Transfer film, method for producing resin pattern, and method for producing conductive pattern

Abstract

Provided are a transfer film and the like which have higher sensitivity than conventional transfer films and which can form a high-resolution resin pattern when forming a resin pattern on a substrate by exposure using a direct drawing method. The present invention provides a transfer film provided with a temporary support and a photosensitive resin layer disposed on the temporary support, the photosensitive resin layer containing an alkali-soluble resin, a polymerizable compound, a photopolymerization initiator, and a compound represented by formula (1), and an application thereof.

Description

Technical Field

[0001] This invention relates to a method for manufacturing a transfer film, a resin pattern, and a conductive pattern. Background Technology

[0002] Because the number of steps required to obtain a specified pattern is small, a method is widely used in which a photosensitive resin layer is deposited on any substrate using a transfer film, the photosensitive resin layer is exposed, and then developed.

[0003] For example, Patent Document 1 and Patent Document 2 describe a lithographic printing plate having a photosensitive layer on a support formed of a photosensitive composition containing a specific sensitizing pigment, an initiator compound, and a specific compound.

[0004] Patent document 3 describes a pattern forming material characterized by having at least a support and a photosensitive layer formed on the support by a photosensitive composition comprising at least an adhesive, a polymerizable compound, a photopolymerization initiator compound and a sensitizer, wherein the haze value of the support is 5.0% or less, the I / O value of the adhesive is 0.300 to 0.650, and the sensitizer is at least one of a polycyclic aromatic hydrocarbon compound.

[0005] Patent Document 1: Japanese Patent Application Publication No. 2007-47770

[0006] Patent Document 2: Japanese Patent No. 4570857

[0007] Patent Document 3: Japanese Patent No. 4646759

[0008] When forming resin patterns on a substrate using direct-draw exposure, higher sensitivity than before is required. Furthermore, it is sometimes desirable to obtain resin patterns with higher resolution than before using direct-draw exposure. Summary of the Invention

[0009] One embodiment of the present invention aims to solve the problem of providing a transfer film that has higher sensitivity than before and is capable of forming high-resolution resin patterns when forming resin patterns on a substrate by exposure using a direct drawing method.

[0010] Furthermore, another embodiment of the present invention aims to solve the problem of providing a method for manufacturing a resin pattern using the above-described transfer film and a method for manufacturing a conductive pattern.

[0011] The methods used to solve the above problems include the following approaches.

[0012] <1>

[0013] A transfer film comprising a temporary support and a photosensitive resin layer disposed on the temporary support.

[0014] The photosensitive resin layer comprises an alkali-soluble resin, a polymerizable compound, a photopolymerization initiator, and a compound represented by the following formula (1).

[0015] [Chemical Formula 1]

[0016]

[0017] In equation (1), X represents an oxygen atom or -N(R) 1 )-, Y represents an aryl or heterocyclic group that can have substituents, R 1 R 2 R 3 and R 4 Y and R represent hydrogen atoms or monovalent substituents independently, respectively. 1 R 2 R 3 or R 4 They can bond together to form a ring.

[0018] <2>

[0019] according to <1> The transfer film, wherein,

[0020] In equation (1), R 2 and R 4 Each can be an alkyl group having 1 to 20 carbon atoms and may have substituents.

[0021] <3>

[0022] according to <1> or <2> The transfer film, wherein,

[0023] Alkali-soluble resins include resins having at least one type of structural unit selected from the group consisting of compounds represented by the following formulas (R1) and (R2).

[0024] [Chemical Formula 2]

[0025]

[0026] In equation (R1), R 11 It represents a hydrogen atom or a methyl group.

[0027] In equation (R2), R 12 T represents a hydrogen atom or a methyl group, and T represents a single bond or a divalent linker.

[0028] <4>

[0029] according to <1> to <3> In any one of the transfer films, wherein,

[0030] Polymerizable compounds include those represented by the following formula (P1).

[0031] [Chemical Formula 3]

[0032]

[0033] In equation (P1), R 21 and R 22 Each of the following can independently represent a hydrogen atom or a methyl group. A can independently represent -C2H4-, B can independently represent -C3H6-, n1 and n3 can independently represent integers from 1 to 39, and n1+n3 can be integers from 2 to 40. n2 and n4 can independently represent integers from 0 to 29, and n2+n4 can be integers from 0 to 30.

[0034] <5>

[0035] according to <1> to <4> In any one of the transfer films, wherein,

[0036] 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.

[0037] <6>

[0038] according to <1> to <5> In any one of the transfer films, wherein,

[0039] The photopolymerization initiator includes at least one selected from the group consisting of hexaaryl biimidazole compounds, oxime compounds, alkyl phenyl ketone compounds, acetophenone compounds, and acylphosphine oxide compounds.

[0040] <7>

[0041] according to <1> to <6> In any one of the transfer films, wherein,

[0042] The photosensitive resin layer further comprises a resin having at least one of the structural units selected from the group consisting of compounds represented by the following formula (A1).

[0043] [Chemical Formula 4]

[0044]

[0045] In equation (A1), R 31 R represents a hydrogen atom or a methyl group. 41It indicates an alkylene group with 1 to 10 carbon atoms, and L indicates an organopolysiloxane residue, trialkylsilyl, or tri(trialkylsiloxy)silyl.

[0046] <8>

[0047] according to <1> to <7> The transfer film according to any one of the following further comprises at least one selected from the group consisting of nitrogen-containing heterocyclic compounds and sulfur-containing heterocyclic compounds.

[0048] <9>

[0049] according to <1> to <8> The transfer film described in any one of the above examples has an intermediate layer between the temporary support and the photosensitive resin layer.

[0050] <10>

[0051] according to <1> to <9> The transfer film described in any one of the above examples has a thermoplastic resin layer between the temporary support and the photosensitive resin layer.

[0052] <11>

[0053] A method for manufacturing a resin pattern, comprising the following steps:

[0054] by <1> to <10> The method of contacting the photosensitive resin layer in the transfer film in any one of the above-mentioned transfer films with the substrate, and the process of bonding the transfer film to the substrate;

[0055] The process of exposing the laminated photosensitive resin layer to a pattern; and

[0056] The process of developing the exposed photosensitive resin layer to form a resin pattern.

[0057] In the pattern exposure process, direct drawing is performed using exposure light with wavelengths of 390nm to 420nm as the main wavelength.

[0058] <12>

[0059] according to <11> The method for manufacturing the resin pattern further includes a step of peeling off a temporary support after the step of bonding the transfer film to the substrate and before the step of pattern exposure.

[0060] <13>

[0061] according to <11> or <12> The method for manufacturing the resin pattern further includes a step of heating the exposed photosensitive resin layer before developing the exposed photosensitive resin layer.

[0062] <14>

[0063] A method for manufacturing a conductive pattern, comprising the following steps:

[0064] use <11> to <13> The method for manufacturing a resin pattern according to any one of the following is a step of forming a resin pattern on a substrate;

[0065] The process of plating on areas of the substrate where no resin pattern has been formed; and

[0066] The process of removing resin patterns.

[0067] <15>

[0068] A method for manufacturing a conductive pattern, comprising the following steps:

[0069] use <11> to <13> The method for manufacturing a resin pattern according to any one of the following is a step of forming a resin pattern on a conductive substrate;

[0070] A process of etching areas of a conductive substrate where no resin pattern has been formed; and

[0071] The process of removing resin patterns.

[0072] Invention Effects

[0073] According to one embodiment of the present invention, a transfer film is provided that has higher sensitivity than before and is capable of forming high-resolution resin patterns when forming resin patterns on a substrate by exposure using a direct drawing method.

[0074] Furthermore, according to another embodiment of the present invention, a method for manufacturing a resin pattern using the above-described transfer film and a method for manufacturing a conductive pattern are provided. Attached Figure Description

[0075] Figure 1 This is a schematic cross-sectional view showing an example of the transfer film involved in the present invention. Detailed Implementation

[0076] The present invention will now be described in detail. The description of the constituent elements described below is sometimes based on representative embodiments of the present invention, but the present invention is not limited to such embodiments.

[0077] Furthermore, in this invention, the term “~”, which indicates a numerical range, is used to encompass the values ​​recorded before and after it as a lower limit and an upper limit.

[0078] In the numerical ranges described in this specification, the upper or lower limit of one numerical range can be replaced with the upper or lower limit of another numerical range described in other stages. Furthermore, the upper or lower limit of the numerical ranges described in this specification can be replaced with the values ​​shown in the embodiments.

[0079] Furthermore, in the designation of groups (atomic groups) in this invention, the designations of unsubstituted and non-substituted groups include groups without substituents, and also include groups with substituents. For example, "alkyl" includes not only alkyl groups without substituents (unsubstituted alkyl groups), but also alkyl groups with substituents (substituted alkyl groups).

[0080] Furthermore, in this invention, a combination of two or more preferred methods is a more preferred method.

[0081] In this invention, when a composition contains multiple substances equivalent to each component, unless otherwise specified, the amount of each component in the composition refers to the total amount of the multiple substances present in the composition.

[0082] In this invention, the term "process" is not only an independent process, but also includes any process that can achieve its intended purpose, even if it cannot be clearly distinguished from other processes.

[0083] In this invention, "(meth)acrylic acid" is a concept that includes both acrylic acid and methacrylic acid, "(meth)acrylate" is a concept that includes both acrylate and methacrylate, and "(meth)acryloyl" is a concept that includes both acryloyl and methacryloyl.

[0084] Furthermore, unless otherwise specified, the weight-average molecular weight (Mw) and number-average molecular weight (Mn) in this invention are determined by gel permeation chromatography (GPC) analysis using columns of TSKgel GMHxL, TSKgel G4000HxL, and TSKgel G2000HxL (all product names manufactured by TOSOH CORPORATION), through the solvent THF (tetrahydrofuran) and a differential refractometer, and are calculated using polystyrene as a standard substance.

[0085] In this invention, unless otherwise specified, the molecular weight of a compound having a molecular weight distribution is a weight-average molecular weight.

[0086] In this invention, unless otherwise specified, the ratio of the structural units of the polymer is a mass ratio.

[0087] In this invention, "solid component" refers to components other than solvents contained in the composition.

[0088] The present invention will now be described in detail.

[0089] [Transfer film]

[0090] The transfer film of the present invention 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).

[0091] [Chemical Formula 5]

[0092]

[0093] In equation (1), X represents an oxygen atom or -N(R) 1 )-, Y represents an aryl or heterocyclic group that can have substituents, R 1 R 2 R 3 and R 4 Y and R represent hydrogen atoms or monovalent substituents independently, respectively. 1 R 2 R 3 or R 4 They can bond together to form a ring.

[0094] Through in-depth research, the inventors discovered that by adopting the above-described structure, higher sensitivity than before is achieved, and high-resolution resin patterns can be formed when resin patterns are formed on a substrate using exposure via a direct drawing method.

[0095] Although the mechanism of action for these excellent effects is not yet clear, the following inferences can be made.

[0096] Generally, when forming resin patterns, there are two exposure methods: exposure via a photomask (mask exposure method) and exposure based on direct drawing (direct drawing method).

[0097] In the direct drawing method, because the pattern is drawn individually, the exposure time tends to be longer compared to the mask exposure method. Therefore, higher sensitivity is required when using the direct drawing method.

[0098] In the transfer film of the present invention, the photosensitive resin layer comprises an alkali-soluble resin, a polymerizable compound and a photopolymerization initiator, as well as a compound represented by formula (1), thereby obtaining a resin pattern with high sensitivity and high resolution.

[0099] On the other hand, there is no record of the compound represented by formula (1) in Patent Document 1 and Patent Document 3.

[0100] Furthermore, the photosensitive layer described in Patent Documents 1 and 2 is the photosensitive layer of the lithographic printing plate original, which differs from the technical concept of the photosensitive resin layer in the transfer film. In the lithographic printing plate original, assuming the use of a thin film (e.g., with a thickness of 1...) μPatterns are formed (approximately m thick), without assuming the improvement of thick films (e.g., thickness of 10). μ Resolution under conditions of m or higher.

[0101] The following is an example of a specific implementation method to illustrate the transfer film.

[0102] Figure 1 The transfer film 20 shown has a temporary support 11, a transfer layer 12 comprising a thermoplastic resin layer 13, an intermediate layer 15 and a photosensitive resin layer 17, and a protective film 19.

[0103] in addition, Figure 1 The transfer film 20 shown is configured with a protective film 19, but it is also possible to omit the protective film 19.

[0104] and, Figure 1 The transfer film 20 shown is configured with a thermoplastic resin layer 13 and an intermediate layer 15, but it is also possible to omit the thermoplastic resin layer 13 or the intermediate layer 15, or to have both the thermoplastic resin layer 13 and the intermediate layer 15.

[0105] The following is an explanation of the various elements that make up the transfer film.

[0106] <Temporary support>

[0107] The temporary support is a support that supports the photosensitive resin layer and can be peeled off.

[0108] The temporary support can be a single layer or a multilayer structure consisting of two or more layers.

[0109] Examples of temporary supports include, for example, a temporary support consisting only of a substrate; a laminate having a substrate and a particle-containing layer disposed on one side of the substrate; and a laminate having a substrate and particle-containing layers disposed on both sides of the substrate.

[0110] Examples of substrates that can be used to form a temporary support include glass, resin film, and paper. From the viewpoints of strength, flexibility, and light transmittance, a resin film is preferred as the substrate for forming the temporary support.

[0111] Examples of resin films include polyethylene terephthalate (PET) films, cellulose triacetate films, polystyrene films, and polycarbonate films. Among these, PET films are preferred, and biaxially stretched PET films are more preferred.

[0112] When a particle-containing layer is disposed on one or two sides of the substrate, the particle-containing layer can be one layer or two or more layers.

[0113] Regarding the particle-containing layer, it can be formed, for example, by coating a particle-containing layer composition onto a substrate and allowing it to dry. Furthermore, the particle-containing layer can also be prepared by co-extrusion during the manufacture of a resin film. The particle-containing layer composition preferably contains an adhesive polymer and particles. The type of adhesive polymer is not particularly limited, and can be appropriately selected according to the purpose. Examples of adhesive polymers include acrylic resins, urethane resins, olefin resins, styrene-butadiene resins, ester resins, vinyl chloride resins, and vinylidene chloride resins. When preparing the particle-containing layer by co-extrusion, PET is preferably used as the adhesive polymer.

[0114] The particle-containing layer may contain one type of adhesive polymer and particles individually, or it may contain two or more types.

[0115] The particles contained in the particle-containing layer are not particularly limited and can be appropriately selected according to the purpose. The content of particles in the particle-containing layer can be appropriately adjusted according to the amount of particles added to the composition for the particle-containing layer. In this specification, the particles contained in the particle-containing layer are referred to as "added particles".

[0116] The added particles are distinct from impurities accidentally introduced during the manufacturing process of the temporary support and particles formed during the manufacturing process of the temporary support. The added particles are preferably particles that do not melt at 200°C.

[0117] In temporary supports, it is possible to determine whether particles have been added, for example, by using the following methods. The shape and distribution of added particles are usually uniform, so they can be identified by observation using an optical microscope.

[0118] As added particles, examples include inorganic particles and organic particles.

[0119] Examples of inorganic particles include particles of inorganic oxides such as silicon dioxide, titanium dioxide, zirconium dioxide, magnesium oxide, and aluminum oxide.

[0120] Examples of organic particles include particles of polymers such as acrylic resins, polyesters, polyurethanes, polycarbonates, polyolefins, and polystyrene.

[0121] When the temporary support has a particle-containing layer, the added particles contained in the particle-containing layer are preferably inorganic oxide particles.

[0122] There is no particular limitation on the average particle size of the added particles, for example, 0.1 μm to 10 μm. The average particle size is determined by cutting 100 nm thick slices using an ultramicrotome and measuring them using TEM (transmission electron microscopy).

[0123] From the viewpoint of ease of forming a photosensitive resin layer on the transfer film and ease of operation when attaching it to the circuit board, 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. The upper limit of the thickness is not particularly limited, for example, it is 200 μm.

[0124] Temporary supports can also be recycled products. Examples of recycled products include membranes that have been cleaned, fragmented, and then used as raw materials for membrane fabrication. A specific example of a recycled product is the Ecouse series from TORAY INDUSTRIES, INC.

[0125] <Photosensitive resin layer>

[0126] The photosensitive resin layer is preferably a negative photosensitive resin layer in which the solubility of the exposed portion in the developer is reduced by exposure and the non-exposed portion is removed by development.

[0127] From the viewpoints of pattern shape, surface roughness and resolution, the average thickness of the photosensitive resin layer is preferably 3μm to 50μm, more preferably 5μm to 25μm, and even more preferably 5μm to 20μm.

[0128] The photosensitive resin layer comprises an alkali-soluble resin, a polymerizable compound, a photopolymerization initiator, and a compound represented by the following formula (1).

[0129] (The compound represented by formula (1))

[0130] The photosensitive resin layer contains the compound represented by formula (1).

[0131] [Chemical Formula 6]

[0132]

[0133] In equation (1), X represents an oxygen atom or -N(R) 1 )-, Y represents an aryl or heterocyclic group that can have substituents, R 1 R 2 R 3 and R 4 Y and R represent hydrogen atoms or monovalent substituents independently, respectively. 1 R 2 R 3 or R 4 They can bond together to form a ring.

[0134] [Y]

[0135] Y represents an aryl or heterocyclic group that can have substituents.

[0136] Examples of aryl groups include those with 6 to 20 carbon atoms, such as phenyl, naphthyl, anthraceneyl, phenanthryl, indene, acenaphthene, and fluorenyl. Phenyl is preferred among these.

[0137] As a heterocyclic group, for example, heterocyclic groups having heteroatoms such as nitrogen atom, oxygen atom, sulfur atom, etc. can be cited.

[0138] The heterocyclic group can be an aliphatic heterocyclic group or an aromatic heterocyclic group (i.e., a heteroaryl group).

[0139] Examples of aromatic heterocyclic compounds that constitute aromatic heterocyclic groups include thiophene, thiathrone, furan, pyran, isobenzofuran, chromene, guarbenzene, pyrrole, pyrazole, isothiazazole, isoxazole, pyrazine, pyrimidine, pyridazine, indoleazine, isoyindoleazine, indole, indazole, purine, quinazine, isoquinoline, naphthidine, quinazoline, cyclophosphine, pteridine, carbazole, caroline, phenanthrene, acridine, phenanthrene, phthalazine, phenarsazine, furazine, and phenoxazine.

[0140] Substituents that can be present as the aryl or heterocyclic group represented by Y include, for example, halogen atoms (-F, -Br, -Cl, -I), hydroxyl, alkyl, alkoxy, aryl, aryloxy, mercapto, alkylthio, arylthio, alkyldithio, aryldithio, amino, N-alkylamino, N,N-dialkylamino, N-arylamino, N,N-diarylamino, N-alkyl-N-arylamino, carbamoyloxy, N-alkylcarbamoyloxy, N-arylcarbamoyloxy, N,N-dialkylcarbamoyloxy, N,N-diarylcarbamoyloxy, N-alkyl-N-arylcarbamoyloxy, alkyl sulfoxy group, aryl sulfoxy group. (group), acyloxy group, acylthio group, acylamino group, N-alkylamide group, N-arylamide group, urea group, N'-alkylurea group, N',N'-dialkylurea group, N'-arylurea group, N',N'-diarylurea group, N'-alkyl-N'-arylurea group, N-alkylurea group, N'-arylurea group, N'-alkyl-N-alkylurea group, N'-alkyl-N-arylurea group, N',N'-dialkyl-N-alkylurea group, N',N'-dialkyl-N-arylurea group, N'-aryl-N-alkylurea group, N'-aryl-N-arylurea group, N',N'-diaryl-N-alkylurea group, N',N'-diaryl-N-alkylurea group, N',N'-diaryl-N-alkylurea group, N',N'-diaryl-N-alkylurea group, N',N'-diaryl-N-alkylurea group N-arylureoyl, N'-alkyl-N'-aryl-N-alkylureoyl, N'-alkyl-N'-aryl-N-arylureoyl, alkoxycarbonylamino, aryloxycarbonylamino, N-alkyl-N-alkoxycarbonylamino, N-alkyl-N-aryloxycarbonylamino, N-aryl-N-alkoxycarbonylamino, N-aryl-N-aryloxycarbonylamino, formyl, acyl, carboxyl, alkoxycarbonyl, aryloxycarbonyl, carbamoyl, N-alkylcarbamoyl, N,N-dialkylcarbamoyl, N-arylcarbamoyl, N,N-diarylcarbamoyl, N-alkyl-N-arylcarbamoyl, alkylsulfinyl (alkyl) sulfinyl group), aryl sulfinyl group, alkyl sulfinyl group, aryl sulfinyl group, sulfonyl (-SO3H) and its conjugate base, alkoxy sulfinyl group, aryloxy sulfinyl group, amino sulfinyl group, N-alkyl amino sulfinyl group, N,N-dialkyl amino sulfinyl group, N-aryl amino sulfinyl group, N,N-diaryl amino sulfinyl group, N-alkyl-N-aryl amino sulfinyl group, amino sulfinyl group, N-alkyl amino sulfinyl group, N,N-dialkyl amino sulfinyl group, N-aryl amino sulfinyl group, N,N-Diarylaminosulfonyl, N-alkyl-N-arylaminosulfonyl, phosphonyl (-PO3H2) and its conjugate base, dialkylphosphonyl (-PO3(alkyl)2), diarylphosphonyl (-PO3(aryl)2), alkylarylphosphonyl (-PO3(alkyl)(aryl)), monoalkylphosphonyl (-PO3H(alkyl)) and its conjugate base, monoarylphosphonyl (-PO3H(aryl)) and its conjugate base, phosphonyloxy (- OPO3H2) and its conjugate bases, dialkylphosphonoyloxy (-OPO3(alkyl)2), diarylphosphonoyloxy (-OPO3(aryl)2), alkylarylphosphonoyloxy (-OPO3(alkyl)(aryl)), monoalkylphosphonoyloxy (-OPO3H(alkyl)) and its conjugate bases, monoarylphosphonoyloxy (-OPO3H(aryl)) and its conjugate bases, cyano, nitro, aryl, heteroaryl, alkenyl, ynyl, and silyl.

[0141] The aryl or heterocyclic group represented by Y may or may not have substituents.

[0142] From the perspective of high sensitivity and high resolution, Y is preferably an aryl group with substituents (i.e., a substituted aryl group).

[0143] From the viewpoint of high sensitivity and high resolution, the substituents of the substituted aryl group are preferably selected from at least one of the group consisting of alkoxy, N,N-dialkylamino and N,N-diarylamino.

[0144] The number of carbon atoms in the alkoxy group is preferably 1 to 3. Examples of alkoxy groups include methoxy and ethoxy groups.

[0145] The number of carbon atoms in the alkyl group constituting the N,N-dialkylamino group is preferably 1 to 3, each independently. Examples of N,N-dialkylamino groups include, for example, N,N-dimethylamino and N,N-diethylamino.

[0146] The number of carbon atoms in the aryl groups constituting the N,N-diarylamino group is preferably 6 to 20, each independently. For example, N,N-diphenylamino can be cited as an example of an N,N-diarylamino group.

[0147] [X]

[0148] X represents an oxygen atom or -N(R) 1 )-. R 1 This indicates a hydrogen atom or a substituent with a valence of 1.

[0149] As R 1 Examples of substituents mentioned in Y above can be cited.

[0150] R 1 Preferably alkyl or aryl.

[0151] Alkyl groups can be straight-chain alkyl groups, branched alkyl groups, or cycloalkyl groups.

[0152] Examples of aryl groups include those described in Y above.

[0153] From the perspective of high sensitivity and high resolution, X is preferably an oxygen atom.

[0154] [R] 2 ]

[0155] R 2 This indicates a hydrogen atom or a substituent with a valence of 1.

[0156] As R 2 Examples of substituents mentioned in Y above can be cited.

[0157] R 2 Preferably alkyl or aryl. Alkyl or aryl groups may have substituents.

[0158] Alkyl groups can be straight-chain alkyl groups, branched alkyl groups, or cycloalkyl groups.

[0159] Examples of aryl groups include those described in Y above.

[0160] From the perspective of high sensitivity and high resolution, R 2 Preferably, it is an alkyl group having 1 to 20 carbon atoms, more preferably a straight-chain alkyl group or a branched alkyl group having 1 to 10 carbon atoms, or a cycloalkyl group having 3 to 8 carbon atoms.

[0161] As R 2 Examples include methyl, ethyl, n-propyl, n-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, hexadecyl, octadecyl, eicosyl, isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, neopentyl, 1-methylbutyl, isohexyl, 2-ethylhexyl, 2-methylhexyl, cyclohexyl, cyclopentyl, and 2-norbornyl.

[0162] [R] 3 ]

[0163] R 3 This indicates a hydrogen atom or a substituent with a valence of 1.

[0164] As R 3 Examples of substituents mentioned in Y above can be cited.

[0165] From the perspective of high sensitivity and high resolution, R 3 Hydrogen atoms are preferred.

[0166] [R] 4 ]

[0167] R 4 This indicates a hydrogen atom or a substituent with a valence of 1.

[0168] As R 4 Examples of substituents mentioned in Y above can be cited.

[0169] R 4 Preferably alkyl or aryl. Alkyl or aryl groups may have substituents.

[0170] Alkyl groups can be straight-chain alkyl groups, branched alkyl groups, or cycloalkyl groups.

[0171] Examples of aryl groups include those described in Y above.

[0172] From the perspective of high sensitivity and high resolution, R 4 Preferably, it is an alkyl group having 1 to 20 carbon atoms, more preferably a straight-chain alkyl group or a branched alkyl group having 1 to 10 carbon atoms, or a cycloalkyl group having 3 to 8 carbon atoms.

[0173] In particular, from the viewpoint of high sensitivity and high resolution, R 2 and R 4 Preferably, each is an alkyl group having 1 to 20 carbon atoms that may have substituents, and more preferably, an unsubstituted alkyl group having 1 to 20 carbon atoms.

[0174] In addition, when an alkyl group has substituents, "number of carbon atoms" refers to the number of carbon atoms contained in the alkyl group other than the substituents.

[0175] If R 2 and R 4 If the compound is alkyl, then the compound represented by formula (1) exhibits excellent sensitivity, especially when irradiated with light of predominant wavelengths of 390 nm to 420 nm. The reason for this is not entirely clear, but it is inferred as follows: The compound represented by formula (1) becomes excited by light of the aforementioned wavelengths, and then reacts with a polymerization initiator, thus initiating the reaction. It is speculated that if R... 2 and R 4 If it is alkyl, the lifetime of the excited state is long and / or the energy transfer rate from the excited state to the polymerization initiator is faster, resulting in excellent sensitivity.

[0176] Y can be related to R 1 R 2 R 3 or R 4 They bond together to form a ring. From the viewpoint of the exposure sensitivity of the photosensitive resin layer, Y and R are preferred. 1 R2 R 3 or R 4 They do not bond with each other separately to form a ring.

[0177] Examples of compounds represented by formula (1) include the following compounds.

[0178] [Chemical Formula 7]

[0179]

[0180] [Chemical Formula 8]

[0181]

[0182]

[0183] The content of the compound represented by formula (1) relative to the total amount of the photosensitive resin layer 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. There is no particular upper limit on the content of the photopolymerization initiator. The content of the compound represented by formula (1) relative to the total amount of the photosensitive resin layer is preferably 70% by mass or less, more preferably 50% by mass or less.

[0184] The compound represented by formula (1) can be obtained, for example, by a condensation reaction of an acidic core or an acidic core having an active methylene group with a substituted or unsubstituted aromatic compound or heterocyclic compound. The compound represented by formula (1) can be synthesized, for example, with reference to Japanese Patent Publication No. 59-28329 and Japanese Patent Application Publication No. 2003-228148.

[0185] As an acidic nucleus, examples include, for instance, saturated / unsaturated ring structures composed of carbon, nitrogen, and / or sulfur (oxygen, sulfur, selenium, and tellurium) atoms, as described in James's "The Theory of the Photographic Process," 4th edition, Macmillan, 1977, pp. 197–200, but not limited to these.

[0186] (Alkali-soluble resin)

[0187] The photosensitive resin layer contains an alkali-soluble resin.

[0188] In addition, in this specification, "alkali solubility" means that the solubility of 100g of a 1% by mass aqueous solution of sodium carbonate at 22°C is 0.1g or more.

[0189] There are no particular limitations on the type of alkali-soluble resin; for example, known alkali-soluble resins used as etching resists can be preferably cited.

[0190] Furthermore, the alkali-soluble resin is preferably an adhesive polymer.

[0191] As an alkali-soluble resin, an alkali-soluble resin having acid groups is preferred.

[0192] Among them, polymer A, which will be described later, is preferred as an alkali-soluble resin.

[0193] -Polymer A-

[0194] The preferred alkali-soluble resin is one containing polymer A.

[0195] From the viewpoint of achieving better resolution by suppressing the swelling of the photosensitive resin layer caused by the developer, the acid value of polymer A is preferably less than 220 mg KOH / g, more preferably less than 200 mg KOH / g, and even more preferably less than 190 mg KOH / g.

[0196] There is no particular limitation on the lower limit of the acid value of polymer A, but from the viewpoint of better developability, it is preferably 60 mg KOH / g or more, and more preferably 120 mg KOH / g or more.

[0197] Additionally, the acid value is the mass [mg] of potassium hydroxide required to neutralize 1g of the sample; in this specification, the unit is stated as mgKOH / g. The acid value can be calculated, for example, based on the average content of acid groups in the compound.

[0198] The acid value of polymer A can be adjusted by the types of structural units that make up polymer A and the content of structural units containing acid groups.

[0199] The weight-average molecular weight of polymer A is preferably between 5,000 and 500,000. If the weight-average molecular weight is below 500,000, the resolution and developability are improved, and therefore it is preferred.

[0200] The weight-average molecular weight is more preferably 100,000 or less, and even more preferably 60,000 or less. 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 aggregate and the properties of the unexposed film, such as edge melting and chipping, when it is set as a photosensitive resin laminate.

[0201] The weight-average molecular weight is more preferably 10,000 or more, further preferably 20,000 or more, and especially preferably 30,000 or more.

[0202] Edge melting refers to the degree to which the photosensitive resin layer easily overflows from the end face of the roller when the transfer film is rolled into a roller shape. Chipping refers to the degree to which chips easily scatter when the unexposed film is cut with a cutter. If these chips adhere to the upper surface of the photosensitive resin laminate, they can cause the film to transfer to the mask and become defective in subsequent exposure processes. The dispersion 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. Dispersion is the ratio of weight-average molecular weight to number-average molecular weight (weight-average molecular weight / number-average molecular weight).

[0203] From the viewpoint of suppressing linewidth thickening or resolution degradation due to focus position shift during exposure, polymer A is preferably a structural unit comprising a polymerizable monomer having an aromatic hydrocarbon group. Examples of aromatic hydrocarbon groups include, for example, substituted or unsubstituted phenyl groups and substituted or unsubstituted aralkyl groups.

[0204] The content of structural units derived from polymeric monomers having aromatic hydrocarbon groups is preferably 10% to 95% by mass relative to the total amount of polymer A, more preferably 20% to 80% by mass.

[0205] 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.).

[0206] The polymerizable monomer having an aromatic hydrocarbon group is preferably a compound represented by the following formulas (R1) and (R2).

[0207] [Chemical Formula 9]

[0208]

[0209] In equation (R1), R 11 It represents a hydrogen atom or a methyl group.

[0210] In equation (R2), R 12 T represents a hydrogen atom or a methyl group, and T represents a single bond or a divalent linker.

[0211] That is, from the viewpoint of high sensitivity and high resolution, the alkali-soluble resin is preferably a resin that includes at least one of the structural units selected from compounds represented by formula (R1) and formula (R2).

[0212] Examples of compounds represented by formula (R1) include styrene and α-methylstyrene.

[0213] In formula (R2), the divalent linking group represented by T can be, for example, an alkylene group having 1 to 10 carbon atoms and an arylene group having 6 to 20 carbon atoms.

[0214] Examples of compounds represented by formula (R2) include benzyl (meth)acrylate and phenylethyl (meth)acrylate.

[0215] The content of at least one of the structural units selected from the group consisting of compounds represented by formula (R1) and formula (R2) is preferably 30% to 70% by mass relative to the total amount of polymer A, more preferably 40% to 65% by mass, and even more preferably 45% to 60% by mass.

[0216] The polymer A containing 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 monomer selected from the group consisting of a first monomer and a second monomer described later.

[0217] Polymer A, which does not contain polymerizable monomers having aromatic hydrocarbon groups, is preferably obtained by polymerizing the first monomer, and more preferably by copolymerizing the first monomer with the second monomer.

[0218] The first monomer is a polymerizable monomer that has a carboxyl group in its molecule. Examples of first monomers include (meth)acrylic acid, fumaric acid, cinnamic acid, crotonic acid, itaconic acid, 4-vinylbenzoic acid, maleic anhydride, and maleic half ester.

[0219] The first monomer is preferably (meth)acrylic acid.

[0220] The content of structural units derived from the first monomer relative to the total amount of polymer A is preferably 5% to 50% by mass, more preferably 10% to 40% by mass, and even more preferably 15% to 35% by mass.

[0221] The second monomer is a non-acidic polymerizable monomer. Examples of second monomers include methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, tert-butyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, cyclohexyl methacrylate, 2-ethylhexyl methacrylate, etc. (meth)acrylates; vinyl acetate and other vinyl alcohol esters; and (meth)acrylonitrile, etc.

[0222] The second monomer is preferably methyl methacrylate, 2-ethylhexyl methacrylate or n-butyl methacrylate, and is particularly preferably methyl methacrylate.

[0223] The content of structural units derived from the second monomer relative to the total amount of polymer A is preferably 5% to 50% by mass, more preferably 10% to 30% by mass, and even more preferably 15% to 25% by mass.

[0224] For example, polymer A is preferably a copolymer containing structural units derived from methacrylic acid, structural units derived from methyl methacrylate, and structural units derived from styrene; or a copolymer containing structural units derived from methacrylic acid and structural units derived from benzyl methacrylate, etc.

[0225] The photosensitive resin composition of the present invention may contain only one type of polymer A, or two or more types. In the case of two or more types, it is preferable to combine two polymer A types containing structural units derived from polymeric monomers having aromatic hydrocarbon groups, or to combine polymer A containing structural units derived from polymeric monomers having aromatic hydrocarbon groups and polymer A not containing structural units derived from polymeric monomers having aromatic hydrocarbon groups. In the latter case, the proportion of polymer A containing structural units derived from polymeric monomers having aromatic hydrocarbon groups relative to the total amount of polymer A is preferably 50% by mass or more, more preferably 70% by mass or more, further preferably 80% by mass or more, and particularly preferably 90% by mass or more.

[0226] Polymer A may have branched or alicyclic structures in its side chains. Furthermore, polymer A may have straight-chain structures in its side chains. For example, branched or alicyclic structures can be introduced into the side chains of polymer A by using polymerizable monomers containing groups having branched structures in their side chains or polymerizable monomers containing groups having alicyclic structures in their side chains. The groups having alicyclic structures can be monocyclic or polycyclic.

[0227] Examples of polymerizable monomers that include a branched group in the side chain include isopropyl methacrylate, isobutyl methacrylate, sec-butyl methacrylate, tert-butyl methacrylate, isoamyl methacrylate, tert-amyl methacrylate, sec-amyl methacrylate, 2-octyl methacrylate, 3-octyl methacrylate, and tert-octyl methacrylate.

[0228] The polymerizable monomer containing a branched group in the side chain is preferably isopropyl methacrylate, isobutyl methacrylate, or tert-butyl methacrylate, and more preferably isopropyl methacrylate or tert-butyl methacrylate.

[0229] Specific examples of polymerizable monomers containing alicyclic groups in their side chains include monomers having monocyclic aliphatic hydrocarbon groups and monomers having polycyclic aliphatic hydrocarbon groups. Furthermore, (meth)acrylates having alicyclic hydrocarbon groups with 5 to 20 carbon atoms are also examples. Examples of polymerizable monomers containing alicyclic groups in their side chains include (meth)acrylate (bicyclo[2.2.1]heptyl-2) ester, (meth)acrylate-1-adamantyl ester, (meth)acrylate-2-adamantyl ester, (meth)acrylate-3-methyl-1-adamantyl ester, (meth)acrylate-3,5-dimethyl-1-adamantyl ester, (meth)acrylate-3-ethyladamantyl ester, (meth)acrylate-3-methyl-5-ethyl-1-adamantyl ester, (meth)acrylate-3,5,8-triethyl-1-adamantyl ester, (meth)acrylate-3,5-dimethyl-8-ethyl-1-adamantyl ester, (meth)acrylate-2-methyl-2-adamantyl ester, (meth)acrylate-2 -Ethyl-2-adamantyl ester, (meth)acrylate 3-hydroxy-1-adamantyl ester, (meth)acrylate octahydro-4,7-menthol indole-5-yl ester, (meth)acrylate octahydro-4,7-menthol indole-1-yl methyl ester, (meth)acrylate-1-menthyl ester, (meth)acrylate tricyclodecane, (meth)acrylate-3-hydroxy-2,6,6-trimethyl-bicyclo[3.1.1]heptyl ester, (meth)acrylate-3,7,7-trimethyl-4-hydroxy-bicyclo[4.1.0]heptyl ester, (meth)acrylate (nor)bornyl ester, (meth)acrylate isobornyl ester, (meth)acrylate fenestrate, (meth)acrylate-2,2,5-trimethylcyclohexyl ester and (meth)acrylate cyclohexyl ester. In the above, the preferred materials are cyclohexyl methacrylate, norborneol methacrylate, isoborneol methacrylate, 1-adamantyl methacrylate, 2-adamantyl methacrylate, fentanyl methacrylate, 1-menthyl methacrylate, and tricyclodecane methacrylate, and more preferably cyclohexyl methacrylate, norborneol methacrylate, isoborneol methacrylate, 2-adamantyl methacrylate, and tricyclodecane methacrylate.

[0230] The synthesis of polymer A is preferably carried out by adding an appropriate amount of free radical polymerization initiator such as benzoyl peroxide or azoisobutyronitrile to a solution obtained by diluting one or more monomers described above with solvents such as acetone, methyl ethyl ketone, or isopropanol, and then heating and stirring. Sometimes, a portion of the mixture is added dropwise to the reaction solution while the synthesis is being carried out. After the reaction is complete, solvent is sometimes added further to adjust to the desired concentration. As a synthesis method, in addition to solution polymerization, bulk polymerization, suspension polymerization, or emulsion polymerization can also be used.

[0231] The glass transition temperature (Tg) of polymer A is preferably 30°C or higher and 135°C or lower. By using polymer A with a Tg of 135°C or lower in the photosensitive resin layer, it is possible to suppress linewidth thickening or resolution degradation due to focus position shift during exposure. From this viewpoint, the Tg of polymer A is more preferably 130°C or lower, further preferably 120°C or lower, and especially preferably 110°C or lower. Furthermore, from the viewpoint of improving edge melt resistance, it is preferable to use polymer A with a Tg of 30°C or higher. From this viewpoint, the Tg of polymer A is more preferably 40°C or higher, further preferably 50°C or higher, especially preferably 60°C or higher, and most preferably 70°C or higher.

[0232] The photosensitive resin layer may also contain resins other than alkali-soluble resins.

[0233] Examples of resins other than alkali-soluble resins include acrylic resins, styrene-acrylic acid copolymers (wherein the styrene content is less than 40% by mass), polyurethane resins, polyvinyl alcohol, polyvinyl formal, polyamide resins, polyester resins, epoxy resins, polyacetal resins, polyhydroxystyrene resins, polyimide resins, polybenzoxazole resins, polysiloxane resins, polyethyleneimine, polyallylamine, and polyalkylene glycols.

[0234] The photosensitive resin layer may contain only one type of alkali-soluble resin or two or more types.

[0235] The content of alkali-soluble resin relative to the total amount of the photosensitive resin layer 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. From the viewpoint of controlling the development time, it is preferable to set the ratio of alkali-soluble resin to the photosensitive resin layer to 90% by mass or less. On the other hand, from the viewpoint of improving resistance to edge melting, it is preferable to set the ratio of alkali-soluble resin to the photosensitive resin layer to 10% by mass or more.

[0236] (polymeric compounds)

[0237] The photosensitive resin layer contains polymeric compounds.

[0238] In this invention, a polymerizable compound refers to a compound having polymerizable groups.

[0239] Alkali-soluble resins can have polymerizable groups, but photosensitive resin layers contain polymerizable compounds in addition to alkali-soluble resins.

[0240] Polymerizable compounds can have polymerizable groups that are either thermally polymerizable or photopolymerizable.

[0241] Examples of thermopolymerizable groups include epoxy groups and oxobutyric groups.

[0242] The polymerizable group is preferably a photopolymerizable group, and more preferably a photoradical polymerizable group.

[0243] From a reactivity point of view, the photopolymerizable group is preferably a group containing an olefinic unsaturated group, more preferably (meth)acryloyl, vinylphenyl, vinyl ether, styryl or allyl, further preferably (meth)acryloyl (i.e., CH2=CH-C(=O)- or CH2=C(CH3)-C(=O)-), and especially preferably (meth)acryloyloxy or (meth)acryloylamino.

[0244] From the viewpoint of superior photosensitivity of the photosensitive resin layer, it is preferable to be a compound having one or more olefin unsaturated groups (i.e., olefin unsaturated compounds), and more preferably a compound having two or more olefin unsaturated groups in one molecule (i.e., polyfunctional olefin unsaturated compounds).

[0245] Furthermore, from the viewpoint of superior resolution and exfoliation properties, the number of olefinic unsaturated groups in a molecule of an olefinic unsaturated compound is preferably 6 or less.

[0246] -Polymerizing compound B1-

[0247] The photosensitive resin layer is preferably a polymeric compound B1 containing at least one aromatic ring and two olefinic unsaturated groups in one molecule.

[0248] From the viewpoint of superior resolution, the content of polymeric compound B1 relative to the total amount of polymeric compound B 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. There is no particular upper limit to the content of polymeric compound B1. From the viewpoint of peelability, the content of polymeric compound B1 relative to the total amount of polymeric compound B 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.

[0249] Examples of aromatic rings in polymerizable compound B1 include, for instance, 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 of these. The aromatic ring in polymerizable compound B1 is preferably an aromatic hydrocarbon ring, more preferably a benzene ring. Furthermore, the aforementioned aromatic ring may have substituents.

[0250] From the viewpoint of improving resolution by suppressing the swelling of the photosensitive resin layer caused by the developer, polymeric compound B1 is preferably having a bisphenol backbone.

[0251] 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). The bisphenol A skeleton is preferred.

[0252] As a polymeric compound B1 having a bisphenol skeleton, examples include compounds having a bisphenol skeleton and two polymeric groups (preferably (meth)acryloyl groups) bonded to both ends of the bisphenol skeleton.

[0253] The bisphenol backbone can be directly bonded to the polymerizable group, or it can be bonded via one or more alkene oxygen groups. The alkene oxygen groups bonded to the bisphenol backbone are preferably ethyleneoxy or propyleneoxy, more preferably ethyleneoxy. There is no particular limitation on the number of alkene oxygen groups bonded to the bisphenol backbone. The number of alkene oxygen groups is preferably 4 to 16 per molecule, more preferably 6 to 14.

[0254] Regarding polymeric compound B1 having a bisphenol skeleton, it is described in paragraphs 0072 to 0080 of Japanese Patent Application Publication No. 2016-224162, the contents of which are incorporated herein by reference.

[0255] The polymerizable compound B1 is preferably a difunctional olefinic unsaturated compound having a bisphenol A backbone, more preferably 2,2-bis(4-((meth)acryloyloxypolyalkoxy)phenyl)propane.

[0256] Examples of 2,2-bis(4-((meth)acryloyloxypolyalkoxy)phenyl)propane include, for instance, 2,2-bis(4-(methacryloyloxydiethoxy)phenyl)propane (FA-324M, manufactured by Hitachi Chemical Co., Ltd.), 2,2-bis(4-(methacryloyloxyethoxypropoxy)phenyl)propane, 2,2-bis(4-(methacryloyloxypentathoxy)phenyl)propane (BPE-500, manufactured by Shin-Nakamura Chemical Co., Ltd.), 2,2-bis(4-(methacryloyloxydodecethoxytetrapropoxy)phenyl)propane (FA-3200MY, manufactured by Hitachi Chemical Co., Ltd.), and 2,2-bis(4-(methacryloyloxypentadecaethoxy)phenyl)propane (BPE-1300, manufactured by Shin-Nakamura Chemical Co., Ltd.). 2,2-bis(4-(methacryloyloxydiethoxy)phenyl)propane (BPE-200, manufactured by Shin-Nakamura Chemical Co., Ltd.) and ethoxylated (10) bisphenol A diacrylate (NK Ester A-BPE-10, manufactured by Shin-Nakamura Chemical Co., Ltd.).

[0257] As a polymerizable compound B1, examples include compounds represented by the following formula (P1).

[0258] From the viewpoint of transferability and resolution, the polymerizable compound is preferably a compound represented by the following formula (P1).

[0259] [Chemical Formula 10]

[0260]

[0261] In equation (P1), R 21 and R 22 Each of the following can independently represent a hydrogen atom or a methyl group. A can independently represent -C2H4-, B can independently represent -C3H6-, n1 and n3 can independently represent integers from 1 to 39, and n1+n3 can be integers from 2 to 40. n2 and n4 can independently represent integers from 0 to 29, and n2+n4 can be integers from 0 to 30.

[0262] Furthermore, the repeating units of -(AO)- and -(B-0)- can be arranged randomly or in blocks. In the case of a block arrangement, either -(AO)- or -(BO)- can be on the diphenyl side.

[0263] n1+n2+n3+n4 is preferably 2 to 20, more preferably 2 to 16, and even more preferably 2 to 8.

[0264] Furthermore, n2+n4 is preferably 0 to 10, more preferably 0 to 4, even more preferably 0 to 2, and especially preferably 0.

[0265] The photosensitive resin layer may contain only one polymeric compound B1 or two or more.

[0266] From the viewpoint of achieving superior resolution, the content of polymeric compound B1 relative to the total amount of the photosensitive resin layer is preferably 5% by mass or more, more preferably 10% by mass or more. There is no particular upper limit to the content of polymeric compound B1. From the viewpoint of improving transferability and resistance to edge melting, the content of polymeric compound B1 is preferably 70% by mass or less, more preferably 60% by mass or less.

[0267] -Polymerizing compound B2-

[0268] The photosensitive resin layer is preferably a polymeric compound B2 containing two olefinic unsaturated groups without an aromatic ring.

[0269] Examples of polymerizable compounds B2 include, for example, alkylene glycol di(meth)acrylate, polyalkylene glycol di(meth)acrylate, urethane di(meth)acrylate, and trimethylolpropane diacrylate.

[0270] Examples of alkylene glycol di(meth)acrylates include tricyclodecanediethanol diacrylate (A-DCP, manufactured by Shin-Nakamura Chemical Co., Ltd.), tricyclodecanediethanol dimethacrylate (DCP, manufactured by Shin-Nakamura Chemical Co., Ltd.), 1,9-nonanediol diacrylate (A-NOD-N, manufactured by Shin-Nakamura Chemical Co., Ltd.), 1,6-hexanediol diacrylate (A-HD-N, manufactured by Shin-Nakamura Chemical Co., Ltd.), ethylene glycol dimethacrylate, 1,10-decanediol diacrylate, and neopentyl glycol di(meth)acrylate.

[0271] Examples of polyalkylene glycol di(meth)acrylates include, for example, polyethylene glycol di(meth)acrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate and polypropylene glycol di(meth)acrylate.

[0272] Examples of urethane dimethacrylates include, for example, propylene oxide-modified urethane dimethacrylates and ethylene oxide and propylene oxide-modified urethane dimethacrylates. Commercially available examples include, for example, 8UX-015A (manufactured by Taisei Fine Chemical Co., Ltd.), UA-32P (manufactured by Shin-Nakamura Chemical Co., Ltd.), and UA-1100H (manufactured by Shin-Nakamura Chemical Co., Ltd.).

[0273] -Polymerizing compound B3-

[0274] The photosensitive resin layer is preferably a polymeric compound B3 containing three or more olefinic unsaturated groups.

[0275] Examples of polymerizable compounds B3 include, for example, dipentaerythritol (tris / tetras / penta / hexa)methacrylate, pentaerythritol (tris / tetra)methacrylate, trimethylolpropane tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, trimethylolethane tri(meth)acrylate, isocyanurate tri(meth)acrylate, glycerol tri(meth)acrylate, and their epoxide-modified forms.

[0276] Here, "(tri / tetra / penta / hexa)meth)acrylate" refers to the concept that includes tri(meth)acrylate, tetra(meth)acrylate, penta(meth)acrylate and hexa(meth)acrylate, and "(tri / tetra)meth)acrylate" refers to the concept that includes tri(meth)acrylate and tetra(meth)acrylate.

[0277] Examples of epoxide-modified olefinic compounds with three or more functions include, for instance, caprolactone-modified (meth)acrylate compounds (KAYARAD DPCA-20, manufactured by Nippon Kayaku Co., Ltd.; A-9300-1CL, manufactured by Shin-Nakamura Chemical Co., Ltd.), epoxide-modified (meth)acrylate compounds (KAYARAD RP-1040, manufactured by Nippon Kayaku Co., Ltd.; ATM-35E and A-9300, manufactured by Shin-Nakamura Chemical Co., Ltd.; EBECRYL 135, manufactured by DAICEL-ALLNEX LTD.), ethoxylated glycerol triacrylate (A-GLY-9E, manufactured by Shin-Nakamura Chemical Co., Ltd.), and ARONIX TO-2349 (TOAGOSEI). (Manufactured by TOAGOSEI CO., LTD.), ARONIX M-520 (manufactured by TOAGOSEI CO., LTD.) and ARONIX M-510 (manufactured by TOAGOSEI CO., LTD.).

[0278] From the viewpoint of resolution, the polymerizable compound is preferably 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.

[0279] The photosensitive resin layer may contain polymeric compounds other than polymeric compounds B1, B2 and B3.

[0280] There are no particular limitations on other polymerizable compounds, and appropriate choices can be made from previously known compounds. Examples of other polymerizable compounds B include compounds having one olefinic unsaturated group in one molecule (i.e., monofunctional olefinic unsaturated compounds).

[0281] Furthermore, other polymeric compound B can be a polymeric compound with an acid group as described in paragraphs 0025 to 0030 of Japanese Patent Application Publication No. 2004-239942.

[0282] Examples of monofunctional alkenyl 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.

[0283] The photosensitive resin layer preferably comprises polymeric compound B1 and polymeric compound B2. In this case, the mass ratio of polymeric compound B1 to polymeric compound B2 (polymeric compound B1:polymeric 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.

[0284] The photosensitive resin layer may contain only one type of polymeric compound or two or more types.

[0285] The content of the polymeric compound relative to the total amount of the photosensitive resin layer is preferably 10% to 70% by mass, more preferably 20% to 60% by mass, and even more preferably 20% to 50% by mass.

[0286] (Photopolymerization initiator)

[0287] The photosensitive resin layer contains a photopolymerization initiator.

[0288] Photopolymerization initiators are compounds that can initiate the polymerization of polymerizable compounds through photochemical rays such as ultraviolet light, visible light, and X-rays. There are no particular limitations on photopolymerization initiators; any known photopolymerization initiator can be used.

[0289] Examples of photopolymerization initiators include photoradical polymerization initiators and photocationic polymerization initiators. Among them, photoradical polymerization initiators are preferred.

[0290] From the viewpoint of sensitivity and resin pattern shape, the photoradical polymerization initiator is preferably at least one of the following: selected from hexaarylbiimidazole compounds, oxime compounds, alkyl phenyl ketone compounds, acetophenone compounds and acylphosphine oxide compounds; more preferably, it is selected from at least one of the following: selected from hexaarylbiimidazole compounds and acetophenone compounds; and even more preferably, it is selected from hexaarylbiimidazole compounds.

[0291] Examples of hexaaryl biimidazole compounds include, for example, 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-dichlorophenyl)-4,4',5,5'-tetraphenylbiimidazole. Methoxyphenyl)biimidazole, 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, 2,2'-bis(o-trifluorophenyl)-4,4',5,5'-tetraphenylbiimidazole, etc.

[0292] The photoradical polymerization initiator can be the polymerization initiator described in paragraphs 0031 to 0042 of Japanese Patent Application Publication No. 2011-95716 and paragraphs 0064 to 0081 of Japanese Patent Application Publication No. 2015-14783.

[0293] Commercially available photoradical polymerization initiators include, for example, 2,4-bis(trichloromethyl)-6-[2-(4-methylphenyl)vinyl]-1,3,5-triazine (product name: TAZ-110, manufactured by Midori Kagaku Co., Ltd.), (product name: TAZ-111, manufactured by Midori Kagaku Co., Ltd.), 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole (manufactured by Tokyo Chemical Industry Co., Ltd.), and 1-[4-(phenylthio)phenyl]-1,2-octanedione-2-(O-benzoyl oxime) (product name: Irgacure (registered trademark) OXE-01, BASF Japan). 1-[9-Ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]acetophenone-1-(O-acetyloxime) (Product name: IrgacureOXE-02, manufactured by BASF Japan Ltd.), Irgacure OXE-03 (manufactured by BASF Japan Ltd.), OXE-04 (manufactured by BASF Japan Ltd.), 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-morpholinylpropane-1-one (Product name: Omnirad 907, manufactured by IGM Resins) (Manufactured by BV), 2-hydroxy-1-{4-[4-(2-hydroxy-2-methylpropanoyl)benzyl]phenyl}-2-methylpropane-1-one (product name: Omnirad 127, manufactured by IGM Resins BV), 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)butanone-1 (product name: XMnirad 369, manufactured by IGM Resins BV), 2-hydroxy-2-methyl-1-phenylpropane-1-one (product name: Omnirad 1173, manufactured by IGM Resins BV), 1-hydroxycyclohexylphenyl ketone (product name: Omnirad 184, manufactured by IGM Resins BV), 2,2-dimethoxy-1,2-diphenylethane-1-one (product name: Omnirad 651, manufactured by IGM Resins) Manufactured by BV), 2,4,6-trimethylbenzoyl-diphenylphosphine oxide (product names: Omnirad TPO H, IGM Resins BV)The company manufactures bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide (product name: Omnirad 819, manufactured by IGM Resins BV), oxime ester photopolymerization initiators (product name: Lunar6, manufactured by DKSH Management Ltd.), 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbisimidazole (2-(2-chlorophenyl)-4,5-diphenylimidazolium dimer) (product name: B-CIM, manufactured by Hampford), and 2-(o-chlorophenyl)-4,5-diphenylimidazolium dimer (product name: BCTB, manufactured by Tokyo Chemical Industry Co., Ltd.).

[0294] Photocationic polymerization initiators (photoacid generators) are compounds that generate acids by receiving photochemical radiation. There are no particular limitations on photocationic polymerization initiators; they are compounds that generate acids by sensing photochemical radiation with wavelengths of 300 nm or higher, preferably 300 nm to 450 nm.

[0295] The photocationic polymerization initiator is preferably a photocationic polymerization initiator that produces acids with a pKa of 4 or less, more preferably a photocationic polymerization initiator that produces acids with a pKa of 3 or less, and particularly preferably a photocationic polymerization initiator that produces acids with a pKa of 2 or less. There is no particular limitation on the lower limit of pKa, but for example, -10.0 is preferred.

[0296] Examples of photocationic polymerization initiators include ionic and nonionic photocationic polymerization initiators.

[0297] Examples of ionic photocationic polymerization initiators include, for example, diaryliodonium salts, triarylsulfonium salts, and quaternary ammonium salts.

[0298] The ionic photocationic polymerization initiator can be the ionic photocationic polymerization initiator described in paragraphs 0114 to 0133 of Japanese Patent Application Publication No. 2014-85643.

[0299] Examples of nonionic photocationic polymerization initiators include trichloromethyltriazine compounds, diazomethane compounds, imide sulfonate compounds, and oxime sulfonate compounds. Trichloromethyltriazine compounds, diazomethane compounds, and imide sulfonate compounds may be compounds described in paragraphs 0083 to 0088 of Japanese Patent Application Publication No. 2011-221494. Furthermore, oxime sulfonate compounds may be compounds described in paragraphs 0084 to 0088 of International Patent Publication No. 2018 / 179640.

[0300] The photopolymerization initiator contained in the photosensitive resin layer can be only one type or two or more types.

[0301] The content of the photopolymerization initiator is not particularly limited, but it is preferably 0.5% by mass or more, more preferably 1% by mass or more, and even more preferably 3% by mass or more, relative to the total amount of the photosensitive resin layer. There is no particular upper limit to the content of the photopolymerization initiator. The content of the photopolymerization initiator relative to the total amount of the photosensitive resin layer is preferably 10% by mass or less, more preferably 8% by mass or less.

[0302] (surfactant)

[0303] From the viewpoint of thickness uniformity, the photosensitive resin layer is preferably containing a surfactant.

[0304] In particular, the photosensitive resin layer is preferably a resin comprising at least one of the structural units selected from compounds represented by the following formula (A1).

[0305] A resin (hereinafter also referred to as "resin K") having at least one of the structural units selected from the group consisting of compounds represented by formula (A1) is preferably used as a surfactant.

[0306] [Chemical Formula 11]

[0307]

[0308] In equation (A1), R 31 R represents a hydrogen atom or a methyl group. 41 It indicates an alkylene group with 1 to 10 carbon atoms, and L indicates an organopolysiloxane residue, trialkylsilyl, or tri(trialkylsiloxy)silyl.

[0309] R 41 The alkylene compounds represented can be straight-chain alkylene compounds, branched alkylene compounds, or contain cyclic structures.

[0310] R 41 The alkylene group represented preferably has 1 to 6 carbon atoms.

[0311] L represents organopolysiloxane residues, for example,

[0312] From -(Si(R) 51 )2O) m Si(R 52 )3 indicates,

[0313] R 51 and R 52 Each alkyl group independently represents an alkyl group with 1 to 5 carbon atoms, where m is an integer from 5 to 100.

[0314] R 51 Methyl is preferred.

[0315] R 52 Preferably, it is a straight-chain alkyl group with 1 to 5 carbon atoms.

[0316] m is preferably 5 to 65.

[0317] The alkyl group contained in the trialkylsilyl group represented by L is preferably methyl or ethyl. More preferably, the trialkylsilyl group is trimethylsilyl or triethylsilyl.

[0318] The alkyl group contained in the tri(trialkylsiloxy)silyl group represented by L is preferably methyl or ethyl. More preferably, the tri(trialkylsiloxy)silyl group is tri(trimethylsiloxy)silyl or tri(triethylsiloxy)silyl.

[0319] From the viewpoint of thickness uniformity, L is preferably tris(trialkylsiloxy)silyl.

[0320] Examples of compounds represented by formula (A1) include the following compounds.

[0321] [Chemical Formula 12]

[0322]

[0323] Resin K may contain structural units other than those derived from the structural units of the compound represented by formula (A1).

[0324] The proportion of structural units derived from the compound represented by formula (A1) in resin K is preferably 50% by mass or more to 80% by mass.

[0325] When the photosensitive resin layer contains resin K, the content of resin K relative to the total amount of the photosensitive resin layer is preferably 0.01% to 5% by mass, more preferably 0.05% to 1% by mass.

[0326] (Nitrogen-containing heterocyclic compounds and sulfur-containing heterocyclic compounds)

[0327] The photosensitive resin layer is preferably composed of at least one of the groups selected from nitrogen-containing heterocyclic compounds and sulfur-containing heterocyclic compounds.

[0328] Examples of nitrogen-containing heterocyclic compounds and sulfur-containing heterocyclic compounds include, for example, benzimidazole, 1,2,4-triazole, benzotriazole, tolyltriazole, butylbenzyltriazole, alkyl dithiothiadiazole, alkyl thiol, 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-benzothiazolium thiol, and 2-mercaptobenzimidazole.

[0329] When the photosensitive resin layer contains at least one of the groups selected from nitrogen-containing heterocyclic compounds and sulfur-containing heterocyclic compounds, the resolution is improved by enhancing the adhesion to the substrate during transfer.

[0330] In the photosensitive resin layer, nitrogen-containing heterocyclic compounds and sulfur-containing heterocyclic compounds can function as rust inhibitors.

[0331] 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 above-mentioned compound relative to the total amount of the photosensitive resin layer is preferably 0.01% to 5% by mass, more preferably 0.05% to 1% by mass.

[0332] (Polymerization inhibitor)

[0333] Photosensitive resin layers may also contain polymerization inhibitors.

[0334] Examples of polymerization inhibitors include, for instance, the thermal polymerization inhibitor described in paragraph 0018 of Japanese Patent No. 4502784. Furthermore, examples of polymerization inhibitors include phenothiazine, phenothiazine, 4-methoxyphenol, naphthylamine, cuprous chloride (I), aluminum nitrosophenylhydroxylamine, and diphenylnitrosamine. Among these, the free radical polymerization inhibitor is preferably phenothiazine, phenothiazine, 4-methoxyphenol, or aluminum nitrosophenylhydroxylamine.

[0335] When the photosensitive resin layer contains a polymerization inhibitor, from the viewpoint of the storage stability of the photosensitive resin composition, the content of the polymerization inhibitor is preferably 0.01% to 5% by mass relative to the total amount of the photosensitive resin layer, more preferably 0.05% to 1% by mass.

[0336] (Antioxidants)

[0337] The photosensitive resin layer may contain antioxidants.

[0338] 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, gallnutol, methylhydroquinone, and chlorohydroquinone; and p-methylaminophenol, p-aminophenol, p-hydroxyphenylglycine, and p-phenylenediamine.

[0339] From the viewpoint of achieving better results in this invention, the antioxidant is preferably a 3-pyrazolone, more preferably a 1-phenyl-3-pyrazolone.

[0340] When the photosensitive resin layer contains an antioxidant, the antioxidant content relative to the total amount of the photosensitive resin layer 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. There is no particular upper limit to the antioxidant content, but it is preferably 1% by mass or less.

[0341] (Chain transfer agent)

[0342] The photosensitive resin layer may contain chain transfer agents.

[0343] Examples of chain transfer agents include N-phenylcarbamoylmethyl-N-carboxymethylaniline, N,N-tetraethyl-4,4-diaminobenzophenone, N-phenylglycine, and thiol compounds.

[0344] When the photosensitive resin layer contains a chain transfer agent, the content of the chain transfer agent relative to the total amount of the photosensitive resin layer is preferably 0.01% to 5% by mass, more preferably 0.05% to 1% by mass.

[0345] (pigment)

[0346] The photosensitive resin layer may contain pigments.

[0347] From the viewpoints of visibility of the exposed and unexposed areas, visibility of the developed pattern, and resolution, the photosensitive resin layer is preferably a pigment (hereinafter also referred to as "pigment N") with a maximum absorption wavelength of 450 nm or higher in the wavelength range of 400 nm to 780 nm during color development, and whose maximum absorption wavelength changes with acid, alkali, or free radicals. While the detailed mechanism is not yet clear, the presence of pigment N improves adhesion to adjacent layers (e.g., temporary supports and intermediate layers), resulting in superior resolution.

[0348] In this specification, "the maximum absorption wavelength of the pigment changes due to acid, alkali or free radicals" can refer to any of the following: the pigment in the chromogenic state is decolorized by acid, alkali or free radicals; the pigment in the decolorized state is chromogenic by acid, alkali or free radicals; and the pigment in the chromogenic state changes to another hue.

[0349] Specifically, the pigment can be a compound that changes color from a decolorized state upon exposure, or a compound that changes color from a color-developing state upon exposure. In this case, it can be a pigment whose color-developing or decolorizing state changes upon exposure due to the generation of acids, bases, or free radicals within the photosensitive resin layer, or a pigment whose color-developing or decolorizing state changes upon exposure due to changes in the state (e.g., pH) within the photosensitive resin layer. Furthermore, pigment N can be a pigment whose color-developing or decolorizing state changes upon direct exposure to acids, bases, or free radicals as stimuli without exposure.

[0350] From the viewpoint of visibility and resolution of the exposed and unexposed portions, the pigment is preferably a pigment whose maximum absorption wavelength changes due to acid or free radicals, and more preferably a pigment whose maximum absorption wavelength changes due to free radicals.

[0351] From the viewpoint of visibility and resolution of the exposed and unexposed areas, the photosensitive resin layer is preferably composed of both a pigment (as pigment N) whose maximum absorption wavelength changes with the presence of free radicals and a photoradical polymerization initiator.

[0352] Furthermore, from the viewpoint of visibility of both the exposed and unexposed areas, the pigment is preferably a pigment that develops color through acid, alkali, or free radicals.

[0353] Examples of pigment-generating mechanisms include adding a photoradical polymerization initiator, a photocationic polymerization initiator (photoacid generator), or a photoalkali generator to a photosensitive resin layer, and generating color after exposure by free radicals, acids, or bases generated from the photoradical polymerization initiator, photocationic polymerization initiator, or photoalkali generator.

[0354] From the viewpoint of visibility of the exposed and unexposed portions, the pigment is preferably at a maximum absorption wavelength of 550 nm or more in the wavelength range of 400 nm to 780 nm during color development, more preferably 550 nm to 700 nm, and even more preferably 550 nm to 650 nm.

[0355] Furthermore, a pigment can have only one maximum absorption wavelength in the wavelength range of 400nm to 780nm for color development, or it can have two or more. When pigment N has two or more maximum absorption wavelengths in the wavelength range of 400nm to 780nm for color development, the maximum absorption wavelength with the highest absorbance among the two or more maximum absorption wavelengths can be 450nm or higher.

[0356] The maximum absorption wavelength of the pigment was obtained by measuring the transmission spectrum of a solution containing the pigment in the range of 400 nm to 780 nm (liquid temperature 25 °C) under atmospheric conditions using a spectrophotometer (UV3100, manufactured by Shimadzu Corporation) and detecting the wavelength at which the light intensity becomes minimal (i.e., the maximum absorption wavelength).

[0357] Examples of pigments that develop or decolorize upon exposure include colorless compounds. Examples of pigments that decolorize upon exposure include colorless compounds, diarylmethane pigments, oxazine pigments, ketone pigments, iminonaphthoquinone pigments, azomethyl alkaloid pigments, and anthraquinone pigments. From the viewpoint of visibility of both the exposed and unexposed areas, colorless compounds are preferred.

[0358] Examples of colorless compounds include, for example, colorless compounds having a triarylmethane skeleton (triarylmethane pigments), colorless compounds having a spiropyran skeleton (spiropyran pigments), colorless compounds having a fluorane skeleton (fluorane pigments), colorless compounds having a diarylmethane skeleton (diarylmethane pigments), colorless compounds having a rhodamine lactam skeleton (rhodamine lactam pigments), colorless compounds having an indolephthalide skeleton (indolephthalide pigments), and colorless compounds having a colorless auramine skeleton (colorless auramine pigments).

[0359] The colorless compound is preferably a triarylmethane pigment or a fluorane pigment, and more preferably a colorless compound (triphenylmethane pigment) or a fluorane pigment having a triphenylmethane skeleton.

[0360] From the viewpoint of visibility of both the exposed and unexposed areas, the colorless compound preferably has a lactone ring, a sulfinolone ring, or a sulfonolone ring. The lactone ring, sulfinolone ring, or sulfonolone ring in the colorless compound reacts with a free radical generated from a photoradical polymerization initiator or an acid generated from a photocationic polymerization initiator, changing from a closed-ring state to an open-ring state to produce color, or changing from an open-ring state to a closed-ring state to decolorize. The colorless compound is preferably a compound having a lactone ring, a sulfinolone ring, or a sulfonolone ring that produces color through ring-opening by a free radical or acid; more preferably, a compound having a lactone ring that produces color through ring-opening by a free radical or acid.

[0361] Examples of pigments include, for example, dyes and colorless compounds.

[0362] Examples of dyes include Brilliant Green, Ethyl Violet, Methyl Green, Crystal Violet, Basic Fuchsin, Methyl Violet 2B, Quinaldinine Red, Bengal Rose, Methylamine Yellow, Thymol Blue, Xylenol Blue, Methyl Orange, p-Methyl Red, Congo Red, Benzo[a]rubicin 4B, α-Naphthyl Red, Nile Blue 2B, Nile Blue A, Methyl Violet, Malachite Green, Parafuchsin, Victoria Blue - Naphthalene Sulfonate, Victoria Blue BOH (manufactured by Hodogaya Chemical Co., Ltd.), Oil Blue #603 (manufactured by Orient Chemical Industries Co., Ltd.), Oil Pink #312 (manufactured by Orient Chemical Industries Co., Ltd.), Oil Red 5B (manufactured by Orient Chemical Industries Co., Ltd.), Oil Scarlet #308 (manufactured by Orient Chemical Industries Co., Ltd.), Oil Red OG (manufactured by Orient Chemical Industries Co., Ltd.), and Oil Red RR (manufactured by Orient Chemical Industries Co., Ltd.). Manufactured by Chemical Industries Co., Ltd.), Oil Green #502 (manufactured by Orient Chemical Industries Co., Ltd.), Spillon Red BEH Premium (manufactured by Hodogaya Chemical Co., Ltd.), m-cresol purple, cresol red, rhodamine B, rhodamine 6G, sulforhodamine B, golden amine, 4-p-diethylaminophenyliminonaphthoquinone, 2-carboxyphenylamino-4-p-diethylaminophenyliminonaphthoquinone, 2-carboxystearylamino-4-p-N,N-bis(hydroxyethyl)amino-phenyliminonaphthoquinone, 1-phenyl-3-methyl-4-p-diethylaminophenylimino-5-pyrazolidineone and 1-β-naphthyl-4-p-diethylaminophenylimino-5-pyrazolidineone.

[0363] Examples of colorless compounds include p,p',p”-hexamethyltriaminotriphenylmethane (colorless crystal violet), Pergascript Blue SRB (manufactured by Ciba-Geigy), crystal violet lactone, malachite green lactone, benzoyl colorless methylene blue, 2-(N-phenyl-N-methylamino)-6-(N-p-tolyl-N-ethyl)aminofluorane, 2-phenylamino-3-methyl-6-(N-ethyl-p-tolylamino)fluorane, 3,6-dimethoxyfluorane, 3-(N,N-diethylamino)-5-methyl-7-(N,N-dibenzylamino)fluorane, and 3-(N-cyclohexyl-N-methylamino)- 6-Methyl-7-phenylaminofluorane, 3-(N,N-diethylamino)-6-methyl-7-phenylaminofluorane, 3-(N,N-diethylamino)-6-methyl-7-phenylaminofluorane, 3-(N,N-diethylamino)-6-methyl-7-chlorofluorane, 3-(N,N-diethylamino)-6-methoxy-7-aminofluorane, 3-(N,N-diethylamino)-7-(4-chlorophenylamino)fluorane, 3-(N,N-diethylamino)-7-chlorofluorane, 3-(N 3-(N,N-diethylamino)-7-benzylaminofluorane, 3-(N,N-diethylamino)-7,8-benzofluorane, 3-(N,N-dibutylamino)-6-methyl-7-phenylaminofluorane, 3-(N,N-dibutylamino)-6-methyl-7-phenylaminofluorane, 3-piperidinyl-6-methyl-7-phenylaminofluorane, 3-pyrrolidinyl-6-methyl-7-phenylaminofluorane, 3,3-bis(1-ethyl-2-methylindol-3-yl)phthalolide, 3,3-bis(1-n- Butyl-2-methylindole-3-yl)phthalolide, 3,3-bis(p-dimethylaminophenyl)-6-dimethylaminophthalolide, 3-(4-diethylamino-2-ethoxyphenyl)-3-(1-ethyl-2-methylindole-3-yl)-4-phthalolide, 3-(4-diethylaminophenyl)-3-(1-ethyl-2-methylindole-3-yl)phthalolide and 3',6'-bis(diphenylamino)spiroisobenzofuran-1(3H),9'-[9H]gutyl-3-one.

[0364] From the viewpoints of visibility of the exposed and unexposed areas, visibility of the pattern after development, and resolution, the pigment is preferably a pigment whose maximum absorption wavelength changes through free radicals, and more preferably a pigment that develops color through free radicals.

[0365] The preferred pigments are colorless crystal violet, crystal violet lactone, brilliant green, or Victoria blue naphthalene sulfonate.

[0366] From the viewpoint of visibility of the exposed and unexposed areas, visibility of the developed pattern, and resolution, the pigment content relative to the total amount of the photosensitive resin layer is preferably 0.1% by mass or more, more preferably 0.1% by mass to 10% by mass, even more preferably 0.1% by mass to 5% by mass, and particularly preferably 0.1% by mass to 1% by mass.

[0367] (Other ingredients)

[0368] The photosensitive resin layer may further contain known additives such as metal oxide particles, dispersants, acid proliferators, development promoters, conductive fibers, heat-generating acid agents, ultraviolet absorbers, thickeners, crosslinking agents, and organic or inorganic precipitation inhibitors.

[0369] There are no particular limitations on the preparation method of the photosensitive resin composition. For example, a method can be given by preparing a solution in advance by dissolving each component in the above-mentioned solvent and mixing the obtained solution in a specified proportion.

[0370] <Intermediate Layer>

[0371] The transfer film preferably has an intermediate layer between the temporary support and the photosensitive resin layer.

[0372] By configuring an intermediate layer, it is possible to suppress the mixing of components during the application of multilayer forming compositions and during storage after coating.

[0373] As an intermediate layer, a water-soluble resin layer comprising a water-soluble resin is preferred.

[0374] Furthermore, as the intermediate layer, an oxygen barrier layer with oxygen barrier function, as described as a "separation layer" in Japanese Patent Application Publication No. 5-072724, can also be used. If the intermediate layer is an oxygen barrier layer, the sensitivity during exposure is improved, the time load of the exposure machine is reduced, and the productivity is increased, therefore it is preferred.

[0375] Regarding the oxygen barrier layer that can be used as an intermediate layer, it is acceptable to select appropriately from the known layers described in the aforementioned publications, etc. Among them, 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.

[0376] The following describes the components that the intermediate layer may contain.

[0377] The intermediate layer preferably contains resin.

[0378] The resin described above preferably includes water-soluble resin as part or all of it.

[0379] Examples of resins that can be used as water-soluble resins include, for example, polyvinyl alcohol resins, polyvinylpyrrolidone resins, cellulose resins, acrylamide resins, polyethylene oxide resins, gelatin, vinyl ether resins, polyamide resins, and copolymers thereof.

[0380] Furthermore, copolymers of (meth)acrylic acid / vinyl compounds can also be used as water-soluble resins. Among the copolymers of (meth)acrylic acid / vinyl compounds, copolymers of (meth)acrylic acid / allyl (meth)acrylate are preferred, and copolymers of methacrylic acid / allyl methacrylate are more preferred.

[0381] When the water-soluble resin is a copolymer of (meth)acrylic acid / vinyl compound, the component ratio (mol%) is preferably 90 / 10 to 20 / 80, and more preferably 80 / 20 to 30 / 70.

[0382] The lower limit for 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. Furthermore, the upper limit is preferably 200,000 or less, more preferably 100,000 or less, and even more preferably 50,000 or less.

[0383] The dispersion (Mw / Mn) of the water-soluble resin is preferably 1 to 10, more preferably 1 to 5.

[0384] Furthermore, from the viewpoint of further improving the interlayer mixing suppression capability of the intermediate layer, the resin contained in the intermediate layer is preferably a different resin 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, in the case where the photosensitive resin layer contains polymer A and the thermoplastic resin (alkali-soluble resin) is contained in the thermoplastic resin layer described later, the resin contained in the intermediate layer is preferably a different resin from polymer A and the thermoplastic resin (alkali-soluble resin).

[0385] From the viewpoint of further improving oxygen barrier properties and interlayer mixing inhibition ability, the water-soluble resin preferably contains polyvinyl alcohol, and more preferably contains both polyvinyl alcohol and polyvinylpyrrolidone.

[0386] The intermediate layer may contain one or more water-soluble resins.

[0387] There is no particular limitation on the content of water-soluble resin. From the viewpoint of further improving oxygen barrier properties and interlayer mixing inhibition ability, the total amount of water-soluble resin relative to the water-soluble resin layer (intermediate layer) 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. In addition, there is no particular limitation on its upper limit, for example, it is preferably 99.9% by mass or less, and even more preferably 99.8% by mass or less.

[0388] The intermediate layer may contain known additives such as surfactants, as needed.

[0389] The thickness of the intermediate layer is not particularly limited, but is preferably 0.1 μm to 5 μm, more preferably 0.5 to 3 μm. If the thickness of the water-soluble resin layer (intermediate layer) is within the above range, the oxygen barrier properties will not decrease and the interlayer mixing inhibition ability will be excellent. Furthermore, it can also suppress the increase in the removal time of the intermediate layer during development.

[0390] <Thermoplastic resin layer>

[0391] The transfer film preferably has a thermoplastic resin layer between the temporary support and the photosensitive resin layer. Furthermore, the transfer film preferably has a thermoplastic resin layer between the temporary support and the intermediate layer. By having a thermoplastic resin layer in the transfer film, the tracking accuracy of the transfer film to the substrate during the bonding process is improved, thereby suppressing the incorporation of air bubbles between the substrate and the transfer film. As a result, the adhesion to layers adjacent to the thermoplastic resin layer (e.g., the temporary support) can be ensured.

[0392] The thermoplastic resin layer comprises resin. The resin may comprise thermoplastic resin as a part or all thereof. That is, in one embodiment, the thermoplastic resin layer is preferably also made of thermoplastic resin.

[0393] (Alkali-soluble resins (thermoplastic resins))

[0394] Thermoplastic resin is preferably an alkali-soluble resin.

[0395] Examples of alkali-soluble resins include, for example, acrylic resins, polystyrene resins, styrene-acrylic copolymers, polyurethane resins, polyvinyl alcohol, polyvinyl formal, polyamide resins, polyester resins, epoxy resins, polyacetal resins, polyhydroxystyrene resins, polyimide resins, polybenzoxazole resins, polysiloxane resins, polyethyleneimine, polyallylamine, and polyalkylene glycols.

[0396] From the viewpoint of developability and adhesion to adjacent layers, acrylic resins are preferred as alkali-soluble resins.

[0397] Here, acrylic resin refers to a resin having at least one structural unit selected from the group consisting of structural units derived from (meth)acrylic acid, structural units derived from (meth)acrylate, and structural units derived from (meth)acrylamide.

[0398] As an acrylic resin, the preferred total content of structural units derived from (meth)acrylic acid, structural units derived from (meth)acrylate, and structural units derived from (meth)acrylamide is 50% by mass or more relative to the total amount of acrylic resin.

[0399] The total content of structural units derived from (meth)acrylic acid and structural units derived from (meth)acrylate is preferably 30% to 100% by mass relative to the total amount of acrylic resin, more preferably 50% to 100% by mass.

[0400] Furthermore, the alkali-soluble resin is preferably a polymer with acid groups.

[0401] Examples of acid groups include carboxyl, sulfonyl, phosphate, and phosphonic acid groups, with carboxyl being the most preferred.

[0402] From the viewpoint of developability, alkali-soluble resins are more preferably alkali-soluble resins with an acid value of 60 mg KOH / g or higher, and even more preferably acrylic resins containing carboxyl groups with an acid value of 60 mg KOH / g or higher.

[0403] There is no particular limitation on the upper limit of the acid value of the alkali-soluble resin, but it is preferably below 300 mg KOH / g, more preferably below 250 mg KOH / g, even more preferably below 200 mg KOH / g, and especially preferably below 150 mg KOH / g.

[0404] There are no particular restrictions on the use of carboxyl-containing acrylic resins with an acid value of 60 mg KOH / g or higher, and appropriate selections can be made from known resins.

[0405] For example, examples include the acrylic resin containing carboxyl groups with an acid value of 60 mg KOH / g or more described in paragraph

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

[0033] to

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

[0053] to

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

[0406] The copolymerization ratio of the carboxyl-containing structural units in the above-mentioned acrylic resin containing carboxyl groups is preferably 5% to 50% by mass relative to the total amount of acrylic resin, more preferably 10% to 40% by mass, and even more preferably 12% to 30% by mass.

[0407] From the viewpoint of developability and adhesion to adjacent layers, acrylic resins having structural units derived from (meth)acrylic acid are particularly preferred as alkali-soluble resins.

[0408] Alkali-soluble resins can possess reactive groups. Any group capable of addition polymerization can be considered a reactive group; examples include olefinic unsaturated groups; condensation groups such as hydroxyl and carboxyl groups; and polyaddition reactive groups such as epoxy groups and (terminated) isocyanate groups.

[0409] 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.

[0410] The thermoplastic resin layer may contain one or more alkali-soluble resins.

[0411] From the viewpoint of developability and adhesion to adjacent layers, the content of alkali-soluble resin relative to the total amount of thermoplastic resin layer 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.

[0412] (pigment)

[0413] The thermoplastic resin layer is preferably a pigment (also referred to as "pigment B") that has a maximum absorption wavelength of 450 nm or more in the wavelength range of 400 nm to 780 nm during color development, and whose maximum absorption wavelength changes with acid, alkali or free radical.

[0414] The preferred method for pigment B is the same as that for pigment N, except for the points described later.

[0415] From the viewpoint of visibility and resolution of the exposed and unexposed areas, pigment B is preferably a pigment whose maximum absorption wavelength changes due to acid or free radicals, and more preferably a pigment whose maximum absorption wavelength changes due to acid.

[0416] From the viewpoint of visibility and resolution of the exposed and unexposed areas, the thermoplastic resin layer preferably contains both a pigment (as pigment B) whose maximum absorption wavelength changes with acid and a compound that generates acid upon light (described later).

[0417] The pigment B contained in the thermoplastic resin layer can be one type or two or more types.

[0418] From the viewpoint of visibility of the exposed and unexposed areas, the content of pigment B relative to the total amount of the thermoplastic resin layer is preferably 0.2% by mass or more, more preferably 0.2% by mass to 6% by mass, even more preferably 0.2% by mass to 5% by mass, and particularly preferably 0.25% by mass to 3.0% by mass.

[0419] Here, the content of pigment B refers to the content of pigment when all pigment B contained in the thermoplastic resin layer is set to its color-developing state. The following explanation uses a pigment that develops color via free radicals as an example to illustrate the quantitative method for determining the content of pigment B.

[0420] Solutions were prepared by dissolving 0.001 g and 0.01 g of pigments in 100 mL of methyl ethyl ketone. Irgacure OXE01 (product name, BASF Japan Ltd.) as a photoradical polymerization initiator was added to each solution, and the solutions were irradiated with 365 nm light to generate free radicals, thus setting all pigments to their chromogenic state. Subsequently, under atmospheric conditions, the absorbance of each solution at a liquid temperature of 25 °C was measured using a spectrophotometer (UV3100, manufactured by SHIMADZU CORPORATION) to create calibration curves.

[0421] Next, except that 0.1 g of the thermoplastic resin layer was dissolved in methyl ethyl ketone instead of pigment, the absorbance of the solution that caused the pigment to fully develop color was measured using the same method as described above. The amount of pigment contained in the thermoplastic resin layer was calculated from the absorbance of the obtained solution including the thermoplastic resin layer, based on the calibration curve.

[0422] In addition, the 3g of thermoplastic resin layer is the same as the 3g of solid component of the composition for forming thermoplastic resin layer.

[0423] (Compounds that generate acids, bases, or free radicals through light)

[0424] The thermoplastic resin layer may contain compounds that generate acids, bases, or free radicals upon exposure to light (also referred to simply as "Compound C").

[0425] As compound C, it is preferably a compound that receives photochemical rays such as ultraviolet and visible light to generate acids, bases or free radicals.

[0426] As compound C, known photoacid generators, photoalkali generators, and photoradical polymerization initiators (photoradical generators) can be used.

[0427] (Photo-acid generator)

[0428] From a resolution perspective, the thermoplastic resin layer can contain a photoacid-generating agent.

[0429] As a photoacid generator, the photocationic polymerization initiator that the above-mentioned photosensitive resin layer may contain can be cited as an example, and the preferred method is the same except for the points described later.

[0430] As a photoacid generator, from the viewpoint of sensitivity and resolution, it is preferable to include 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 tightness, it is more preferable to include an oxime sulfonate compound.

[0431] Furthermore, photoacid generators having the following structure are preferred as photoacid generators.

[0432] [Chemical Formula 13]

[0433]

[0434] (Photoradical polymerization initiator)

[0435] The thermoplastic resin layer may contain a photoradical polymerization initiator.

[0436] As photoradical polymerization initiators, examples of photoradical polymerization initiators that can be included in the aforementioned photosensitive resin layer are given, and the preferred methods are also the same.

[0437] (Photo-induced alkali production agent)

[0438] Thermoplastic resin compositions may contain photoalkali-generating agents.

[0439] As a photo-alkali-producing agent, there are no particular limitations as long as it is a well-known photo-alkali-producing agent. Examples include 2-nitrobenzylcyclohexylcarbamate, triphenylmethanol, O-carbamoylhydroxyamide, O-carbamoyl oxime, [[(2,6-dinitrobenzyl)oxy]carbonyl]cyclohexylamine, bis[[(2-nitrobenzyl)oxy]carbonyl]hexane-1,6-diamine, 4-(methylthiobenzoyl)-1-methyl-1-morpholinylethane, and (4-morpholinylbenzoyl) -1-Benzyl-1-dimethylaminopropane, N-(2-nitrobenzyloxycarbonyl)pyrrolidine, hexaminecobalt(III)tris(triphenylmethylborate), 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)-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.

[0440] The thermoplastic resin layer may contain one or more compounds C.

[0441] From the viewpoint of visibility and resolution of the exposed and unexposed areas, the content of compound C relative to the total amount of the thermoplastic resin layer is preferably 0.1% to 10% by mass, more preferably 0.5% to 5% by mass.

[0442] (Plasticizer)

[0443] From the viewpoints of resolution, adhesion to adjacent layers, and developability, the thermoplastic resin layer preferably contains a plasticizer.

[0444] The plasticizer preferably has a lower molecular weight (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.

[0445] There are no particular limitations as long as the plasticizer is a compound that is compatible with alkali-soluble resins and exhibits plasticity. From the viewpoint of imparting plasticity, the plasticizer is preferably a compound containing alkene groups in its molecule, and more preferably a polyalkylene glycol compound. The alkene groups contained in the plasticizer are more preferably polyethoxy or polypropoxy structures.

[0446] Furthermore, from the viewpoint of resolution and storage stability, the plasticizer preferably 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.

[0447] Examples of (meth)acrylate compounds used as plasticizers include polymerizable compounds described in the above-mentioned photosensitive resin layer.

[0448] In the case where the thermoplastic resin layer and the photosensitive resin layer are laminated in direct contact in the transfer film, it is preferable that both the thermoplastic resin layer and the photosensitive resin layer contain the same (meth)acrylate compound. This is because by having the thermoplastic resin layer and the photosensitive resin layer each contain the same (meth)acrylate compound, interlayer diffusion can be suppressed, and storage stability can be improved.

[0449] When the thermoplastic resin layer contains a (meth)acrylate compound as a plasticizer, from the viewpoint of the adhesion between the thermoplastic resin layer and the adjacent layer, it is preferable that the (meth)acrylate compound does not polymerize even in the exposed portion after exposure.

[0450] Furthermore, from the viewpoints of resolution of the thermoplastic resin layer, adhesion to adjacent layers, and developability, polyfunctional (meth)acrylate compounds having two or more (meth)acryloyl groups in one molecule are preferred as (meth)acrylate compounds that can be used as plasticizers.

[0451] Furthermore, (meth)acrylate compounds that can be used as plasticizers are preferably (meth)acrylate compounds having acid groups or urethane (meth)acrylate compounds.

[0452] The plasticizer contained in the thermoplastic resin layer can be one type or two or more types.

[0453] From the viewpoints of resolution of the thermoplastic resin layer, adhesion to adjacent layers, and developability, the content of plasticizer relative to the total amount of the thermoplastic resin layer is preferably 1% to 70% by mass, more preferably 10% to 60% by mass, and even more preferably 20% to 50% by mass.

[0454] (Sensitizer)

[0455] The thermoplastic resin layer may contain sensitizers.

[0456] There are no particular limitations on what can be included as a sensitizer; examples of sensitizers that can be included in a photosensitive resin layer can be cited.

[0457] The thermoplastic resin layer may contain one or more sensitizers.

[0458] The content of the sensitizer can be appropriately selected according to the purpose, but from the viewpoint of improving the sensitivity to the light source and the visibility of the exposed and unexposed parts, it is preferably 0.01% to 5% by mass, more preferably 0.05% to 1% by mass, relative to the total amount of the thermoplastic resin layer.

[0459] (Additives, etc.)

[0460] In addition to the above-mentioned components, the thermoplastic resin layer may also contain known additives such as surfactants, as needed.

[0461] Furthermore, regarding the thermoplastic resin layer, paragraphs

[0189] to

[0193] of Japanese Patent Application Publication No. 2014-085643 are described, and the contents described in that publication are incorporated into this specification.

[0462] There is no particular limitation on the thickness of the thermoplastic resin layer, but from the viewpoint of adhesion to adjacent layers, it is preferably 1 μm or more, 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.

[0463] <Protective film>

[0464] The transfer film of the present invention may have a protective film on the surface of the photosensitive resin layer on the side opposite to the intermediate layer side.

[0465] Resin films can be used as protective films. Examples of such resin films include polypropylene films, polyethylene films, polyester films such as polyethylene terephthalate films, polycarbonate films, and polystyrene films. Among these, from the viewpoint of heat resistance, polyolefin films are preferred, and polypropylene films or polyethylene films are more preferred.

[0466] 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.

[0467] <Application>

[0468] The transfer film of the present invention is preferably used in the manufacturing process film of semiconductor packaging, printed circuit board, flexible printed circuit board, and rewiring layer of interlayer to form circuit wiring disposed on a support substrate such as sheet, metal substrate, ceramic substrate and glass.

[0469] <Method for manufacturing transfer film>

[0470] The method for manufacturing the transfer film of the present invention is not particularly limited, but preferably includes the following steps in sequence: a step of forming a thermoplastic resin layer with a film thickness of 1 μm to 10 μm by coating one side of a temporary support (hereinafter also referred to as the "thermoplastic resin layer forming step"); a step of forming the intermediate layer by coating the side of the thermoplastic resin layer opposite to the side that contacts the temporary support (hereinafter also referred to as the "intermediate layer forming step"); and a step of forming the photosensitive resin layer by coating the side of the intermediate layer opposite to the side that contacts the thermoplastic resin layer (hereinafter also referred to as the "photosensitive resin layer forming step").

[0471] Furthermore, the method for manufacturing the transfer film of the present invention may include a step of forming a protective film on the surface of a photosensitive resin layer (hereinafter referred to as the protective film forming step).

[0472] Furthermore, 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 used individually or in combination.

[0473] (Thermoplastic resin layer formation process)

[0474] The thermoplastic resin layer forming composition used in the thermoplastic resin layer forming process can be prepared by dissolving or dispersing the material contained in the thermoplastic resin layer in a solvent.

[0475] 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.

[0476] Examples of coating methods for thermoplastic resin layer formation compositions include printing, spraying, roller coating, bar coating, curtain coating, spin coating, and slit coating (i.e., slot coating).

[0477] The drying temperature can be set from 80°C to 130°C. Furthermore, the drying temperature refers to the ambient temperature at which the composition for forming the thermoplastic resin layer is dried.

[0478] The drying time can be set from 20 seconds to 600 seconds.

[0479] (Intermediate layer formation process)

[0480] The intermediate layer forming composition used in the intermediate layer forming process can be prepared by dissolving or dispersing the materials (surfactants, etc.) contained in the intermediate layer in a solvent.

[0481] Examples of solvents include water and the aforementioned water-soluble solvents.

[0482] The coating method, drying temperature, and drying time of the composition for forming the intermediate layer are the same as those for the thermoplastic resin layer formation process, and are omitted here.

[0483] (Photosensitive resin layer formation process)

[0484] The photosensitive resin layer forming composition used in the photosensitive resin layer forming process can be prepared by dissolving or dispersing the material contained in the photosensitive resin layer in a solvent.

[0485] Examples of solvents include, for example, 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.

[0486] When fabricating 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 solvent selected from the group consisting of alkylene glycol ethers and alkylene glycol ether acetates. More preferably, the solvent is a mixed solvent comprising at least one solvent selected from the group consisting of alkylene glycol ethers and alkylene glycol ether acetates and at least one solvent selected from the group consisting of ketones and cyclic ethers; even more preferably, it is a mixed solvent comprising at least one solvent selected from the group consisting of alkylene glycol ethers and alkylene glycol ether acetates, a ketone, and a cyclic ether.

[0487] Examples of alkylene glycol ethers include, for example, ethylene glycol monoalkyl ethers, ethylene glycol dialkyl ethers, propylene glycol monoalkyl ethers, propylene glycol dialkyl ethers, diethylene glycol dialkyl ethers, dipropylene glycol monoalkyl ethers, and dipropylene glycol dialkyl ethers.

[0488] Examples of alkylene glycol ether acetates include, for example, ethylene glycol monoalkyl ether acetate, propylene glycol monoalkyl ether acetate, diethylene glycol monoalkyl ether acetate, and dipropylene glycol monoalkyl ether acetate.

[0489] The solvent may be any solvent described in paragraphs 0092 to 0094 of International Publication No. 2018 / 179640 and in paragraph 0014 of Japanese Patent Application Publication No. 2018-177889, the contents of which are incorporated herein by reference.

[0490] The photosensitive resin composition may contain only one solvent or two or more solvents.

[0491] The solvent content is preferably 50 to 1,900 parts by weight, more preferably 100 to 900 parts by weight, relative to 100 parts by weight of the solid component of the photosensitive resin composition.

[0492] The coating method, drying temperature, and drying time of the photosensitive resin composition are the same as those of the thermoplastic resin layer formation process, and are omitted here.

[0493] (Protective film preparation process)

[0494] The protective film preparation process can include the process of adhering the protective film to the surface of the photosensitive resin layer.

[0495] Regarding the lamination of the protective film, it can be performed using known laminators such as vacuum laminators and automatic cutting laminators. The laminator is preferably equipped with any heatable roller, such as a rubber roller, and capable of applying pressure and heating.

[0496] [Methods for manufacturing resin patterns]

[0497] The method for manufacturing the resin pattern of the present invention preferably includes the following steps in sequence: a step of bonding the transfer film to the substrate in such a way that the photosensitive resin layer in the transfer film of the present invention is in contact with the substrate (hereinafter also referred to as the "bonding step"); a step of exposing the photosensitive resin layer to a pattern (hereinafter also referred to as the "exposure step"); and a step of developing the exposed photosensitive resin layer to form a resin pattern (hereinafter also referred to as the "development step"). In the exposure step, direct drawing is performed using exposure light with a wavelength of 390 nm to 420 nm as the main wavelength.

[0498] (Lamination process)

[0499] In the bonding process, it is preferable to contact and press the surface of the photosensitive resin layer side of the transfer film with the substrate. Furthermore, if the substrate is a conductive substrate as described later, it is preferable to contact and press the photosensitive resin layer with the conductive layer.

[0500] When the transfer film has a protective film described later, it is preferable to perform the lamination process after peeling off the protective film.

[0501] As a pressing method, known transfer methods and lamination methods can be cited as examples. In particular, it is preferable to overlap the transfer film onto the circuit board and apply pressure and heat using rollers or the like.

[0502] The bonding of the transfer film to the substrate can be performed using known laminators such as vacuum laminators and automatic cutting laminators.

[0503] There are no specific restrictions on the lamination temperature.

[0504] The lamination temperature is preferably 80°C to 150°C, more preferably 90°C to 150°C, and even more preferably 100°C to 150°C.

[0505] When using a laminator equipped with rubber rollers, the lamination temperature refers to the temperature of the rubber rollers.

[0506] The substrate is preferably a conductive substrate (wiring substrate) having a support substrate and a conductive layer disposed on the support substrate.

[0507] Examples of supporting substrates include resin substrates, glass substrates, and semiconductor substrates.

[0508] Preferred methods for supporting substrates are described, for example, in paragraph 0140 of International Publication No. 2018 / 155193, the contents of which are incorporated herein by reference.

[0509] Furthermore, when the support substrate is a resin substrate, the preferred material for the resin substrate is a substrate containing a cyclic olefin polymer, polyethylene terephthalate, or polyimide.

[0510] The average thickness of the support substrate is not particularly limited and can be set to 5.0 μm to 5000 μm.

[0511] From the viewpoint of conductivity and fine line formation, the conductive layer is preferably selected from at least one layer chosen 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.

[0512] Furthermore, a single conductive layer or two or more conductive layers can be disposed on the support substrate. When two or more conductive layers are disposed, conductive layers of different materials are preferred.

[0513] As a preferred embodiment of the conductive layer, for example, it is described in paragraph 0141 of International Publication No. 2018 / 155193, the contents of which are incorporated herein by reference.

[0514] The conductive substrate is preferably a substrate having at least one of a transparent electrode and a circuitous wiring. Conductive substrates with these structures are preferably used as substrates for touch panels.

[0515] Transparent electrodes can preferably function as electrodes for touch panels. The transparent electrodes are preferably composed of metal oxide films such as ITO (indium tin oxide) and IZO (indium zinc oxide), metal meshes, and metal nanowires.

[0516] Examples of fine metal wires include those made of silver or copper. Among these, silver conductive materials such as silver mesh and silver nanowires are preferred.

[0517] Metal is the preferred material for circuit wiring.

[0518] Examples of metals suitable for use as materials for circuit routing include gold, silver, copper, molybdenum, aluminum, titanium, chromium, zinc, manganese, and alloys composed of two or more of these metals. Copper, molybdenum, aluminum, or titanium are preferred materials for circuit routing, with copper being particularly preferred.

[0519] The substrate can be a substrate on which components that connect semiconductor elements to each other are assembled.

[0520] Examples of components that connect semiconductor elements to each other include components that have wiring patterns formed on a silicon substrate, such as those connecting semiconductor elements to each other.

[0521] 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 set from 50 nm to 2 μm. There are no particular limitations on the method for forming the seed layer; examples include coating a dispersion of metal particles and sintering the coating, sputtering, and vapor deposition.

[0522] From the viewpoint of reducing transmission loss, the dielectric loss tangent of the substrate at 24GHz is preferably 0.05 or less, and more preferably 0.03 or less.

[0523] (Exposure process)

[0524] The exposure process involves patterning the photosensitive resin layer. "Patterned exposure" refers to the method of exposing the resin layer to create a pattern, and specifically, it refers to exposure where there are exposed and unexposed areas.

[0525] There are no particular restrictions on the positional relationship between the exposed and unexposed areas in pattern exposure, and it can be adjusted appropriately.

[0526] Exposure can be performed from the photosensitive resin layer side or from the circuit board side.

[0527] The preferred exposure method is direct exposure. In the method for manufacturing the resin pattern of the present invention, it is preferable to directly draw the photosensitive resin layer.

[0528] As an exposure method, there are also methods that expose through a photomask, but from the point of view, the direct drawing method is advantageous if no photomask is needed.

[0529] On the other hand, in the direct drawing method, since the pattern is drawn individually, there is a tendency for the exposure time to become longer. In the resin pattern manufacturing method of the present invention, since the transfer film of the present invention is used, the exposure time does not become too long even when using the direct drawing method, thus achieving both high sensitivity and high resolution.

[0530] Exposure can be carried out in the atmosphere, under reduced pressure, or in a vacuum.

[0531] There are no particular restrictions on the detailed configuration and specific size of the pattern in the pattern exposure.

[0532] From a high-precision perspective, the pattern width is preferably 10 μm or less, more preferably 5 μm or less, during pattern exposure. There is no particular limitation on the lower limit of the pattern width; for example, it can be 1 μm.

[0533] There are no particular restrictions on the light source used for exposure.

[0534] The preferred exposure light wavelength is 390nm to 420nm. Furthermore, the dominant wavelength refers to the wavelength with the highest intensity.

[0535] There is no specific limit to the amount of exposure.

[0536] The optimal exposure level is 5 mJ / cm. 2 ~200mJ / cm 2 More preferably 10 mJ / cm 2 ~200mJ / cm2 .

[0537] (Developing process)

[0538] In the developing process, the exposed photosensitive resin layer is developed to form a resin pattern.

[0539] The development of the exposed photosensitive resin layer can be performed using a developing solution.

[0540] There are no particular restrictions on the developer; any known developer can be used.

[0541] As a developer, for example, the developer described in Japanese Patent Application Publication No. 5-72724 can be cited.

[0542] The developer is preferably an alkaline aqueous solution.

[0543] Examples of alkaline compounds that can be included 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).

[0544] There is no particular limitation on the pH of alkaline aqueous solutions.

[0545] The pH of the alkaline aqueous solution at 25°C is preferably 8 to 13, more preferably 9 to 12, and even more preferably 10 to 12.

[0546] The content of alkaline compounds in the alkaline aqueous solution is not particularly limited, but for example, it is preferably 0.1% to 5% by mass, more preferably 0.1% to 3% by mass, relative to the total amount of the alkaline aqueous solution.

[0547] There is no particular limitation on the liquid temperature of the developer.

[0548] The liquid temperature of the developer is preferably, for example, 20°C to 40°C.

[0549] Examples of development methods include, for example, spin-dip development, spray development, mist development, spray and spin development, and immersion development.

[0550] As a developing method, the developing method described in paragraph

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

[0551] After the developing process, a rinsing process to remove the developer can be performed. Water or similar substances can be used in the rinsing process.

[0552] After the developing and / or rinsing process, a drying process to remove excess liquid can be performed.

[0553] (Temporary support removal process)

[0554] The method for manufacturing the resin pattern of the present invention preferably includes a step of peeling off a temporary support (hereinafter also referred to as the "temporary support peeling step").

[0555] In the temporary support peeling process, the temporary support in the transfer film is peeled off.

[0556] There are no particular limitations on the method for peeling off the temporary support; the same mechanism as the covering film peeling mechanism described in paragraphs

[0161] to

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

[0557] The temporary support peeling process is preferably performed after the bonding process and before the exposure process. Alternatively, the temporary support peeling process can be performed after the bonding process and before the developing process, or after the exposure process.

[0558] From the viewpoint of suppressing defects in the resin pattern, the temporary support peeling process is preferably performed after the bonding process and before the exposure process.

[0559] In the method for manufacturing the resin pattern of the present invention, it is preferable to further include a step of heating the exposed photosensitive resin layer (hereinafter also referred to as the "heating step") before developing the exposed photosensitive resin layer. By performing the heating step, the reaction of the photosensitive resin layer is promoted, and improvements in resolution and adhesion to the substrate can be expected.

[0560] The heating temperature in the heating process is preferably 40℃~250℃, more preferably 50℃~160℃.

[0561] The heating time in the heating process is preferably 10 seconds to 60 minutes, more preferably 20 seconds to 10 minutes.

[0562] In addition, the method for manufacturing the resin pattern of the present invention 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-baking step").

[0563] In cases where both a post-exposure process and a post-baking process are included, it is preferable to perform the post-baking process after the post-exposure process.

[0564] The preferred exposure level in the post-exposure process is 100 mJ / cm. 2 ~5000mJ / cm 2 More preferably 200 mJ / cm 2 ~3000mJ / cm 2 .

[0565] The heating temperature in the post-baking process is preferably 80℃~250℃, more preferably 90℃~160℃.

[0566] The heating time in the post-baking process is preferably 1 minute to 180 minutes, more preferably 10 minutes to 60 minutes.

[0567] [Methods for manufacturing conductive patterns]

[0568] As a first embodiment, the method for manufacturing the conductive pattern of the present invention preferably includes the following steps in sequence: a step of forming a resin pattern on a conductive substrate using the resin pattern manufacturing method of the present invention; a step of performing a plating process on the area of ​​the conductive substrate where no resin pattern is formed (hereinafter also referred to as the "plating process"); and a step of removing the resin pattern (hereinafter also referred to as the "pattern removal process").

[0569] The details of the process of forming a resin pattern on a conductive substrate are as described above.

[0570] (Plating process)

[0571] Examples of plating methods include electroplating and electroless plating. From a productivity point of view, electroplating is preferred.

[0572] There are no particular restrictions on the metal used in the plating process; any known metal can be used. Examples of usable metals include copper, chromium, lead, nickel, gold, silver, tin, zinc, and alloys of these metals. From the viewpoint of electrical conductivity, copper or its alloys are preferred.

[0573] The average thickness of the coating layer formed by the plating process is not particularly limited and can be set to 0.1μm to 20.0μm.

[0574] (Pattern removal process)

[0575] There are no particular limitations on the method for removing resin patterns; methods such as chemical treatment can be cited, but methods using a removal solution are preferred.

[0576] Examples of removal solutions include those obtained by dissolving inorganic or organic base components in water, dimethyl sulfoxide, N-methylpyrrolidone, or a mixture thereof.

[0577] Examples of inorganic base components include sodium hydroxide and potassium hydroxide.

[0578] Examples of organic base components include primary amine compounds, secondary amine compounds, tertiary amine compounds, and quaternary ammonium salt compounds.

[0579] The preferred temperature of the removal liquid is 30°C to 80°C, and more preferably 50°C to 80°C.

[0580] As a preferred method for removal, one method is to immerse the laminate having the pattern to be removed in a removal solution at a temperature of 50°C to 80°C under stirring for 1 minute to 30 minutes.

[0581] Furthermore, the pattern can be removed using a removal liquid and by known methods such as spraying, spraying, or immersion.

[0582] (Protective layer formation process)

[0583] The method for manufacturing the conductive pattern of the present invention may include a step of forming a protective layer on the surface of the plating layer (hereinafter also referred to as the "protective layer forming step") after the formation of the resin pattern and before the pattern removal step.

[0584] The material constituting the protective layer is preferably a material that is insoluble 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 of these, and resins. Nickel or chromium is preferred as the material constituting the protective layer.

[0585] Methods for forming a protective layer include electroless plating and electroplating, with electroplating being the preferred method.

[0586] The average thickness of the protective layer is not particularly limited and can be set to 0.3μm to 3.0μm.

[0587] (Seed layer removal process)

[0588] When the substrate has a seed layer on its surface, the method for manufacturing the conductive pattern of the present invention 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 fine lines.

[0589] There are no particular limitations on the method for removing the seed layer; it can be done using a known etching solution.

[0590] Examples of etching solutions include ferric chloride solution, copper chloride solution, ammonia-alkali solution, sulfuric acid-hydrogen peroxide mixture, and phosphoric acid-hydrogen peroxide mixture.

[0591] As a second embodiment, the method for manufacturing the conductive pattern of the present invention preferably includes the following steps in sequence: a step of forming a resin pattern on a conductive layer of a conductive substrate (a substrate having a conductive layer) using the resin pattern manufacturing method of the present invention; a step of etching areas of the conductive substrate where no resin pattern is formed (hereinafter also referred to as "etching step"); and a step of removing the resin pattern (hereinafter also referred to as "pattern removal step").

[0592] The details of the process of forming a resin pattern on the substrate are as described above.

[0593] The preferred embodiment of the substrate having a conductive layer is as described above.

[0594] Furthermore, the preferred method of the pattern removal process in the second embodiment is the same as the preferred method of the pattern removal process in the first embodiment.

[0595] (Etching process)

[0596] As a method of etching, well-known etching methods can be cited.

[0597] Specifically, examples include the methods described in paragraphs

[0209] to

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

[0048] to

[0054] of Japanese Patent Application Publication No. 2010-152155, and dry etching methods such as wet etching immersed in etching solution and plasma etching.

[0598] The etching solution used for wet etching can be appropriately selected as acidic or alkaline depending on the object being etched.

[0599] Examples of acidic etching solutions include, for example, an acidic aqueous solution containing at least one acidic compound and an acidic mixed aqueous solution containing the acidic compound and at least one selected from the group consisting of ferric chloride, ammonium fluoride and potassium permanganate.

[0600] The acidic compound (a compound that is soluble in water and exhibits acidity) included 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.

[0601] Examples of alkaline etching solutions include, for example, an alkaline aqueous solution containing at least one alkaline compound and an alkaline mixed aqueous solution of an alkaline compound and a salt (e.g., potassium permanganate).

[0602] The alkaline compound (a compound that is soluble in water and exhibits alkalinity) included 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).

[0603] The etching solution is preferably one that does not dissolve the resist pattern.

[0604] The developing solution used in the developing process can also be used as the etching solution in the etching process. In this case, the developing and etching processes can be performed simultaneously.

[0605] After etching, a rinsing process can be performed to remove the etching solution. Water or similar substances can be used in the rinsing process.

[0606] After etching and / or rinsing, a drying process to remove excess liquid can be performed.

[0607] In addition, the transfer film of the present invention can be used to manufacture circuit wiring substrates.

[0608] The method for manufacturing a circuit wiring substrate can include a process of forming a solder resist layer with openings on the surface of a substrate with a seed layer removed by using a solder resist (hereinafter also referred to as the "solder resist layer forming process").

[0609] The opening is preferably one that exposes the conductive pattern formed on the surface of the substrate.

[0610] As a solder resist, conventionally known resins can be used. Examples of solder resists include azido-cyclopentadiene resins, azido-phenol resins, and chloromethyl polystyrene resins.

[0611] The average thickness of the solder mask layer is not particularly limited and can be set to 5μm to 50μm.

[0612] There are no particular limitations on the method for forming the solder mask layer; it can be done using methods that are already known.

[0613] The method for manufacturing a circuit wiring board can include a step of forming bump electrodes at openings in the solder mask layer. The bump electrodes are preferably connected to conductive patterns exposed at the openings.

[0614] The manufacturing method of the circuit wiring board can include a process of mounting semiconductor elements connected to bump electrodes.

[0615] The semiconductor used is preferably equipped with electrodes, and is preferably connected to bump electrodes.

[0616] After mounting the semiconductor, it is preferable to use a conventionally known sealing material to seal the semiconductor.

[0617] Example

[0618] The present invention will be further described in detail below through embodiments.

[0619] The materials, quantities, proportions, processing contents, and processing steps shown in the following embodiments can be appropriately modified as long as they do not depart from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below.

[0620] <Preparation of Compositions for Forming Photosensitive Resin Layers>

[0621] The components shown in Tables 1 and 2 are mixed to prepare a composition for forming a photosensitive resin layer.

[0622] In addition, the values ​​in the table represent the content of each component in parts by mass.

[0623] (Alkali-soluble resin)

[0624] Polymer A1 was synthesized using a known method. Furthermore, the weight-average molecular weight (Mw) of the synthesized polymer was determined by gel permeation chromatography (GPC) under the following conditions.

[0625] -GPC Conditions-

[0626] Equipment: Manufactured by TOSOH CORPORATION; TOSOH CORPORATION high-speed GPC device HLC-8420GPC (product name)

[0627] Protective tubing: Manufactured by TOSOH CORPORATION, HZ-L

[0628] Separation column: A column manufactured by TOSOH CORPORATION, consisting of three TSK gel Super HZM-N (product name) tubes connected in series.

[0629] Measurement temperature: 40℃

[0630] Eluent: THF (Tetrahydrofuran)

[0631] Flow rates: Sample pump 0.35 mL / min, Reference pump 0.175 mL / min

[0632] Injection volume: 10 μL

[0633] Detector: Differential refractometer

[0634] GPC column calibration standard solution: Synthesis of standard polystyrene-polymer A1 manufactured by TOSOH CORPORATION

[0635] The following shows the monomers used in the synthesis of polymer A1.

[0636] St: Styrene (manufactured by FUJIFILM Wako Pure Chemical Corporation)

[0637] MAA: Methacrylic acid (manufactured by FUJIFILM Wako Pure Chemical Corporation)

[0638] MMA: Methyl methacrylate (manufactured by FUJIFILM Wako Pure Chemical Corporation)

[0639] • Polymer A1: 30% by mass propylene glycol monomethyl ether acetate solution with St / MAA / MMA = 53 / 29 / 19 (mass ratio) and a weight-average molecular weight (Mw) of 70,000.

[0640] (polymeric compounds)

[0641] • Polymerizable compound B1: Product name "BPE-100", 2,2-bis(4-(methacryloyloxyethoxy)phenyl)propane, manufactured by Shin-Nakamura Chemical Co., Ltd.

[0642] • Polymer compound B2: Product name "ARONIX M-270", polypropylene glycol diacrylate (n≈12), manufactured by TOAGOSEI CO., LTD.

[0643] • Polymerizable compound B3a: Product name "A-TMMT", pentaerythritol tetraacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd.

[0644] • Polymerizable compound B3b: Product name "A-TMPT-9EO", ethoxylated trimethylolpropane triacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd.

[0645] (Photopolymerization initiator)

[0646] Hexaaryl biimidazole compounds: Product name "B-CIM", 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, manufactured by Hampford Company.

[0647] • Acetophenone compounds: Product names "Omnirad 651", 2,2-dimethoxy-2-phenylacetophenone, manufactured by IGMresins BV.

[0648] (The compound represented by formula (1))

[0649] Compounds D1 to D6 were used as the compounds represented by formula (1).

[0650] Compound D2 was synthesized by the method described in Japanese Patent No. 4912770

[0235] .

[0651] Compound D3 was synthesized by the method described in Japanese Patent No. 4912770

[0229] .

[0652] Compound D5: synthesized by the method described in Japanese Patent Application Publication No. 2010-265383

[0025] .

[0653] The structural formulas of compounds D1 to D5 are as follows.

[0654] (Sensitizer)

[0655] Compounds DX1 to DX3 were used as sensitizers.

[0656] Compound DX1 was synthesized by the method described in Journal of Medicinal Chemistry (1998), 41(14), 2588-2603.

[0657] Compound DX2: N-Methylacridone (manufactured by Tokyo Chemical Industry Co., Ltd.)

[0658] Compound DX3: 2-Isopropylthioxanthone (manufactured by Tokyo Chemical Industry Co., Ltd.)

[0659] The structural formulas of compounds DX1 to DX3 are as follows.

[0660] [Chemical Formula 14]

[0661]

[0662] Nitrogen-containing heterocyclic compounds: Product name "CBT-1", benzotriazole rust inhibitor, manufactured by JOHOKU CHEMICAL CO., LTD.

[0663] • Sulfur-containing heterocyclic compounds: Product name "2-benzothiazole thiol", manufactured by FUJIFILM Wako Pure Chemical Corporation

[0664] (Polymerization inhibitor)

[0665] • Phenothiazine: Manufactured by Kawaguchi Chemical Industry Co., Ltd.

[0666] (Antioxidants)

[0667] ·1-Phenylon-3-pyrazolidineone: Manufactured by Tokyo Chemical Industry Co., Ltd.

[0668] (pigment)

[0669] • Colorless crystal violet: Manufactured by Tokyo Chemical Industry Co., Ltd.

[0670] (Chain transfer agent)

[0671] N-Phenylacetomethyl-N-carbonylmethylaniline: Manufactured by FUJIFILM Wako Pure Chemical Corporation

[0672] (surfactant)

[0673] • Resin K: was synthesized by the following method.

[0674] 14.0 g of cyclopentanone was added to a 300 mL three-necked flask equipped with a cooling pipe, thermometer, stirring blade, and nitrogen inlet tube, and heated to 80 °C. Over 120 minutes, a mixed solution of 18.00 g (42.6 mmol) of a silicone compound (product name "SilaplaneTM-0701T", manufactured by JNC Corporation), 12.00 g (30.2 mmol) of the following compound (a), 0.25 g (1.1 mmol) of a polymerization initiator (product name "V-601", manufactured by FUJIFILM Wako Pure Chemical Corporation), and 56.00 g of cyclopentanone was added dropwise. After aging for 1 hour, a mixed solution of 0.17 g (0.7 mmol) of the above polymerization initiator and 1.40 g of cyclopentanone was added, and the mixture was aged for another 1 hour. Then, a mixed solution of 0.17 g (0.7 mmol) of the above polymerization initiator and 1.40 g of cyclopentanone was added, and the mixture was allowed to mature for 3 hours to obtain 98.5 g of resin K solution. Finally, propylene glycol monomethyl ether acetate was used to replace the solvent to obtain a 30% by mass propylene glycol monomethyl ether acetate solution of resin K.

[0675] The molecular weight was determined by GPC. The Mw of resin K was 24,700, and the Mw / Mn ratio was 2.8. Furthermore, the reaction was confirmed by NMR.

[0676] In addition, in Table 1, the content of surfactant indicates the content of resin K.

[0677] [Chemical Formula 15]

[0678]

[0679] The structural formula of resin K is as follows. In the following structural formula, the numerical values ​​represent the mass proportions of the structural units.

[0680] [Chemical Formula 16]

[0681]

[0682] (solvent)

[0683] MEK: Methyl Ethyl Ketone

[0684] PGMEA: Propylene Glycol Monomethyl Ether Acetate

[0685] <Preparation of the composition for forming the intermediate layer>

[0686] The following components are mixed to prepare a composition for forming an intermediate layer.

[0687] • KURARAY POVAL PVA-205 (Polyvinyl alcohol, manufactured by Kuraray Co., Ltd.): 3.22 parts by weight

[0688] • Polyvinylpyrrolidone K-30 (manufactured by NIPPON SHOKUBAI CO., LTD.): 1.49 parts by weight

[0689] • BYK-345 (Silicone surfactant, manufactured by BYK Japan KK): 0.0015 parts by weight

[0690] • Ion-exchanged water: 38.12 parts by weight

[0691] • Methanol (manufactured by Mitsubishi Gas Chemical Company, Inc.): 57.17 parts by weight

[0692] <Manufacturing of Transfer Film>

[0693] Using a slit nozzle, the intermediate layer forming composition is applied to a temporary support (product name "lumirrorQS62", manufactured by TORAY INDUSTRIES, INC., polyethylene terephthalate film, 25 μm thick) to achieve a dried thickness of 1.0 μm. The coating of the intermediate layer forming composition is then dried at 90°C for 180 seconds to form the intermediate layer (water-soluble resin layer).

[0694] Using a slit nozzle, the above-mentioned photosensitive resin layer forming composition is applied to the surface of the intermediate layer to achieve a dried thickness of 12.0 μm, and then dried at 100°C for 2 minutes to form a photosensitive resin layer.

[0695] A protective film (product name "TORAYFAN KW37", manufactured by TORAY INDUSTRIES, INC., polypropylene film, thickness: 25μm) is laminated onto the photosensitive resin layer.

[0696] A transfer film was obtained having a temporary support, an intermediate layer, a photosensitive resin layer, and a protective film in sequence.

[0697] The following evaluation was conducted using a transfer film.

[0698] Sensitivity

[0699] A conductive substrate was fabricated by sputtering a 100nm thick copper layer onto a glass substrate.

[0700] The protective film of the transfer film was peeled off. Under lamination conditions of 100°C roller temperature, 0.6MPa linear pressure, and 1.0m / min linear speed, the transfer film was bonded to the conductive substrate by contacting the photosensitive resin layer in the transfer film with the copper layer of the conductive substrate (bonding process).

[0701] Next, the temporary support was peeled off from the obtained laminate with the glass substrate (temporary support peeling process).

[0702] Exposure light from the exposure machine (M-1S, manufactured by MIKASA CO., LTD.) was set to a center wavelength of 405 ± 10 μm via a bandpass filter (HB0405, manufactured by AsahiSpectra Co., Ltd.), and then further exposed via a 41-step stepped wedge (T4105, manufactured by Stouffer Industries, Inc.). The exposure amount (exposure process) was measured using an illuminometer (combined with UIT-201 and UVD-405PD, both manufactured by USHIO INC.) with a 405 nm corresponding light receiver.

[0703] After exposure, the mixture was left to stand for 30 minutes, and then the uncured parts were removed by spraying the developer (35°C, 1.0% by mass potassium carbonate aqueous solution) (development process).

[0704] The minimum exposure required to achieve more than 95% of the residual film thickness after development was read from the OD value of the stepped wedge. The read value was then set as the "Sensitivity".

[0705] <resolution>

[0706] Prepare a copper-clad laminate (copper layer thickness: 35μm), pickle and rinse the substrate, and then dry it.

[0707] The protective film of the transfer film was peeled off. Under lamination conditions of roller temperature 100℃, linear pressure 0.6MPa, and linear speed 1.0m / min, the transfer film and the copper-clad laminate were bonded together by contacting the photosensitive resin layer in the transfer film with the copper layer of the copper-clad laminate (lamination process).

[0708] Next, the temporary support was peeled off from the obtained laminate (temporary support peeling process).

[0709] Using a maskless exposure machine DL-1000 (manufactured by Nanosystem Solutions Inc.) that uses a 405nm laser as a light source, lines and spatial patterns with linewidths of 3μm to 30μm and marked in 1μm increments were exposed. Using the sensitivity of the photosensitive resin layer obtained through sensitivity evaluation as a reference, the exposure amount (exposure process) was set to a 15μm line design, resulting in a residual resist width of 15μm ± 1μm after development.

[0710] After exposure, the mixture is left to stand for 30 minutes. Then, the uncured parts are removed by spraying the developing solution (35°C, 1.0% by mass potassium carbonate aqueous solution), thus forming a resin pattern (developing process).

[0711] Observe the obtained resin patterns and set the width of the pattern with the highest resolution among the remaining resin patterns as the "resolution".

[0712] <rectangularity>

[0713] For the highest resolution pattern, the cross-sectional shape was observed using a SEM (S-4800 manufactured by Hitachi High-Technologies Corporation), and the rectangularity R of the resin pattern was evaluated using the following formula.

[0714] R = WB / WT × 100

[0715] WB refers to the linewidth of the portion extending from the substrate surface to a height equivalent to 10% of the height of the residual resin pattern.

[0716] WT refers to the linewidth of the portion extending from the substrate surface to 90% of the height of the residual resin pattern.

[0717] Furthermore, when WB is less than WT and R is less than 100, the cross-sectional width narrows from the top towards the substrate surface. If R is too small, it can easily cause the resin pattern to collapse or peel off; therefore, R is preferably close to 100.

[0718] When WB is greater than WT and R exceeds 100, the shape is one in which the width of the cross-section extends from the top towards the substrate surface. If R is large, adjacent resin patterns may sometimes contact each other; R is preferably close to 100.

[0719] The evaluation results are shown in Tables 1 and 2.

[0720] [Table 1]

[0721]

[0722] [Table 2]

[0723]

[0724] As shown in Tables 1 and 2, in Examples 1 to 10, the photosensitive resin layer contains an alkali-soluble resin, a polymerizable compound, a photopolymerization initiator, and a compound represented by formula (1). It has high sensitivity and can form high-resolution resin patterns by exposure using the direct drawing method.

[0725] Furthermore, according to the transfer film of the present invention, it is known that resin patterns with high rectangularity can be formed.

[0726] In Comparative Examples 1 to 3, it was found that the photosensitive resin layer did not contain the compound represented by formula (1), and therefore had low sensitivity and low resolution.

[0727] In Examples 2, 4, and 5, in Equation (1), R 2 and R 4 Each of the alkyl groups having 1 to 20 carbon atoms and substituents can be independently used. Compared with Examples 1, 3, 6 to 10, the sensitivity and resolution are higher.

[0728] In Example 1, the polymeric compound included the compound represented by formula (P1), which showed higher resolution compared to Examples 6 and 7.

[0729] In Example 1, the photosensitive resin layer comprises at least one selected from the group consisting of nitrogen-containing heterocyclic compounds and sulfur-containing heterocyclic compounds, and the resolution is higher than that in Example 9.

[0730] [Example 11]

[0731] <Formation of Metal Wiring Patterns>

[0732] A copper-clad laminate (30 μm copper thickness) was prepared. After pickling and rinsing the substrate, it was dried. After peeling off the protective film of the transfer film in Example 1, lamination was performed under lamination conditions of 100°C roller temperature, 0.6 MPa linear pressure, and 1.0 m / min linear speed.

[0733] Next, after peeling the temporary support from the obtained laminate, a maskless exposure machine (DL-1000, manufactured by Nanosystem Solutions Inc.) using a 405nm laser as the light source was used to expose lines and spatial patterns with linewidths of 3μm to 30μm, with 1μm scales. The exposure amount was set to be the same as in Example 1. Within 5 minutes after exposure, heating was performed at 60°C for 30 seconds using a heating plate.

[0734] After heating and letting stand for 30 minutes, the uncured parts are removed by spraying with a developer solution (35°C, 1.0% by mass potassium carbonate aqueous solution), thus forming a resin pattern.

[0735] The patterned substrate was cleaned using a degreasing solution manufactured by Rohm and Haas Company, followed by rinsing with water. After soft etching with ammonium persulfate, it was rinsed with water. Next, a copper plating solution manufactured by Rohm and Haas Company was used at a current density of 1.25 A / dm². 2 The substrate was plated to a height of 4.0 ± 0.5 μm. The plated substrate was then immersed in a stripping solution (manufactured by KANTO CHEMICAL CO., INC.) to remove the remaining resin pattern, thus forming a metal wiring pattern.

[0736] By using the transfer film of the present invention, high-precision plating patterns can be obtained.

[0737] Symbol Explanation

[0738] 11-Temporary support, 12-Transfer layer, 17-Photosensitive resin layer, 13-Thermoplastic resin layer, 15-Intermediate layer, 19-Protective film, 20-Transfer film.

Claims

1. A transfer film comprising a temporary support and a photosensitive resin layer disposed on the temporary support, The photosensitive resin layer comprises an alkali-soluble resin, a polymerizable compound, a photopolymerization initiator, and a compound represented by the following formula (1). In equation (1), X represents an oxygen atom or -N(R) 1 )-, Y represents an aryl or heterocyclic group optionally having substituents, R 1 R 2 R 3 and R 4 Y and R represent hydrogen atoms or monovalent substituents independently, respectively. 1 R 2 R 3 or R 4 They can be selectively bonded together to form a ring.

2. The transfer film according to claim 1, wherein, In the above formula (1), R 2 and R 4 Each is independently an alkyl group having 1 to 20 carbon atoms, optionally having a substituent.

3. The transfer film according to claim 1, wherein, The alkali-soluble resin comprises a resin having at least one structural unit selected from the group consisting of compounds represented by the following formulas (R1) and (R2). In equation (R1), R 11 Indicates a hydrogen atom or a methyl group. In equation (R2), R 12 T represents a hydrogen atom or a methyl group, and T represents a single bond or a divalent linker.

4. The transfer film according to claim 1, wherein, The polymerizable compound comprises a compound represented by the following formula (P1), In equation (P1), R 21 and R 22 Each of the following can independently represent a hydrogen atom or a methyl group. A can independently represent -C2H4-, B can independently represent -C3H6-, n1 and n3 can independently represent integers from 1 to 39, and n1+n3 can be integers from 2 to 40. n2 and n4 can independently represent integers from 0 to 29, and n2+n4 can be integers from 0 to 30.

5. The transfer film according to claim 1, wherein, The polymeric 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 hexaaryl biimidazole compounds, oxime compounds, alkyl phenyl ketone 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 of the structural units selected from the group consisting of compounds represented by the following formula (A1). In equation (A1), R 31 R represents a hydrogen atom or a methyl group. 41 It indicates an alkylene group with 1 to 10 carbon atoms, and L indicates an organopolysiloxane residue, trialkylsilyl, or tri(trialkylsiloxy)silyl.

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, wherein an intermediate layer is provided between the temporary support and the photosensitive resin layer.

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

11. A method for manufacturing a resin pattern, comprising the following steps: A process of bonding the transfer film to the substrate in such a way that the photosensitive resin layer in the transfer film according to any one of claims 1 to 10 is in contact with the substrate; The process of exposing the laminated photosensitive resin layer to a pattern; and The process of developing the exposed photosensitive resin layer to form a resin pattern. In the process of pattern exposure, direct drawing is performed using exposure light with a wavelength of 390nm to 420nm as the main wavelength.

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

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

14. A method for manufacturing a conductive pattern, comprising the following steps: The process of forming a resin pattern on a substrate using the resin pattern manufacturing method according to claim 11; The process of plating the substrate in areas where no resin pattern is formed; and The process of removing the resin pattern.

15. A method for manufacturing a conductive pattern, comprising the following steps: The process of forming a resin pattern on a conductive substrate using the resin pattern manufacturing method according to claim 11. A process of etching the areas of the conductive substrate where no resin pattern has been formed. and The process of removing resin patterns.

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