Method for manufacturing transfer film, resin pattern, and conductive pattern

Abstract

To provide a transfer film, etc., that has higher sensitivity than conventional films and can form high-resolution resin patterns on a substrate using exposure with a direct writing method. [Solution] A transfer film and its application comprising a temporary support and a photosensitive resin layer disposed on the temporary support, wherein the photosensitive resin layer contains an alkali-soluble resin, a polymerizable compound, a photopolymerization initiator, and a compound represented by the following formula (1).

Description

Technical Field

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

Background Art

[0002] A method of disposing a photosensitive resin layer on an arbitrary substrate using a transfer film, exposing the photosensitive resin layer, and further developing it is widely used because the number of steps for obtaining a predetermined pattern is small.

[0003] For example, Patent Document 1 and Patent Document 2 describe a lithographic printing plate original having a photosensitive layer composed of a photosensitive composition containing a specific sensitizing dye, an initiator compound, and a specific compound on a support. Patent Document 3 describes at least a support and a photosensitive layer composed of a photosensitive composition containing at least a binder, a polymerizable compound, a photopolymerization initiation system compound, and a sensitizer on the support, wherein the haze value of the support is 5.0% or less, the I / O value of the binder is 0.300 to 0.650, and the sensitizer is at least one kind of condensed ring system compound. A pattern forming material is described.

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Patent Document 2

Patent Document 3

Summary of the Invention

Problems to be Solved by the Invention

[0005] When forming a resin pattern on a substrate by exposure using the direct drawing method, higher sensitivity than conventional is required. Also, when obtaining a resin pattern with higher resolution than conventional by exposure using the direct drawing method, there were cases where it was demanded.

[0006] The problem to be solved by one embodiment of the present disclosure is to provide a transfer film that has higher sensitivity than conventional and is capable of forming a high-resolution resin pattern when forming a resin pattern on a substrate by exposure using the direct drawing method. Another problem to be solved by other embodiments of the present disclosure is to provide a method for manufacturing a resin pattern and a method for manufacturing a conductive pattern using the above transfer film.

Means for Solving the Problems

[0007] The means for solving the above problems include the following aspects. <1> A transfer film comprising a temporary support and a photosensitive resin layer disposed on the temporary support, where the photosensitive resin layer contains an alkali-soluble resin, a polymerizable compound, a photoinitiator, and a compound represented by the following formula (1).

Chemical formula

[0008] According to one embodiment of the present disclosure, a transfer film is provided that has higher sensitivity than conventional films and is capable of forming a high-resolution resin pattern on a substrate when forming a resin pattern using exposure with a direct writing method. Furthermore, other embodiments of this disclosure provide a method for manufacturing a resin pattern using the above-mentioned transfer film, and a method for manufacturing a conductive pattern. [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] [Transfer film] The transfer film of this disclosure comprises a temporary support and a photosensitive resin layer disposed on the temporary support, the photosensitive resin layer comprising an alkali-soluble resin, a polymerizable compound, a photopolymerization initiator, and a compound represented by the following formula (1). [ka]

[0012] In formula (1), X is an oxygen atom or -N(R 1 ) represents a -, Y represents an aryl group or heterocyclic group which may have substituents, and R 1 , R 2 , R 3 , and R 4 Each of these independently represents a hydrogen atom or a monovalent substituent, and Y and R 1 , R 2 , R 3 , or R 4 These elements may be joined together to form a ring.

[0013] As a result of diligent research by the inventors, it was found that by adopting the above configuration, higher sensitivity is achieved than in conventional methods, and that high-resolution resin patterns can be formed on a substrate when exposure using the direct writing method. The mechanism by which this produces excellent effects is not clear, but it is hypothesized as follows.

[0014] Generally, when forming resin patterns, there are two exposure methods: exposure via a photomask (mask exposure method) and exposure by direct drawing (direct drawing method). In the direct drawing method, the pattern is drawn individually, so the exposure time tends to be longer compared to the mask exposure method. Therefore, when using the direct drawing method, higher sensitivity is required. In the transfer film of this disclosure, the photosensitive resin layer contains a compound represented by formula (1) along with an alkali-soluble resin, a polymerizable compound, and a photopolymerization initiator, thereby providing a highly sensitive and high-resolution resin pattern.

[0015] On the other hand, Patent Documents 1 and 3 do not contain any description of the compound represented by formula (1). Furthermore, the photosensitive layers described in Patent Documents 1 and 2 are photosensitive layers for lithographic printing plates, and their technical concept differs from that of the photosensitive resin layer in transfer films. In lithographic printing plates, it is assumed that patterns will be formed with thin films (for example, about 1 μm thick), and it is not assumed that resolution will be improved with thick films (for example, 10 μm or more thick).

[0016] The following describes a specific embodiment of the transfer film.

[0017] 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.

[0018] 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.

[0019] 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.

[0020] The following describes each element that makes up the transfer film.

[0021] <Provisional support> The temporary support is a removable support that supports the photosensitive resin layer.

[0022] The temporary support may be a single layer or a laminate consisting of two or more layers stacked together. Examples of temporary supports include those consisting only of a substrate; a laminate comprising a substrate and a particle-containing layer disposed on one side of the substrate; and a laminate comprising a substrate and particle-containing layers disposed on both sides of the substrate.

[0023] Examples of substrates that constitute the temporary support include glass, resin film, and paper. From the viewpoint of strength, flexibility, and light transmittance, the substrate constituting the temporary support is preferably a resin film.

[0024] Examples of resin films include polyethylene terephthalate (PET) film, cellulose triacetate film, polystyrene film, and polycarbonate film. Among these, the resin film is preferably a PET film, and more preferably a biaxially oriented PET film.

[0025] If a particle-containing layer is arranged on one or both sides of the substrate, the particle-containing layer may be one layer or two or more layers.

[0026] The particle-containing layer is formed, for example, by applying a particle-containing layer composition to a substrate and drying it. Alternatively, the particle-containing layer can be formed by co-extrusion during the formation of a resin film. The particle-containing layer composition preferably contains a binder polymer and particles. The type of binder polymer is not particularly limited and can be appropriately selected depending on the purpose. Examples of binder polymers include acrylic resins, urethane resins, olefin resins, styrene-butadiene resins, ester resins, vinyl chloride resins, and vinylidene chloride resins. When forming the particle-containing layer by co-extrusion, PET is preferably used as the binder polymer.

[0027] The particle-containing layer may contain one type of binder polymer and one type of particle, or it may contain two or more types.

[0028] The particles contained in the particle-containing layer are not particularly limited and can be appropriately selected depending on the purpose. The particle content in the particle-containing layer can be appropriately adjusted by the amount of particles added to the particle-containing layer composition. In this specification, the particles contained in the particle-containing layer are referred to as "added particles".

[0029] The added particles are distinct from impurities that are unexpectedly introduced during the manufacturing process of the temporary support, and from particles that are formed during the manufacturing process of the temporary support. Preferably, the added particles are those that do not melt at 200°C.

[0030] In a temporary support, whether or not a particle is an added particle can be determined, for example, by the following method. Added particles usually have uniform shape and distribution, so they can be identified by observation with an optical microscope.

[0031] Examples of added particles include inorganic particles and organic particles.

[0032] 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).

[0033] Examples of organic particles include acrylic resin, polyester, polyurethane, and polycarbonate. Examples include polymer particles such as nates, polyolefins, and polystyrene.

[0034] 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.

[0035] 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.

[0036] The thickness of the temporary support is preferably 10 μm or more, more preferably 15 μm or more, and even more preferably 20 μm or more, from the viewpoint of ease of forming the photosensitive resin layer on the transfer film and ease of handling when bonding to the circuit board. The upper limit of the thickness is not particularly limited, for example, 200 μm.

[0037] 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.

[0038] <Photosensitive resin layer> 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.

[0039] The average thickness of the photosensitive resin layer is preferably 3 μm to 50 μm, more preferably 5 μm to 25 μm, and even more preferably 5 μm to 20 μm, from the viewpoint of pattern shape, surface roughness, and resolution.

[0040] The photosensitive resin layer comprises an alkali-soluble resin, a polymerizable compound, a photopolymerization initiator, and a compound represented by the following formula (1).

[0041] (The compound represented by formula (1)) The photosensitive resin layer contains a compound represented by formula (1).

[0042] [ka]

[0043] In formula (1), X is an oxygen atom or -N(R 1 ) represents a -, Y represents an aryl group or heterocyclic group which may have substituents, and R 1 , R 2 , R 3 , and R 4 Each of these independently represents a hydrogen atom or a monovalent substituent, and Y and R 1 , R 2 , R 3 , or R 4 These elements may be joined together to form a ring.

[0044] [Y] Y represents an aryl group or heterocyclic group which may have substituents.

[0045] Examples of aryl groups include those having 6 to 20 carbon atoms, such as phenyl, naphthyl, anthryl, phenanthryl, indenyl, acenabutenyl, and fluorenyl groups. Among these, the aryl group is preferably a phenyl group.

[0046] Examples of heterocyclic groups include heterocyclic groups having heteroatoms such as nitrogen, oxygen, and sulfur atoms.

[0047] The heterocyclic group may be an aliphatic heterocyclic group or an aromatic heterocyclic group (i.e., a heteroaryl group).

[0048] Examples of aromatic heterocycles constituting an aromatic heterocyclic group include thiophene, thiathlene, furan, pyran, isobenzofuran, chromene, xanthene, phenoxazine, pyrrole, pyrazole, isothiazole, isoxazole, pyrazine, pyrimidine, pyridazine, indidine, isoindolidine, indoile, indazole, purine, quinoridine, isoquinoline, phthalazine, naphthyridine, quinazoline, cinolin, pteridine, carbazole, carboline, phenanthryn, acridine, perimidine, phenanthrolin, phthalazine, phenalzadine, phenoxazine, furazan, and phenoxazine.

[0049] Substituents that the aryl group or heterocyclic group represented by Y may have include, for example, halogen atoms (-F, -Br, -Cl, -I), hydroxyl groups, alkyl groups, alkoxy groups, aryl groups, aryloxy groups, mercapto groups, alkylthio groups, arylthio groups, alkyldithio groups, aryldithio groups, amino groups, N-alkylamino groups, N,N-dialkylamino groups, N-arylamino groups, N,N-diarylamino groups, N-alkyl-N-arylamino groups, acyloxy groups, carbamoyloxy groups, N-alkylcarbamoylo Xy group, N-arylcarbamoyloxy group, N,N-dialkylcarbamoyloxy group, N,N-diarylcarbamoyloxy group, N-alkyl-N-arylcarbamoyloxy group, alkylsulfoxy group, arylsulfoxy group, acyloxy group, acylthio group, acylamino group, N-alkylacylamino group, N-arylacylamino group, ureido group, N'-alkylureido group, N',N'-dialkylureido group, N'-arylureido group, N',N'-diarylureido group, N'-alkyl-N'-arylureido N-alkylureid group, N-arylureid group, N'-alkyl-N-alkylureid group, N'-alkyl-N-arylureid group, N',N'-dialkyl-N-alkylureid group, N',N'-dialkyl-N-arylureid group, N'-aryl-N-alkylureid group, N',N'-diaryl-N-alkylureid group, N',N'-diaryl-N-arylureid group, N'-alkyl-N'-aryl-N-alkylureid group, N'-alkyl-N'-arylureid group aryl-N-arylureide group, alkoxycarbonylamino group, allyloxycarbonylamino group, N-alkyl-N-alkoxycarbonylamino group, N-alkyl-N-allyloxycarbonylamino group, N-aryl-N-alkoxycarbonylamino group, N-aryl-N-allyloxycarbonylamino group, formyl group, acyl group, carboxyl group, alkoxycarbonyl group, allyloxycarbonyl group, carbamoyl group, N-alkylcarbamoyl group, N,N-dialkylcarbamoyl group, N-arylcarbamoyl group, N,N-diarylcarbamoyl group, N-alkyl-N-arylcarbamoyl group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, sulfo group (-SO3H) and its conjugated base group, alkoxysulfonyl group, aryloxysulfonyl group, sulfinamoyl group, N-alkylsulfinamoyl group, N,N-dialkylsulfinamoyl group, N-arylsulfinamoyl group, N,N-diarylsulfinamoyl group, N-alkyl-N-arylsulfinamoyl group, sulfamoyl group, N-alkylsulfamoyl group, N,N-dialkylsulfamoyl group, N-arylsulfamoyl group, N,N-diarylsulfamoyl group, N-alkyl-N-arylsulfamoyl group, phosphono group (-PO3H2) and its conjugated base group, dialkylphosphono group (-PO3(alkyl)2) Examples include diarylphosphono groups (-PO3(aryl)2), alkylarylphosphono groups (-PO3(alkyl)(aryl)), monoalkylphosphono groups (-PO3H(alkyl)) and their conjugate bases, monoarylphosphono groups (-PO3H(aryl)) and their conjugate bases, phosphonooxy groups (-OPO3H2) and their conjugate bases, dialkylphosphonooxy groups (-OPO3(alkyl)2), diarylphosphonooxy groups (-OPO3(aryl)2), alkylarylphosphonooxy groups (-OPO3(alkyl)(aryl)), monoalkylphosphonooxy groups (-OPO3H(alkyl)) and their conjugate bases, monoarylphosphonooxy groups (-OPO3H(aryl)) and their conjugate bases, cyano groups, nitro groups, aryl groups, heteroaryl groups, alkenyl groups, alkynyl groups, and silyl groups.

[0050] The aryl group or heterocyclic group represented by Y may or may not have substituents.

[0051] In particular, from the viewpoint of high sensitivity and high resolution, Y is preferably a substituted aryl group (i.e., a substituted aryl group).

[0052] From the viewpoint of high sensitivity and high resolution, the substituent on the substituted aryl group is preferably at least one selected from the group consisting of an alkoxy group, an N,N-dialkylamino group, and an N,N-diarylamino group.

[0053] The alkoxy group preferably has 1 to 3 carbon atoms. Examples of alkoxy groups include methoxy and ethoxy groups. The number of carbon atoms in each alkyl group constituting the N,N-dialkylamino group is preferably 1 to 3. Examples of N,N-dialkylamino groups include the N,N-dimethylamino group and the N,N-diethylamino group. The number of carbon atoms in each aryl group constituting the N,N-diarylamino group is preferably 6 to 20. An example of an N,N-diarylamino group is the N,N-diphenylamino group.

[0054] [X] X is an oxygen atom or -N(R 1 ) represents R 1 represents a hydrogen atom or a monovalent substituent. R 1 Examples of substituents represented by this symbol include those described in Y above. R 1 It is preferable that this is an alkyl group or an aryl group. The alkyl group may be a linear alkyl group, a branched alkyl group, or a cycloalkyl group.

[0055] Examples of aryl groups include the aryl group described in Y above.

[0056] In particular, from the viewpoint of high sensitivity and high resolution, X is preferably an oxygen atom.

[0057] [R 2 ] R 2 represents a hydrogen atom or a monovalent substituent. R 2Examples of substituents represented by this symbol include those described in Y above. R 2 The alkyl or aryl group is preferably an alkyl group or an aryl group. The alkyl or aryl group may have substituents.

[0058] The alkyl group may be a linear alkyl group, a branched alkyl group, or a cycloalkyl group.

[0059] Examples of aryl groups include the aryl group described in Y above.

[0060] In particular, from the standpoint of high sensitivity and high resolution, R 2 It is preferably an alkyl group having 1 to 20 carbon atoms, more preferably a linear alkyl group or branched alkyl group having 1 to 10 carbon atoms, or a cycloalkyl group having 3 to 8 carbon atoms.

[0061] R 2 Examples of these groups include methyl group, ethyl group, n-propyl group, n-butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, hexadecyl group, octadecyl group, eicosyl group, isopropyl group, isobutyl group, s-butyl group, t-butyl group, isopentyl group, neopentyl group, 1-methylbutyl group, isohexyl group, 2-ethylhexyl group, 2-methylhexyl group, cyclohexyl group, cyclopentyl group, and 2-norbornyl group.

[0062] [R 3 ] R 3 represents a hydrogen atom or a monovalent substituent. R 3 Examples of substituents represented by this symbol include those described in Y above. In particular, from the standpoint of high sensitivity and high resolution, R 3 It is preferable that it be a hydrogen atom.

[0063] [R 4 ] R 4 represents a hydrogen atom or a monovalent substituent. R 4 Examples of substituents represented by this symbol include those described in Y above. R 4 The alkyl or aryl group is preferably an alkyl group or an aryl group. The alkyl or aryl group may have substituents. The alkyl group may be a linear alkyl group, a branched alkyl group, or a cycloalkyl group.

[0064] Examples of aryl groups include the aryl group described in Y above.

[0065] In particular, from the standpoint of high sensitivity and high resolution, R 4 It is preferably an alkyl group having 1 to 20 carbon atoms, more preferably a linear alkyl group or branched alkyl group having 1 to 10 carbon atoms, or a cycloalkyl group having 3 to 8 carbon atoms.

[0066] In particular, from the standpoint of high sensitivity and high resolution, R 2 and R 4 Each of these is preferably an alkyl group having 1 to 20 carbon atoms, which may have substituents, and more preferably an unsubstituted alkyl group having 1 to 20 carbon atoms. Furthermore, when an alkyl group has substituents, "number of carbon atoms" refers to the number of carbon atoms contained in the alkyl group excluding the substituents.

[0067] R 2 and R 4 When the alkyl group is present, the compound represented by formula (1) exhibits excellent sensitivity, particularly when irradiated with light whose dominant wavelength is 390 nm to 420 nm. The reason for this is not entirely clear, but it is presumed to be as follows: The compound represented by formula (1) becomes excited by light of the above wavelengths, and then initiates a reaction by reacting with a polymerization initiator. 2 and R 4If the alkyl group is present, it is presumed that the excited state lifetime will be longer, and / or the energy transfer rate from the excited state to the polymerization initiator will be faster, resulting in superior sensitivity.

[0068] Y and R 1 , R 2 , R 3 , or R 4 These may be bonded to each other to form a ring. From the viewpoint of the exposure sensitivity of the photosensitive resin layer, Y and R 1 , R 2 , R 3 , or R 4 Preferably, these elements are not bonded to each other to form a ring.

[0069] Examples of compounds represented by formula (1) include the following:

[0070] [ka]

[0071] [ka] JPEG2026061800000010.jpg130158

[0072] The content of the compound represented by formula (1) is preferably 0.01% by mass or more, more preferably 0.03% by mass or more, and even more preferably 0.05% by mass or more, based on the total amount of the photosensitive resin layer. There is no particular upper limit on the content of the photopolymerization initiator. The content of the compound represented by formula (1) is preferably 70% by mass or less, and more preferably 50% by mass or less, based on the total amount of the photosensitive resin layer.

[0073] The compound represented by formula (1) can be obtained, for example, by a condensation reaction between an acidic nucleus, or an acidic nucleus having an active methylene group, and a substituted or unsubstituted aromatic compound or heterocyclic compound. The compound represented by formula (1) can be synthesized, for example, by referring to Japanese Patent Publication No. 59-28329 and Japanese Patent Application Publication No. 2003-228148.

[0074] Examples of acidic nuclei include, for example, those described in James, ed., "The Theory of the Photographic Process," 4th edition, Macmillan Press, 1977, pp. 197-200; saturated / unsaturated cyclic compounds consisting of carbon, nitrogen, and / or chalcogen (oxygen, sulfur, selenium, and tellurium) atoms, and compounds with structures in which some of these elements are further substituted.

[0075] (Alkali-soluble resin) The photosensitive resin layer contains 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.

[0076] -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.

[0077] 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.

[0078] 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 photosensitive resin laminate. 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.

[0079] Edge fusing refers to the degree to which the photosensitive resin layer tends to protrude from the end face of a roll when the transfer film is wound into a roll. Cut-tip properties refer to the degree to which chips tend to fly off when the unexposed film is cut with a cutter. If these chips adhere to the upper surface of the photosensitive resin laminate, 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).

[0080] From the viewpoint of suppressing line width thickening and resolution deterioration when the focal position shifts during exposure, polymer A preferably contains constituent 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 constituent 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.

[0081] 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.).

[0082] In particular, polymerizable monomers having aromatic hydrocarbon groups are preferably compounds represented by the following formulas (R1) and (R2).

[0083] [ka]

[0084] In formula (R1), R 11represents a hydrogen atom or a methyl group. In formula (R2), R 12 represents a hydrogen atom or a methyl group, and T represents a single bond or a divalent linking group.

[0085] In other words, from the viewpoint of high sensitivity and high resolution, it is preferable that the alkali-soluble resin includes a resin having at least one selected from the group consisting of constituent units derived from compounds represented by formulas (R1) and (R2).

[0086] Examples of compounds represented by formula (R1) include styrene and α-methylstyrene.

[0087] In formula (R2), examples of the divalent linking group represented by T include alkylene groups having 1 to 10 carbon atoms and arylene groups having 6 to 20 carbon atoms.

[0088] Examples of compounds represented by formula (R2) include benzyl (meth)acrylate and phenylethyl (meth)acrylate.

[0089] The content of at least one selected from the group consisting of constituent units derived from compounds represented by formulas (R1) and (R2) is preferably 30% to 70% by mass, more preferably 40% to 65% by mass, and even more preferably 45% to 60% by mass, relative to the total amount of polymer A.

[0090] 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.

[0091] 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.

[0092] 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 constituent 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 35% by mass, relative to the total amount of polymer A.

[0093] 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 constituent units derived from the second monomer is preferably 5% to 50% by mass, more preferably 10% to 30% by mass, and even more preferably 15% to 25% by mass, relative to the total amount of polymer A.

[0094] For example, polymer A is preferably a copolymer containing constituent units derived from methacrylic acid, methyl methacrylate, and styrene; or a copolymer containing constituent units derived from methacrylic acid and benzyl methacrylate.

[0095] 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.

[0096] 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.

[0097] 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.

[0098] 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.

[0099] 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.

[0100] 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 the photosensitive resin layer, 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.

[0101] The photosensitive resin layer 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.

[0102] The alkali-soluble resin contained in the photosensitive resin layer may be one type or two or more types.

[0103] 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 total amount of the photosensitive resin layer. A ratio of 90% by mass or less of alkali-soluble resin relative to the photosensitive resin layer 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 relative to the photosensitive resin layer is preferable from the viewpoint of improving edge fusing resistance.

[0104] (polymerizable compound) The photosensitive resin layer contains polymerizable compounds. In this disclosure, "polymerizable compound" means a compound having a polymerizable group.

[0105] The alkali-soluble resin may have polymerizable groups, but the photosensitive resin layer contains polymerizable compounds in addition to the alkali-soluble resin.

[0106] The polymerizable groups in a polymerizable compound may be thermally polymerizable groups or photopolymerizable groups. Examples of thermopolymerizable groups include epoxy groups and oxetane groups.

[0107] The polymerizable group is preferably a photopolymerizable group, and more preferably a photoradical polymerizable group.

[0108] From the viewpoint of reactivity, the photopolymerizable group is preferably a group containing an ethylenically unsaturated group, 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.

[0109] 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.

[0110] Furthermore, in terms of superior resolution and exfoliation properties, it is preferable that the number of ethylenically unsaturated groups in one molecule of the ethylenically unsaturated compound be six or less.

[0111] -Polymerizable compound B1- The photosensitive resin layer preferably contains polymerizable compound B1 having at least one aromatic ring and two ethylenically unsaturated groups in one molecule.

[0112] 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, relative to the total amount of polymerizable compound B, 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, relative to the total amount of polymerizable compound B.

[0113] 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.

[0114] 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.

[0115] 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.

[0116] 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.

[0117] 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.

[0118] 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.

[0119] 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.

[0120] Examples of 2,2-bis(4-((meth)acryloxypolyalkoxy)phenyl)propane include 2,2-bis(4-(methacryloxydiethoxy)phenyl)propane (FA-324M, manufactured by Hitachi Chemical Co., Ltd.), 2,2-bis(4-(methacryloxyethoxypropoxy)phenyl)propane, 2,2-bis(4-(methacryloxypentaethoxy)phenyl)propane (BPE-500, manufactured by Shin Nakamura Chemical Industry Co., Ltd.), and 2,2-bis(4-(methacryloxydodecate) Examples include oxytetrapropoxy)phenyl)propane (FA-3200MY, manufactured by Hitachi Chemical Co., Ltd.), 2,2-bis(4-(methacryloxypentadecaethoxy)phenyl)propane (BPE-1300, manufactured by Shin Nakamura Chemical Industry Co., Ltd.), 2,2-bis(4-(methacryloxydiethoxy)phenyl)propane (BPE-200, manufactured by Shin Nakamura Chemical Industry Co., Ltd.), and ethoxylated (10)bisphenol A diacrylate (NK ester A-BPE-10, manufactured by Shin Nakamura Chemical Industry Co., Ltd.).

[0121] 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).

[0122] [ka]

[0123] In formula (P1), R 21 and R 22Each 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.

[0124] n1+n2+n3+n4 is preferably between 2 and 20, more preferably between 2 and 16, and even more preferably between 2 and 8.

[0125] 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.

[0126] The polymerizable compound B1 contained in the photosensitive resin layer may be one type or two or more types.

[0127] The content of polymerizable compound B1 is preferably 5% by mass or more, and more preferably 10% by mass or more, relative to the total amount of the photosensitive resin layer, 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.

[0128] -Polymerizable compound B2- The photosensitive resin layer preferably contains polymerizable compound B2, which does not have an aromatic ring and has two ethylenically unsaturated groups.

[0129] Examples of polymerizable compound B2 include alkylene glycol di(meth)acrylate, polyalkylene glycol di(meth)acrylate, urethane di(meth)acrylate, and trimethylolpropane diacrylate.

[0130] 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.

[0131] 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.

[0132] 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.).

[0133] -Polymerizable compound B3- The photosensitive resin layer preferably contains polymerizable compound B3 having three or more ethylenically unsaturated groups.

[0134] Examples of polymerizable compound B3 include dipentaerythritol (tri / tetra / penta / hexa)(meth)acrylate, pentaerythritol (tri / tetra)(meth)acrylate, trimethylolpropane tri(meth)acrylate, ditrimethylolpropanetetra(meth)acrylate, trimethylolethane tri(meth)acrylate, isocyanuric acid tri(meth)acrylate, glycerin tri(meth)acrylate, and alkylene oxide modified products thereof.

[0135] 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.

[0136] 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.).

[0137] In particular, from the viewpoint of resolution, it is preferable that the polymerizable compound contains at least one selected from the group consisting of trimethylolpropane tri(meth)acrylate, ethylene oxide-modified trimethylolpropane tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, and ethylene oxide-modified pentaerythritol tetra(meth)acrylate.

[0138] The photosensitive resin layer may contain polymerizable compounds other than polymerizable compounds B1, B2, and B3. Other polymerizable compounds are not particularly limited and can be appropriately selected from conventionally known compounds. Examples of other polymerizable compounds B include compounds having one ethylenically unsaturated group in one molecule (i.e., monofunctional ethylenically unsaturated compounds).

[0139] Furthermore, the other polymerizable compound B may be a polymerizable compound having an acid group as described in paragraphs 0025 to 0030 of Japanese Patent Application Publication No. 2004-239942.

[0140] 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.

[0141] The photosensitive resin layer preferably contains polymerizable compound B1 and polymerizable compound B2. In this case, the mass ratio of polymerizable compound B1 to polymerizable compound B2 (polymerizable compound B1:polymerizable compound B2) is preferably 1:1 to 5:1, more preferably 1.2:1 to 4:1, and even more preferably 1.5:1 to 3:1.

[0142] The polymerizable compound contained in the photosensitive resin layer may be one type or two or more types.

[0143] 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, based on the total amount of the photosensitive resin layer.

[0144] (Photopolymerization initiator) The photosensitive resin layer contains a photopolymerization initiator.

[0145] 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.

[0146] Examples of photopolymerization initiators include photoradical polymerization initiators and photocationic polymerization initiators. Among these, photoradical polymerization initiators are preferred.

[0147] The photoradical polymerization initiator preferably contains at least one selected from the group consisting of hexaarylbiimidazole compounds, oxime compounds, alkylphenone compounds, acetophenone compounds, and acylphosphine oxide compounds, more preferably contains at least one selected from the group consisting of hexaarylbiimidazole compounds and acetophenone compounds, and even more preferably contains a hexaarylbiimidazole compound, from the viewpoint of sensitivity and resin pattern shape.

[0148] Examples of hexaarylbiimidazole compounds include 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(o-bromophenyl))4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(o,p-dichlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, and 2,2'-bis(o-chlorophenyl)-4,4',5,5'-tetra(m-methoxyf Examples include phenyl(biidazole), 2,2'-bis(o,o'-dichlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(o-nitrophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(o-methylphenyl)-4,4',5,5'-tetraphenylbiimidazole, and 2,2'-bis(o-trifluorophenyl)-4,4',5,5'-tetraphenylbiimidazole.

[0149] 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.

[0150] 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.).

[0151] A photocationic polymerization initiator (photoacid generator) is a compound that generates acid upon receiving active light. While there are no particular limitations on the photocationic polymerization initiator, it is preferable that it is a compound that is sensitive to active light with a wavelength of 300 nm or more, preferably 300 nm to 450 nm, and generates acid.

[0152] 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.

[0153] Examples of photocationic polymerization initiators include ionic photocationic polymerization initiators and nonionic photocationic polymerization initiators.

[0154] Examples of ionic photocationic polymerization initiators include onium salt compounds such as diaryliodonium salts and triarylsulfonium salts, and quaternary ammonium salts.

[0155] 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.

[0156] 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.

[0157] The photopolymerization initiator contained in the photosensitive resin layer may be one type or two or more types.

[0158] 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, based on the total amount of the photosensitive resin layer. 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, based on the total amount of the photosensitive resin layer.

[0159] (Surfactants) From the viewpoint of uniformity of thickness, the photosensitive resin layer preferably contains a surfactant.

[0160] In particular, the photosensitive resin layer preferably contains a resin having at least one selected from the group consisting of constituent units derived from the compound represented by the following formula (A1). A resin (hereinafter also referred to as "resin K") having at least one selected from the group consisting of constituent units derived from the compound represented by formula (A1) is preferably used as a surfactant.

[0161] [ka]

[0162] In formula (A1), R 31 R represents a hydrogen atom or a methyl group.41 represents an alkylene group having 1 to 10 carbon atoms, and L represents an organopolysiloxane residue, a trialkylsilyl group, or a tris(trialkylsilyloxy)silyl group.

[0163] R 41 The alkylene group represented by may be a linear alkylene group, a branched alkylene group, or may include a cyclic structure. R 41 The number of carbon atoms in the alkylene group represented by is preferably 1 to 6.

[0164] The organopolysiloxane residue represented by L is, for example, -(Si(R 51 )2O) m Si(R 52 ) is represented by 3, R 51 and R 52 Each of these independently represents an alkyl group having 1 to 5 carbon atoms, and m is an integer between 5 and 100. R 51 It is preferable that it be a methyl group. R 52 It is preferable that it is a linear alkyl group having 1 to 5 carbon atoms. m is preferably between 5 and 65.

[0165] The alkyl group in the trialkylsilyl group represented by L is preferably a methyl group or an ethyl group. More preferably, the trialkylsilyl group is a trimethylsilyl group or a triethylsilyl group. The alkyl group in the tris(trialkylsilyloxy)silyl group represented by L is preferably a methyl group or an ethyl group. More preferably, the tris(trialkylsilyloxy)silyl group is a tris(trimethylsilyloxy)silyl group or a tris(triethylsilyloxy)silyl group.

[0166] In particular, from the viewpoint of uniformity of thickness, L is preferably a tris(trialkylsilyloxy)silyl group.

[0167] Examples of compounds represented by formula (A1) include the following:

[0168] [ka]

[0169] Resin K may contain other constituent units other than those derived from the compound represented by formula (A1). The proportion of constituent units derived from the compound represented by formula (A1) in resin K is preferably 50% by mass or more to 80% by mass.

[0170] If the photosensitive resin layer contains resin K, the content of resin K is preferably 0.01% to 5% by mass, and more preferably 0.05% to 1% by mass, relative to the total amount of the photosensitive resin layer.

[0171] (Nitrogen-containing heterocyclic compounds and sulfur-containing heterocyclic compounds) The photosensitive resin layer preferably contains at least one selected from the group consisting of nitrogen-containing heterocyclic compounds and sulfur-containing heterocyclic compounds.

[0172] Examples of nitrogen-containing heterocyclic compounds and sulfur-containing heterocyclic compounds include benzimidazole, 1,2,4-triazole, benzotriazole, tolyltriazole, butylbenzyltriazole, alkyldithiothiadiazole, alkylthiol, 2-aminopyrimidine, 5,6-dimethylbenzimidazole, 2-amino-5-mercapto-1,3,4-thiadiazole, 2,5-dimercapto-1,3,4-thiadiazole, 2-mercaptopyrimidine, 2-mercaptobenzoxazole, 2-benzothiazolthiol, and 2-mercaptobenzimidazole.

[0173] If the photosensitive resin layer contains at least one compound selected from the group consisting of nitrogen-containing heterocyclic compounds and sulfur-containing heterocyclic compounds, the resolution is improved by enhancing adhesion to the substrate during transfer.

[0174] In the photosensitive resin layer, nitrogen-containing heterocyclic compounds and sulfur-containing heterocyclic compounds may function as rust inhibitors.

[0175] When the photosensitive resin layer contains at least one compound selected from the group consisting of nitrogen-containing heterocyclic compounds and sulfur-containing heterocyclic compounds, the content of the compound is preferably 0.01% to 5% by mass, and more preferably 0.05% to 1% by mass, based on the total amount of the photosensitive resin layer.

[0176] (Polymerization inhibitor) The photosensitive resin layer may contain a polymerization inhibitor.

[0177] 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.

[0178] If the photosensitive resin layer 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 total amount of the photosensitive resin layer, from the viewpoint of storage stability of the photosensitive resin composition.

[0179] (Antioxidant) The photosensitive resin layer may contain an antioxidant.

[0180] 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.

[0181] If the photosensitive resin layer 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 total amount of the photosensitive resin layer. There is no particular upper limit to the antioxidant content, but 1% by mass or less is preferred.

[0182] (Chain transfer agent) The photosensitive resin layer may contain a chain transfer agent.

[0183] Examples of chain transfer agents include N-phenylcarbamoylmethyl-N-carboxymethylaniline, and N,N-tetraethyl-4,4-diaminobenzophenone, N-phenylglycine, and thiol compounds.

[0184] If the photosensitive resin layer contains a chain transfer agent, the content of the chain transfer agent is preferably 0.01% to 5% by mass, and more preferably 0.05% to 1% by mass, relative to the total amount of the photosensitive resin layer.

[0185] (dye) The photosensitive resin layer may contain a dye. The photosensitive resin layer 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 higher, and whose maximum absorption wavelength changes with the presence of an acid, base, or radical, from the viewpoint of visibility of the exposed and unexposed areas, pattern visibility after development, and resolution. Although the detailed mechanism is unknown, the presence of dye N improves adhesion with adjacent layers (e.g., temporary support and intermediate layer) and results in superior resolution.

[0186] 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.

[0187] 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.

[0188] 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.

[0189] From the viewpoint of visibility of the exposed and unexposed areas, as well as resolution, the photosensitive resin layer preferably contains both a dye N whose maximum absorption wavelength changes due to radicals, and a photoradical polymerization initiator.

[0190] 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.

[0191] 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 layer, and after exposure, the color is developed by radicals, acids, or bases generated from the photoradical polymerization initiator, photocationic polymerization initiator, or photobase generator.

[0192] 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.

[0193] 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.

[0194] 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).

[0195] 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.

[0196] Examples of the leuco compound include a leuco compound having a triarylmethane skeleton (triarylmethane-based dye), a leuco compound having a spiropyran skeleton (spiropyran-based dye), a leuco compound having a fluoran skeleton (fluoran-based dye), a leuco compound having a diarylmethane skeleton (diarylmethane-based dye), a leuco compound having a rhodamine lactam skeleton (rhodamine lactam-based dye), a leuco compound having an indolyl phthalide skeleton (indolyl phthalide-based dye), and a leuco compound having a leuco auramine skeleton (leuco auramine-based dye).

[0197] Among them, the leuco compound is preferably a triarylmethane-based dye or a fluoran-based dye, and more preferably a leuco compound having a triphenylmethane skeleton (triphenylmethane-based dye) or a fluoran-based dye.

[0198] From the viewpoint of visibility of the exposed portion and the non-exposed portion, the leuco compound preferably has a lactone ring, a sultine ring or a sultone ring. The lactone ring, sultine ring or sultone ring possessed by the leuco compound changes from a closed-ring state to an open-ring state and develops color, or changes from an open-ring state to a closed-ring state and fades by reacting with a radical generated from a photo radical polymerization initiator or an acid generated from a photo cationic polymerization initiator. The leuco compound preferably has a lactone ring, a sultine ring or a sultone ring and is a compound that develops color by ring-opening with a radical or an acid, and more preferably has a lactone ring and is a compound that develops color by ring-opening with a radical or an acid.

[0199] Examples of the dye 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.

[0200] 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.

[0201] 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.

[0202] The dye is preferably Leucocrystal violet, crystal violet lactone, brilliant green, or Victoria pure blue naphthalene sulfonate.

[0203] 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 total amount of the photosensitive resin layer.

[0204] (Other ingredients) The photosensitive resin layer may further contain known additives such as metal oxide particles, dispersants, acid growth agents, development accelerators, conductive fibers, thermoacid generators, ultraviolet absorbers, thickeners, crosslinking agents, and organic or inorganic precipitation inhibitors.

[0205] 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 predetermined proportions.

[0206] <Middle class> The transfer film preferably includes an intermediate layer between the temporary support and the photosensitive resin layer.

[0207] By incorporating an intermediate layer, mixing of components can be suppressed when applying multiple layer-forming compositions and during storage after application.

[0208] 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.

[0209] 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.

[0210] The following describes the various components that the intermediate layer may contain.

[0211] The intermediate layer preferably contains a resin.

[0212] The above resin preferably contains a water-soluble resin as part or all of it.

[0213] Examples of resins that can be used as water-soluble resins include polyvinyl alcohol-based resins, polyvinylpyrrolidone-based resins, cellulose-based resins, acrylamide-based resins, polyethylene oxide-based resins, gelatin, vinyl ether-based resins, polyamide resins, and copolymers thereof.

[0214] Furthermore, as the water-soluble resin, copolymers of (meth)acrylic acid / vinyl compounds can also be used. Among the copolymers of (meth)acrylic acid / vinyl compounds, copolymers of (meth)acrylic acid / (meth)acrylate are preferred, and copolymers of methacrylic acid / methacrylate are more preferred.

[0215] When the water-soluble resin is a copolymer of (meth)acrylic acid / vinyl compound, the composition ratio (mol%) is preferably, for example, 90 / 10 to 20 / 80, and more preferably 80 / 20 to 30 / 70.

[0216] The lower limit of the weight average molecular weight of the water-soluble resin is preferably 5,000 or more, more preferably 7,000 or more, and even more preferably 10,000 or more. Further, as the upper limit thereof, 200,000 or less is preferable, 100,000 or less is more preferable, and 50,000 or less is even more preferable. The dispersity (Mw / Mn) of the water-soluble resin is preferably from 1 to 10, and more preferably from 1 to 5.

[0217] In addition, in terms of further improving the ability to suppress interlayer mixing in the intermediate layer, the resin contained in the intermediate layer is preferably a resin different from the resin contained in the layer disposed on one side of the intermediate layer and the resin contained in the layer disposed on the other side. For example, when 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, the resin contained in the intermediate layer is preferably a resin different from polymer A and the thermoplastic resin (alkali-soluble resin).

[0218] The water-soluble resin preferably contains polyvinyl alcohol, and more preferably contains both polyvinyl alcohol and polyvinyl pyrrolidone, in terms of improving oxygen barrier properties and the ability to suppress interlayer mixing.

[0219] The water-soluble resin contained in the intermediate layer may be one kind or two or more kinds.

[0220] The content of the water-soluble resin is not particularly limited, but in terms of improving oxygen barrier properties and the ability to suppress interlayer mixing, 50% by mass or more is preferable, 70% by mass or more is more preferable, 80% by mass or more is even more preferable, and 90% by mass or more is particularly preferable, based on the total amount of the water-soluble resin layer (intermediate layer). Further, the upper limit thereof is not particularly limited, but for example, 99.9% by mass or less is preferable, and 99.8% by mass or less is even more preferable.

[0221] The intermediate layer may contain known additives such as surfactants as necessary.

[0222] 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.

[0223] <Thermoplastic resin layer> The transfer film preferably includes a thermoplastic resin layer between the temporary support and the photosensitive resin layer. Furthermore, 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 lamination process, suppressing the inclusion of air bubbles between the substrate and the transfer film. As a result, adhesion between the thermoplastic resin layer and adjacent layers (e.g., the temporary support) can be ensured.

[0224] 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.

[0225] (Alkali-soluble resin (thermoplastic resin)) The thermoplastic resin is preferably an alkali-soluble resin.

[0226] 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.

[0227] As the alkali-soluble resin, acrylic resin is preferred from the viewpoint of developability and adhesion to adjacent layers.

[0228] 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.

[0229] 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 amount of the acrylic resin.

[0230] 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 amount of acrylic resin.

[0231] Furthermore, the alkali-soluble resin is preferably a polymer having acidic groups.

[0232] Examples of acidic groups include carboxyl groups, sulfol groups, phosphate groups, and phosphonic acid groups, with carboxyl groups being preferred.

[0233] 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.

[0234] 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.

[0235] 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.

[0236] 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.

[0237] 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 amount of the acrylic resin.

[0238] 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.

[0239] 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.

[0240] 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.

[0241] The alkali-soluble resin contained in the thermoplastic resin layer may be one type or two or more types.

[0242] From the viewpoint of developability and adhesion to adjacent layers, the content of alkali-soluble resin is preferably 10% to 99% by mass, more preferably 20% to 90% by mass, even more preferably 40% to 80% by mass, and particularly preferably 50% to 75% by mass, relative to the total amount of thermoplastic resin layer.

[0243] (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 at the time of color development is 450 nm or higher, and whose maximum absorption wavelength changes with the presence of an acid, base, or radical.

[0244] 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.

[0245] 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.

[0246] 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.

[0247] The dye B contained in the thermoplastic resin layer may be one type or two or more types.

[0248] 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 amount of the thermoplastic resin layer.

[0249] 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.

[0250] (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.

[0251] 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.

[0252] As compound C, known photoacid generators, photobase generators, and photoradical polymerization initiators (photoradical generators) can be used.

[0253] (Photoacid generator) The thermoplastic resin layer may contain a photoacid generator from the viewpoint of resolution.

[0254] 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.

[0255] 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.

[0256] [ka]

[0257] (Photoradical polymerization initiator) The thermoplastic resin layer may contain a photoradical polymerization initiator.

[0258] 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.

[0259] (Photobase Generator) The thermoplastic resin composition may contain a photobase generator.

[0260] 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.

[0261] The compound C contained in the thermoplastic resin layer may be one type or two or more types.

[0262] 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 amount of the thermoplastic resin layer.

[0263] (Plasticizer) The thermoplastic resin layer preferably contains a plasticizer from the viewpoint of resolution, adhesion to adjacent layers, and developability.

[0264] 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.

[0265] 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.

[0266] 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.

[0267] Examples of (meth)acrylate compounds used as plasticizers include the polymerizable compounds described above as being included in the photosensitive resin layer.

[0268] 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 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.

[0269] 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.

[0270] 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.

[0271] 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.

[0272] The plasticizer contained in the thermoplastic resin layer may be one type or two or more types.

[0273] 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 amount of the thermoplastic resin layer.

[0274] (Sensitizer) The thermoplastic resin layer may contain a sensitizer.

[0275] The sensitizer is not particularly limited and may include sensitizers that may be included in the photosensitive resin layer.

[0276] The thermoplastic resin layer may contain one type of sensitizer or two or more types.

[0277] The amount of sensitizer can be appropriately selected depending on the purpose, but from the viewpoint of improving sensitivity to the light source and visibility of the exposed and unexposed areas, 0.01% to 5% by mass and more preferably 0.05% to 1% by mass relative to the total amount of the thermoplastic resin layer is preferred.

[0278] (Additives, etc.) In addition to the above components, the thermoplastic resin layer may also contain known additives such as surfactants as needed.

[0279] 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.

[0280] 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.

[0281] <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.

[0282] 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, and more preferably a polypropylene film or polyethylene film.

[0283] 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.

[0284] <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.

[0285] <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.

[0286] (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 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.

[0287] (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.

[0288] (Photosensitive resin layer formation process) A photosensitive resin layer forming composition used in the photosensitive resin layer forming process can be prepared by dissolving or dispersing the material to be contained in the photosensitive resin layer in a solvent.

[0289] 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.

[0290] 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.

[0291] 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.

[0292] 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.

[0293] 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.

[0294] 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.

[0295] 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.

[0296] (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.

[0297] [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"). In the exposure step, it is preferable to directly draw with exposure light having a main wavelength of 390 nm to 420 nm.

[0298] (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.

[0299] 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.

[0300] The transfer film and substrate can be bonded together using a known laminator such as a vacuum laminator or an auto-cut laminator.

[0301] 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.

[0302] The substrate is preferably a conductive substrate (wiring substrate) having a support substrate and a conductive layer disposed on the support substrate.

[0303] 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 5000 μm.

[0304] 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.

[0305] 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.

[0306] 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.

[0307] 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.

[0308] 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.

[0309] 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.

[0310] (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.

[0311] The positional relationship between the exposed and unexposed areas in pattern exposure is not particularly limited and can be adjusted as appropriate.

[0312] Exposure may be performed from the photosensitive resin layer side or from the circuit board side.

[0313] The exposure method is preferably direct exposure. In the method for manufacturing a resin pattern according to this disclosure, it is preferable to draw directly onto the photosensitive resin layer.

[0314] While there are other exposure methods, such as those using a photomask, direct imaging has the advantage of not requiring a photomask. On the other hand, in direct drawing methods, the exposure time tends to be long because the pattern is drawn individually. In the resin pattern manufacturing method of the present disclosure, since the transfer film of the present disclosure is used, even when using the direct drawing method, it is possible to achieve both high sensitivity and high resolution without the exposure time becoming too long.

[0315] Exposure may be performed in the atmosphere, under reduced pressure, or under vacuum.

[0316] The detailed arrangement and specific size of the pattern in pattern exposure are not particularly limited.

[0317] From the viewpoint of achieving high resolution, in pattern exposure, the pattern width is preferably 10 μm or less, and more preferably 5 μm or less. The lower limit of the pattern width is not particularly limited, and is, for example, 1 μm.

[0318] The light source for exposure is not particularly limited.

[0319] The exposure light is preferably primarily in the 390nm to 420nm wavelength range. The primary wavelength is the wavelength with the highest intensity.

[0320] The amount of exposure is not particularly limited. The exposure dose is 5 mJ / cm². 2 ~200 mJ / cm² 2 Preferably, it is 10 mJ / cm 2 ~200 mJ / cm 2 It is preferable that it be so.

[0321] (Development process) In the development process, the exposed photosensitive resin layer is developed to form a resin pattern.

[0322] The exposed photosensitive resin layer can be developed using a developing solution.

[0323] 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.

[0324] 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).

[0325] 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.

[0326] 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 amount of the alkaline aqueous solution.

[0327] The temperature of the developing solution is not particularly limited. The developer solution temperature is preferably, for example, 20°C to 40°C.

[0328] Examples of development methods include paddle development, shower development, spray development, shower and spin development, and dip development.

[0329] As for the development method, the development method described in paragraph

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

[0330] 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.

[0331] After the developing process and / or rinsing process, a drying process may be performed to remove excess liquid.

[0332] (Temporary support removal process) The method for manufacturing a resin pattern according to this disclosure preferably includes a step of peeling off a temporary support (hereinafter also referred to as the "temporary support peeling step").

[0333] 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.

[0334] The temporary support peeling step is preferably performed after the bonding step and before the exposure step. The temporary support peeling step may also be performed after the bonding step and before the developing step, or after the exposure step.

[0335] From the viewpoint of 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.

[0336] In the method for manufacturing a resin pattern according to the present disclosure, it is preferable to further include a step of heating the photosensitive resin layer after exposure (hereinafter also referred to as the "heating step") before developing the photosensitive resin layer after exposure. By performing the heating step, the reaction of the photosensitive resin layer is promoted, and an improvement in resolution and adhesion to the substrate can be expected.

[0337] The heating temperature in the heating process is preferably 40°C to 250°C, and more preferably 50°C to 160°C. The heating time in the heating process is preferably 10 seconds to 60 minutes, and more preferably 20 seconds to 10 minutes.

[0338] The method for manufacturing a resin pattern according to this disclosure may include a step of further exposing the resin pattern formed after development (hereinafter also referred to as the "post-exposure step") and / or a step of further heating the formed resin pattern (hereinafter also referred to as the "post-bake step").

[0339] When both a post-exposure process and a post-bake process are included, it is preferable to perform the post-bake process after the post-exposure process.

[0340] The exposure amount in the post-exposure process is preferably 100 mJ / cm 2 to 5000 mJ / cm 2 and more preferably 200 mJ / cm 2 to 3000 mJ / cm 2

[0341] The heating temperature in the post-bake process is preferably 80°C to 250°C, and more preferably 90°C to 160°C. The heating time in the post-bake process is preferably 1 minute to 180 minutes, and more preferably 10 minutes to 60 minutes.

[0342] [Method for manufacturing a conductive pattern] As a first embodiment, the method for manufacturing a conductive pattern of the present disclosure includes, in this order, a step of forming a resin pattern on a conductive substrate using the method for manufacturing a resin pattern of the present disclosure, a step of performing a plating process (hereinafter, also referred to as a "plating step") on a region of the conductive substrate where the resin pattern is not formed, and a step of removing the resin pattern (hereinafter, also referred to as a "pattern removal step").

[0343] The details of the step of forming a resin pattern on a conductive substrate are as described above.

[0344] (Plating step) Examples of the plating method include electrolytic plating and electroless plating. Among these, from the viewpoint of productivity, electrolytic plating is preferable for plating.

[0345] The metal used for the plating process is not particularly limited, and known metals can be used. Examples of metals that can be used include copper, chromium, lead, nickel, gold, silver, tin, zinc, alloys of these metals, etc. From the viewpoint of conductivity, copper or its alloy is preferable.

[0346] ​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.

[0347] (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.

[0348] 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.

[0349] (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.

[0350] Methods for forming the protective layer include electroless plating and electroplating, with electroplating being preferred.

[0351] The average thickness of the protective layer is not particularly limited and can be between 0.3 μm and 3.0 μm.

[0352] (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.

[0353] 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.

[0354] 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 conductive 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").

[0355] 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.

[0356] (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.

[0357] For wet etching, the etching solution used can be appropriately selected as either acidic or alkaline depending on the object being etched.

[0358] 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.

[0359] 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.

[0360] 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).

[0361] 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).

[0362] It is preferable that the etching solution does not dissolve the resist pattern.

[0363] 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.

[0364] 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.

[0365] After etching and / or rinsing, a drying process may be performed to remove excess liquid.

[0366] 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.

[0367] 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.

[0368] 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. [Examples]

[0369] The present disclosure will be further described 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.

[0370] <Preparation of a composition for forming a photosensitive resin layer> A photosensitive resin layer-forming composition was prepared by mixing the components shown in Tables 1 and 2. The values ​​in the table represent the content of each component in parts by mass.

[0371] (Alkali-soluble resin) Polymer A1 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.

[0372] -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

[0373] -Synthesis of Polymer A1- The monomers used in the synthesis of polymer A1 are shown below. St: Styrene (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) MAA: Methacrylic acid (manufactured by Fujifilm Wako Pure Chemical Corporation) MMA: Methyl methacrylate (manufactured by Fujifilm Wako Pure Chemical Corporation)

[0374] Polymer A1: St / MAA / MMA = 53 / 29 / 19 (mass ratio), weight-average molecular weight (Mw) 70,000 in a 30% by mass propylene glycol monomethyl ether acetate solution.

[0375] (polymerizable compound) • Polymerizable compound B1: Product name "BPE-100", 2,2-bis(4-(methacryloylethoxy)phenyl)propane, manufactured by Shin-Nakamura Chemical Industry Co., Ltd. • Polymerizable compound B2: Product name "Arronix M-270", polypropylene glycol diacrylate (n≒12), manufactured by Toagosei Co., Ltd. • Polymerizable compound B3a: Product name "A-TMMT", pentaerythritol tetraacrylate, manufactured by Shin-Nakamura Chemical Industry Co., Ltd. • Polymerizable compound B3b: Product name "A-TMPT-9EO", ethoxylated trimethylolpropane triacrylate, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.

[0376] (Photopolymerization initiator) • Hexaarylbiimidazole compound: Product name "B-CIM", 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, manufactured by Hampford. • Acetophenone compound: Product name "Omnirad651", 2,2-dimethoxy-2-phenylacetophenone, manufactured by IGM Resins BV.

[0377] (The compound represented by formula (1)) Compounds D1 to D6 were used as compounds represented by formula (1).

[0378] Compound D2 was synthesized by the method described in

[0235] of Japanese Patent Publication No. 4912770. Compound D3 was synthesized by the method described in

[0229] of Japanese Patent Publication No. 4912770. Compound D5 was synthesized by the method described in

[0025] of Japanese Patent Publication No. 2010-265383.

[0379] The structural formulas of compounds D1 to D5 are as follows:

[0380] (Sensitizer) Compounds DX1 to DX3 were used as sensitizers. Compound DX1 was synthesized by the method described in Journal of Medicinal Chemistry (1998), 41(14), 2588-2603. Compound DX2: N-methylacridone (manufactured by Tokyo Chemical Industry Co., Ltd.) Compound DX3: 2-Isopropylthioxanthone (manufactured by Tokyo Chemical Industry Co., Ltd.)

[0381] The structural formulas of compounds DX1 to DX3 are as follows:

[0382] [ka]

[0383] • Nitrogen-containing heterocyclic compound: Product name "CBT-1", benzotriazole-based rust inhibitor, manufactured by Johoku Chemical Industry Co., Ltd. • Sulfur-containing heterocyclic compound: Product name "2-benzothiazolethiol", manufactured by Fujifilm Wako Pure Chemical Corporation.

[0384] (Polymerization inhibitor) • Phenothiazine: Manufactured by Kawaguchi Chemical Co., Ltd.

[0385] (Antioxidant) • 1-Phenyl-3-pyrazolidone: Manufactured by Tokyo Chemical Industry Co., Ltd.

[0386] (dye) • Leucocrystal violet: Manufactured by Tokyo Chemical Industry Co., Ltd.

[0387] (Chain transfer agent) N-phenylcarbamoylmethyl-N-carboxymethylaniline: Manufactured by Fujifilm Wako Pure Chemical Corporation

[0388] (Surfactants) • Resin K: Synthesized using the following method. A 300 mL three-necked flask equipped with a condenser, thermometer, stirring blade, and nitrogen inlet tube was heated to 80°C with 14.0 g of cyclopentanone. A mixed solution of 18.00 g (42.6 mmol) of a silicone compound (product name "Cylaprene TM-0701T", manufactured by JNC Corporation), 12.00 g (30.2 mmol) of compound (a) below, 0.25 g (1.1 mmol) of a polymerization initiator (product name "V-601", manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), and 56.00 g of cyclopentanone was added dropwise over 120 minutes. After aging for 1 hour, a mixed solution of 0.17 g (0.7 mmol) of the polymerization initiator and 1.40 g of cyclopentanone was added, and the mixture was aged for another 1 hour. Furthermore, a mixed solution of 0.17 g (0.7 mmol) of the polymerization initiator and 1.40 g of cyclopentanone was added, and the mixture was aged for 3 hours to obtain 98.5 g of resin K solution. Finally, the solvent was replaced with propylene glycol monomethyl ether acetate to obtain a 30% by mass propylene glycol monomethyl ether acetate solution of resin K. The molecular weight was measured by GPC. The Mw of resin K was 24,700, and the Mw / Mn ratio was 2.8. The reaction progress was also confirmed by NMR. Note that in Table 1, the surfactant content indicates the content of resin K.

[0389] [ka]

[0390] The structural formula of resin K is as follows. In the structural formula below, the numerical values ​​indicate the mass ratio of the constituent units.

[0391] [ka]

[0392] (solvent) MEK: Methyl ethyl ketone PGMEA: Propylene glycol monomethyl ether acetate

[0393] <Preparation of composition for forming the intermediate layer> The following components were mixed to prepare a composition for forming an intermediate layer. • Kuraray Poval PVA-205 (polyvinyl alcohol, manufactured by Kuraray Co., Ltd.): 3.22 parts by mass • Polyvinylpyrrolidone K-30 (manufactured by Nippon Shokubai Co., Ltd.): 1.49 parts by mass • BYK-345 (silicone-based surfactant, manufactured by Bic Chemie Japan Co., Ltd.): 0.0015 parts by mass • Ion-exchanged water: 38.12 parts by mass Methanol (manufactured by Mitsubishi Gas Chemical Company, Inc.): 57.17 parts by mass

[0394] <Manufacturing of transfer film> An intermediate layer-forming composition was applied to a temporary support (product name "Lumirror QS62", manufactured by Toray Industries, Inc., polyethylene terephthalate film, 25 μm thick) using a slit nozzle so that the thickness after drying was 1.0 μm. The coating of the intermediate layer-forming composition was dried at 90°C for 180 seconds to form an intermediate layer (water-soluble resin layer). The above-mentioned photosensitive resin layer-forming composition was applied to the surface of the formed intermediate layer using a slit-shaped nozzle so that the thickness after drying was 12.0 μm, and the photosensitive resin layer was formed by drying at 100°C for 2 minutes. A protective film (product name "Trefan KW37", manufactured by Toray Industries, Inc., polypropylene film, thickness: 25 μm) was laminated onto the photosensitive resin layer.

[0395] A transfer film was obtained having a temporary support, an intermediate layer, a photosensitive resin layer, and a protective film in this order.

[0396] The following evaluations were performed using transfer film.

[0397] <Sensitivity> A conductive substrate was fabricated by forming a 100 nm thick copper layer on a glass substrate using sputtering. The protective film was removed from the transfer film. The transfer film and the conductive substrate were bonded together under lamination conditions of roll temperature 100°C, linear pressure 0.6 MPa, and linear speed 1.0 m / min, so that the photosensitive resin layer on the transfer film was in contact with the copper layer on the conductive substrate (bonding process).

[0398] Next, the temporary support was peeled off from the resulting laminate with the glass substrate (temporary support peeling step).

[0399] The exposure light from the exposure unit (M-1S, manufactured by Mikasa Corporation) was filtered through a bandpass filter (HB0405, manufactured by Asahi Spectroscopic Co., Ltd.) to set the center wavelength to 405 ± 10 μm, and then further exposed through a 41-step wedge tablet (T4105, manufactured by Stouffer Industries, Inc.). The exposure amount was measured using an illuminance meter with a 405 nm compatible photodetector (a combination of UIT-201 and UVD-405PD, both manufactured by Ushio Inc.) (exposure process).

[0400] After exposure, the uncured areas were removed by spraying a developer solution (35°C, 1.0% potassium carbonate aqueous solution) with a shower (developing process).

[0401] The minimum exposure required to retain 95% or more of the film thickness after development was read from the OD value of the step wedge tablet. This read value was defined as "sensitivity."

[0402] <Resolution> A copper-clad laminate (copper layer thickness: 35 μm) was prepared, the substrate was pickled, rinsed, and then dried.

[0403] The protective film was removed from the transfer film. The transfer film and the copper-clad laminate were bonded together under lamination conditions of roll temperature 100°C, linear pressure 0.6 MPa, and linear speed 1.0 m / min, such that the photosensitive resin layer of the transfer film was in contact with the copper layer of the copper-clad laminate (bonding process).

[0404] Next, the temporary support was peeled off from the resulting laminate (temporary support peeling step). Using a DL-1000 maskless exposure machine (manufactured by Nano System Solutions Co., Ltd.) with a 405nm laser as the light source, line-and-space patterns with line widths of 3μm to 30μm in 1μm increments were exposed. Based on the sensitivity of the photosensitive resin layer obtained through sensitivity evaluation, the exposure amount was set so that a resist with a width of 15μm ± 1μm remained after development for a 15μm line design (exposure process). After exposure, the uncured areas were removed by spraying a developer solution (35°C, 1.0% potassium carbonate aqueous solution) with a shower, and a resin pattern was formed (development process).

[0405] The obtained resin patterns were observed, and the width of the pattern with the highest resolution among the remaining resin patterns was defined as the "resolution."

[0406] <Rectangularity> The cross-sectional shape of the highest-resolution pattern was observed using a scanning electron microscope (S-4800, Hitachi High-Technologies Corporation), and the rectangularity R of the resin pattern was evaluated using the following formula. R = WB / WT × 100 WB refers to "the line width at a point that is 10% of the height of the remaining resin pattern from the substrate surface." WT stands for "the line width at a point corresponding to 90% of the height of the remaining resin pattern from the substrate surface."

[0407] Furthermore, if WB is smaller than WT and R is less than 100, the cross-sectional shape will have a width that narrows from the top towards the substrate surface. If R is too small, the resin pattern is prone to tilting and peeling, so it is desirable for R to be close to 100. When WB is greater than WT and R is greater than 100, the cross-sectional shape widens from the top towards the substrate surface. If R is large, adjacent resin patterns may come into contact with each other, so it is desirable for R to be close to 100.

[0408] The evaluation results are shown in Tables 1 and 2.

[0409] [Table 1]

[0410] [Table 2]

[0411] As shown in Tables 1 and 2, in Examples 1 to 10, the photosensitive resin layer contained an alkali-soluble resin, a polymerizable compound, a photopolymerization initiator, and a compound represented by formula (1), resulting in high sensitivity and enabling the formation of high-resolution resin patterns by exposure using the direct writing method. Furthermore, it was found that the transfer film of this disclosure can form a resin pattern with high rectangularity. In Comparative Examples 1 to 3, it was found that the photosensitive resin layer did not contain the compound represented by formula (1), resulting in low sensitivity and low resolution.

[0412] In Examples 2, 4, and 5, in formula (1), R 2 and R 4 However, each of these was independently an alkyl group having 1 to 20 carbon atoms, which may have substituents, and it was found that they had higher sensitivity and resolution compared to Examples 1, 3, and 6-10.

[0413] In Example 1, the polymerizable compound included the compound represented by formula (P1), and it was found to have higher resolution compared to Examples 6 and 7.

[0414] In Example 1, the photosensitive resin layer contained at least one selected from the group consisting of nitrogen-containing heterocyclic compounds and sulfur-containing heterocyclic compounds, and it was found to have higher resolution compared to Example 9.

[0415] [Example 11] <Formation of metal wiring patterns> A copper-clad laminate (30 microns copper thickness) was prepared, and after pickling and rinsing the substrate, it was dried. After peeling off the protective film from the transfer film of Example 1, it was laminated under the following conditions: roll temperature 100°C, linear pressure 0.6 MPa, and linear speed 1.0 m / min. Next, the temporary support was peeled off the obtained laminate, and a line and space pattern with line widths of 3 μm to 30 μm in 1 μm increments was exposed using a maskless exposure machine DL-1000 (manufactured by Nano System Solutions Co., Ltd.) with a 405 nm laser as the light source. The exposure amount was the same as in Example 1. Within 5 minutes after exposure, heating was performed at 60°C for 30 seconds using a hot plate. After heating and letting it stand for 30 minutes, the uncured areas were removed by spraying a developing solution (35°C, 1.0% potassium carbonate aqueous solution) with a shower, and a resin pattern was formed. The resulting patterned substrate was cleaned with a degreasing solution from Rohm & Haas, and then rinsed with water. After soft etching with ammonium persulfate, it was rinsed with water. Next, a copper plating solution from Rohm & Haas was used at a current density of 1.25 A / dm². 2 Plating was performed so that the plating height was 4.0 ± 0.5 μm. After plating, the substrate was immersed in a stripping solution (manufactured by Kanto Chemical Co., Ltd.) to remove the remaining resin pattern and form a metal wiring pattern. By using the transfer film of this disclosure, a high-definition plating pattern could be obtained. [Explanation of symbols]

[0416] 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. The device comprises a temporary support and a photosensitive resin layer disposed on the temporary support, The photosensitive resin layer is a transfer film comprising an alkali-soluble resin, a polymerizable compound, a photopolymerization initiator, and a compound represented by the following formula (1). 【Chemistry 1】 In formula (1), X represents an oxygen atom or -N(R １ ), Y represents an aryl group or a heterocyclic group which may have a substituent, R １ , R ２ , R ３ , and R ４ each independently represents a hydrogen atom or a monovalent substituent, and Y and R １ , R ２ , R ３ , or R ４ may each be bonded to one another to form a ring.

2. In the above formula (1), R ２ and R ４ The transfer film according to claim 1, wherein each of them is an alkyl group having 1 to 20 carbon atoms, which may have substituents.

3. The transfer film according to claim 1, wherein the alkali-soluble resin comprises a resin having at least one selected from the group consisting of constituent units derived from compounds represented by the following formulas (R1) and (R2). 【Chemistry 2】 In formula (R1), R １１ represents a hydrogen atom or a methyl group. In formula (R2), R １２ represents a hydrogen atom or a methyl group, and T represents a single bond or a divalent linking group.

4. The transfer film according to claim 1, wherein the polymerizable compound comprises a compound represented by the following formula (P1). 【Transformation 3】 In formula (P1), R ２１ and R ２２ Each of these independently represents a hydrogen atom or a methyl group, and A independently represents -C ２ H ４ - represents B, and each is independently -C ３ H ６ The expression represents a negative value, where n1 and n3 independently represent integers from 1 to 39, and n1 + n3 is an integer from 2 to 40. N2 and n4 independently represent integers from 0 to 29, and n2 + n4 is an integer from 0 to 30.

5. The transfer film according to claim 1, wherein the polymerizable compound comprises at least one selected from the group consisting of trimethylolpropane tri(meth)acrylate, ethylene oxide-modified trimethylolpropane tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, and ethylene oxide-modified pentaerythritol tetra(meth)acrylate.

6. The transfer film according to claim 1, wherein the photopolymerization initiator comprises at least one selected from the group consisting of hexaarylbiimidazole compounds, oxime compounds, alkylphenone compounds, acetophenone compounds, and acylphosphine oxide compounds.

7. The transfer film according to claim 1, wherein the photosensitive resin layer further comprises a resin having at least one selected from the group consisting of constituent units derived from a compound represented by the following formula (A1). 【Chemistry 4】 In formula (A1), R ３１ R represents a hydrogen atom or a methyl group. ４１ represents an alkylene group having 1 to 10 carbon atoms, and L represents an organopolysiloxane residue, a trialkylsilyl group, or a tris(trialkylsilyloxy)silyl group.

8. The transfer film according to claim 1, further comprising at least one selected from the group consisting of nitrogen-containing heterocyclic compounds and sulfur-containing heterocyclic compounds.

9. The transfer film according to claim 1, further comprising an intermediate layer between the temporary support and the photosensitive resin layer.

10. The transfer film according to claim 1, further comprising a thermoplastic resin layer between the temporary support and the photosensitive resin layer.

11. A step of bonding the transfer film and the substrate such that the photosensitive resin layer in the transfer film according to any one of claims 1 to 10 is in contact with the substrate, A step of pattern exposure to the photosensitive resin layer after lamination, The process includes, in this order, developing the photosensitive resin layer after exposure to form a resin pattern, A method for manufacturing a resin pattern, wherein the pattern exposure step involves directly drawing the pattern using exposure light with a main wavelength of 390 nm to 420 nm.

12. The method for manufacturing a resin pattern according to claim 11, further comprising the step of peeling off the temporary support after the step of bonding the transfer film and the substrate, and before the step of exposure of the pattern.

13. The method for manufacturing a resin pattern according to claim 11, further comprising the step of heating the photosensitive resin layer after exposure before developing the photosensitive resin layer after exposure.

14. A step of forming a resin pattern on a substrate using the resin pattern manufacturing method described in claim 11, The process includes performing a plating treatment on the region of the substrate where the resin pattern is not formed, A method for manufacturing a conductive pattern, comprising the steps of removing the aforementioned resin pattern and, in this order.

15. A step of forming a resin pattern on a conductive substrate using the resin pattern manufacturing method described in claim 11, A step of etching the region of the conductive substrate where no resin pattern is formed, The process of removing the resin pattern, A method for manufacturing a conductive pattern having the following elements in this order.

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