemical Corporation)

[0391] Polymer A-1: ​​The structure was as shown below, with a weight-average molecular weight (Mw) of 30,000 and an acid value of 124 mgKOH / g. Polymer A-2: The structure was as shown below, with a weight-average molecular weight (Mw) of 60,000 and an acid value of 131 mgKOH / g.

[0392] The numbers in parentheses below for each polymer represent the mass ratio.

[0393] [ka]

[0394] (polymerizable compound) BPE-500: 2,2-bis(4-(methacryloxypentaethoxy)phenyl)propane, manufactured by Shin-Nakamura Chemical Industry Co., Ltd. BPE-100: 2,2-bis(4-(methacryloxyethoxy)phenyl)propane, manufactured by Shin-Nakamura Chemical Industry Co., Ltd. • Aronics M-270: Polypropylene glycol diacrylate (n≒12), manufactured by Toagosei Co., Ltd., listed as "M-270" in the table. A-TMPT-9EO: Ethoxylated trimethylolpropane triacrylate, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.

[0395] (Polymerization initiator) • B-CIM: 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, manufactured by Hampford. Irgacure OXE02: Ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-1-(O-acetyloxime), manufactured by BASF Japan Ltd., listed as "OXE02" in the table.

[0396] (Sensitizer) • EAB-F: 4,4'-bis(diethylamino)benzophenone, obtained from Sanyo Trading Co., Ltd.

[0397] (Polymerization inhibitor) • Phenothiazine: Manufactured by Kawaguchi Chemical Co., Ltd.

[0398] (Antioxidant) • 1-Phenyl-3-pyrazolidone: Manufactured by Tokyo Chemical Industry Co., Ltd.

[0399] (Chain transfer agent) N-phenylcarbamoylmethyl-N-carboxymethylaniline: Manufactured by Fujifilm Wako Pure Chemical Corporation

[0400] (dye) • Leucocrystal violet: Manufactured by Tokyo Chemical Industry Co., Ltd.

[0401] (solvent) PGMEA: Propylene glycol monomethyl ether acetate MEK: Methyl ethyl ketone MFG: Propylene glycol monomethyl ether

[0402] <Preparation of photosensitive resin composition> A photosensitive resin composition was prepared by mixing each component according to the table. The values ​​in the table represent the content of each component in parts by mass.

[0403] <Manufacturing of transfer film> A photosensitive resin layer was formed by applying the prepared photosensitive resin composition onto a temporary support (product name "16KS40", manufactured by Toray Industries, Inc., polyethylene terephthalate film, 16 μm thick) using a slit-shaped nozzle, and then drying the photosensitive resin composition at 80°C for 2 minutes.

[0404] A protective film (product name: Alphan® E200C3, thickness: 18 μm, polypropylene film, manufactured by Oji F-Tex Co., Ltd.) was laminated to the exposed surface of the photosensitive resin layer using heat lamination.

[0405] A transfer film was obtained having a temporary support, a photosensitive resin layer, and a protective film in that order.

[0406] The following evaluations were performed using transfer film.

[0407] <1.Flexibility> 1-1. Manufacturing of evaluation laminates A 5 nm thick nickel-chromium (8 / 2) layer was deposited on a 25 μm thick polyimide substrate by vapor deposition. Next, the substrate was immersed in an electroless plating catalyst containing lead chloride (PdCl2) (Activator Neogant 834, manufactured by Attec Japan Co., Ltd., product name) heated to 35°C for 5 minutes, and then immersed in an electroless copper plating solution (Print Gant MSK-DK, manufactured by Attec Japan Co., Ltd., product name) at room temperature for 15 minutes to form a 0.8 μm thick copper layer, thus preparing a polyimide substrate with a copper layer.

[0408] The transfer film was cut to a size of 30 mm x 100 mm, and the protective film was peeled off. Using a roll laminator, the transfer film after the protective film had been peeled off was bonded to a copper-layered polyimide substrate under the conditions of a temperature of 100°C, a linear pressure of 0.5 MPa, and a linear speed (so-called lamination speed) of 1 m / min. A photosensitive resin layer and a temporary support were then placed on the surface of the copper-layered polyimide substrate in that order. A laminate for evaluation was thus obtained.

[0409] 1-2. Evaluation Test The obtained evaluation laminate was autoclaved under the conditions of a pressure of 0.45 MPa, a temperature of 50°C, and a processing time of 1 hour. After processing, an exposure mask was placed in close contact with the temporary support surface of the laminate. The exposure mask used was a glass mask with a line and space pattern with a line width of 20 μm. Light was irradiated from the exposure mask side using a high-pressure mercury lamp exposure machine (model: MAP-1200L, main wavelength: 365 nm, manufactured by Dainippon Kaken Co., Ltd.) via a 365 nm mercury exposure bandpass filter HB0365 (manufactured by Asahi Spectroscopic Co., Ltd.). The exposure amount was adjusted so that the width of the resist pattern obtained after development in the portion of the exposure mask corresponding to the 20 μm pattern was equal to the pattern width of the mask (i.e., 20 μm).

[0410] Next, the temporary support was peeled off and the development process was performed. A 1.0 mass% sodium carbonate aqueous solution at a liquid temperature of 30°C was used as the developer. The development time was set to twice the minimum development time. "Minimum development time" refers to the shortest time required for the unexposed photosensitive resin layer to completely dissolve by the development process. The development method used was shower development. Specifically, first, the shortest time required for the unexposed photosensitive resin layer to completely dissolve by shower development was determined, and then shower development was performed on the pattern-exposed photosensitive resin layer for twice the minimum development time. After development, an AirKnife treatment was performed to remove the developer, followed by a 30-second shower treatment with pure water at a liquid temperature of 25°C, and then another AirKnife treatment. As a result, a laminated substrate having a resin pattern was obtained.

[0411] For laminated substrates with resin patterns, the minimum diameter at which no cracks occurred along a 20 μm line was measured using a Gardner mandrel bending tester. Then, the flexibility was evaluated according to the following evaluation criteria. In the evaluation criteria below, "A," "B," and "C" represent practically acceptable levels, with "A" being the most preferable.

[0412] -Evaluation Criteria- A: Less than 1mm B: 1mm or more and less than 1.5mm C: 1.5mm or more and less than 2mm D: 2mm or more and less than 3mm E: 3mm or more

[0413] <2. Peel Strength> 2-1. Manufacturing of evaluation laminates A copper-layered polyimide substrate and an evaluation laminate were obtained in the same manner as described in "1-1. Manufacturing of the evaluation laminate" under "1. Flexibility" above.

[0414] The obtained evaluation laminate was autoclaved under the conditions of a pressure of 0.45 MPa, a temperature of 50°C, and a processing time of 1 hour. After processing, the temporary support surface of the laminate was irradiated with light using a high-pressure mercury lamp exposure machine (model: MAP-1200L, main wavelength: 365 nm, manufactured by Dainippon Kaken Co., Ltd.) through a 365 nm mercury exposure bandpass filter HB0365 (manufactured by Asahi Spectroscopic Co., Ltd.) to obtain a cured film. The exposure dose was the same as that used for the flexibility evaluation.

[0415] 2-2. Evaluation Test The temporary support was removed from the resulting laminate, and the cured film side was attached to a 1.1 mm thick glass using double-sided tape. A 180° peel test was performed on the laminate attached to the glass using Tensilon (model number: Tensilon RTF-1210, manufactured by A&D Co., Ltd.) at a peeling speed of 20 mm / min to remove the copper-layered polyimide substrate, and the peeling force was measured. The peel strength was then evaluated according to the evaluation criteria below. In the evaluation criteria below, "A," "B," and "C" represent practically acceptable levels, with "A" being the most preferable.

[0416] -Evaluation Criteria- A: The peeling force is 100 mN / cm or more. B: The peeling force is in the range of 70 mN / cm or more and less than 100 mN / cm. C: The peeling force is in the range of 50 mN / cm or more and less than 70 mN / cm. D: The peeling force is in the range of 30 mN / cm or more and less than 50 mN / cm. E: The peeling force is less than 30 mN / cm.

[0417] [Table 9]

[0418] [Table 10]

[0419] [Table 11]

[0420] [Table 12]

[0421] As shown in Tables 9 to 12, in Examples 1 to 27, it was found that using a photosensitive resin composition containing a specific polymer, an alkali-soluble resin, a polymerizable compound, and a photopolymerization initiator resulted in excellent flexibility and high peel strength. In other words, it was found that resin patterns with excellent adhesion could be formed.

[0422] Comparative Examples 1 to 5 showed inferior adhesion because they did not contain the specific polymer.

[0423] In Example 1, the specific polymer contained a structural unit having a group represented by formula (1A), and it was found to have superior flexibility and high peel strength compared to Example 12.

[0424] In Example 1, it was found that the specific polymer contained a structural unit having a group represented by formula (1C), and that it had higher peel strength compared to Example 10.

[0425] In Example 1, it was found that the specific polymer had crosslinkable functional groups, exhibiting superior flexibility and higher peel strength compared to Example 20.

[0426] In Example 1, it was found that the specific polymer had a (meth)acryloyl group as a crosslinkable functional group, and exhibited superior flexibility and high peel strength compared to Example 23.

[0427] In Example 1, the specific polymer had an ethylenic double bond as a crosslinkable functional group, and the number of atoms in the shortest linking chain between the ethylenic double bond and the main chain of the specific polymer was 3 to 8. It was found to have superior flexibility compared to Example 21.

[0428] In Example 2, the content of the specific polymer was 0.01% by mass or more, and it was found to have superior flexibility compared to Example 3. In Example 6, the content of the specific polymer was 0.01% by mass or more, and it was found to have superior flexibility compared to Example 7. In Example 4, the content of the specific polymer was 3% by mass or less, and it was found that the peel strength was higher compared to Example 5. In Example 8, the content of the specific polymer was 3% by mass or less, and it was found that the peel strength was higher compared to Example 9. [Explanation of Symbols]

[0429] 11: Temporary support 12: Transfer layer 17: Photosensitive resin layer 13: Thermoplastic resin layer 15: Middle Class 19: Protective film 20: Transfer film

Claims

1. A photosensitive resin composition comprising a polymer containing a structural unit having a group represented by the following formula (1), and a structural unit having at least one selected from the group consisting of a silyl group and a fluoro group; an alkali-soluble resin; a polymerizable compound; and a photopolymerization initiator. 【Chemistry 1】 In formula (1), R １ and R ２ Each of these independently represents a hydrogen atom or substituent, and * represents a bonding site with other structures.

2. The photosensitive resin composition according to claim 1, wherein the structural unit having the group represented by formula (1) is a structural unit having the group represented by the following formula (1A). 【Chemistry 2】 In formula (1A), R １１ , R １２ , R １３ , and R １４ Each of these independently represents a hydrogen atom or substituent, and * represents a bonding site with other structures.

3. The photosensitive resin composition according to claim 1, wherein the structural unit having the group represented by formula (1) is a structural unit having the group represented by the following formula (1B). 【Transformation 3】 In formula (1B), * represents a bonding site with another structure.

4. The photosensitive resin composition according to claim 1, wherein the polymer further has a crosslinkable functional group.

5. The photosensitive resin composition according to claim 4, wherein the crosslinkable functional group has an ethylenic double bond, and the number of atoms in the shortest linking chain connecting the ethylenic double bond and the main chain of the polymer is 3 to 8.

6. The photosensitive resin composition according to claim 4, wherein the crosslinkable functional group is a (meth)acryloyl group.

7. The photosensitive resin composition according to claim 1, wherein the structural unit having the group represented by formula (1) is a structural unit having the group represented by the following formula (1C). 【Chemistry 4】 In formula (1C), * represents a bonding site with another structure.

8. The photosensitive resin composition according to claim 1, wherein the content of the polymer is 0.01% by mass to 3% by mass with respect to the solid content of the photosensitive resin composition.

9. A transfer film comprising a temporary support and a photosensitive resin layer disposed on the temporary support and formed from a photosensitive resin composition according to any one of claims 1 to 8.

10. A step of bonding the transfer film and the substrate such that the photosensitive resin layer in the transfer film according to claim 9 is in contact with the substrate, The process of pattern exposure to the photosensitive resin layer, A process of developing the photosensitive resin layer after exposure to form a resin pattern, It has them in this order, A method for manufacturing a resin pattern, comprising the step of peeling off the temporary support after the bonding step and before the step of developing the photosensitive resin layer after exposure.

11. A step of forming the resin pattern on a substrate using the resin pattern manufacturing method described in claim 10, A step of performing a plating treatment on the region of the substrate where the resin pattern is not formed, A step of removing the aforementioned resin pattern, A method for manufacturing a conductive pattern having the following elements in this order.

12. A step of forming the resin pattern on a conductive substrate using the resin pattern manufacturing method described in claim 10, A step of etching the region of the conductive substrate where the resin pattern is not formed, A step of removing the aforementioned resin pattern, A method for manufacturing a conductive pattern having the following elements in this order.

13. A polymer comprising a structural unit having a group represented by the following formula (1), and a structural unit having at least one selected from the group consisting of a silyl group and a fluoro group. 【Transformation 5】 In formula (1), R １ and R ２ Each of these independently represents a hydrogen atom or substituent, and * represents a bonding site with other structures.

14. The polymer according to claim 13, wherein the structural unit having the group represented by formula (1) is a structural unit having the group represented by the following formula (1A). 【Transformation 6】 In formula (1A), R １１ , R １２ , R １３ , and R １４ each independently represents a hydrogen atom or a substituent, and * represents a bonding site with another structure.

15. The polymer according to claim 13 or claim 14, wherein the structural unit having the group represented by formula (1) is a structural unit having the group represented by the following formula (1B). 【Transformation 7】 In formula (1B), * represents a bonding site with another structure.

16. The polymer according to claim 13 or claim 14, further having a crosslinking functional group.

17. The polymer according to claim 16, wherein the crosslinkable functional group has an ethylenic double bond, and the number of atoms in the shortest linking chain connecting the ethylenic double bond and the main chain of the polymer is 3 to 8.

18. The polymer according to claim 16, wherein the crosslinkable functional group is a (meth)acryloyl group.

19. The polymer according to claim 13 or claim 14, wherein the structural unit having the group represented by formula (1) is a structural unit having the group represented by the following formula (1C). 【Transformation 8】 In formula (1C), * represents a bonding site with another structure.

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