Photosensitive resin composition, transfer film, method for producing resin pattern, and method for producing conductive pattern

Abstract

Provided is a photosensitive resin composition capable of forming a resin pattern having improved shape defects and excellent resolution. The photosensitive resin composition includes: an alkali-soluble resin including a crosslinkable group having a double bond; a polyfunctional (meth) acrylate; the total double bond content in the solid content of the photosensitive resin composition is 2.00 mmol / g or more with respect to the total amount of the solid content of the photosensitive resin composition, and the ratio of the number of double bonds based on the acryloyl group to the total number of double bonds in the solid content of the photosensitive resin composition is 10-50%. The molar ratio of the content of the polymerization inhibitor to the content of the double bond based on the acryloyl group is 0.001-0.015.

Description

Technical Field

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

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

[0003] For example, Patent Document 1 describes a method for manufacturing a laminate with a conductor pattern, comprising: a bonding step in which the transfer film having a temporary support and a photosensitive composition layer is bonded to the substrate such that the surface of the transfer film opposite to the temporary support side is in contact with the metal layer of a substrate having a metal layer on its surface; an exposure step in which the photosensitive composition layer is pattern-exposed; a developing step in which the exposed photosensitive composition layer is developed to form a resist pattern; and a plating step in which the metal layer located in the area where the resist pattern is not disposed is plating. The process includes: a bonding process; a peeling process to peel off the resist pattern; and a removal process to remove the metal layer exposed by the peeling process and form a conductor pattern on the substrate. A temporary support peeling process is included between the bonding process and the exposure process or between the exposure process and the development process. The photosensitive composition layer comprises a resin having crosslinking groups, the resin having a weight-average molecular weight of 3000 or more, and the mass ratio of polymeric compounds other than the resin contained in the photosensitive composition layer to the resin is 0.85 or less.

[0004] Patent Document 1: Japanese Patent Application Publication No. 2023-35807

[0005] When forming resin patterns on a substrate using a photosensitive resin composition, shape defects (e.g., trailing, undercutting, etc.) sometimes occur in the resin pattern. It is necessary to balance the improvement of shape defects with resolution. Summary of the Invention

[0006] One embodiment of the present invention aims to solve the problem of providing a photosensitive resin composition that can form resin patterns with improved shape and excellent resolution.

[0007] Furthermore, another embodiment of the present invention aims to solve the problem of providing a transfer film using the above-described photosensitive resin composition, a method for manufacturing a resin pattern, and a method for manufacturing a conductive pattern.

[0008] The means used to solve the above problems include the following methods.

[0009] <1>

[0010] A photosensitive resin composition comprising:

[0011] Alkali-soluble resins containing crosslinking groups with double bonds;

[0012] Polyfunctional (meth)acrylates; and

[0013] Polymerization inhibitor,

[0014] The total double bond content in the solid component of the photosensitive resin composition is 2.00 mmol / g or more relative to the total solid component of the photosensitive resin composition.

[0015] The proportion of acryloyl double bonds in the total number of double bonds in the solid component of the photosensitive resin composition is 10% to 50%.

[0016] The molar ratio of the content of the polymerization inhibitor to the content of the acryloyl-based double bond is 0.001 to 0.015.

[0017] <2>

[0018] According to the photosensitive resin composition described in <1>, wherein,

[0019] The number of double bonds in the alkali-soluble resin accounts for 20% to 40% of the total number of double bonds in the solid component of the photosensitive resin composition.

[0020] <3>

[0021] According to the photosensitive resin composition described in <1> or <2>, wherein,

[0022] The crosslinking group is (meth)acryloyloxy.

[0023] <4>

[0024] The photosensitive resin composition according to any one of <1> to <3>, wherein,

[0025] Polyfunctional (meth)acrylates include difunctional (meth)acrylates.

[0026] <5>

[0027] A transfer film comprising:

[0028] Temporary support structure; and

[0029] A photosensitive resin layer disposed on a temporary support and formed of any one of the photosensitive resin compositions described in <1> to <4>.

[0030] <6>

[0031] According to <5>, the transfer film has an intermediate layer between the temporary support and the photosensitive resin layer.

[0032] <7>

[0033] According to the transfer film described in <5> or <6>, it has a thermoplastic resin layer between the temporary support and the photosensitive resin layer.

[0034] <8>

[0035] According to the transfer film described in <7>, wherein,

[0036] The thermoplastic resin layer contains light-fading compounds.

[0037] <9>

[0038] A method for manufacturing a resin pattern, comprising the following steps:

[0039] A process of bonding a transfer film to a substrate in such a way that the photosensitive resin layer in the transfer film described in any one of <5> to <8> comes into contact with the substrate;

[0040] The process of exposing the laminated photosensitive resin layer to a pattern;

[0041] The process of heating the exposed photosensitive resin layer; and

[0042] The process of developing a heated photosensitive resin layer to form a resin pattern.

[0043] <10>

[0044] According to the method for manufacturing resin patterns described in <9>, wherein,

[0045] The process of heating the exposed photosensitive resin layer is carried out at a heating temperature of 50℃~90℃ and a heating time of 20 seconds~80 seconds.

[0046] <11>

[0047] The method for manufacturing resin patterns according to <9> or <10> 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 exposing the pattern.

[0048] <12>

[0049] The method for manufacturing a resin pattern according to any one of <9> to <11>, wherein,

[0050] The surface elevation difference of the heated photosensitive resin layer is less than 0.1 μm.

[0051] <13>

[0052] A method for manufacturing a conductive pattern, comprising the following steps:

[0053] The process of forming a resin pattern on a substrate using any one of <9> to <12>.

[0054] The process of plating on areas of the substrate where no resin pattern has been formed; and

[0055] The process of removing resin patterns.

[0056] <14>

[0057] A method for manufacturing a conductive pattern, comprising the following steps:

[0058] The method for manufacturing a resin pattern using any one of <9> to <12> is a step of forming a resin pattern on a conductive substrate.

[0059] A process of etching areas of a conductive substrate where no resin pattern has been formed; and

[0060] The process of removing resin patterns.

[0061] Invention Effects

[0062] According to one embodiment of the present invention, a photosensitive resin composition is provided, which is capable of forming resin patterns with improved shape and excellent resolution.

[0063] Furthermore, according to another embodiment of the present invention, a transfer film using the above-described photosensitive resin composition, a method for manufacturing a resin pattern, and a method for manufacturing a conductive pattern are provided. Attached Figure Description

[0064] Figure 1 This is a schematic cross-sectional view showing an example of the transfer film involved in the present invention. Detailed Implementation

[0065] The present invention will now be described in detail. Sometimes, the constituent elements described below are explained according to representative embodiments of the present invention, but the present invention is not limited to these embodiments.

[0066] Furthermore, in this invention, the term "~" indicating a numerical range is used to encompass the numerical values ​​recorded before and after it as both a lower and upper limit.

[0067] In this specification, within a range of values ​​described in stages, the upper or lower limit of one range can be replaced with the upper or lower limit of another range of values ​​described in stages. Furthermore, within the ranges of values ​​described in this specification, the upper or lower limit can be replaced with the values ​​shown in the embodiments.

[0068] Furthermore, in the marking of groups (atomic groups) in this invention, the markings without substitution and non-substitution 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).

[0069] Furthermore, in this invention, a combination of two or more preferred methods is a more preferred method.

[0070] Furthermore, in this invention, when multiple substances conforming to each component are present in the composition, unless otherwise specified, the amount of each component in the composition represents the total amount of the multiple substances present in the composition.

[0071] In this invention, the term "process" includes not only independent processes, but also processes that can achieve their intended purpose, even when they cannot be clearly distinguished from other processes.

[0072] 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.

[0073] Furthermore, unless otherwise specified, the weight-average molecular weight (Mw) and number-average molecular weight (Mn) in this invention are as follows: obtained by using a gel permeation chromatography (GPC) analysis apparatus with columns of TSKgel GMHxL, TSKgel G4000HxL, and TSKgel G2000HxL (all product names manufactured by TOSOH CORPORATION), detecting with the solvent THF (tetrahydrofuran), using a differential refractometer, and converting with polystyrene as a standard substance.

[0074] In this invention, unless otherwise specified, the molecular weight of the compounds represented by the molecular weight distribution is the weight-average molecular weight.

[0075] In this invention, unless otherwise specified, the ratio of the structural units of the polymer is a mass ratio.

[0076] In this invention, "solid component" refers to the components contained in the composition other than the solvent.

[0077] The present invention will now be described in detail.

[0078] [Photosensitive Resin Composition]

[0079] The photosensitive resin composition of the present invention comprises: an alkali-soluble resin containing crosslinking groups having double bonds; a polyfunctional (meth)acrylate; and a polymerization inhibitor. The total double bond content in the solid component of the photosensitive resin composition is 2.00 mmol / g or more relative to the total amount of solid components of the photosensitive resin composition. The proportion of acryloyl-based double bonds in the total number of double bonds in the solid component of the photosensitive resin composition is 10% to 50%. The molar ratio of the polymerization inhibitor content to the acryloyl-based double bond content is 0.001 to 0.015.

[0080] Through in-depth research, the inventors discovered that by adopting the above-described structure, it is possible to form resin patterns with improved shape and excellent resolution.

[0081] Although the mechanism of action of its excellent effects is not yet clear, it is speculated to be as follows.

[0082] The total double bond content in the solid component of the photosensitive resin composition is 2.00 mmol / g or more relative to the total solid component of the photosensitive resin composition. Furthermore, the proportion of acryloyl-based double bonds in the total double bond content of the photosensitive resin composition is 10% to 50%, and the molar ratio of the polymerization inhibitor content to the acryloyl-based double bond content is 0.001 to 0.015. Therefore, defects in the obtained resin pattern (tailing, undercut, etc.) are improved, and the resolution is excellent. By having a total double bond content of 2.00 mmol / g or more, swelling during the developing process is suppressed, and the resolution is improved. Moreover, by having an acryloyl-based double bond proportion of 10% to 50%, the shape is easily made uniform.

[0083] On the other hand, Patent Document 1 does not contain any information regarding the proportion of acryloyl-based double bonds in the total number of double bonds in the solid component of the photosensitive resin composition being 10% to 50%.

[0084] <Alkali-soluble resins>

[0085] The photosensitive resin composition of the present invention comprises an alkali-soluble resin.

[0086] In addition, in this specification, "alkali solubility" means that the solubility is greater than 0.1g in 100g of a 1% by mass aqueous solution of sodium carbonate at 22°C.

[0087] Alkali-soluble resins contain cross-linking groups with double bonds.

[0088] By incorporating cross-linking groups into alkali-soluble resins, the strength of the resulting resin patterns is improved, and shape defects are suppressed.

[0089] The photosensitive resin composition of the present invention contains double bonds derived from crosslinking groups contained in alkali-soluble resins and double bonds derived from polyfunctional (meth)acrylates.

[0090] The proportion of the number of double bonds in the alkali-soluble resin to the total number of double bonds in the solid component of the photosensitive resin composition is preferably 20% to 40%, more preferably 25% to 35%.

[0091] If the above ratio is 20% or higher, swelling is suppressed by forming cross-linking points with the alkali-soluble resin, thus improving resolution.

[0092] If the above ratio is below 40%, it is less likely to produce shape defects such as trailing shape or undercut.

[0093] The proportion of double bonds in the alkali-soluble resin to the total number of double bonds in the solid component of the photosensitive resin composition can be calculated using the following formula.

[0094] The percentage of double bonds in the alkali-soluble resin (%) = {(content of double bonds in the solid component of the photosensitive resin composition by the alkali-soluble resin) / (total double bond content in the solid component of the photosensitive resin composition)} × 100

[0095] The content of double bonds in alkali-soluble resins and the calculation method for the total double bond content will be described later.

[0096] Alkali-soluble resins preferably contain crosslinking groups in their side chains.

[0097] In this specification, "main chain" refers to the longest bonded chain in the molecule of the polymer compound that constitutes the resin, and "side chain" refers to a group of atoms that branch off from the main chain.

[0098] From the perspective of curability, the crosslinking group is preferably a free radical polymerizable group with olefin double bonds.

[0099] Examples of free radical polymerizable groups include vinyl, vinyl ether, allyl, and (meth)acryloyloxy.

[0100] The crosslinking group is preferably (meth)acryloyloxy.

[0101] The alkali-soluble resin preferably contains at least one structural unit with a crosslinking group.

[0102] As a structural unit containing crosslinking groups, examples of structural units shown below can be cited.

[0103] [Chemical Formula 1]

[0104]

[0105] From the viewpoint of curability and the strength of the obtained resin pattern, the content of structural units containing crosslinking groups relative to the total amount of alkali-soluble resin is preferably 5% to 70% by mass, more preferably 10% to 50% by mass, and even more preferably 20% to 40% by mass.

[0106] As a method for introducing crosslinking groups into alkali-soluble resins, the following methods can be used: reacting compounds such as epoxy compounds, capped isocyanate compounds, isocyanate compounds, vinyl sulfone compounds, aldehyde compounds, hydroxymethyl compounds, and carboxylic anhydrides with functional groups such as hydroxyl, carboxyl, primary amino, secondary amino, acetoacetyl, and sulfonyl groups.

[0107] A preferred example of a method for introducing crosslinking groups into an alkali-soluble resin is a method in which a polymer having carboxyl groups is synthesized by polymerization, and then a portion of the carboxyl groups of the obtained resin is reacted with glycidyl (meth)acrylate by a polymer reaction, thereby introducing (meth)acryloyloxy groups into the polymer. By this method, an alkali-soluble resin having (meth)acryloyloxy groups in its side chains can be obtained.

[0108] From the perspective of alkali-soluble properties, alkali-soluble resins are preferably (meth)acrylic resins.

[0109] In this invention, (meth)acrylic resin refers to a resin containing structural units derived from (meth)acrylic compounds.

[0110] Examples of (meth)acrylic acid compounds include (meth)acrylic acid, (meth)acrylates, (meth)acrylamide, and (meth)acrylonitrile.

[0111] Examples of (meth)acrylates include alkyl (meth)acrylates, tetrahydrofurfuryl (meth)acrylate, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, glycidyl (meth)acrylate, benzyl (meth)acrylate, 2,2,2-trifluoroethyl (meth)acrylate, and 2,2,3,3-tetrafluoropropyl (meth)acrylate, with alkyl (meth)acrylates being preferred.

[0112] Examples of (meth)acrylamides include diacetone acrylamide and other acrylamides.

[0113] The alkyl group in (meth)acrylate can be either straight-chain or branched.

[0114] Examples of alkyl methacrylates include methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, pentyl methacrylate, hexyl methacrylate, heptyl methacrylate, octyl methacrylate, 2-ethylhexyl methacrylate, nonyl methacrylate, decyl methacrylate, undecyl methacrylate, and dodecyl methacrylate, which are alkyl methacrylates having alkyl groups having 1 to 12 carbon atoms.

[0115] Alkyl methacrylates are preferably alkyl methacrylates having 1 to 4 carbon atoms, and more preferably methyl methacrylate or ethyl methacrylate.

[0116] From the viewpoint of further improving alkaline developability, alkali-soluble resins preferably contain structural units having acid groups. Examples of acid groups include carboxyl groups, sulfonyl groups, phosphate groups, and phosphonic acid groups.

[0117] The alkali-soluble resin more preferably contains structural units having carboxyl groups, and even more preferably contains structural units derived from (meth)acrylic acid.

[0118] When the alkali-soluble resin contains structural units with acid groups, from the viewpoint of excellent developability, the content of structural units with acid groups is preferably 10% by mass or more relative to the total amount of the alkali-soluble resin. From the viewpoint of excellent alkali resistance, the upper limit of the content of structural units with acid groups relative to the total amount of the alkali-soluble resin is preferably 50% by mass or less, more preferably 40% by mass or less.

[0119] Alkali-soluble resins more preferably contain structural units derived from alkyl methacrylates.

[0120] When the alkali-soluble resin contains structural units derived from alkyl (meth)acrylate, the content of the structural units derived from alkyl (meth)acrylate relative to the total amount of the alkali-soluble resin is preferably 1% to 90% by mass, more preferably 1% to 50% by mass, and even more preferably 1% to 30% by mass.

[0121] The alkali-soluble resin preferably comprises at least one of the structural units selected from (meth)acrylic acid and structural units derived from (meth)acrylic acid alkyl esters, and more preferably comprises both structural units derived from (meth)acrylic acid and structural units derived from (meth)acrylic acid alkyl esters.

[0122] In particular, the alkali-soluble resin preferably includes at least one of the structural units selected from the group consisting of structural units derived from methacrylic acid and structural units derived from alkyl methacrylates, and more preferably includes both structural units derived from methacrylic acid and structural units derived from alkyl methacrylates.

[0123] From the viewpoint of achieving better results with the present invention, the alkali-soluble resin preferably has an aromatic ring, and more preferably contains structural units having an aromatic ring.

[0124] Examples of monomers that form structural units with aromatic rings include monomers with aralkyl groups, styrene, and polymerizable styrene derivatives (e.g., methylstyrene, vinyltoluene, tert-butoxystyrene, acetoxystyrene, 4-vinylbenzoic acid, styrene dimers, and styrene trimers).

[0125] As monomers for forming structural units with aromatic rings, monomers having aralkyl groups or styrene are preferred.

[0126] Examples of aryl alkyl groups include substituted or unsubstituted phenylalkyl groups, substituted or unsubstituted benzyl groups, with substituted or unsubstituted benzyl groups being preferred.

[0127] Examples of monomers containing phenyl alkyl groups include phenyl ethyl (meth)acrylate.

[0128] Examples of monomers having a benzyl group include (meth)acrylates (e.g., benzyl (meth)acrylate and benzyl chloride (meth)acrylate) and vinyl monomers having a benzyl group (e.g., vinyl benzyl chloride and vinyl benzyl alcohol), with benzyl (meth)acrylate being preferred.

[0129] From the viewpoint of achieving better results with the present invention, the alkali-soluble resin more preferably contains structural units derived from styrene.

[0130] When the alkali-soluble resin contains structural units with aromatic rings, from the viewpoint of achieving better results in this invention, the total amount of structural units with aromatic rings relative to the total amount of the alkali-soluble resin is preferably 5% to 90% by mass, more preferably 10% to 70% by mass, and even more preferably 20% to 60% by mass.

[0131] The photosensitive resin composition of the present invention may contain only one type of alkali-soluble resin or two or more types.

[0132] The content of the alkali-soluble resin relative to the total solid content of the photosensitive resin composition 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 the alkali-soluble resin to the photosensitive resin composition 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 the alkali-soluble resin to the photosensitive resin composition to 10% by mass or more.

[0133] The glass transition temperature (Tg) of the alkali-soluble resin is preferably 50°C or higher, more preferably 60°C or higher, and even more preferably 70°C or higher. If the Tg is 50°C or higher, the resistance to edge melting is improved.

[0134] The glass transition temperature (Tg) of the alkali-soluble resin is preferably below 135°C, more preferably below 130°C, even more preferably below 120°C, and particularly preferably below 110°C. If Tg is below 135°C, it is possible to suppress line width thickening and resolution reduction when the focal position shifts during exposure.

[0135] The Tg of alkali-soluble resins was determined by differential scanning calorimetry.

[0136] The weight-average molecular weight of the alkali-soluble resin 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.

[0137] 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 aggregates and the properties of the unexposed film, such as edge melting and chipping, when used as a transfer film.

[0138] The weight-average molecular weight is more preferably 10,000 or more, more preferably 20,000 or more, and especially preferably 30,000 or more.

[0139] 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 debris easily scatters when the unexposed film is cut with a cutter. If this debris adheres to the upper surface of the transfer film, it can be transferred to the mask in subsequent exposure processes, resulting in defective products. The dispersion of the alkali-soluble resin is preferably 1.0 to 6.0, more preferably 1.0 to 5.0, even more preferably 1.0 to 4.0, and particularly preferably 1.0 to 3.0. Dispersion is the ratio of weight-average molecular weight to number-average molecular weight (weight-average molecular weight / number-average molecular weight).

[0140] The photosensitive resin composition may contain resins other than alkali-soluble resins.

[0141] 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, polyethylene formaldehyde, polyamide resins, polyester resins, epoxy resins, polyacetal resins, polyhydroxystyrene resins, polyimide resins, polybenzoxazole resins, polysiloxane resins, polyethyleneimine, polyallylamine, and polyalkylene glycols.

[0142] <Polyfunctional (meth)acrylates>

[0143] The photosensitive resin composition of the present invention contains polyfunctional (meth)acrylates.

[0144] There are no particular limitations on polyfunctional (meth)acrylates as long as they are compounds having two or more (meth)acryloyloxy groups.

[0145] Polyfunctional (meth)acrylates can be difunctional (meth)acrylates or trifunctional (meth)acrylates or more.

[0146] From the perspective of balancing resolution and peelability, multifunctional (meth)acrylates preferably contain difunctional (meth)acrylates.

[0147] -Compound B1-

[0148] As a polyfunctional (meth)acrylate, an example is a difunctional (meth)acrylate having at least one aromatic ring in one molecule (hereinafter also referred to as "compound B1").

[0149] From a resolution perspective, multifunctional (meth)acrylates preferably contain compound B1.

[0150] From the viewpoint of superior resolution, the content of compound B1 relative to the total amount of polyfunctional (meth)acrylate 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 compound B1. From the viewpoint of peelability, the content of compound B1 relative to the total amount of polyfunctional (meth)acrylate 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.

[0151] Examples of aromatic rings in compound B1 include aromatic hydrocarbon rings such as benzene rings, naphthalene rings, and anthracene rings; aromatic heterocycles such as thiophene rings, furan rings, pyrrole rings, imidazole rings, triazole rings, and pyridine rings; and their fused rings. The aromatic ring in compound B1 is preferably an aromatic hydrocarbon ring, more preferably a benzene ring. Furthermore, the aforementioned aromatic ring may have substituents.

[0152] From the viewpoint of improving resolution by suppressing the swelling of the photosensitive resin layer caused by the developer, compound B1 preferably has a bisphenol backbone.

[0153] 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.

[0154] Compound B1 having a bisphenol skeleton can be exemplified by compounds having a bisphenol skeleton and two (meth)acryloyloxy groups bonded to both ends of the bisphenol skeleton.

[0155] The bisphenol backbone can be directly bonded to the (meth)acryloyloxy group, or it can be bonded via one or more alkene oxygen groups. The alkene oxygen groups bonded to the bisphenol backbone are preferably ethoxide or propoxide, more preferably ethoxide. 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.

[0156] Regarding 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.

[0157] Compound B1 is preferably a difunctional (meth)acrylate having a bisphenol A backbone, more preferably 2,2-bis(4-((meth)acryloyloxypolyalkoxy)phenyl)propane.

[0158] Examples of 2,2-bis(4-((methacryloyloxypolyalkoxy)phenyl)propane include 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-(methacryloyloxydodecylethoxytetrapropoxy)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.), 2,2-bis(4-(methacryloylethoxy)phenyl)propane (BPE-100, manufactured by Shin-Nakamura Chemical Co., Ltd.), 2,2-bis(4-(acryloylethoxy)phenyl)propane (ABE-300, 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.).

[0159] Compound B1 can be represented by the following formula (P1).

[0160] From the viewpoint of resolution, compound B1 preferably comprises a compound represented by the following formula (P1).

[0161] [Chemical Formula 2]

[0162]

[0163] 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, and n2 and n4 can independently represent integers from 0 to 29 and n2+n4 can be integers from 0 to 30.

[0164] Furthermore, the repeating units of -(AO)- and -(BO)- can be arranged randomly or in blocks. When arranged in blocks, either -(AO)- or -(BO)- can be on the diphenyl side.

[0165] n1+n2+n3+n4 is preferably 2 to 20, more preferably 2 to 16, and even more preferably 2 to 8.

[0166] Furthermore, n2+n4 is preferably 0 to 10, more preferably 0 to 4, even more preferably 0 to 2, and especially preferably 0.

[0167] The photosensitive resin composition may contain only one or more compounds B1.

[0168] From the viewpoint of achieving superior resolution, the content of compound B1 relative to the solid content of the photosensitive resin composition is preferably 10% by mass or more, more preferably 20% by mass or more. There is no particular upper limit to the content of compound B1. From the viewpoint of improving transferability and resistance to edge melting, the content of compound B1 is preferably 70% by mass or less, more preferably 60% by mass or less.

[0169] -Compound B2-

[0170] As a polyfunctional (meth)acrylate, examples include difunctional (meth)acrylates (hereinafter also referred to as "compound B2") that do not have an aromatic ring.

[0171] Examples of compound B2 include alkylene glycol di(meth)acrylate, polyalkylene glycol di(meth)acrylate, urethane di(meth)acrylate, and trimethylolpropane diacrylate.

[0172] 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.

[0173] Examples of polyalkylene glycol di(meth)acrylates include polyethylene glycol di(meth)acrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, and polypropylene glycol di(meth)acrylate.

[0174] Examples of urethane di(meth)acrylates include propylene oxide-modified urethane di(meth)acrylates and ethylene oxide and propylene oxide-modified urethane di(meth)acrylates. Commercially available examples include 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.).

[0175] -Compound B3-

[0176] As a polyfunctional (meth)acrylate, examples of (meth)acrylates with three or more functions (hereinafter also referred to as "compound B").

[0177] Examples of 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.

[0178] Here, "(tri / tetra / penta / hexa)meth)acrylate" is a concept that includes tri(meth)acrylate, tetra(meth)acrylate, penta(meth)acrylate and hexa(meth)acrylate, and "(tri / tetra)meth)acrylate" is a concept that includes tri(meth)acrylate and tetra(meth)acrylate.

[0179] Examples of epoxide-modified (meth)acrylates with three or more functions include caprolactone-modified (meth)acrylate compounds (KAYARAD DPCA-20, manufactured by Nippon Kayaku Co., Ltd.; A-9300-1CL, manufactured by Shin-Nakamura Chemical 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 trimethacrylate (A-GLY-9E, manufactured by Shin-Nakamura Chemical Co., Ltd.), ARONIX TO-2349 (manufactured by TOAGOSEICO.,LTD.), and ARONIX... M-520 (manufactured by TOAGOSEI CO.,LTD.) and ARONIX M-510 (manufactured by TOAGOSEI CO.,LTD.).

[0180] The photosensitive resin composition may contain polymeric compounds other than polyfunctional (meth)acrylates.

[0181] There are no particular limitations on other polymerizable compounds, and appropriate choices can be made from previously known compounds. Examples of other polymerizable compounds include compounds having one olefinic unsaturated group per molecule (i.e., monofunctional olefinic unsaturated compounds).

[0182] Furthermore, other polymerizable compounds may be polymerizable compounds with acid groups as described in paragraphs 0025 to 0030 of Japanese Patent Application Publication No. 2004-239942.

[0183] 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.

[0184] The photosensitive resin composition preferably comprises compound B1 and compound B2. In this case, the mass ratio of compound B1 to compound B2 (compound B1: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.

[0185] The content of polyfunctional (meth)acrylate relative to the total amount of solid components in the photosensitive resin composition is preferably 10% to 70% by mass, more preferably 20% to 60% by mass, and even more preferably 20% to 50% by mass.

[0186] <Photopolymerization Initiator>

[0187] The photosensitive resin composition of the present invention preferably contains a photopolymerization initiator.

[0188] Photopolymerization initiators are compounds that initiate the polymerization of polymerizable compounds using 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.

[0189] Examples of photopolymerization initiators include photoradical polymerization initiators and photocationic polymerization initiators. Among them, photoradical polymerization initiators are preferred.

[0190] Examples of photoradical polymerization initiators include photopolymerization initiators with an oxime ester skeleton, photopolymerization initiators with an α-aminoalkylphenyl ketone skeleton, photopolymerization initiators with an α-hydroxyalkylphenyl ketone skeleton, photopolymerization initiators with an acylphosphine oxide skeleton, and photopolymerization initiators with an N-phenylglycine skeleton.

[0191] Furthermore, from the viewpoints of photosensitivity, visibility of the exposed and unexposed areas, and resolution, the photosensitive resin composition preferably includes at least one selected from the group consisting of 2,4,5-triarylimidazolium dimers and their derivatives as a photoradical polymerization initiator. Additionally, the two 2,4,5-triarylimidazolium skeletons in the 2,4,5-triarylimidazolium dimer and its derivatives may be identical or different.

[0192] Examples of derivatives of 2,4,5-triarylimidazolium dimers include 2-(o-chlorophenyl)-4,5-diphenylimidazolium dimer, 2-(o-chlorophenyl)-4,5-di(methoxyphenyl)imidazolium dimer, 2-(o-fluorophenyl)-4,5-diphenylimidazolium dimer, 2-(o-methoxyphenyl)-4,5-diphenylimidazolium dimer, and 2-(p-methoxyphenyl)-4,5-diphenylimidazolium dimer.

[0193] 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.

[0194] Examples of photoradical polymerization initiators include ethyl dimethylaminobenzoate (DBE, CAS No. 10287-53-3), benzoin methyl ether, (p,p'-dimethoxybenzyl) and benzophenone.

[0195] 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-acetyl oxime) (Product name: Irgacure OXE-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-morpholinylprop-1-one (Product name: Omnirad 907, manufactured by IGM Resins BV). Omnirad 127 (manufactured by IGM Resins BV), 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)butanone-1 ...hydroxy-2-methyl-1-phenylpropanone-1-one (manufactured by IGM Resins BV), 1-hydroxycyclohexylphenyl ketone (manufactured by IGM Resins BV), 2,2-dimethoxy-1,2-diphenylethyl-1-one (manufactured by IGM Resins BV), 2,4,6-trimethylbenzoyl-diphenylphosphine oxide (manufactured by IGM Resins BV), 2-hydroxy-1-dimethylamino-1-(4-morpholinylphenyl)butanone-1 (manufactured by IGM Resins BV), 2-hydroxy-2-dimethylamino-1-(4-morpholinylphenyl)butanone-1 (manufactured by IGM Resins BV), 2-hydroxy-2-dimethylamino-1-(4-morpholinylphenyl)butanone-1 (manufactured by IGM Resins BV), 2-hydroxy-2-dimethylamino-1-phenylpropanone-1-one (manufactured by IGM Resins BV), 2-hydroxy-2-dimethylamino-1-phenylpropanone-1-one (manufactured by IGM Resins BV), 2,4,6-trimethylbenzoyl-2-diphenylphosphine oxide (manufactured by IGM Resins BV), 2,4,6-trimethylbenzoyl-2-diphenylphosphine oxide (manufactured by IGM Resins BV). TPO H, manufactured by IGM Resins BV), bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide (product name: Omnirad 819, IGM Resins BV)(Manufactured), oxime ester photopolymerization initiators (product name: Lunar 6, manufactured by DKSH Japan KK), 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole (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.).

[0196] Photocationic polymerization initiators (photoacid generators) are compounds that receive photochemical rays to generate acids. There are no particular limitations on the photocationic polymerization initiator, but compounds that sense and generate acids from photochemical rays with wavelengths of 300 nm or higher (preferably 300 nm to 450 nm) are preferred. Furthermore, even compounds that do not directly sense photochemical rays with wavelengths of 300 nm or higher, as long as they sense and generate acids from photochemical rays with wavelengths of 300 nm or higher by being used in conjunction with a sensitizer, can preferably be used in combination with the sensitizer.

[0197] Photocationic polymerization initiators are preferably those that produce acids with a pKa of 4 or less, more preferably those that produce acids with a pKa of 3 or less, and particularly preferably those that produce acids with a pKa of 2 or less. The lower limit of the pKa is not particularly limited, but is preferably -10.0 for example.

[0198] Examples of photocationic polymerization initiators include ionic and nonionic photocationic polymerization initiators.

[0199] Examples of ionic photocationic polymerization initiators include onium salts such as diaryl sulfonium salts and triaryl sulfonium salts, as well as quaternary ammonium salts.

[0200] 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.

[0201] Examples of nonionic photocationic polymerization initiators include trichloromethyl symmetrical triazine compounds, diazomethane compounds, imide sulfonate compounds, and oxime sulfonate compounds. The trichloromethyl symmetrical triazine compounds, diazomethane compounds, and imide sulfonate compounds can be those described in paragraphs 0083 to 0088 of Japanese Patent Application Publication No. 2011-221494. Furthermore, the oxime sulfonate compounds can be those described in paragraphs 0084 to 0088 of International Patent Application Publication No. 2018 / 179640.

[0202] The photopolymerization initiator contained in the photosensitive resin composition may be only one type or two or more types.

[0203] 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 solid content of the photosensitive resin composition. There is no particular upper limit to the content of the photopolymerization initiator. The content of the photopolymerization initiator relative to the solid content of the photosensitive resin composition is preferably 10% by mass or less, more preferably 8% by mass or less.

[0204] <Sensitizer>

[0205] The photosensitive resin composition of the present invention may contain a sensitizer.

[0206] There are no particular limitations on the sensitizers used; known sensitizers, dyes, and pigments can be used. Examples of sensitizers include dialkylaminobenzophenone compounds, pyrazoline compounds, anthracene compounds, coumarin compounds, xanthone compounds, thioxanthone compounds, acridinone compounds, oxazole compounds, benzoxazole compounds, thiazole compounds, benzothiazole compounds, triazole compounds (e.g., 1,2,4-triazole), piracene compounds, triazine compounds, thiophene compounds, naphthalenedicarboximide compounds, triarylamine compounds, and aminoacridine compounds.

[0207] The photosensitive resin composition may contain only one type of sensitizer or two or more types.

[0208] When a photosensitive resin composition contains a sensitizer, the content of the sensitizer can be appropriately selected according to the purpose. From the viewpoint of improving sensitivity to light sources and improving the curing speed based on the balance between polymerization rate and chain transfer, the content of the sensitizer relative to the solid content of the photosensitive resin composition is preferably 0.01% to 5% by mass, more preferably 0.05% to 1% by mass.

[0209] <Polymerization Inhibitor>

[0210] The photosensitive resin composition of the present invention contains a polymerization inhibitor.

[0211] Examples of polymerization inhibitors include the thermal polymerization inhibitor described in paragraph 0018 of Japanese Patent No. 4502784. Furthermore, examples of polymerization inhibitors include phenothiazine, phenotoxazine, 4-methoxyphenol, naphthylamine, cuprous chloride, aluminum nitrosophenylhydroxylamine, and diphenylnitrosamine. Among these, the free radical polymerization inhibitor is preferably phenothiazine, phenotoxazine, 4-methoxyphenol, or aluminum nitrosophenylhydroxylamine.

[0212] When the photosensitive resin composition contains a polymerization inhibitor, from the viewpoint of the storage stability of the photosensitive resin composition, the content of the polymerization inhibitor relative to the solid content of the photosensitive resin composition is preferably 0.01% to 5% by mass, more preferably 0.05% to 1% by mass.

[0213] In the photosensitive resin composition of the present invention, the molar ratio of the content of the polymerization inhibitor to the content of the acryloyl-based double bond is 0.001 to 0.015.

[0214] If the above molar ratio is 0.001 or higher, the reaction based on the diffusion of the growth monomer with acryloyl group proceeds uniformly, and the shape and resolution of the resin pattern are improved.

[0215] If the above molar ratio is below 0.015, the diffusion of acryloyl-containing growth monomers in the exposed and unexposed areas can be controlled, and the resolution is improved.

[0216] Based on the above viewpoint, a molar ratio of 0.001 to 0.010 is more preferable.

[0217] The content of acryloyl-based double bonds was calculated using the same method as that used to calculate the total double bond content in the solid components of the photosensitive resin composition.

[0218] <Antioxidants>

[0219] The photosensitive resin composition of the present invention may contain antioxidants.

[0220] Examples of antioxidants include 3-pyrazolone derivatives such as 1-phenyl-3-pyrazolone (also known as phenidone), 1-phenyl-4,4-dimethyl-3-pyrazolone, and 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolone; polyhydroxybenzenes such as hydroquinone, catechol, galloquinone, methylhydroquinone, and chlorohydroquinone; and p-methylaminophenol, p-aminophenol, p-hydroxyphenylglycine, and p-phenylenediamine.

[0221] From the viewpoint of achieving better results in this invention, the antioxidant is preferably a 3-pyrazolone, and more preferably a phenyl-3-pyrazolone.

[0222] When the photosensitive resin composition contains an antioxidant, the content of the antioxidant relative to the solid content of the photosensitive resin composition 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 content of the antioxidant, but it is preferably 1% by mass or less.

[0223] <Chain transfer agent>

[0224] The photosensitive resin composition of the present invention may contain a chain transfer agent.

[0225] Examples of chain transfer agents include N-phenylcarbamoylmethyl-N-carboxymethylaniline and N,N-tetraethyl-4,4-diaminobenzophenone.

[0226] When the photosensitive resin composition contains a chain transfer agent, the content of the antioxidant relative to the solid content of the photosensitive resin composition is preferably 0.01% to 5% by mass, more preferably 0.05% to 1% by mass.

[0227] <pigment>

[0228] The photosensitive resin composition of the present invention may contain pigments.

[0229] From the viewpoints of visibility of the exposed and unexposed areas, visibility of the developed pattern, and resolution, the photosensitive resin composition of the present invention preferably contains a pigment (hereinafter also simply referred to as "pigment N") whose maximum absorption wavelength in the wavelength range of 400 nm to 780 nm during color development is 450 nm or more and whose maximum absorption wavelength changes with acid, alkali, or free radicals. Although the detailed mechanism is not yet clear, the presence of pigment N improves adhesion to adjacent layers (e.g., temporary supports and intermediate layers) and results in superior resolution.

[0230] In this specification, the phrase "the maximum absorption wavelength of a pigment changes due to acid, alkali, or free radicals" can refer to any of the following: a pigment in a chromogenic state is decolorized by acid, alkali, or free radicals; a pigment in a decolorized state is chromogenic by acid, alkali, or free radicals; or a pigment in a chromogenic state is transformed into a chromogenic state of other hues.

[0231] 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 changes in the state (e.g., pH) within the photosensitive resin layer due to acids, bases, or free radicals. Furthermore, pigment N can be a pigment whose color-developing or decolorizing state changes directly upon exposure to acids, bases, or free radicals as stimuli without exposure.

[0232] From the viewpoint of visibility and resolution of the exposed and unexposed areas, pigments are preferably pigments whose maximum absorption wavelength changes due to acid or free radicals, and more preferably pigments whose maximum absorption wavelength changes due to free radicals.

[0233] From the viewpoint of visibility and resolution of the exposed and unexposed areas, the photosensitive resin composition preferably contains both a pigment whose maximum absorption wavelength as pigment N changes with free radicals and a photoradical polymerization initiator.

[0234] 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.

[0235] As an example of the color-developing mechanism of pigments, one can cite the addition of photoradical polymerization initiators, photocationic polymerization initiators (photoacid generators), or photoalkali generators to a photosensitive resin composition, where color is developed by free radicals, acids, or bases generated from the photoradical polymerization initiator, photocationic polymerization initiator, or photoalkali generator after exposure.

[0236] From the viewpoint of visibility of the exposed and unexposed portions, the maximum absorption wavelength in the wavelength range of 400nm to 780nm during pigment color development is preferably 550nm or higher, more preferably 550nm to 700nm, and even more preferably 550nm to 650nm.

[0237] Furthermore, a pigment may have only one maximum absorption wavelength in the wavelength range of 400 nm to 780 nm for color development, or it may have two or more. When pigment N has two or more maximum absorption wavelengths in the wavelength range of 400 nm for color development, the maximum absorption wavelength with the highest absorbance among the two or more maximum absorption wavelengths must be 450 nm or higher.

[0238] The maximum absorption wavelength of the pigment was obtained by measuring the transmission spectrum of the pigment-containing solution (liquid temperature 25°C) in the range of 400 nm to 780 nm using a spectrophotometer (UV3100, manufactured by Shimadzu Corporation) under atmospheric conditions, and detecting the wavelength at which the light intensity becomes minimal (i.e., the maximum absorption wavelength).

[0239] 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, xanthones, iminonaphthoquinone pigments, azomethyl alkaloid pigments, and anthraquinone pigments. From the viewpoint of visibility of both exposed and unexposed areas, colorless compounds are preferred.

[0240] Examples of colorless compounds include colorless compounds with a triarylmethane skeleton (triarylmethane pigments), colorless compounds with a spiropyran skeleton (spiropyran pigments), colorless compounds with a fluorane skeleton (fluorane pigments), colorless compounds with a diarylmethane skeleton (diarylmethane pigments), colorless compounds with a rhodamine lactam skeleton (rhodamine lactam pigments), colorless compounds with an indolephthalide skeleton (indolephthalide pigments), and colorless compounds with a colorless goldenrodine skeleton (colorless goldenrodine pigments).

[0241] The colorless compound is preferably a triarylmethane pigment or a fluorane pigment, and more preferably a colorless compound (triphenylmethane pigment) or a fluorane pigment with a triphenylmethane skeleton.

[0242] From the viewpoint of visibility of both the exposed and unexposed areas, colorless compounds preferably have a lactone ring, a sulfinolone ring, or a sulfonolone ring. The lactone ring, sulfinolone ring, or sulfonolone ring in a colorless compound reacts with free radicals generated from a photoradical polymerization initiator or acids 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. Colorless compounds are preferably compounds having a lactone ring, a sulfinolone ring, or a sulfonolone ring that develop color through ring-opening by free radicals or acids, and more preferably compounds having a lactone ring that develop color through ring-opening by free radicals or acids.

[0243] Examples of pigments include dyes and colorless compounds.

[0244] Examples of dyes include brilliant green, ethyl violet, methyl green, crystal violet, basic fuchsine, methyl violet 2B, quinaldine red, rose bengal, metanil yellow, thymol sulfonphthalein, xylenol blue, methyl orange, p-methyl red, Congo red, benzopurpurine 4B, α-naphthyl red, nile blue 2B, nile blue A, methyl violet, malachite green, parafuchsin, Victoria pure blue-naphthalene sulfonate, Victoria pure blue BOH (manufactured by Hodogaya Chemical Co., Ltd.), Oil Blue #603 (manufactured by Orient Chemical Industries Co., Ltd.), and Oil Pink #312 (manufactured by Orient Chemical Industries). 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.), Oil Red RR (manufactured by Orient Chemical Industries Co., Ltd.), Oil Green #502 (manufactured by Orient Chemical Industries Co., Ltd.), Spilonred BEH Special (Hodogaya Chemical Co., Ltd.) (Manufactured by Co., Ltd.), m-cresol purple, cresol red, rhodamine B, rhodamine 6G, sulforhodamine B, auramine, 4-p-diethylaminophenyliminonaphthoquinone, 2-carboxyanisto-4-p-diethylaminophenyliminonaphthoquinone, 2-carboxystearylamino-4-p-N,N-bis(hydroxyethyl)amino-phenyliminonaphthoquinone, 1-phenyl-3-methyl-4-p-diethylaminophenylimino-5-pyrazolone and 1-β-naphthyl-4-p-diethylaminophenylimino-5-pyrazolone.

[0245] Examples of colorless compounds include p,p',p''-hexamethyltriaminotriphenylmethane (colorless crystal violet), Pergascript Blue SRB (manufactured by Ciba-Geigy AG), crystal violet lactone, malachite green lactone, benzoyl colorless methylene blue, 2-(N-phenyl-N-methylamino)-6-(N-p-tolyl-N-ethyl)aminofluorane, 2-anilino-3-methyl-6-(N-ethyl-p-tolyl)fluorane, 3,6-dimethoxyfluorane, 3-(N,N-diethylamino)-5-methyl-7-(N,N-dibenzylamino)fluorane, 3-(N-cyclohexyl-N-methylamino)-6-methyl-7-anilinofluorane, 3 -(N,N-diethylamino)-6-methyl-7-aniline fluorane, 3-(N,N-diethylamino)-6-methyl-7-dimethylphenylaminofluorane, 3-(N,N-diethylamino)-6-methyl-7-chlorofluorane, 3-(N,N-diethylamino)-6-methoxy-7-aminofluorane, 3-(N,N-diethylamino)-7-(4-chloroaniline)fluorane, 3-(N,N-diethylamino)-7-chlorofluorane, 3-(N,N-diethylamino)-7-chlorofluorane, 3-(N,N-diethylamino)-6-methyl-7-aniline fluorane 3-(N,N-diethylamino)-7,8-benzofluorane, 3-(N,N-dibutylamino)-6-methyl-7-aniline fluorane, 3-(N,N-dibutylamino)-6-methyl-7-dimethylphenylaminofluorane, 3-piperidin-6-methyl-7-aniline fluorane, 3-pyrrolidin-6-methyl-7-aniline fluorane, 3,3-bis(1-ethyl-2-methylindole-3-yl)phthalide, 3,3-bis(1-n-butyl) 3,3-bis(p-dimethylaminophenyl)-6-dimethylaminophthalide, 3-(4-diethylamino-2-ethoxyphenyl)-3-(1-ethyl-2-methylindole-3-yl)-4-azaphthalide lactone, 3-(4-diethylaminophenyl)-3-(1-ethyl-2-methylindole-3-yl)phthalide and 3',6'-bis(diphenylamino)spiroisobenzofuran-1(3H),9'-[9H]xanthon-3-one.

[0246] From the viewpoint of visibility of the exposed and unexposed areas, visibility of the developed pattern, 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.

[0247] The preferred pigments are colorless crystal violet, crystal violet lactone, bright green, or Victoria blue naphthalene sulfonate.

[0248] From the viewpoint of visibility of the exposed and unexposed areas, visibility of the developed pattern, and resolution, the pigment content relative to the solid content of the photosensitive resin composition 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.

[0249] <surfactants>

[0250] From the viewpoint of thickness uniformity, the photosensitive resin composition of the present invention may contain a surfactant.

[0251] Examples of surfactants include anionic surfactants, cationic surfactants, nonionic surfactants, and amphoteric surfactants. Among these, nonionic surfactants are preferred.

[0252] Examples of nonionic surfactants include polyoxyethylene higher alkyl ethers, polyoxyethylene higher alkylphenyl ethers, higher fatty acid diesters of polyoxyethylene glycol, silicone nonionic surfactants, and fluorinated nonionic surfactants.

[0253] From the perspective of improving resolution, the photosensitive resin composition preferably contains a fluorinated nonionic surfactant. This is believed to be because the presence of a fluorinated nonionic surfactant in the photosensitive resin composition inhibits the penetration of the etching solution into the photosensitive resin layer, thereby reducing lateral etching.

[0254] Commercially available fluorinated nonionic surfactants include MEGAFACE F-551, F-552 and F-554 (all manufactured by DIC Corporation).

[0255] <Solvent>

[0256] The photosensitive resin composition of the present invention preferably contains a solvent.

[0257] If the photosensitive resin composition of the present invention contains a solvent, it tends to be easier to form a photosensitive resin layer by coating.

[0258] Examples of solvents include alkylene glycol ethers, alkylene glycol ether acetates, alcohols (e.g., methanol and ethanol), ketones (e.g., acetone and methyl ethyl ketone), aromatic hydrocarbons (e.g., toluene), aprotic polar solvents (e.g., N,N-dimethylformamide), cyclic ethers (e.g., tetrahydrofuran), esters, amides, lactones, and mixed solvents containing two or more of these.

[0259] 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.

[0260] Examples of alkylene glycol ethers include 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.

[0261] Examples of alkylene glycol ether acetates include ethylene glycol monoalkyl ether acetate, propylene glycol monoalkyl ether acetate, diethylene glycol monoalkyl ether acetate, and dipropylene glycol monoalkyl ether acetate.

[0262] 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.

[0263] The photosensitive resin composition may contain only one solvent or two or more solvents.

[0264] 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.

[0265] <Other Ingredients>

[0266] The photosensitive resin composition of the present invention 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 anti-precipitating agents.

[0267] There are no particular limitations on the preparation method of the photosensitive resin composition. For example, a method can be given by pre-preparing a solution by dissolving each component in the solvent mentioned above, and then mixing the obtained solution in a specified ratio.

[0268] <Double bond content>

[0269] In the photosensitive resin composition of the present invention, the total double bond content in the solid component of the photosensitive resin composition is 2.00 mmol / g or more relative to the total amount of solid component of the photosensitive resin composition.

[0270] If the total double bond content is 2.00 mmol / g or higher, the obtained resin pattern will have an excellent shape.

[0271] From the viewpoint of further improving the shape of the resin pattern, the total double bond content is preferably 1.50 mmol / g or more, and more preferably 1.80 mmol / g or more.

[0272] From the viewpoint of resist stripping properties, the total double bond content is preferably 3.50 mmol / g or less, more preferably 3.00 mmol / g or less.

[0273] The total double bond content mentioned above can be calculated as the sum of the double bond content of compounds containing double bonds contained in the solid components of the photosensitive resin composition.

[0274] When the photosensitive resin composition of the present invention contains only an alkali-soluble resin and a polyfunctional (meth)acrylate as compounds having double bonds, the total double bond content is the sum of the double bond content of the alkali-soluble resin and the double bond content of the polyfunctional (meth)acrylate.

[0275] When a compound with double bonds is a compound without structural units, the double bond content can be calculated using the following methods.

[0276] Double bond content = (content of compounds with double bonds relative to the solid content of the photosensitive resin composition) × (number of double bonds in the compounds with double bonds) / (molecular weight of the compounds with double bonds)

[0277] When a compound containing double bonds is a compound that has double bonds in its structural units, the double bond content can be calculated using the following method. In the following formula, "MD" represents a structural unit containing double bonds.

[0278] Double bond content = (content of compounds with double bonds relative to the solid content of the photosensitive resin composition) × (content of MD relative to the total amount of compounds with double bonds) × (number of double bonds contained in MD) / (molecular weight of MD)

[0279] The double bond content can be adjusted by the type and content of alkali-soluble resin and polyfunctional (meth)acrylate.

[0280] From the viewpoint of resolution, the double bond content of the alkali-soluble resin relative to the total amount of solid components in the photosensitive resin composition is preferably 0.30 mmol / g to 1.50 mmol / g, more preferably 0.70 mmol / g to 1.20 mmol / g.

[0281] Furthermore, from the viewpoint of resolution and pattern shape, the double bond content of the polyfunctional (meth)acrylate relative to the total amount of solid components in the photosensitive resin composition is preferably 0.80 mmol / g to 2.00 mmol / g, more preferably 1.00 mmol / g to 1.80 mmol / g.

[0282] <Based on the number of double bonds of acryloyl groups>

[0283] In the photosensitive resin composition of the present invention, the proportion of the number of acryloyl-based double bonds in the total number of double bonds in the solid component of the photosensitive resin composition is 10% to 50%.

[0284] If the proportion of the above-mentioned acryloyl-based double bonds is more than 10%, the diffusivity of the growth monomers in the polymerization is improved, and the shape of the resin pattern becomes more uniform.

[0285] Furthermore, if the proportion of the above-mentioned acryloyl-based double bonds is less than 50%, the resolution is excellent.

[0286] Based on the above viewpoint, the preferred ratio of the number of double bonds based on acryloyl groups is 10% to 50%.

[0287] The proportion based on the number of double bonds of acryloyl groups is calculated using the following method.

[0288] First, the content of acryloyl-based double bonds is calculated using the same method as that used to calculate the total double bond content in the solid components of the photosensitive resin composition.

[0289] Next, the proportion of double bonds based on acryloyl groups is calculated according to the following formula.

[0290] The percentage of acryloyl-based double bonds (%) = {(content of acryloyl-based double bonds) / (total double bond content)} × 100

[0291] [Transfer film]

[0292] The transfer film of the present invention comprises a temporary support and a photosensitive resin layer disposed on the temporary support and formed from the above-described photosensitive resin composition.

[0293] The photosensitive resin layer formed from the photosensitive resin composition can be a photosensitive resin layer containing the solid components of the photosensitive resin composition.

[0294] The following is an example of a specific implementation method to illustrate the transfer film.

[0295] 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.

[0296] in addition, Figure 1 The transfer film 20 shown is configured with a protective film 19, but it may also be configured without a protective film 19.

[0297] and, Figure 1 The transfer film 20 shown is configured with a thermoplastic resin layer 13 and an intermediate layer 15, but it may also be configured without a thermoplastic resin layer 13 or an intermediate layer 15, or with both a thermoplastic resin layer 13 and an intermediate layer 15.

[0298] The following is an explanation of the various elements that make up the transfer film.

[0299] <Temporary Support>

[0300] The temporary support is a peelable support that supports the photosensitive resin layer.

[0301] The temporary support can be a single layer or a multilayer structure consisting of two or more layers.

[0302] Examples of temporary supports include: 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.

[0303] 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.

[0304] 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.

[0305] When a particle-containing layer is disposed on one or two sides of a substrate, the particle-containing layer can be one layer or two or more layers.

[0306] 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 comprises 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.

[0307] The particle layer may contain one type of adhesive polymer and particles individually, or it may contain two or more types.

[0308] 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".

[0309] 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.

[0310] 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.

[0311] As added particles, examples include inorganic particles and organic particles.

[0312] Examples of inorganic particles include silicon dioxide, titanium dioxide, zirconium dioxide, magnesium oxide, and aluminum oxide.

[0313] Examples of organic particles include particles of polymers such as acrylic resins, polyesters, polyurethanes, polycarbonates, polyolefins, and polystyrene.

[0314] When the temporary support has a particle-containing layer, the added particles contained in the particle-containing layer are preferably inorganic oxide particles.

[0315] The average particle size of the added particles is not particularly limited, for example, it is 0.1 μm to 10 μm. The average particle size is determined by cutting a 100 nm thick slice using an ultramicrotome and measuring it using TEM (transmission electron microscopy).

[0316] From the viewpoint of suppressing deformation of the circuit board bonded to the transfer film, the thickness of the temporary support is preferably 25 μm or more, more preferably 50 μm or more, and even more preferably 75 μm or more. There is no particular upper limit to the thickness; for example, it can be 200 μm.

[0317] Temporary supports can be recycled materials. Examples of recycled materials include used membranes that have been cleaned, shredded, and then used as raw materials for membrane fabrication. A specific example of a recycled material is the Ecouse series from TORAY INDUSTRIES, INC.

[0318] <Photosensitive resin layer>

[0319] The photosensitive resin layer is formed from the photosensitive resin composition of the present invention.

[0320] The photosensitive resin layer preferably comprises the solid components of the photosensitive resin composition of the present invention.

[0321] When the photosensitive resin composition contains a solvent, the photosensitive resin layer in the transfer film contains at least the components of the photosensitive resin composition other than the solvent (i.e., solid components). In this case, the photosensitive resin layer may further contain a solvent. As an example of a photosensitive resin layer containing a solvent, when a photosensitive resin composition containing a solvent is coated and dried to form a photosensitive resin layer, solvent remains in the photosensitive resin layer even after drying.

[0322] The photosensitive resin layer is preferably a negative photosensitive resin layer in which the solubility of the exposed portion in the developer decreases due to exposure and the non-exposed portion is removed by development.

[0323] From the viewpoint of pattern shape, surface roughness and resolution, the average thickness of the photosensitive resin layer is preferably 0.5 μm to 30 μm, more preferably 1 μm to 10 μm, and even more preferably 1 μm to 5 μm.

[0324] <Intermediate Layer>

[0325] The transfer film preferably includes an intermediate layer between the temporary support and the photosensitive resin layer.

[0326] 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.

[0327] As an intermediate layer, a water-soluble resin layer comprising a water-soluble resin is preferred.

[0328] 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 improved, therefore it is preferred.

[0329] The oxygen barrier layer that can be used as the intermediate layer may be appropriately selected 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.

[0330] The following describes the components that the intermediate layer may contain.

[0331] The intermediate layer preferably contains resin.

[0332] The resins described above preferably include water-soluble resins as part or all of them.

[0333] Examples of resins that can be used as water-soluble resins include polyvinyl alcohol resins, polyvinylpyrrolidone resins, cellulose resins, acrylamide resins, polyethylene oxide resins, gelatin, vinyl ether resins, polyamide resins, and copolymers thereof.

[0334] 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.

[0335] 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.

[0336] 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.

[0337] The dispersion (Mw / Mn) of the water-soluble resin is preferably 1 to 10, more preferably 1 to 5.

[0338] 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, when the photosensitive resin layer contains an alkali-soluble resin and the thermoplastic resin layer (described later) contains a thermoplastic resin (alkali-soluble resin), the resin contained in the intermediate layer is preferably a different resin from the alkali-soluble resin and the thermoplastic resin (alkali-soluble resin) contained in the photosensitive resin layer.

[0339] From the viewpoint of further improving oxygen barrier properties and interlayer mixing inhibition ability, it is preferable that the water-soluble resin contains polyvinyl alcohol, and more preferably it contains both polyvinyl alcohol and polyvinylpyrrolidone.

[0340] The intermediate layer may contain one or more types of water-soluble resin.

[0341] 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, it is preferably 50% by mass or more, more preferably 70% by mass or more, further preferably 80% by mass or more, and especially preferably 90% by mass or more, relative to the total mass of the water-soluble resin layer (intermediate layer). In addition, there is no particular limitation on its upper limit, for example, it is preferably 99.9% by mass or less, and more preferably 99.8% by mass or less.

[0342] The intermediate layer may contain known additives such as surfactants, as needed.

[0343] 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.

[0344] <Thermoplastic resin layer>

[0345] The transfer film preferably includes a thermoplastic resin layer between the temporary support and the photosensitive resin layer. Furthermore, the transfer film preferably includes a thermoplastic resin layer between the temporary support and the intermediate layer. By including a thermoplastic resin layer in the transfer film, the substrate tracking during the bonding process between the transfer film and the substrate is improved, thereby suppressing the incorporation of air bubbles between the substrate and the transfer film. As a result, adhesion to layers adjacent to the thermoplastic resin layer (e.g., the temporary support) can be ensured.

[0346] The thermoplastic resin layer comprises resin. The resin may comprise thermoplastic resin as a part or all thereof. That is, in one embodiment, the resin of the thermoplastic resin layer is also preferably a thermoplastic resin.

[0347] (Alkali-soluble resin (thermoplastic resin))

[0348] Thermoplastic resin is preferably an alkali-soluble resin.

[0349] Examples of alkali-soluble resins include acrylic resins, polystyrene resins, styrene-acrylic copolymers, polyurethane resins, polyvinyl alcohol, polyethylene formaldehyde, polyamide resins, polyester resins, epoxy resins, polyacetal resins, polyhydroxystyrene resins, polyimide resins, polybenzoxazole resins, polysiloxane resins, polyethyleneimine, polyallylamine, and polyalkylene glycols.

[0350] From the viewpoint of developability and adhesion to adjacent layers, acrylic resins are preferred as alkali-soluble resins.

[0351] 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.

[0352] As an acrylic resin, the total content of structural units derived from (meth)acrylic acid, structural units derived from (meth)acrylate, and structural units derived from (meth)acrylamide is preferably 50% by mass or more relative to the total mass of the acrylic resin.

[0353] 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 mass of acrylic resin, and more preferably 50% to 100% by mass.

[0354] Furthermore, the alkali-soluble resin is preferably a polymer with acid groups.

[0355] Examples of acid groups include carboxyl, sulfonyl, phosphate, and phosphonic acid groups, with carboxyl being the preferred group.

[0356] 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.

[0357] There is no particular limit to 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.

[0358] There are no particular restrictions on the type of acrylic resin containing carboxyl groups with an acid value of 60 mg KOH / g or higher, and it is possible to appropriately select from known resins.

[0359] Examples include the acrylic resin containing carboxyl groups with an acid value of 60 mg KOH / g or higher described in paragraph

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

[0053] to

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

[0360] 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 mass of the acrylic resin, more preferably 10% to 40% by mass, and even more preferably 12% to 30% by mass.

[0361] 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.

[0362] Alkali-soluble resins can have 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 addition polymerization reactive groups such as epoxy groups and (terminated) isocyanate groups.

[0363] 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.

[0364] The thermoplastic resin layer may contain one or more alkali-soluble resins.

[0365] From the viewpoint of developability and adhesion to adjacent layers, the content of alkali-soluble resin relative to the total mass of the 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.

[0366] (pigment)

[0367] The thermoplastic resin layer preferably contains a pigment (also referred to as "pigment B") with 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 radicals.

[0368] Except for the points described later, the preferred form of pigment B is the same as the preferred form of pigment N described above.

[0369] 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.

[0370] From the viewpoint of visibility and resolution of the exposed and unexposed areas, the thermoplastic resin layer preferably contains both a pigment whose maximum absorption wavelength as pigment B changes with acid and a compound that generates acid through light, as described later.

[0371] The thermoplastic resin layer may contain one or more pigments B.

[0372] From the viewpoint of visibility of the exposed and unexposed areas, the content of pigment B relative to the total mass 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.

[0373] Here, the content of pigment B refers to the amount of pigment that makes all pigments B contained in the thermoplastic resin layer reach their colored state. The following explanation uses pigments that develop color via free radicals as an example to illustrate the quantitative method for determining the content of pigment B.

[0374] Solutions were prepared by dissolving 0.001 g and 0.01 g of pigment in 100 mL of methyl ethyl ketone. A photoradical polymerization initiator (trade name: Irgacure OXE01, manufactured by BASF Japan Ltd.) was added to each solution, and the solutions were irradiated with 365 nm light, thereby generating free radicals and causing all pigments to reach their chromatic state. Then, 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), and calibration curves were constructed.

[0375] Next, 0.1 g of the thermoplastic resin layer was dissolved in methyl ethyl ketone instead of the pigment. The absorbance of the solution that caused the pigment to fully develop color was then measured using the same method as described above. Based on the calibration curve, the amount of pigment contained in the thermoplastic resin layer was calculated from the absorbance of the obtained solution containing the thermoplastic resin layer.

[0376] 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.

[0377] (Compounds that generate acids, bases, or free radicals through light)

[0378] The thermoplastic resin layer may contain compounds that generate acids, bases, or free radicals through light (also referred to as "compound C").

[0379] As compound C, it is preferred to be a compound that receives photochemical rays such as ultraviolet and visible light to generate acids, bases or free radicals.

[0380] As compound C, known photoacid generators, photoalkali generators, and photoradical polymerization initiators (photoradical initiators) can be used.

[0381] (Photochromic compounds)

[0382] From a resolution perspective, the thermoplastic resin layer preferably contains a light-fading compound.

[0383] Photochromic compounds are compounds that fade due to structural changes such as decomposition and isomerization caused by light irradiation.

[0384] As photosensitive compounds, examples of photocationic polymerization initiators that may be contained in the aforementioned photosensitive resin layer are as follows, except for the points described later, the preferred forms are also the same.

[0385] As a photosensitive compound, 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 adhesion, it is more preferable to include an oxime sulfonate compound.

[0386] Furthermore, as a photo-fading compound, a photo-fading compound having the following structure is preferred.

[0387] [Chemical Formula 3]

[0388]

[0389] (Photoradical polymerization initiator)

[0390] The thermoplastic resin layer may contain a photoradical polymerization initiator.

[0391] As photoradical polymerization initiators, examples of photoradical polymerization initiators that may be contained in the above-mentioned photosensitive resin layer are given, and the preferred forms are also the same.

[0392] (Photo-alkali-producing agent)

[0393] Thermoplastic resin compositions may contain photoalkali-generating agents.

[0394] As a photoalkali-generating agent, there are no particular limitations as long as it is a well-known photoalkali-generating 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, (4-morpholinylbenzoyl) )-1-benzyl-1-dimethylaminopropane, N-(2-nitrobenzyloxycarbonyl)pyrrolidine, tris(triphenylmethylboronic acid)hexaminecobalt(III), 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone, 2,6-dimethyl-3,5-diacetyl-4-(2-nitrophenyl)-1,4-dihydropyridine and 2,6-dimethyl-3,5-diacetyl-4-(2,4-dinitrophenyl)-1,4-dihydropyridine.

[0395] The thermoplastic resin layer may contain one or more compounds C.

[0396] From the viewpoint of visibility and resolution of the exposed and unexposed areas, the content of compound C relative to the total mass of the thermoplastic resin layer is preferably 0.1% to 10% by mass, more preferably 0.5% to 5% by mass.

[0397] (Plasticizer)

[0398] From the viewpoints of resolution, adhesion to adjacent layers, and developability, the thermoplastic resin layer preferably contains a plasticizer.

[0399] Preferably, the molecular weight (weight-average molecular weight when it is an oligomer or polymer with a molecular weight distribution) of the plasticizer is less than that of the alkali-soluble resin. The molecular weight (weight-average molecular weight) of the plasticizer is preferably 200 to 2,000.

[0400] There are no particular limitations on plasticizers as long as they are compounds that exhibit plasticity when miscible with alkali-soluble resins. From the viewpoint of imparting plasticity, plasticizers preferably contain alkene groups in their molecules, and more preferably polyalkylene glycol compounds. The alkene groups contained in the plasticizer are more preferably polyvinyloxy or polyacryloxy structures.

[0401] 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.

[0402] Examples of (meth)acrylate compounds used as plasticizers include (meth)acrylate compounds described as polymerizable compounds contained in the aforementioned photosensitive resin compositions.

[0403] When a thermoplastic resin layer and a photosensitive resin layer are laminated in direct contact in a 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.

[0404] 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 also preferable that the (meth)acrylate compound does not polymerize in the exposed portion after exposure.

[0405] 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.

[0406] Furthermore, (meth)acrylate compounds that can be used as plasticizers are preferably (meth)acrylate compounds having acid groups or urethane (meth)acrylate compounds.

[0407] The thermoplastic resin layer may contain one type of plasticizer or two or more types.

[0408] From the viewpoints of resolution, adhesion to adjacent layers, and developability of the thermoplastic resin layer, the content of plasticizer relative to the total mass 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.

[0409] (sensitizer)

[0410] The thermoplastic resin layer may contain a sensitizer.

[0411] There are no particular limitations on the sensitizers used; examples of sensitizers that may be contained in the aforementioned photosensitive resin layers can be cited.

[0412] The thermoplastic resin layer may contain one or more sensitizers.

[0413] 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 mass of the thermoplastic resin layer.

[0414] (Additives, etc.)

[0415] In addition to the above-mentioned components, the thermoplastic resin layer may also contain known additives such as surfactants, as needed.

[0416] 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.

[0417] The thickness of the thermoplastic resin layer is not particularly limited, but from the viewpoint of adhesion to adjacent layers, it is preferably 1 μm or more, 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.

[0418] <Protective film>

[0419] 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.

[0420] 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. From the viewpoint of heat resistance, polyolefin films are preferred, polypropylene films or polyethylene films are more preferred, and polyethylene films are even more preferred.

[0421] 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.

[0422] <Uses>

[0423] The transfer film of the present invention is preferably used in the formation of circuit wiring on a support substrate such as a sheet, metal substrate, ceramic substrate, or glass in the manufacturing process film of semiconductor packaging, printed circuit board, flexible printed circuit board, and intermediate rewiring layer.

[0424] <Method for manufacturing transfer film>

[0425] The method for manufacturing the transfer film of the present invention is not particularly limited, but preferably includes, in sequence: a step of forming a thermoplastic resin layer by coating on 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 on the side of the thermoplastic resin layer opposite to the side in contact with the temporary support (hereinafter also referred to as the "intermediate layer forming step"); and a step of forming the photosensitive resin layer by coating on the side of the intermediate layer opposite to the side in contact with the thermoplastic resin layer (hereinafter also referred to as the "photosensitive resin layer forming step").

[0426] 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).

[0427] 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.

[0428] (Thermoplastic resin layer formation process)

[0429] 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.

[0430] Examples of solvents include the water-soluble solvents mentioned above, 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.

[0431] Examples of coating methods for thermoplastic resin layer formation compositions include printing, spraying, roller coating, bar coating, curtain coating, spin coating, and stencil coating (i.e., slot coating).

[0432] 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.

[0433] The drying time can be set from 20 seconds to 600 seconds.

[0434] (Intermediate layer formation process)

[0435] 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.

[0436] Examples of solvents include water and the aforementioned water-soluble solvents.

[0437] 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.

[0438] (Photosensitive resin layer formation process)

[0439] 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.

[0440] (Protective film preparation process)

[0441] The protective film preparation process can include the process of adhering the protective film to the surface of the photosensitive resin layer.

[0442] The protective film lamination can be performed using known laminators such as vacuum laminators and automatic cutting laminators. The laminator preferably has any heatable rollers, such as rubber rollers, and is capable of applying pressure and heating.

[0443] [Methods for manufacturing resin patterns]

[0444] The method for manufacturing the resin pattern of the present invention preferably includes, in sequence: a step of bonding the transfer film and 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"); a step of heating the exposed photosensitive resin layer (hereinafter also referred to as the "post-exposure baking step"); and a step of developing the heated photosensitive resin layer to form a resin pattern (hereinafter also referred to as the "developing step").

[0445] (Lamination process)

[0446] In the bonding process, it is preferable to bring the surface of the photosensitive resin layer side of the transfer film into contact with the substrate and press it together. Furthermore, when the substrate is a conductive substrate as described later, it is preferable to bring the photosensitive resin layer into contact with the conductive layer and press it together.

[0447] When the transfer film has a protective film described later, it is preferable to perform the lamination process after peeling off the protective film.

[0448] Examples of pressing methods include known transfer methods and lamination methods. In particular, it is preferable to overlap the transfer film onto the circuit board and apply pressure and heat using rollers or the like.

[0449] The bonding of the transfer film to the substrate can be performed using known laminators such as vacuum laminators and automatic cutting laminators.

[0450] There is no specific limit to the lamination temperature.

[0451] 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.

[0452] When using a laminator equipped with rubber rollers, the lamination temperature refers to the temperature of the rubber rollers.

[0453] The substrate is preferably a conductive substrate (wiring substrate) having a support substrate and a conductive layer disposed on the support substrate.

[0454] Examples of supporting substrates include resin substrates, glass substrates, and semiconductor substrates.

[0455] As a preferred form of support substrate, for example, it is described in paragraph 0140 of International Publication No. 2018 / 155193, the contents of which are incorporated herein by reference.

[0456] 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.

[0457] The average thickness of the support substrate is not particularly limited and can be set from 5.0 μm to 200.0 μm.

[0458] From the viewpoint of conductivity and fine line formation, at least one layer selected from the group consisting of a free metal layer, a conductive metal oxide layer, a graphene layer, a carbon nanotube layer, and a conductive polymer layer is preferred as the conductive layer.

[0459] 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.

[0460] Preferred forms of conductive layers are described, for example, in paragraph 0141 of International Publication No. 2018 / 155193, the contents of which are incorporated herein by reference.

[0461] As a conductive substrate, a substrate having at least one of a transparent electrode and a circuitous wiring is preferred. Such a conductive substrate can be preferably used as a substrate for a touch panel.

[0462] Transparent electrodes are preferably designed to function as electrodes for touch panels. They are preferably composed of metal oxide films such as ITO (indium tin oxide) and IZO (indium zinc oxide), metal meshes, or metal nanowires.

[0463] Examples of fine metal wires include those made of silver and copper. Among these, silver conductive materials such as silver mesh and silver nanowires are preferred.

[0464] Metals are preferred as materials for circuit wiring.

[0465] Regarding metals suitable for use as materials for circuit routing, examples include gold, silver, copper, molybdenum, aluminum, titanium, chromium, zinc, manganese, and alloys composed of two or more of these metallic elements. Copper, molybdenum, aluminum, or titanium are preferred materials for circuit routing, with copper being particularly preferred.

[0466] The substrate can be a substrate on which components that connect semiconductor elements to each other are assembled.

[0467] 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.

[0468] 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.

[0469] 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.

[0470] (Exposure process)

[0471] The exposure process involves patterning the photosensitive resin layer. "Patterned exposure" refers to exposure that creates a patterned shape, with both exposed and unexposed areas.

[0472] There are no particular restrictions on the positional relationship between the exposed and unexposed areas in pattern exposure, and it can be adjusted appropriately.

[0473] Exposure can be performed from the photosensitive resin layer side or from the circuit board side.

[0474] Exposure can be performed by contact exposure, which involves bringing a mask (also known as a "photomask") into contact with a photosensitive resin layer.

[0475] Furthermore, in addition to contact exposure, exposure methods can include proximity exposure, lens projection exposure, mirror projection exposure, or direct exposure using an exposure laser. In the case of lens projection exposure, an exposure machine with an appropriate lens numerical aperture (NA) can be used according to the required resolution and depth of focus. In the case of direct exposure, it is possible to draw directly on the photosensitive resin layer or to perform reduced-size projection exposure on the photosensitive resin layer via a lens.

[0476] Furthermore, exposure can be performed under atmospheric conditions, under reduced pressure, or in a vacuum. During exposure, a liquid such as water can be placed between the light source and the photosensitive resin layer.

[0477] From the perspective of further improving resolution, the preferred exposure method is projection exposure, and a more preferred method is lens projection exposure.

[0478] There are no particular restrictions on the detailed configuration and specific size of the pattern in the pattern exposure.

[0479] From a high-precision perspective, in pattern exposure, the pattern width is preferably 5 μm or less, more preferably 2.5 μm or less. There is no particular limitation on the lower limit of the pattern width; for example, it can be 1.0 μm.

[0480] There are no particular restrictions on the light source used for exposure.

[0481] As a light source, for example, a light source that can illuminate the wavelength region of the exposure section that can be cured (e.g., 365nm or 405nm) can be cited.

[0482] Specific examples of light sources include various lasers; semiconductor light sources such as light-emitting diodes (LEDs); and discharge lamps such as ultra-high pressure mercury lamps, high pressure mercury lamps, and metal halide lamps.

[0483] There is no specific limit to the amount of exposure.

[0484] The optimal exposure level is 5 mJ / cm. 2 ~200mJ / cm 2 More preferably 10 mJ / cm 2 ~200mJ / cm 2 .

[0485] (Post-exposure baking process)

[0486] In the post-exposure baking process, the exposed photosensitive resin layer is heated.

[0487] In the photosensitive resin composition of the present invention, the proportion of acryloyl-based double bonds in the total number of double bonds in the solid component of the photosensitive resin composition is 10% to 50%, which is higher than conventional proportions. In the photosensitive resin composition, if the proportion of acryloyl-based double bonds is within the above range and the exposed photosensitive resin layer is heated, the reaction distribution originating from standing waves becomes more uniform, and the tailing and undercut of the resin pattern are suppressed. That is, the uniformity of the resin pattern shape is improved.

[0488] The baking process after exposure is preferably carried out at a heating temperature of 50℃~90℃ and a heating time of 20 seconds~80 seconds.

[0489] If the heating temperature is above 50°C, it is easy to achieve the effect of improving the shape of the resin pattern through heating.

[0490] If the heating temperature is below 90℃, the thermosetting reaction can be suppressed.

[0491] Based on the above viewpoints, the preferred heating temperature is 50℃~90℃.

[0492] If the heating time is more than 20 seconds, it is easy to achieve the effect of improving the shape of the resin pattern through heating.

[0493] If the heating time is less than 80 seconds, the thermosetting reaction can be suppressed.

[0494] Based on the above viewpoints, the heating time is preferably 30 to 60 seconds.

[0495] The surface elevation difference of the photosensitive resin layer after the exposure and baking process is preferably less than 0.1 μm, more preferably less than 0.05 μm. The lower limit of the above elevation difference is not particularly limited, and the elevation difference can be 0 μm.

[0496] The surface elevation difference of the photosensitive resin layer was determined by the following method.

[0497] The cross-section of the cut resin pattern was measured using a scanning electron microscope (SEM).

[0498] (Developing process)

[0499] In the developing process, the heated photosensitive resin layer is developed to form a resin pattern.

[0500] The development of the exposed photosensitive resin layer can be performed using a developing solution.

[0501] There are no particular restrictions on the developer; any known developer can be used.

[0502] As a developer, for example, the developer described in Japanese Patent Application Publication No. 5-72724 can be cited.

[0503] The developer is preferably an alkaline aqueous solution.

[0504] Examples of alkaline compounds that can be contained in alkaline aqueous solutions include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, and choline (2-hydroxyethyltrimethylammonium hydroxide).

[0505] There is no particular limitation on the pH of alkaline aqueous solutions.

[0506] 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.

[0507] The content of alkaline compounds in the alkaline aqueous solution is not particularly limited, but is preferably 0.1% to 5% by mass, more preferably 0.1% to 3% by mass, relative to the total mass of the alkaline aqueous solution.

[0508] There is no particular temperature limit for the developer solution.

[0509] The temperature of the developer solution is preferably, for example, 20°C to 40°C.

[0510] Examples of development methods include rotary immersion development, spray development, misting development, spray and rotation development, and immersion development.

[0511] As a developing method, the developing method described in paragraph

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

[0512] 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.

[0513] After the developing process and / or rinsing, a drying process can be performed to remove excess liquid.

[0514] (Temporary support stripping process)

[0515] The method for manufacturing the resin pattern of the present invention preferably includes a step of peeling off a temporary support in the transfer film (hereinafter also referred to as the "temporary support peeling step").

[0516] The method for peeling off the temporary support is not particularly limited, and the same mechanism as the film peeling mechanism described in paragraphs

[0161] to

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

[0517] The temporary support peeling process is preferably performed after the bonding process and before the developing process. Alternatively, the temporary support peeling process can be performed after the bonding process and before the exposure process, or it can be performed after the exposure process.

[0518] From the perspective of suppressing free radical polymerization caused by oxygen during exposure and preventing mask contamination, the temporary support peeling process is preferably performed after the bonding process and the exposure process and before the developing process.

[0519] From the viewpoint of improving the resolution of the resin pattern and suppressing defects in the resin pattern, the temporary support peeling process is preferably performed after the bonding process and before the exposure process.

[0520] In addition, the method for manufacturing the resin pattern of the present invention may include a step of further exposing the formed resin pattern (hereinafter also referred to as the "post-exposure step") and / or a step of further heating the formed resin pattern (hereinafter also referred to as the "post-baking step").

[0521] When both post-exposure and post-baking processes are included, it is preferable to perform the post-baking process after the post-exposure process.

[0522] 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 .

[0523] The heating temperature in the post-baking process is preferably 80℃~250℃, more preferably 90℃~160℃.

[0524] The heating time in the post-baking process is preferably 1 minute to 180 minutes, more preferably 10 minutes to 60 minutes.

[0525] [Methods for manufacturing conductive patterns]

[0526] As a first embodiment, preferably, the method for manufacturing the conductive pattern of the present invention includes, in sequence, a step of forming a resin pattern on a substrate using the resin pattern manufacturing method of the present invention; a step of performing a plating process on a region of the 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").

[0527] The details of the process of forming a resin pattern on the substrate are as described above.

[0528] (Plating process)

[0529] Examples of plating methods include electroplating and electroless plating. From a productivity point of view, electroplating is preferred.

[0530] There are no particular restrictions on the metals 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.

[0531] The average thickness of the coating layer formed by the plating process is not particularly limited and can be set from 0.1 μm to 20.0 μm.

[0532] (Pattern removal process)

[0533] There are no particular limitations on the method for removing resin patterns. Methods such as removal by chemical treatment can be cited, but removal by a removal solution is preferred.

[0534] Examples of removal solutions include those obtained by dissolving inorganic or organic base components in water, dimethyl sulfoxide, N-methylpyrrolidone, or a mixture thereof.

[0535] Examples of inorganic base components include sodium hydroxide and potassium hydroxide.

[0536] Examples of organic base components include primary amine compounds, secondary amine compounds, tertiary amine compounds, and quaternary ammonium salt compounds.

[0537] The preferred temperature of the removal liquid is 30°C to 80°C, and more preferably 50°C to 80°C.

[0538] 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.

[0539] Furthermore, the pattern can be removed using a removal liquid and by known methods such as spraying, spraying, or immersion.

[0540] (Protective layer formation process)

[0541] 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 resin pattern is formed and before the pattern removal step.

[0542] 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, their alloys, and resins. Nickel or chromium is preferred as the material constituting the protective layer.

[0543] Methods for forming a protective layer include electroless plating and electroplating, with electroplating being the preferred method.

[0544] The average thickness of the protective layer is not particularly limited and can be set from 0.3μm to 3.0μm.

[0545] (Seed layer removal process)

[0546] When a 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.

[0547] There is no particular limitation on the method for removing the seed layer; it can be done using a known etching solution.

[0548] 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.

[0549] As a second embodiment, preferably, the method for manufacturing the conductive pattern of the present invention includes, 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 a region of the 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").

[0550] The details of the process of forming a resin pattern on the substrate are as described above.

[0551] The preferred form of the substrate having the conductive layer is as described above.

[0552] 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.

[0553] (Etching process)

[0554] As a method of etching, well-known etching methods can be cited.

[0555] 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.

[0556] The etching solution used in wet etching can be appropriately selected as acidic or alkaline depending on the object being etched.

[0557] 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.

[0558] The acidic compound contained in the acidic aqueous solution (a compound that exhibits acidity when dissolved in water) is preferably selected from at least one of the group consisting of hydrochloric acid, sulfuric acid, nitric acid, acetic acid, hydrofluoric acid, oxalic acid, and phosphoric acid.

[0559] Examples of alkaline etching solutions include alkaline aqueous solutions containing at least one alkaline compound and alkaline mixed aqueous solutions of alkaline compounds and salts (e.g., potassium permanganate).

[0560] The alkaline compound contained in the alkaline aqueous solution (a compound that is soluble in water and exhibits alkalinity) is preferably selected from at least one of the group consisting of sodium hydroxide, potassium hydroxide, ammonia, organic amines and salts of organic amines (e.g., tetramethylammonium hydroxide).

[0561] Preferably, the etching solution does not dissolve the resist pattern.

[0562] 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.

[0563] After etching, a rinsing process can be performed to remove the etching solution. Water or similar substances can be used in the rinsing process.

[0564] A drying process to remove excess liquid can be performed after etching and / or rinsing.

[0565] Alternatively, the transfer film of the present invention can be used to manufacture circuit wiring substrates.

[0566] The method for manufacturing a circuit wiring substrate may include a step of forming a solder resist layer with openings on the surface of the substrate after the seed layer has been removed using a solder resist (hereinafter also referred to as the "solder resist layer forming step").

[0567] Preferably, the opening exposes the conductive pattern formed on the surface of the substrate.

[0568] As a solder resist, conventionally known solder resists can be used. Examples of solder resists include azide-cyclopentadiene resins, azide-phenol resins, and chloromethyl polystyrene resins.

[0569] The average thickness of the solder resist layer is not particularly limited and can be set from 5μm to 50μm.

[0570] There are no particular limitations on the method for forming the solder resist layer; it can be done using methods that are known in the past.

[0571] The method for manufacturing a circuit wiring substrate can include a step of forming bump electrodes at openings in a solder resist layer. The bump electrodes are preferably connected to conductive patterns exposed at the openings.

[0572] The manufacturing method of the circuit wiring board can include a process of mounting semiconductor elements connected to bump electrodes.

[0573] The semiconductor it carries preferably has electrodes, and preferably is connected to bump electrodes.

[0574] Preferably, after mounting the semiconductor, a conventionally known sealing material is used to seal the semiconductor.

[0575] Semiconductor Packaging

[0576] Semiconductor packaging preferably includes the aforementioned circuit wiring substrate.

[0577] <Manufacturing Methods of Printed Circuit Boards>

[0578] The transfer film of this invention can be used in the manufacture of printed circuit boards.

[0579] The manufacturing method of a printed circuit board includes, for example, a step in the manufacturing method of the above-described laminate that involves performing at least one of the following processes on a patterned substrate: etching or plating. The etching or plating of the substrate can be performed by using a developed pattern as a mask and etching or plating the surface of the substrate using a known method.

[0580] Furthermore, a process for removing residual film, such as resin etching based on a solution containing permanganate or plasma-based resin ashing, can be performed before etching or plating.

[0581] Etching solutions used in etching processes can include, for example, copper chloride solutions, ferric chloride solutions, and alkaline etching solutions. For plating, examples include copper plating, solder plating, nickel plating, and gold plating.

[0582] After etching or plating, the pattern can be removed, for example, using an aqueous solution that is more alkaline than the alkaline aqueous solution used for development. Examples of such a strongly alkaline aqueous solution include a 1% to 10% (w / w) sodium hydroxide aqueous solution and a 1% to 10% (w / w) potassium hydroxide aqueous solution. Furthermore, examples of removal methods include immersion and spraying. Additionally, the printed circuit board with the pattern can be a multilayer printed circuit board and may also have small-diameter through-holes.

[0583] When plating a substrate with a conductive layer, it is necessary to remove the conductor layer other than the pattern. Examples of such removal methods include: light etching after stripping the pattern; or stripping the pattern after plating with solder, covering the wiring with solder, and then using an etchable etchant to treat only the conductor layer not covered by the solder.

[0584] <Evaporation Mask>

[0585] The transfer film of the present invention can be used, particularly preferably, for the micro-processing of metal substrates for vapor deposition masks with micro-uneven surfaces.

[0586] The method for manufacturing a vapor deposition mask includes the step of etching a patterned substrate as described in the method for manufacturing the laminate. The etching of the substrate can be performed by using a developed pattern as a mask and etching the surface of the substrate using known methods.

[0587] After etching, the pattern can be removed, for example, using an aqueous solution that is more alkaline than the alkaline aqueous solution used for development. Examples of such a strongly alkaline aqueous solution include a 1% to 10% sodium hydroxide aqueous solution and a 1% to 10% potassium hydroxide aqueous solution. Furthermore, examples of removal methods include immersion and spraying.

[0588] Example

[0589] The present invention will be described in more detail below through examples.

[0590] The materials, quantities, proportions, processing contents, and processing order 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.

[0591] <Preparation of Photosensitive Resin Compositions>

[0592] The components used in the preparation of the photosensitive resin composition are as follows.

[0593] (Alkali-soluble resin)

[0594] Alkali-soluble resins A1 to A4 used polymers synthesized using known methods. Furthermore, the weight-average molecular weight (Mw) of the synthesized polymers was determined by gel permeation chromatography (GPC) under the following conditions.

[0595] -GPC Conditions-

[0596] Device: Manufactured by TOSOH CORPORATION, TOSOH CORPORATION High-Speed ​​GPC Device HLC-8420GPC (Product Name)

[0597] Protective tubing: Made by TOSOH CORPORATION, HZ-L

[0598] Separation column: Manufactured by TOSOH CORPORATION, consisting of three TSK gel Super HZM-N (product name) tubes connected in series.

[0599] Measurement temperature: 40℃

[0600] Eluent: THF (tetrahydrofuran)

[0601] Flow rate: Sample pump 0.35 mL / min, reference pump 0.175 mL / min

[0602] Injection volume: 10 μL

[0603] Detector: Differential refractometer

[0604] GPC column calibration standard solution: Standard polystyrene prepared by TOSOH CORPORATION

[0605] -Alkali-soluble resin A1-

[0606] 67g of propylene glycol monomethyl ether was placed in a flask and heated to 90°C under a nitrogen atmosphere. After 3 hours, a solution containing 63.7g of styrene, 1.3g of methyl methacrylate, 35g of methacrylic acid, and 4g of polymerization initiator V-601 (manufactured by FUJIFILM Wako Pure Chemical Corporation) dissolved in 33g of propylene glycol monomethyl ether was added dropwise. After the addition was complete, 1g of V-601 was added three times every hour. The reaction was then allowed to continue for another 3 hours. After the reaction, the reaction solution was diluted with 33g of propylene glycol monomethyl ether acetate and 100g of propylene glycol monomethyl ether. Under an air atmosphere, the diluted reaction solution was heated to 100°C, and 0.53g of tetraethylammonium bromide and 0.26g of p-methoxyphenol were added. After 20 minutes, 32g of glycidyl methacrylate (BLEMMER G, manufactured by NOF CORPORATION) was added dropwise to the solution. After reacting the liquid at 100°C for 7 hours, it was diluted with propylene glycol monomethyl ether acetate to obtain a solution of alkali-soluble resin A1 with a solid content of 30%.

[0607] Alkali-soluble resin A1: St / MAA / MMA / MAA-GMA = 63.7 / 19 / 1.3 / 16 (mass ratio), weight-average molecular weight 18,000

[0608] -Alkali-soluble resins A2 and A3-

[0609] Alkali-soluble resins A2 and A3 were synthesized using the same method as alkali-soluble resin A1.

[0610] Alkali-soluble resin A2: St / MAA / MMA / MAA-GMA = 47.7 / 19 / 1.3 / 32 (mass ratio), weight-average molecular weight 18,000

[0611] Alkali-soluble resin A3: St / MAA / MMA / MAA-GMA = 31.7 / 19 / 1.3 / 48 (mass ratio), weight-average molecular weight 18,000

[0612] St: Styrene (manufactured by FUJIFILM Wako Pure Chemical Corporation)

[0613] MAA: Methacrylic acid (manufactured by FUJIFILM Wako Pure Chemical Corporation)

[0614] MMA: Methyl methacrylate (manufactured by FUJIFILM Wako Pure Chemical Corporation)

[0615] MAA-GMA: A structure obtained by adding glycidyl methacrylate to structural units derived from methacrylic acid.

[0616] -Alkali-soluble resin A4-

[0617] Under a nitrogen atmosphere, a solution containing monomer M1, methacrylic acid, methyl methacrylate, styrene, polymerization initiator V-601, and N-methylpyrrolidone was added dropwise over 2 hours to N-methylpyrrolidone (21.5 g) heated to 90 °C. After the addition of the solution, 0.5 g of V-601 was added dropwise three times every hour. The mixture was allowed to react at 90 °C for 3 hours, then cooled to room temperature. The reaction solution was diluted with N-methylpyrrolidone, and triethylamine and 4-methoxyphenol were added, followed by stirring at room temperature for 12 hours. The reaction solution was diluted with methanol, and then the diluted solution was added dropwise to a mixture of concentrated hydrochloric acid and distilled water. The precipitated powder was extracted by filtration. The powder was stirred in 1000 g of distilled water, and the filtration process was repeated three times until the filtrate was neutral. The obtained powder was dried in a 50-degree blower dryer and diluted with propylene glycol monomethyl ether acetate to obtain a solution of alkali-soluble resin A4 with a solid content concentration of 30%.

[0618] [Chemical Formula 4]

[0619]

[0620] The structure of alkali-soluble resin A4 is as follows. The numerical values ​​of each structural unit represent the mass ratio. The weight-average molecular weight of alkali-soluble resin A4 is 18,000.

[0621] [Chemical Formula 5]

[0622]

[0623] (Polyfunctional (meth)acrylates)

[0624] BPE-100: 2,2-bis(4-(methacryloylethoxy)phenyl)propane, manufactured by Shin-Nakamura Chemical Co., Ltd.

[0625] BPE-500: 2,2-bis(4-(methacryloyloxypentethoxy)phenyl)propane, manufactured by Shin-Nakamura Chemical Co., Ltd.

[0626] ABE-300: 2,2-bis(4-(acryloylethoxy)phenyl)propane, manufactured by Shin-Nakamura Chemical Co., Ltd.

[0627] • A-DCP: Tricyclodecanediethanol diacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd.

[0628] • ARONIX M-270: Polypropylene glycol diacrylate (n≈12), manufactured by TOAGOSEI CO., LTD., see "M-270" in the table.

[0629] (Polymerization initiator)

[0630] • B-CIM: 2,2'-Bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbisimidazole, manufactured by Hampford Company

[0631] (sensitizer)

[0632] ·SB-PI 701: 4,4'-bis(diethylamino)benzophenone, manufactured by SANYO TRADING CO.,LTD.

[0633] (Chain transfer agent)

[0634] N-Phenylacetomethyl-N-carbonylmethylaniline: Produced by FUJIFILM Wako Pure Chemical Corporation

[0635] (pigment)

[0636] • Colorless crystal violet: Manufactured by Tokyo Chemical Industry Co., Ltd.

[0637] (Rust inhibitor)

[0638] • CBT-1: Carboxybenzotriazole, manufactured by Johoku Chemical Co., Ltd.

[0639] (Polymerization inhibitor)

[0640] • TDP-G: Phenothiazine, manufactured by Kawaguchi Chemical Industry Co., Ltd.

[0641] (surfactant)

[0642] • Polymer W1: A polymer synthesized by the following methods.

[0643] 14.0 g of cyclopentanone was added to a 300 mL three-necked flask equipped with a cooling tube, thermometer, stirring blade, and nitrogen inlet tube, and the mixture was heated to 80 °C. After 120 minutes, a mixed solution of 18.00 g (42.6 mmol) of SILAPLANE TM-0701T (JNC Corporation), 12.00 g (30.2 mmol) of compound (a) below, 0.25 g (1.1 mmol) of V-601 (manufactured by FUJIFILM Wako Pure Chemical 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 V-601 and 1.40 g of cyclopentanone was added, and aging was carried out for another hour. Then, a mixed solution of 0.17 g (0.7 mmol) of V-601 and 1.40 g of cyclopentanone was added again, and aging was carried out for 3 hours, yielding a solution of 98.5 g of the target polymer W1.

[0644] The obtained W1 has a weight-average molecular weight (Mw) of 24,700 and an Mw / Mn ratio of 2.8. Furthermore, the reaction was confirmed by NMR.

[0645] [Chemical Formula 6]

[0646]

[0647] The structure of polymer W1 is as follows. The numerical values ​​of each structural unit represent the mass ratio.

[0648] [Chemical Formula 7]

[0649]

[0650] (solvent)

[0651] MMPG-Ac: 1-Methoxy-2-propylacetic acid ester

[0652] MEK: Methyl Ethyl Ketone

[0653] PGME: Propylene Glycol Monomethyl Ether

[0654] The photosensitive resin compositions P1-P6 and P1a-P3a were prepared by mixing the components according to the description in Table 1.

[0655] In addition, the values ​​in the table represent the content of each component in parts by mass.

[0656] [Table 1]

[0657]

[0658] <Preparation of the composition for forming the intermediate layer>

[0659] The components used in the preparation of the composition for forming the intermediate layer are as follows.

[0660] (Resin)

[0661] • PVA: Polyvinyl alcohol, product name "KURARAY POVAL PVA-205", manufactured by Kuraray Co., Ltd.

[0662] • PVP: Polyvinylpyrrolidone, product name "Polyvinylpyrrolidone K-30", manufactured by NIPPON SHOKUBAICO.,LTD.

[0663] • HPMC: Hydroxypropyl methylcellulose, product name "METOLOSE 60SH-03", manufactured by Shin-Etsu Chemical Co., Ltd.

[0664] (surfactant)

[0665] • Silicone surfactant, product name "BYK-345", manufactured by BYK Japan KK.

[0666] (solvent)

[0667] Pure water

[0668] MeOH: Methanol

[0669] The components were mixed according to the description in Table 2 to prepare composition M1 for forming an intermediate layer.

[0670] In addition, the values ​​in the table represent the content of each component in parts by mass.

[0671] [Table 2]

[0672]

[0673] <Preparation of compositions for thermoplastic resin layer formation>

[0674] The components used in the preparation of the composition for forming thermoplastic resin layers are as follows.

[0675] (Resin)

[0676] • A copolymer of benzyl methacrylate (BzMA), methacrylic acid (MAA), and acrylic acid (AA) (BzMA:MAA:AA = 55:25:20 (mass ratio)), weight average molecular weight (Mw) = 25,000

[0677] (Plasticizer)

[0678] • A-DCP: Tricyclodecanediethanol diacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd.

[0679] ·8UX-015A: Carbamate acrylate, manufactured by Taisei Fine Chemical Co., Ltd.

[0680] ARONIX TO-2349: A polyfunctional acrylate with a carboxyl group (manufactured by TOAGOSEI CO.,LTD.)

[0681] (Rust inhibitor)

[0682] • CBT-1: Carboxybenzotriazole, manufactured by Johoku Chemical Co., Ltd.

[0683] (Polymerization inhibitor)

[0684] • TDP-G: Phenothiazine, manufactured by Kawaguchi Chemical Industry Co., Ltd.

[0685] (Photo-acid generator)

[0686] Compound 1: Represented by the following structure.

[0687] [Chemical Formula 8]

[0688]

[0689] Compound 2: Represented by the following structure.

[0690] [Chemical Formula 9]

[0691]

[0692] (surfactant)

[0693] Polymer W1

[0694] (solvent)

[0695] MMPG-Ac: 1-Methoxy-2-propylacetic acid ester

[0696] MEK: Methyl Ethyl Ketone

[0697] PGME: Propylene Glycol Monomethyl Ether

[0698] Thermoplastic resin layer forming compositions T1 to T3 were prepared by mixing the components according to the description in Table 3.

[0699] In addition, the values ​​in the table represent the content of each component in parts by mass.

[0700] [Table 3]

[0701]

[0702] <Manufacturing of Transfer Film>

[0703] Table 4 shows the types of photosensitive resin compositions used to form photosensitive resin layers, the types of thermoplastic resin compositions used to form thermoplastic resin layers, and the types of intermediate layer compositions used to form intermediate layers.

[0704] Using a slit nozzle, a thermoplastic resin layer forming composition is applied to a temporary support (polyethylene terephthalate film, thickness: 16 μm, haze: 0.12%) until the coating width is 1.0 μm and the dried layer thickness is 6.0 μm. The formed coating is dried at 80°C for 40 seconds to form a thermoplastic resin layer. Using a slit nozzle, an intermediate layer forming composition is applied to the formed thermoplastic resin layer until the coating width is 1.0 μm and the dried layer thickness is 1.2 μm. The coating is dried at 80°C for 40 seconds to form an intermediate layer. Using a slit nozzle, a photosensitive resin composition is applied to the formed intermediate layer until the coating width is 1.0 μm and the dried layer thickness is 3.0 μm, and then dried in a convection oven at 100°C for 2 minutes to form a photosensitive resin layer. A transfer film was made by laminating a protective film (polypropylene film, thickness: 12μm, haze: 0.2%) onto a photosensitive resin layer.

[0705] The following evaluation was conducted using the prepared transfer film.

[0706] <Resolution>

[0707] A silicon wafer with a seed layer formed thereon was prepared as a substrate.

[0708] The prepared transfer film was laminated onto the substrate (lamination process). The lamination was performed using a 100°C hot roller at a pressure of 0.7 MPa and a speed of 2 m / min.

[0709] Next, the temporary support was removed (temporary support removal process).

[0710] The pattern was exposed through a mask using a projection exposure device with a theoretical resolution of 1.5µm that uses a high-pressure mercury lamp as a light source (exposure process).

[0711] When using a 41-level step scale manufactured by Stouffer for exposure and developing for 2.0 times the minimum development time, the exposure is set to an exposure with a residual step count of 13. Furthermore, the minimum development time refers to the time taken from unexposed conditions until the photosensitive resin layer is completely removed.

[0712] As a mask, a mask containing a wiring pattern (L=1μm~2μm, 0.1μm scale, 10 lines) with a line width (L) / spacing (S) of 1 / 1 was used in the resin pattern.

[0713] After exposure, the exposed photosensitive resin layer was heated at the heating temperature and heating time shown in Table 5 (post-exposure baking process). In Example 8, the post-exposure baking process was not performed.

[0714] After exposure, development was performed for twice the shortest development time to obtain a resin pattern.

[0715] The L / S value of the pattern without residue or peeling is used as the "resolution" value.

[0716] <Shape>

[0717] The resin pattern obtained at the aforementioned resolution was cut along a direction perpendicular to the substrate. The cross-section of the resin pattern was observed using a scanning electron microscope (SEM: S-4800 (Hitachi High-Tech Corporation)). Perpendicular lines were drawn from the two corners of the resin pattern's head (outermost side) towards its bottom. The distances between the bottom corners of the resin pattern and the perpendicular lines were measured, and the average values ​​were calculated.

[0718] Additionally, a "tail" is formed when the bottom corner of a resin pattern is located outside the vertical line.

[0719] When the bottom corner of a resin pattern is inside the vertical line, it is called "undercut".

[0720] A: The average distance is less than 0.05μm.

[0721] B: The average distance is greater than 0.05μm and less than 0.1μm.

[0722] C: The average distance is greater than 0.1 μm and less than 0.15 μm.

[0723] D: The average distance exceeds 0.15 μm.

[0724] The evaluation results are shown in Table 5.

[0725] In Table 5, the "total double bond content", "content of acryloyl-based double bonds", "content of methacryloyl-based double bonds" and "content of double bonds in alkali-soluble resins" are based on the total amount of solid components in the photosensitive resin composition.

[0726] "The proportion of acryloyl-based double bonds" refers to the proportion of acryloyl-based double bonds in the total number of double bonds in the solid component of the photosensitive resin composition.

[0727] "The proportion of double bonds in the alkali-soluble resin" refers to the proportion of double bonds in the alkali-soluble resin to the total number of double bonds in the solid component of the photosensitive resin composition.

[0728] "Inhibitor / Acryloyl-based Double Bond" refers to the molar ratio of the inhibitor content to the acryloyl-based double bond content.

[0729]

[0730] As shown in Table 4, in Examples 1 to 12, the photosensitive resin composition comprises: an alkali-soluble resin containing crosslinking groups having double bonds; a polyfunctional (meth)acrylate; and a polymerization inhibitor. The total double bond content in the solid component of the photosensitive resin composition is 2.00 mmol / g or more relative to the total amount of solid components in the photosensitive resin composition. The proportion of acryloyl-based double bonds in the total number of double bonds in the solid component of the photosensitive resin composition is 10% to 50%. The molar ratio of the polymerization inhibitor content to the acryloyl-based double bond content is 0.001 to 0.015. Therefore, a resin pattern with good shape and excellent resolution can be formed.

[0731] On the other hand, in Comparative Example 1, the proportion of double bonds based on acryloyl groups was less than 10%, and the shape of the resin pattern was poor.

[0732] In Comparative Example 2, the proportion of double bonds based on acryloyl groups exceeded 50%, resulting in poor resin pattern shape.

[0733] In Comparative Example 3, the total double bond content in the solid component of the photosensitive resin composition was less than 2.00 mmol / g, indicating that the resin pattern had poor shape and resolution.

[0734] In Example 2, the proportion of double bonds in the alkali-soluble resin is more than 20%, indicating that the shape of the resin pattern is better than that in Example 1.

[0735] In Example 3, the proportion of double bonds in the alkali-soluble resin was less than 40%, indicating that the shape of the resin pattern was better compared to Example 4.

[0736] Furthermore, the surface elevation difference of the photosensitive resin layer was measured using the transfer film of Example 12.

[0737] Similar to the resolution evaluation method described above, the bonding process, the temporary support peeling process, the exposure process, and the post-exposure baking process were implemented.

[0738] The obtained photosensitive resin layer has a shape with a convex cross-section for the transmissive portion and a concave cross-section for the light-shielding portion during pattern exposure, with an L / S = 2μm / 2μm pattern, and a concave-convex spacing of 2μm. The surface elevation difference of the photosensitive resin layer is 0.03μm.

[0739] Symbol Explanation

[0740] 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 photosensitive resin composition comprising: Alkali-soluble resins containing crosslinking groups with double bonds; Polyfunctional (meth)acrylates; and Polymerization inhibitor, The total double bond content in the solid component of the photosensitive resin composition is 2.00 mmol / g or more relative to the total solid component of the photosensitive resin composition. The proportion of acryloyl double bonds in the total number of double bonds in the solid component of the photosensitive resin composition is 10% to 50%. The molar ratio of the content of the polymerization inhibitor to the content of the acryloyl-based double bond is 0.001 to 0.

015.

2. The photosensitive resin composition according to claim 1, wherein, The number of double bonds in the alkali-soluble resin accounts for 20% to 40% of the total number of double bonds in the solid component of the photosensitive resin composition.

3. The photosensitive resin composition according to claim 1, wherein, The crosslinking group is (meth)acryloyloxy.

4. The photosensitive resin composition according to claim 1, wherein, The polyfunctional (meth)acrylates comprise difunctional (meth)acrylates.

5. A transfer film comprising: Temporary support structure; and A photosensitive resin layer disposed on the temporary support and formed of the photosensitive resin composition according to any one of claims 1 to 4.

6. The transfer film according to claim 5, wherein an intermediate layer is provided between the temporary support and the photosensitive resin layer.

7. The transfer film according to claim 5, wherein a thermoplastic resin layer is provided between the temporary support and the photosensitive resin layer.

8. The transfer film according to claim 7, wherein, The thermoplastic resin layer contains a light-fading compound.

9. A method for manufacturing a resin pattern, comprising the following steps: The process of bonding the transfer film to the substrate in such a way that the photosensitive resin layer in the transfer film of claim 5 comes into contact with the substrate; The process of exposing the laminated photosensitive resin layer to a pattern; The process of heating the exposed photosensitive resin layer; and The process of developing a heated photosensitive resin layer to form a resin pattern.

10. The method for manufacturing a resin pattern according to claim 9, wherein, The process of heating the exposed photosensitive resin layer is carried out at a heating temperature of 50°C to 90°C and a heating time of 20 to 80 seconds.

11. The method for manufacturing a resin pattern according to claim 9, 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.

12. The method for manufacturing a resin pattern according to claim 9, wherein, The surface elevation difference of the heated photosensitive resin layer is less than 0.1 μm.

13. A method for manufacturing a conductive pattern, comprising the following steps: The process of forming the resin pattern on a substrate using the resin pattern manufacturing method according to claim 9; The process of plating the substrate in areas where the resin pattern is not formed; and The process of removing the resin pattern.

14. A method for manufacturing a conductive pattern, comprising the following steps: The process of forming the resin pattern on a conductive substrate using the resin pattern manufacturing method of claim 9. A process of etching the area of ​​the conductive substrate where the resin pattern is not formed. and The process of removing the resin pattern.

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